USOO8546622B2

(12) United States Patent (10) Patent No.: US 8,546,622 B2

Jevtic et al. (45) Date of Patent: *Oct. 1, 2013
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U.S. PATENT DOCUMENTS
Primary Examiner — Elvis O Price
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2,882.244. A 4, 1959 Milton 11 Claims, 4 Drawing Sheets
 US 8,546,622 B2
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PROCESS FOR MAKING ETHANOL FROM acetic acid in the presence of a catalyst to form ethanol,
ACETIC ACID USING ACDC CATALYSTS wherein the hydrogenation has a selectivity to ethanol of at
CROSS REFERENCE TO RELATED
least 65% wherein the catalyst comprises a first metal on an
APPLICATIONS
acidic Support selected from the group consisting of (i) an
acidic Support material selected from the group consisting of
This is a continuation-in-part application of U.S. applica iron oxide, alumina, Silica/aluminas, titania, Zirconia, and
tion Ser. No. 12/699,024, filed Feb. 2, 2010; U.S. application mixtures thereof, and (ii) a Support material modified with an
acidic modifier.
Ser. No. 12/698.947, filed Feb. 2, 2010; U.S. application Ser. In a second embodiment, the present invention is directed
No. 12/588,727, filed Oct. 26, 2009; and U.S. application Ser. 10 to a process for producing ethanol, comprising hydrogenating
No. 12/221,141, filed Jul. 31, 2008. This application also is a acetic acid in the presence of a first catalyst to form an inter
continuation-in-part of U.S. application Ser. No. 12/852.227,
filed Aug. 6, 2010, which claims priority to U.S. Provisional mediate product comprising ethanol and unreacted acetic
App. No. 61/300,815, filed Feb. 2, 2010, and U.S. Provisional acid; and hydrogenating the unreacted acetic acid in the
App. No. 61/332,696, filed May 7, 2010. This application also present of a second catalyst to form ethanol. The first catalyst
is a continuation-in-part of U.S. application Ser. No. 12/852, 15 comprising a catalyst comprising one or more metals, a sili
269, filed Aug. 6, 2010, which claims priority to U.S. Provi caceous Support, and at least one basic Support modifier. The
sional App. No. 61/300,815, filed Feb. 2, 2010 and U.S. second catalyst comprises a first metal on an acidic Support
Provisional App. No. 61/332,699, filed May 7, 2010. The selected from the group consisting of (i) an acidic Support
entireties of these applications are incorporated herein by material selected from the group consisting of iron oxide,
reference. alumina, silica/aluminas, titania, Zirconia, and mixtures
FIELD OF THE INVENTION
thereof, and (ii) a Support material modified with an acidic
modifier.
The present invention relates generally to processes for In a third embodiment, the present invention is directed to
a process for producing ethanol, comprising hydrogenating
producing ethanol and, in particular, to processes for produc 25 acetic acid in the presence of a first catalyst and a second
ing ethanol from the hydrogenation of acetic acid using acidic catalyst in a reactor to form ethanol. The first catalyst may be
catalysts.
in a first reactor region and the second catalyst may be in a
BACKGROUND OF THE INVENTION second reactor region, that is separated from the first reactor
region. The first catalyst comprising a catalyst comprising
Ethanol for industrial use is conventionally produced from 30 one or more metals, a silicaceous Support, and at least one
petrochemical feed stocks, such as oil, natural gas, or coal, basic Support modifier. The second catalyst comprises a first
from feed stock intermediates, such as Syngas, or from metal on an acidic support selected from the group consisting
starchy materials or cellulose materials, such as corn or Sugar of: (i) an acidic Support material selected from the group
cane. Conventional methods for producing ethanol from pet consisting of iron oxide, alumina, silica/aluminas, titania,
rochemical feed stocks, as well as from cellulose materials, 35 Zirconia, and mixtures thereof, and (ii) a Support material
include the acid-catalyzed hydration of ethylene, methanol modified with an acidic modifier.
homologation, direct alcohol synthesis, and Fischer-TropSch In a fourth embodiment, the present invention is directed to
synthesis. Instability in petrochemical feed stock prices con a process for recovering ethanol, comprising hydrogenating
tributes to fluctuations in the cost of conventionally produced an acetic acid feed stream in a reactor comprising a catalyst to
ethanol, making the need for alternative sources of ethanol 40 form a crude ethanol product. The catalyst comprises a first
production all the greater when feedstock prices rise. Starchy metal on an acidic Support selected from the group consisting
materials, as well as cellulose material, are converted to etha of (i) an acidic Support material selected from the group
nol by fermentation. However, fermentation is typically used consisting of iron oxide, alumina, silica/aluminas, titania,
for consumer production of ethanol for fuels or consumption. Zirconia, and mixtures thereof, and (ii) a Support material
In addition, fermentation of starchy or cellulose materials 45 modified with an acidic modifier. The process further com
competes with food sources and places restraints on the prises separating at least a portion of the crude ethanol prod
amount of ethanol that can be produced for industrial use. uct in a first column into a first distillate comprising ethanol,
Ethanol production via the reduction of alkanoic acids
and/or other carbonyl group-containing compounds has been water and ethyl acetate, and a first residue comprising acetic
widely studied, and a variety of combinations of catalysts, acid; separating at least a portion of the first distillate in a
Supports, and operating conditions have been mentioned in 50 second column into a second distillate comprising ethyl
the literature. During the reduction of alkanoic acid, e.g., acetate and a second residue comprising ethanol and water;
acetic acid, other compounds are formed with ethanol or are returning at least a portion of the second distillate to the
formed in side reactions. These impurities and byproducts reactor; and separating at least a portion of the second residue
limit the production and recovery of ethanol from such reac in a third column into a third distillate comprising ethanol and
tion mixtures. For example, during hydrogenation, esters are 55 a third residue comprising water.
produced that together with ethanol and/or water, form azeo The acidic modifier used in embodiments of the present
tropes, which are difficult to separate. In addition, when con invention preferably is selected from the group consisting of
version is incomplete, unreacted acid remains in the crude oxides of Group IVB metals, oxides of Group VB metals,
ethanol product, which must be removed to recover ethanol. oxides of Group VIB metals, oxides of Group VIIB metals,
Thus, the need remains for improved processes for produc 60 oxides of Group VIIIB metals, aluminum oxides, and mix
ing ethanol via alkanoic acid reduction, which yield crude tures thereof.
ethanol products containing fewer impurities and byproducts.
BRIEF DESCRIPTION OF DRAWINGS
SUMMARY OF THE INVENTION
65 The invention is described in detail below with reference to
In a first embodiment, the present invention is directed to a the appended drawings, wherein like numerals designate
process for producing ethanol, comprising hydrogenating similar parts.
 US 8,546,622 B2
3 4
FIG. 1 is a schematic diagram of a hydrogenation system in converted to a compound other than acetic acid. Conversion is
accordance with one embodiment of the present invention. expressed as a mole percentage based on acetic acid in the
FIG. 2A is a schematic diagram of a reaction Zone having feed. Selectivity is expressed as a mole percent based on
dual reactors in accordance with one embodiment of the converted acetic acid. It should be understood that each com
present invention. pound converted from acetic acid has an independent selec
FIG.2B is a schematic diagram of a reaction Zone having a tivity and that selectivity is independent from conversion. For
reactor with two reactor regions in accordance with another example, if 50 mole % of the converted acetic acid is con
embodiment of the present invention. verted to ethanol, the ethanol selectivity is 50%.
FIG. 3 is a graph of acetic acid conversion in accordance At low conversion of acetic acid, e.g. less than about 50%,
with an example of the present invention. 10 an acidic catalyst tends to show increased selectivity to ethyl
FIG. 4 is a graph of acetic acid conversion of different acetate over ethanol. Thus, in some embodiments of the
catalysts in accordance with an example of the present inven present invention, to produce ethanol, the conversion of acetic
tion. acid is preferably greater than 70%, e.g., greater than 80%,
greater than 90% or greater than 95%.
DETAILED DESCRIPTION OF THE INVENTION 15 In the inventive processes, the selectivity to ethanol is
preferably at least 65%, e.g., at least 70%, at least 80%, at
The present invention relates to processes for producing least 85%, or at least 90%. At lower conversions of acetic
ethanol and to processes for recovering ethanol from a crude acid, around 70%, the selectivity to ethanol may be approxi
ethanol product. The crude acetic acid product, in one mately 30% to 40%. Preferably, as the acetic acid conversion
embodiment, is produced by a hydrogenation process com increases the selectivity to the ethanol also increases. In addi
prising hydrogenating acetic acid in the presence of an acidic tion, the selectivity to ethyl acetate may below, e.g., less than
catalyst. In one embodiment, the acidic catalyst comprises a 35%, less than 30%, less than 10%, or less than 5%. Prefer
first metal on an acidic Support. In one embodiment, the acidic ably, the hydrogenation process also have low selectivity to
catalyst comprises a first metal on an Support and an acidic undesirable products, such as methane, ethane, and carbon
Support modifier. 25 dioxide. The selectivity to these undesirable products prefer
During hydrogenation of acetic acid, there are other side ably is less than 4%, e.g., less than 2% or less than 1%. More
reactions that produce impurities and byproducts. One prin preferably, these undesirable products are not readily detect
cipal side reaction is an equilibrium reaction between acetic able in the crude ethanol product. Formation of alkanes may
acid/ethanol and ethyl acetate/water also occurs. The two below. Ideally less than 2% of the acetic acid passed over the
main reactions are: 30 catalystis converted to alkanes, e.g., less than 1%, or less than
HOAc+2H-esEtOH+HO Reaction 1 O.5%.
Embodiments of the present invention provide for
HOAc+EtOHe sEtOAc+HO Reaction 2 increased productivity of ethanol at high conversions of acetic
Reaction 2 is reversible and the equilibrium constant, Keq acid. When acetic acid conversion is preferably greater than
is given by Equation 1: 35 90%, the selectivity to ethanol preferably is at least 70%.
Selectivity may continue to increase as conversion of acetic
acid increases.
k° (EtOAc)(H.O. Equation 1 The term “productivity,” as used herein, refers to the grams
K =- r=
“ k-2 T HOAc)(EtOH of a specified product, e.g., ethanol, formed during the hydro
40 genation per kilogram of catalyst used per hour. A productiv
ity of at least 200 grams of ethanol per kilogram catalyst per
Generally, to produce ethanol the reaction conditions favor hour is preferred, e.g., at least 400 or at least 600. In terms of
the first reaction over the second reaction, which consumes ranges, the productivity preferably is from 200 to 3,000 grams
ethanol and increases the ethyl acetate byproducts in the of ethanol per kilogram catalyst per hour, e.g., from 400 to
crude ethanol product. In U.S. Pub. No. 2010/0197985, the 45 2,500 or from 600 to 2,000.
entirety of which is incorporated herein by reference, the first Embodiments of the present invention provide for increase
reaction is favored and is promoted by the use of a catalyst productivity at high conversion of acetic acid. At 70% or
comprising a basic modifier. greater acetic acid conversion the productivity of ethanol is at
In Some embodiments, the present invention uses an acidic least 350 grams of ethanol per kilogram catalyst per hour.
catalyst, which preferably comprises a first metal on an acidic 50 Productivity may continue to increase as conversion of acetic
support. Without being bound by theory, it is believed that the acid increases.
second reaction is promoted in the presence of acid. Also in The hydrogenation of acetic acid to form ethanol and water
the vapor phase, K is believed to decrease at higher tem is conducted in the present of an acidic catalyst. In one
peratures. In embodiments of the present invention, K, may embodiment, hydrogenation catalysts comprises a first metal
be less than 20, e.g., less than 15 or less than 12. Preferably, 55 on an acidic Support and optionally one or more of a second
K may be less than 6, e.g., less than 4 or less than 3. As such, metal, a third metal or additional metals. The first and
the acidic catalyst increases forward and reverse reaction optional second and third metals may be selected from Group
rates for the equilibrium reaction. In embodiments where IB, IIB, IIIB, IVB, VB, VIIB, VIIB, VIII transitional metals,
K>1, and under reaction conditions that favor high conver a lanthanide metal, an actinide metal or a metal selected from
sions of acetic acid, the selectivity to ethanol is Surprisingly 60 any of Groups IIIA, IVA, VA, and VIA. Preferred metal com
and unexpectedly high. The productivity of ethanol also binations for some exemplary catalyst compositions include
increases at high conversions. Increasing conversion and platinum/tin, platinum/ruthenium, platinum/rhenium, palla
selectivity to ethanol advantageously reduce the amount of dium/ruthenium, palladium/rhenium, cobalt/palladium,
byproducts in the crude ethanol product and, as a result, may cobalt/platinum, cobalt?chromium, cobalt/ruthenium, silver/
improve the efficiency of recovering ethanol. 65 palladium, copper/palladium, nickel/palladium, gold/palla
For purposes of the present invention, the term “conver dium, ruthenium/rhenium, and ruthenium/iron. Exemplary
sion” refers to the amount of acetic acid in the feed that is catalysts are further described in U.S. Pat. No. 7,608,744 and
 US 8,546,622 B2
5 6
U.S. Pub. Nos. 2010/002.9995 and 2010/0197985, the entire ity of the support material. The total weight of the support
ties of which are incorporated herein by reference. material or modified Support material, based on the total
In one exemplary embodiment, the catalyst comprises a weight of the catalyst, preferably is from 75 wt.% to 99.9
first metal selected from the group consisting of copper, iron, wt.%, e.g., from 78 wt.% to 97 wt.%, or from 80 wt.% to 95
cobalt, nickel, ruthenium, rhodium, palladium, osmium, iri wt.%. In embodiments that use a modified Support material,
dium, platinum, titanium, Zinc, chromium, rhenium, molyb the catalyst may comprise the Support modifier in an amount
denum, and tungsten. Preferably, the first metal is selected from 0.1 wt.% to 50 wt.%, e.g., from 0.2 wt.% to 25 wt.%,
from the group consisting of platinum, palladium, cobalt, from 0.5 wt.% to 15 wt.%, or from 1 wt.% to 8 wt.%, based
nickel, and ruthenium. More preferably, the first metal is on the total weight of the catalyst.
selected from platinum and palladium. When the first metal 10 Suitable Support materials may include, for example,
comprises platinum, it is preferred that the catalyst comprises stable metal oxide-based Supports or ceramic-based supports.
platinum in an amount less than 5 wt.%, e.g., less than 3 Preferred support materials include are selected from the
wt.% or less than 1 wt.%, due to the high demand for group consisting of silica, silica/alumina, calcium metasili
platinum. cate, pyrogenic silica, high purity silica, carbon, iron oxide,
As indicated above, the catalyst optionally further com 15 alumina, silica/aluminas, titania, Zirconia, and mixtures
prises a second metal, which typically would function as a thereof. In one preferred embodiment, an acidic Support
promoter. If present, the second metal preferably is selected material may be used for the catalyst. Acidic Support materi
from the group consisting of copper, molybdenum, tin, chro als are selected from the group consisting of iron oxide,
mium, iron, cobalt, Vanadium, tungsten, palladium, platinum, alumina, silica/aluminas, titania, Zirconia, and mixtures
lanthanum, cerium, manganese, ruthenium, rhenium, gold, thereof.
and nickel. More preferably, the second metal is selected from In the production of ethanol, the catalyst Support material
the group consisting of copper, tin, cobalt, rhenium, and may be modified with a support modifier. Preferably, the
nickel. More preferably, the second metal is selected from tin catalyst Support material that are basic or neutral. Such as
and rhenium. silica, metasilicate, pyrogenic silica, high purity silica, car
If the catalyst includes two or more metals, e.g., a first 25 bon, or mixtures thereof are modified with an acidic support
metal and a second metal, the first metal optionally is present modifier. Acidic support materials may also be modified with
in the catalyst in an amount from 0.1 to 10 wt.%, e.g., from an acidic Support modifier. In some embodiments, the acidic
0.1 to 5 wt.%, or from 0.1 to 3 wt.%. The second metal Support modifier adjusts the Support material by increasing
preferably is present in an amount from 0.1 and 20 wt.%, e.g., the number or availability of acid sites. The acidic sites pro
from 0.1 to 10 wt.%, or from 0.1 to 5 wt.%. In one embodi 30 mote the kinetic rate of the esterification equilibrium. Prefer
ment, the metal loading of the acidic catalyst may be reduced. ably, the support modifier is an acidic modifier that has a low
This may advantageously decrease the costs associated with volatility or no volatility. Suitable acidic support modifiers
catalyst having higher metal loadings. Thus, in embodiments may be selected from the group consisting of oxides of
having reduced metal loadings, the first metal may be present Group IVB metals, oxides of Group VB metals, oxides of
in amounts from 0.1 to 1.7 wt.% and the second metal may be 35 Group VIB metals, oxides of Group VIIB metals, oxides of
present in amounts from 0.1 to 1.3 wt.%. For catalysts com Group VIIIB metals, aluminum oxides, and mixtures thereof.
prising two or more metals, the two or more metals may be Acidic support modifiers include those selected from the
alloyed with one another or may comprise a non-alloyed group consisting of TiO, ZrO2, NbOs, Ta-Os, Al2O. B.O.
metal Solution or mixture. POs, and SbO. Preferred acidic support modifiers include
The preferred metal ratios may vary depending on the 40 those selected from the group consisting of TiO, ZrO.
metals used in the catalyst. In some exemplary embodiments, NbOs, Ta-Os, and Al-O. The acidic modifier may also
the mole ratio of the first metal to the second metal is from include WO, MoO, FeO, CrOs. VO, MnO, CuO,
10:1 to 1:10, e.g., from 4:1 to 1:4, from 2:1 to 1:2, from 1.5:1 COO, BiO.
to 1:1.5 or from 1.1:1 to 1:1.1. In one embodiment, to favor In one preferred aspect of the present invention, the acidic
selectivity to ethanol where the catalyst comprises platinum 45 catalyst comprises:
and tin, the Pt/Sn molar ratio preferably is from 0.4:0.6 to (i) a first metal comprising a Group VIII metal,
0.6:0.4, e.g., from 0.45:0.55 to 0.55:0.45 or about 1:1. In (ii) a second metal comprising copper, molybdenum, tin,
another embodiment, to favor selectivity to ethanol in chromium, iron, cobalt, Vanadium, tungsten, palladium, plati
embodiments where the catalyst comprises rhenium and pal num, lanthanum, cerium, manganese, ruthenium, rhenium,
ladium, the Re/Pd molar ratio preferably is from 0.6:0.4 to 50 gold, and nickel, and
0.85:0.15, e.g., from 0.7:0.3 to 0.85:0.15, or a molar ratio of (iii) an acidic support that comprises an acidic Support
about 0.75:0.25. material selected from the group consisting of iron oxide,
The catalyst may also comprise a third metal selected from alumina, silica/aluminas, titania, Zirconia, and mixtures
any of the metals listed above in connection with the first or thereof.
second metal, so long as the third metal is different from the 55 The acidic Support may further comprise an acidic Support
first and second metals. In preferred aspects, the third metal is modifier.
selected from the group consisting of cobalt, palladium, In another preferred aspect of the present invention, the
ruthenium, copper, Zinc, platinum, tin, and rhenium. More acidic catalyst comprises:
preferably, the third metal is selected from cobalt, palladium, (i) a first metal comprising a Group VIII metal,
and ruthenium. When present, the total weight of the third 60 (ii) a second metal comprising copper, molybdenum, tin,
metal preferably is from 0.05 and 4 wt.%, e.g., from 0.1 to 3 chromium, iron, cobalt, Vanadium, tungsten, palladium, plati
wt.%, or from 0.1 to 2 wt.%. num, lanthanum, cerium, manganese, ruthenium, rhenium,
In addition to the one or more metals, the inventive acidic gold, and nickel, and
catalysts, in Some embodiments, further comprise an acidic (iii) an acidic support that comprises a Support material and
Support material or modified Support material. A modified 65 an acidic Support modifier.
Support material comprises a Support material and an acidic A preferred silica support material is SS61138 High Sur
Support modifier. An acidic Support modified adjusts the acid face Area (HSA) Silica Catalyst Carrier from Saint-Gobain N
 US 8,546,622 B2
7 8
or Pro. The Saint-Gobain N or Pro SS61138 silica contains pressure drop through the reactor bed may be experienced at
approximately 95 wt.% high Surface area silica; a Surface high space velocities, e.g., 5000 hr' or 6,500 hr'.
area of about 250 m/g; a median pore diameter of about 12 Although the reaction consumes two moles of hydrogen
nm, an average pore volume of about 1.0 cm/g as measured per mole of acetic acid to produce one mole of ethanol, the
by mercury intrusion porosimetry and a packing density of 5 actual molar ratio of hydrogen to acetic acid in the feed stream
about 0.352 g/cm (22 lb/ft). may vary from about 100:1 to 1:100, e.g., from 50:1 to 1:50,
A preferred silica/alumina support material is KA-160 from 20:1 to 1:2, or from 12:1 to 1:1. Most preferably, the
(Sud Chemie) silica spheres having a nominal diameter of molar ratio of hydrogen to acetic acid is greater than 2:1, e.g.,
about 5 mm, a density of about 0.562 g/ml, in absorptivity of 10
greater than 4:1 or greater than 8:1.
about 0.583 g HO/g support, a surface area of about 160 to Contact or residence time can also vary widely, depending
175 m/g, and a pore volume of about 0.68 ml/g. upon Such variables as amount of acetic acid, catalyst, reactor,
As will be appreciated by those of ordinary skill in the art, temperature and pressure. Typical contact times range from a
Support materials are selected Such that the catalyst system is fraction of a second to more than several hours when a cata
Suitably active, selective and robust under the process condi 15 lyst system other than a fixed bed is used, with preferred
tions employed for the formation of ethanol. contact times, at least for vaporphase reactions, of from 0.1 to
The metals of the catalysts may be dispersed throughout 100 seconds, e.g., from 0.3 to 80 seconds or from 0.4 to 30
the Support, coated on the outer Surface of the Support (egg seconds.
shell) or decorated on the surface of the support. The raw materials, acetic acid and hydrogen, used in con
The catalyst compositions suitable for use with the present nection with the process of this invention may be derived
invention preferably are formed through metal impregnation from any Suitable source including natural gas, petroleum,
of the modified Support, although other processes such as coal, biomass, and so forth. As examples, acetic acid may be
chemical vapor deposition may also be employed. Such produced via methanol carbonylation, acetaldehyde oxida
impregnation techniques are described in U.S. Pat. No. 7,608, tion, ethylene oxidation, oxidative fermentation, and anaero
744, U.S. Pub. Nos. 2010/002.9995, and 2010/0197985, the 25 bic fermentation. As petroleum and natural gas prices fluctu
entireties of which are incorporated herein by reference. ate, becoming either more or less expensive, methods for
Embodiments of the invention may include a variety of producing acetic acid and intermediates such as methanol and
reactor configurations using a fixed bed reactor or a fluidized carbon monoxide from alternate carbon Sources have drawn
bed reactor, as one of skill in the art will readily appreciate. In increasing interest. In particular, when petroleum is relatively
many embodiments of the present invention, an “adiabatic 30 expensive compared to natural gas, it may become advanta
reactor can be used; that is, there is little or no need for geous to produce acetic acid from Synthesis gas (“syngas)
internal plumbing through the reaction Zone to add or remove that is derived from any available carbon source. U.S. Pat. No.
heat. In other embodiments, radial flow reactor or reactors 6,232,352, the disclosure of which is incorporated herein by
may be employed, or a series of reactors may be employed reference, for example, teaches a method of retrofitting a
with or with out heat exchange, quenching, or introduction of 35 methanol plant for the manufacture of acetic acid. By retro
additional feed material. Alternatively, a shell and tube reac fitting a methanol plant, the large capital costs associated with
tor provided with a heat transfer medium may be used. In CO generation for a new acetic acid plant are significantly
many cases, the reaction Zone may be housed in a single reduced or largely eliminated. All or part of the Syn gas is
vessel or in a series of vessels with heat exchangers therebe diverted from the methanol synthesis loop and supplied to a
tWeen. 40 separator unit to recover CO and hydrogen, which are then
In preferred embodiments, the catalyst is employed in a used to produce acetic acid. In addition to acetic acid, such a
fixedbed reactor, e.g., in the shape of a pipe or tube, where the process can also be used to make hydrogen which may be
reactants, typically in the vapor form, are passed over or utilized in connection with this invention.
through the catalyst. Other reactors, such as fluid or ebullient Methanol carbonylation processes suitable for production
bed reactors, can be employed. In some instances, the hydro 45 of acetic acid are described in U.S. Pat. Nos. 7,208,624,
genation catalysts may be used in conjunction with an inert 7,115,772, 7,005,541, 6,657,078, 6,627,770, 6,143,930,
material to regulate the pressure drop of the reactant stream 5,599,976, 5,144,068, 5,026,908, 5,001,259, and 4,994,608,
through the catalyst bed and the contact time of the reactant the disclosure of which is incorporated herein by reference.
compounds with the catalyst particles. Optionally, the production of ethanol may be integrated with
The hydrogenation reaction may be carried out in either the 50 Such methanol carbonylation processes.
liquid phase or vapor phase. Preferably, the reaction is carried U.S. Pat. No. RE 35,377, also incorporated herein by ref
out in the vapor phase under the following conditions. The erence, provides a method for the production of methanol by
reaction temperature may range from 125°C. to 350° C., e.g., conversion of carbonaceous materials such as oil, coal, natu
from 200° C. to 325°C., from 225°C. to 300° C., or from 250° ral gas and biomass materials. The process includes hydro
C. to 300° C. The pressure may range from 10 KPa to 3000 55 gasification of Solid and/or liquid carbonaceous materials to
KPa (about 1.5 to 435 psi), e.g., from 50 KPa to 2300 KPa, or obtain a process gas which is steam pyrolized with additional
from 100 KPa to 1500 KPa. The reactants may be fed to the natural gas to form synthesis gas. The syngas is converted to
reactor at a gas hourly space velocity (GHSV) of greater than methanol which may be carbonylated to acetic acid. The
500 hr', e.g., greater than 1000 hr', greater than 2500 hr' method likewise produces hydrogen which may be used in
or even greater than 5000 hr'. In terms of ranges the GHSV 60 connection with this invention as noted above. U.S. Pat. No.
may range from 50 hr' to 50,000 e.g., from 500 hr' to 5,821,111, which discloses a process for converting waste
30,000 hr', from 1000 hr' to 10,000 hr', or from 1000 hr' biomass through gasification into synthesis gas as well as
to 6500 hr. U.S. Pat. No. 6,685,754, the disclosures of which are incor
The hydrogenation optionally is carried out at a pressure porated herein by reference.
just sufficient to overcome the pressure drop across the cata 65 In one optional embodiment, the acetic acid fed to the
lytic bed at the GHSV selected, although there is no bar to the hydrogenation reaction may also comprise other carboxylic
use of higher pressures, it being understood that considerable acids and anhydrides, as well as acetaldehyde and acetone.
 US 8,546,622 B2
10
Preferably, a suitable acetic acid feed stream comprises one or ketones, alkanes, and carbon dioxide, if detectable, collec
more of the compounds selected from the group consisting of tively may be present in amounts less than 10 wt.%, e.g., less
acetic acid, acetic anhydride, acetaldehyde, ethyl acetate, and than 6 wt.% or less than 4 wt.%. In terms of ranges, other
mixtures thereof. These other compounds may also be hydro components may be present in an amount from 0.1 to 10
genated in the processes of the present invention. In some wt.%, e.g., from 0.1 to 6 wt.%, or from 0.1 to 4 wt.%.
embodiments, the present of carboxylic acids, such as pro Exemplary embodiments of crude ethanol compositional
panoic acid or its anhydride, may be beneficial in producing ranges are provided in Table 1.
propanol.
Alternatively, acetic acid in vapor form may be taken TABLE 1
directly as crude product from the flash vessel of a methanol 10
CRUDEETHANOL PRODUCT COMPOSITIONS
carbonylation unit of the class described in U.S. Pat. No.
6,657,078, the entirety of which is incorporated herein by Conc. Conc. Conc. Conc.
reference. The crude vapor product, for example, may be fed Component (wt.%) (wt.%) (wt.%) (wt.%)
directly to the ethanol synthesis reaction Zones of the present Ethanol S to 70 10 to 70 15 to 70 25 to 70
invention without the need for condensing the acetic acid and 15
Acetic Acid O to 80 O to SO O to 25 O to 10
light ends or removing water, saving overall processing costs. Water S to 35 S to 30 10 to 30 10 to 26
The acetic acid may be vaporized at the reaction tempera Ethyl Acetate O to 30 O to 20 O to 15 O to 10
ture, following which the vaporized acetic acid can be fed Acetaldehyde O to 10 O to 3 O.1 to 3 O.2 to 2
Others O.1 to 10 O.1 to 6 0.1 to 4
along with hydrogen in an undiluted State or diluted with a
relatively inert carrier gas, such as nitrogen, argon, helium,
carbon dioxide and the like. For reactions run in the vapor FIG. 1 shows a hydrogenation system 100 suitable for the
phase, the temperature should be controlled in the system hydrogenation of acetic acid and separating ethanol from the
such that it does not fall below the dew point of acetic acid. In crude reaction mixture according to one embodiment of the
one embodiment the acetic acid may be vaporized at the invention. System 100 comprises reaction Zone 101 and dis
boiling point of acetic acid at the particular pressure, and then 25 tillation Zone 102. Reaction Zone 101 comprises reactor 103.
the vaporized acetic acid may be further heated to the reactor hydrogen feed line 104 and acetic acid feed line 105. Distil
inlet temperature. In another embodiment, the acetic acid is lation Zone 102 comprises flasher 106, first column 107.
transferred to the vapor state by passing hydrogen, recycle second column 108, and third column 109. Hydrogen and
gas, another Suitable gas, or mixtures thereof through the acetic acid are fed to a vaporizer 110 via lines 104 and 105,
acetic acid at a temperature below the boiling point of acetic 30 respectively, to create a vapor feed stream in line 111 that is
acid, thereby humidifying the carrier gas with acetic acid directed to reactor 103. In one embodiment, lines 104 and 105
vapors, followed by heating the mixed vapors up to the reactor may be combined and jointly fed to the vaporizer 110, e.g., in
inlet temperature. Preferably, the acetic acid is transferred to one stream containing both hydrogen and acetic acid. The
the vapor by passing hydrogen and/or recycle gas through the temperature of the vapor feed stream in line 111 is preferably
acetic acid at a temperature at or below 125°C., followed by 35 from 100° C. to 350° C., e.g., from 120° C. to 310° C. or from
heating of the combined gaseous stream to the reactor inlet 150° C. to 300° C. Any feed that is not vaporized is removed
temperature. from vaporizer 110, as shown in FIG. 1, and may be recycled
In various embodiments, the crude ethanol product pro thereto. In addition, although FIG. 1 shows line 111 being
duced by the hydrogenation process, before any Subsequent directed to the top of reactor 103, line 111 may be directed to
processing, Such as purification and separation, will typically 40 the side, upper portion, or bottom of reactor 103. Further
comprise unreacted acetic acid, ethanol and water. As used modifications and additional components to reaction Zone
herein, the term "crude ethanol product” refers to any com 101 are described below in FIGS 2A and 2B.
position comprising from 5 to 70 wt.% ethanol and from 5 to Reactor 103 contains the catalyst that is used in the hydro
35 wt.% water. In some exemplary embodiments, the crude genation of the carboxylic acid, preferably acetic acid. In one
ethanol product comprises ethanol in an amount from 5 wt.% 45 embodiment, one or more guard beds (not shown) may be
to 70 wt.%, e.g., from 10 wt.% to 60 wt.%, or from 15 wt.% used to protect the catalyst from poisons or undesirable impu
to 50 wt.%, based on the total weight of the crude ethanol rities contained in the feed or return/recycle streams. Such
product. Preferably, the crude ethanol product contains at guard beds may be employed in the vapor or liquid streams.
least 10 wt.% ethanol, at least 15 wt.% ethanol or at least 20 Suitable guard bed materials are known in the art and include,
wt.% ethanol. The crude ethanol product typically will fur 50 for example, carbon, silica, alumina, ceramic, or resins. In
ther comprise unreacted acetic acid, depending on conver one aspect, the guard bed media is functionalized to trap
Sion, for example, in an amount of less than 90 wt.%, e.g., less particular species such as Sulfur or halogens. During the
than 80 wt.% or less than 70 wt.%. In terms of ranges, the hydrogenation process, a crude ethanol product stream is
unreacted acetic acid is preferably from 0 to 90 wt.%, e.g., withdrawn, preferably continuously, from reactor 103 via line
from 5 to 80 wt.%, from 15 to 70 wt.%, from 20 to 70 wt.% 55 112. The crude ethanol product stream may be condensed and
or from 25 to 65 wt.%. As water is formed in the reaction fed to flasher 106, which, in turn, provides a vapor stream and
process, water will generally be present in the crude ethanol a liquid stream. The flasher 106 in one embodiment prefer
product, for example, in amounts ranging from 5 to 35 wt.%. ably operates at a temperature of from 50° C. to 500° C., e.g.,
e.g., from 10 to 30 wt.% or from 10 to 26 wt.%. Ethyl acetate from 70° C. to 400° C. or from 100° C. to 350° C. In one
may also be produced during the hydrogenation of acetic acid 60 embodiment, the pressure of flasher 106 preferably is from 50
or through side reactions and may be present, for example, in KPa to 2000 KPa, e.g., from 75 KPa to 1500 KPa or from 100
amounts ranging from 0 to 20 wt.%, e.g., from 0 to 15 wt.%. to 1000 KPa. In one preferred embodiment the temperature
from 1 to 12 wt.% or from 3 to 10 wt.%. Acetaldehyde may and pressure of the flasher is similar to the temperature and
also be produced through side reactions and may be present, pressure of the reactor 103.
for example, in amounts ranging from 0 to 10 wt.%, e.g., from 65 The vapor stream exiting the flasher 106 may comprise
0 to 3 wt.%, from 0.1 to 3 wt.% or from 0.2 to 2 wt.%. Other hydrogen and hydrocarbons, which may be purged and/or
components, such as, for example, esters, ethers, aldehydes, returned to reaction Zone 101 via line 113. As shown in FIG.
 US 8,546,622 B2
11 12
1, the returned portion of the vapor stream passes through condensed and refluxed, for example, at a ratio of from 10:1
compressor 114 and is combined with the hydrogen feed and to 1:10, e.g., from 3:1 to 1:3 or from 1:2 to 2:1.
co-fed to vaporizer 110. Any of columns 107, 108 or 109 may comprise any distil
The liquid from flasher 106 is withdrawn and pumped as a lation column capable of separation and/or purification. The
feed composition via line 115 to the side of first column 107. 5 columns preferably comprise tray columns having from 1 to
also referred to as the acid separation column. The contents of 150 trays, e.g., from 10 to 100 trays, from 20 to 95 trays or
line 115 typically will be substantially similar to the product from 30 to 75 trays. The trays may be sieve trays, fixed valve
obtained directly from the reactor, and may, in fact, also be trays, movable valvetrays, or any other Suitable designknown
characterized as a crude ethanol product. However, the feed in the art. In other embodiments, a packed column may be
composition in line 115 preferably has substantially no 10 used. For packed columns, structured packing or random
hydrogen, carbon dioxide, methane or ethane, which are packing may be employed. The trays or packing may be
removed by flasher 106. Exemplary components of liquid in arranged in one continuous column or they may be arranged
line 115 are provided in Table 2. It should be understood that in two or more columns such that the vapor from the first
liquid line 115 may contain other components, not listed, section enters the second section while the liquid from the
15 second section enters the first section, etc.
Such as components in the feed. The associated condensers and liquid separation vessels
that may be employed with each of the distillation columns
TABLE 2 may be of any conventional design and are simplified in FIG.
FEED COMPOSITION 1. As shown in FIG. 1, heat may be supplied to the base of
each column or to a circulating bottom stream through a heat
Conc. Conc. Conc. exchanger or reboiler. Other types of reboilers, such as inter
(wt.%) (wt.%) (wt.%) nal reboilers, may also be used in some embodiments. The
Ethanol S to 70 10 to 70 25 to 70 heat that is provided to reboilers may be derived from any heat
Acetic Acid <8O O to SO O to 10 generated during the process that is integrated with the reboil
Water
Ethyl Acetate
S to 35
<30
S to 30
O.OO1 to 20
10 to 26
1 to 10
25 ers or from an external Source Such as another heat generating
Acetaldehyde <10 O.OO1 to 3 O.1 to 3 chemical process or a boiler. Although one reactor and one
Acetal <5 O.OO1 to 2 O.OOS to 1 flasher are shown in FIG. 1, additional reactors, flashers,
Acetone <5 O.OOOS to O.OS O.001 to O.O3 condensers, heating elements, and other components may be
Other Esters
Other Ethers
<5
<5
<O.OOS
<O.OOS
<0.001
<0.001
used in embodiments of the present invention. As will be
Other Alcohols <5 <O.OOS <0.001
30 recognized by those skilled in the art, various condensers,
pumps, compressors, reboilers, drums, valves, connectors,
separation vessels, etc., normally employed in carrying out
The amounts indicated as less than (<) in the tables chemical processes may also be combined and employed in
throughout present application are preferably not present and the processes of the present invention.
if present may be present in trace amounts or in amounts 35 The temperatures and pressures employed in any of the
greater than 0.0001 wt.%. columns may vary. As a practical matter, pressures from 10
The “other esters' in Table 2 may include, but are not KPa to 3000 KPa will generally be employed in these Zones
limited to, ethyl propionate, methyl acetate, isopropyl although in some embodiments Subatmospheric pressures
acetate, n-propyl acetate, n-butyl acetate or mixtures thereof. may be employed as well as Superatmospheric pressures.
The “other ethers’ in Table 2 may include, but are not limited 40 Temperatures within the various Zones will normally range
to, diethyl ether, methyl ethyl ether, isobutyl ethyl ether or between the boiling points of the composition removed as the
mixtures thereof. The “other alcohols' in Table 2 may distillate and the composition removed as the residue. It will
include, but are not limited to, methanol, isopropanol, n-pro be recognized by those skilled in the art that the temperature
panol, n-butanol or mixtures thereof. In one embodiment, the at a given location in an operating distillation column is
feed composition, e.g., line 115, may comprise propanol, e.g., 45 dependent on the composition of the material at that location
isopropanol and/or n-propanol, in an amount from 0.001 to and the pressure of column. In addition, feed rates may vary
depending on the size of the production process and, if
0.1 wt.%, from 0.001 to 0.05 wt.% or from 0.001 to 0.03 described, may be generically referred to in terms of feed
wt.%. It should be understood that these other components weight ratios.
may be carried through in any of the distillate or residue 50 When column 107 is operated understandard atmospheric
streams described herein and will not be further described pressure, the temperature of the residue exiting in line 116
herein, unless indicated otherwise. from column 107 preferably is from 95°C. to 120° C., e.g.,
In one embodiment, the conversion of acetic acid may be from 105° C. to 117° C. or from 110° C. to 115° C. The
greater than 95%, and the crude ethanol product in line 115 temperature of the distillate exiting in line 117 from column
may contain less than 5 wt.% acetic acid. In Such embodi 55 107 preferably is from 70° C. to 110° C., e.g., from 75° C. to
ments, the acid separation column 107 may be skipped and 95° C. or from 80° C. to 90° C. In other embodiments, the
line 115 may be introduced directly to second column 108, pressure of first column 107 may range from 0.1 KPa to 510
also referred to herein as a light ends column. KPa, e.g., from 1 KPa to 475 KPa or from 1 KPa to 375 KPa.
In the embodiment shown in FIG. 1A, line 115 is intro Exemplary components of the distillate and residue compo
duced in the lower part of first column 107, e.g., lower half or 60 sitions for first column 107 are provided in Table 3 below. It
lower third. In first column 107, unreacted acetic acid, a should also be understood that the distillate and residue may
portion of the water, and other heavy components, if present, also contain other components, not listed, such as compo
are removed from the composition in line 115 and are with nents in the feed. For convenience, the distillate and residue of
drawn, preferably continuously, as residue. Some or all of the the first column may also be referred to as the “first distillate'
residue may be returned and/or recycled back to reaction Zone 65 or “first residue.” The distillates or residues of the other col
101 via line 116. First column 107 also forms an overhead umns may also be referred to with similar numeric modifiers
distillate, which is withdrawn in line 117, and which may be (second, third, etc.) in order to distinguish them from one
 US 8,546,622 B2
13 14
another, but Such modifiers should not be construed as requir 102 for temporarily storing the liquid component from line
ing any particular separation order. 115, for example from 1 to 24 hours, optionally at a tempera
ture of about 21°C., and corresponding to an ethyl acetate
TABLE 3 formation of from 0.01 wt.% to 1.0 wt.% respectively. In
FIRST COLUMN
addition, the rate at which the non-catalyzed reaction occurs
may increase as the temperature of the crude ethanol product
Conc. Conc. Conc. is increased. For example, as the temperature of the crude
(wt.%) (wt.%) (wt.%) ethanol product in line 115 increase from 4°C. to 21°C., the
Distillate
10
rate of ethyl acetate formation may increase from about 0.01
Ethanol 5 to 75 10 to 70 25 to 70
wt.% per hour to about 0.005 wt.% per hour. Thus, in one
Water 10 to 40 15 to 35 20 to 35
embodiment, the temperature of liquid components in line
Acetic Acid <2 O.001 to O.S O.O1 to 0.2 115 or in the optional holding tank is maintained at a tem
Ethyl Acetate <60 O to 20 O to 10 perature less than 21°C., e.g., less than 4°C. or less than -10°
Acetaldehyde <10 O.001 to 5 O.O1 to 4 C.
Acetal <0.1 <0.1 <O.OS 15
Acetone <O.OS O.001 to O.O3 O.O1 to O.O25 In addition, it has now been discovered that the above
Residue described equilibrium reaction may also favor ethanol forma
Acetic Acid 60 to 100 70 to 95 85 to 92
tion in the top region of first column 107.
Water <30 1 to 20 1 to 15 The distillate, e.g., overhead stream, of column 107 option
Ethanol <1 <0.9 <0.07 ally is condensed and refluxed as shown in FIG.1, preferably,
at a reflux ratio of 1:5 to 10:1. The distillate in line 117
As shown in Table 3, without being bound by theory, it has preferably comprises ethanol, ethyl acetate, and water, along
Surprisingly and unexpectedly been discovered that when any with other impurities, which may be difficult to separate due
amount of acetal is detected in the feed that is introduced to to the formation of binary and tertiary azeotropes.
the acid separation column (first column 107), the acetal 25 The first distillate in line 117 is introduced to the second
appears to decompose in the column Such that less or even no column 108, also referred to as the “light ends column.”
detectable amounts are present in the distillate and/or residue. preferably in the middle part of column 108, e.g., middle half
Depending on the reaction conditions, the crude ethanol or middle third. As one example, when a 25 tray column is
product exiting reactor 103 in line 112 may comprise ethanol, utilized in a column without water extraction, line 117 is
30
acetic acid (unconverted), ethyl acetate, and water. After exit introduced attray 17. In one embodiment, the second column
ing reactor 103, a non-catalyzed equilibrium reaction may 108 may be an extractive distillation column. In such embodi
occur between the components contained in the crude ethanol ments, an extraction agent, such as water, may be added to
product until it is added to flasher 106 and/or first column 107. second column 108. If the extraction agent comprises water,
This equilibrium reaction tends to drive the crude ethanol 35
it may be obtained from an external Source or from an internal
product to an equilibrium between ethanol/acetic acid and return/recycle line from one or more of the other columns,
ethyl acetate/water, as shown below (Reaction 2). such as via optional line 121".
EtOH+HOAces EtOAc+HO Reaction 2 Second column 108 may be a tray column or packed col
umn. In one embodiment, second column 108 is a tray column
In the event the crude ethanol product is temporarily stored, having from 5 to 70 trays, e.g., from 15 to 50 trays or from 20
e.g., in a holding tank, prior to being directed to distillation 40 to 45 trays.
Zone 102, extended residence times may be encountered. Although the temperature and pressure of second column
Generally, the longer the residence time between reaction 108 may vary, when at atmospheric pressure the temperature
Zone 101 and distillation Zone 102, the greater the formation of the second residue exiting in line 118 from second column
of ethyl acetate. For example, when the residence time 108 preferably is from 60° C. to 90° C., e.g., from 70° C. to
between reaction Zone101 and distillation Zone102 is greater 45 90°C. or from 80° C. to 90° C. The temperature of the second
than 5 days, significantly more ethyl acetate may form at the distillate exiting in line 120 from second column 108 prefer
expense of ethanol. Thus, shorter residence times between ably is from 50° C. to 90° C., e.g., from 60° C. to 80° C. or
reaction Zone 101 and distillation Zone 102 are generally from 60°C. to 70° C. Column 108 may operate at atmospheric
preferred in order to maximize the amount of ethanol formed. pressure. In other embodiments, the pressure of second col
In one embodiment, a holding tank (not shown), is included 50 umn 108 may range from 0.1 KPa to 510 KPa, e.g., from 1
between the reaction Zone 101 and distillation Zone 102 for KPa to 475 KPa or from 1 KPa to 375 KPa. Exemplary
temporarily storing the liquid component from line 115 for up components for the distillate and residue compositions for
to 5 days, e.g., up to 1 day, or up to 1 hour. In a preferred second column 108 are provided in Table 4 below. It should be
embodiment no tank is included and the condensed liquids understood that the distillate and residue may also contain
are fed directly to the first distillation column 107. In addition, 55 other components, not listed. Such as components in the feed.
the rate at which the non-catalyzed reaction occurs may
increase as the temperature of the crude ethanol product, e.g., TABLE 4
in line 115, increases. These reaction rates may be particu
larly problematic at temperatures exceeding 30° C., e.g., SECOND COLUMN
exceeding 40° C. or exceeding 50° C. Thus, in one embodi 60
Conc. Conc. Conc.
ment, the temperature of liquid components in line 115 or in (wt.%) (wt.%) (wt.%)
the optional holding tank is maintained at a temperature less
Distillate
than 40°C., e.g., less than 30° C. or less than 20°C. One or
more cooling devices may be used to reduce the temperature Ethyl Acetate 10 to 90 25 to 90 SO to 90
of the liquid in line 115. 65 Acetaldehyde 1 to 25 1 to 15 1 to 8
As discussed above, a holding tank (not shown) may be Water 1 to 25 1 to 20 4 to 16
included between the reaction Zone 101 and distillation Zone
 US 8,546,622 B2
TABLE 4-continued TABLE 5-continued
SECOND COLUMN THIRD COLUMN

Conc. Conc. Conc. Conc. Conc. Conc.

(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
Ethanol <30 O.001 to 15 O.O1 to 5 Ethyl Acetate <1 O.001 to OS O.OOS to O.2
Acetal <5 O.001 to 2 O.O1 to 1 Acetic Acid <2 O.001 to OS O.OOS to O.2
Residue

Water
Ethanol
30 to 70
20 to 75
30 to 60
30 to 70
30 to SO
40 to 70
10 Any of the compounds that are carried through the distil
Ethyl Acetate <3 O.001 to 2 O.OO1 to OS lation process from the feed or crude reaction product gener
Acetic Acid <O.S O.001 to O.3 O.OO1 to O.2 ally remain in the third distillate in amounts of less 0.1 wt.%.
based on the total weight of the third distillate composition,
e.g., less than 0.05 wt.% or less than 0.02 wt.%. In one
The weight ratio of ethanol in the second residue to ethanol 15 embodiment, one or more side streams may remove impuri
in the second distillate preferably is at least 3:1, e.g., at least ties from any of the columns 107, 108 and/or 109 in the
6:1, at least 8:1, at least 10:1 or at least 15:1. The weight ratio system 100. Preferably at least one side stream is used to
of ethyl acetate in the second residue to ethyl acetate in the remove impurities from the third column 109. The impurities
second distillate preferably is less than 0.4:1, e.g., less than may be purged and/or retained within the system 100.
0.2:1 or less than 0.1:1. In embodiments that use an extractive The third distillate in line 119 may be further purified to
column with water as an extraction agent as the second col form an anhydrous ethanol product stream, i.e., “finished
umn 108, the weight ratio of ethyl acetate in the second anhydrous ethanol using one or more additional separation
residue to ethyl acetate in the second distillate approaches systems, such as, for example, distillation columns (e.g., a
ZO. finishing column) or molecular sieves.
As shown, the second residue from the bottom of second 25 Returning to second column 108, the distillate in line 120
column 108, which comprises ethanol and water, is fed via preferably is refluxed as shown in FIG. 1, for example, at a
line 118 to third column 109, also referred to as the “product reflux ratio of from 1:10 to 10:1, e.g., from 1:5 to 5:1 or from
column.” More preferably, the second residue in line 118 is 1:3 to 3:1. In one embodiment, all or a portion of the distillate
introduced in the lower part of third column 109, e.g., lower from second column 108 may be recycled to reaction Zone
half or lower third. Third column 109 recovers ethanol, which
30 101 via line 120. As shown in FIG. 1, all or a portion the
preferably is substantially pure other than the azeotropic distillate may be recycled to reactor 103, as shown by line
water content, as the distillate in line 119. The distillate of 120, and may be co-fed with the acetic acid feed line 105. In
one embodiment, ethyl acetate in line 120 does not buildup in
third column 109 preferably is refluxed as shown in FIG. 1A, the reaction Zone 101 and/or distillation Zone 102 due to the
for example, at a reflux ratio of from 1:10 to 10:1, e.g., from 35 presence of the catalyst comprising an acidic Support. Due to
1:3 to 3:1 or from 1:2 to 2:1. The third residue in line 121, the increase in kinetics of the equilibrium reaction, embodi
which preferably comprises primarily water, preferably is ments of the present invention are able to process ethylacetate
removed from the system 100 or may be partially returned to in the feed and/or recycle stream as well. Thus, because of the
any portion of the system 100. Third column 109 is preferably increased kinetics, the recycled ethyl acetate in line 120 may
a tray column as described above and preferably operates at 40 be converted to ethanol, or the generated ethyl acetate may be
atmospheric pressure. The temperature of the third distillate equal to the converted ethyl acetate so there will be certain
exiting in line 119 from third column 109 preferably is from steady state achieved relatively fast and recycled ethyl acetate
60° C. to 110° C., e.g., from 70° C. to 100° C. or from 75° C. concentration will remain constant; withoutbuilding up in the
to 95°C. The temperature of the third residue exiting from recycle loop. A portion of the distillate from second column
third column 109 preferably is from 70° C. to 115° C., e.g., 45 108 may be purged via line 122. Optionally, the second dis
from 80° C. to 110° C. or from 85°C. to 105° C., when the tillate in line 120 may be further purified to remove impuri
column is operated at atmospheric pressure. Exemplary com ties, such as acetaldehyde, using one or more additional col
ponents of the distillate and residue compositions for third umns (not shown) before being returned to the reaction Zone,
column 109 are provided in Table 5 below. It should be as described in co-pending U.S. application Ser. No. 12/852,
understood that the distillate and residue may also contain 50 269, the entirety of which is hereby incorporated by refer
other components, not listed. Such as components in the feed. CCC.
FIGS. 2A and 2B show modified reaction Zones 130 and
TABLE 5 140, respectively. As discussed above, some embodiments of
the present invention may use multiple reactors. In reaction
THIRD COLUMN 55 Zone 130 of FIG. 2A, vapor feed stream 111 is fed to first
reactor 131. Reactor effluent 133 is fed to second reactor 132.
Conc. Conc. Conc.
(wt.%) (wt.%) (wt.%) Preferably, reactor effluent 133 comprises ethanol and unre
acted acetic acid and may have a composition as described
Distillate above in Table 1. Optionally, fresh reactants (not shown) may
Ethanol 7S to 96 80 to 96 85 to 96 60 be fed to the second reactor 132. Crude ethanol product 134 of
Water <12 1 to 9 3 to 8 second reactor is fed to flasher 106. For purposes of illustra
Acetic Acid <1 O.001 to O.1 O.005 to O.O1 tion FIG. 2A shows two reactors. In further embodiments,
Ethyl Acetate <5 O.001 to 4 O.O1 to 3 however, there may be more than two reactors, e.g., more than
Residue
three or more than four. Each of reactors, 131 and 132 of FIG.
Water 7S to 100 80 to 100 90 to 100 65 2A operate within the reaction conditions stated above.
Ethanol <0.8 O.001 to O.S O.OOS to O.OS In the reaction Zone 140 of FIG.2B, vapor feed stream 111
is fed to reactor 141 that comprises multiple reaction regions.
 US 8,546,622 B2
17 18
Reactor 141 comprises at least a first reaction region 142 and The acidic catalyst of the present invention is preferably
a second reaction region 143. Each region may have a differ used in second reactor 132 or second reactor region 143. In
ent catalyst. First reaction region 142 and second reaction one exemplary embodiment, first reactor 131 or first reactor
region 143 may be separated in reactor 141 as shown in FIG. region 142 may comprise a SiO, CaSiO Pt—Sn catalyst,
2B. In other embodiments, first reaction region 142 and sec 5
and the second reactor 133 or second reactor 143 may com
ond reaction region 143 overlap and the respective catalysts prise SiO, TiO, Pt. Sn catalyst. In alternative embodi
may be dispersed between the regions. Crude ethanol product ments, the acidic catalyst may be used in first reactor 131 or
144 of reactor 141, e.g., second reactor region 143, may be fed first reactor region 142.
to flasher 106. Regions 142 and regions 143 operate within The acetic acid conversion in first reactor 131 or first reac
the reaction conditions as stated above. 10
In preferred embodiments, different catalysts may be used tor region 142 may be relatively lower than that of second
in each of the reactors of reactions Zones 130 in FIG. 2B or in reactor 132 or second reactor region 143, respectively. The
acetic acid conversion of the first reactor 131 or first reaction
each of the reaction regions in reaction Zones 140 shown in region 142 may be at least 10%, e.g., at least 20%, at least
FIG.2B. Different catalysts may have different metals and/or 40%, at least 50%, at least 60%, at least 70% or at least 80%.
different supports. In preferred embodiments, the catalyst in 15
In one embodiment, the acetic acid conversion in first reactor
first reactor 131 or first reactor region 142 may be cobalt 131 or first reactor region 142 is from 10% to 80% and is
catalyst as described in U.S. Pat. No. 7,608,744, a platinum/ lower than the conversion of the unreacted acetic acid in
tin catalyst as described in U.S. Pub. No. 2010/002.9995, or a second reactor 132 or second reactor region 143. In second
metal catalyst comprising a basic modifier as described in reactor 132 or second reactor region 143, the conversion of
U.S. Pub. No. 2010/0197959, the entireties of which are the unreacted acetic acid may be increased to at least 70%,
hereby incorporated by reference. e.g., at least 80% or at least 90%. Advantageously, a lower
In some embodiments, the catalyst in first reactor 131 or conversion of acetic acid in first reactor 131 or first reactor
first reactor region 142 is a basic catalyst. Suitable metal region 142 allows the unreacted acid of first reactor 131 or
catalysts that comprise a basic modifier include those having first reactor region 142 to be hydrogenated in second reactor
a first metal and an optional second metal. These metals may 25
132 or second reactor region 143 without the addition of fresh
be the same as those described above with respect to the acidic acetic acid.
supported catalysts of the present invention. Preferably, the The overallethanol selectivity of the dual reactors shown in
first metal is Group VIII metal, selected from the group con FIG. 2A and/or dual reactor regions shown in FIG. 2B may be
sisting of iron, cobalt, nickel, ruthenium, rhodium, palladium, at least 65%, e.g., at least 70%, at least 80%, at least 85%, or
osmium, iridium, and platinum. The optional second metal 30
at least 90%. Ethyl acetate, which may be produced by the
preferably may be selected from the group consisting of cop first reactor 131 or first reactor region 142, may be consumed
per, tin, cobalt, rhenium, and nickel. The catalyst may com in the second reactor 132 or second reactor region 143.
prise from 0.1 to 10 wt.% first metal and from 0.1 to 10 wt.% Finished Ethanol
second metal.
Suitable Support materials may include, for example, 35
The finished ethanol composition obtained by the pro
cesses of the present invention preferably comprises from 75
stable metal oxide-based Supports or ceramic-based supports. to 96 wt.% ethanol, e.g., from 80 to 96 wt.% or from 85 to 96
Preferred Supports include silicaceous Supports, such as wt.% ethanol, based on the total weight of the finished etha
silica, silica/alumina, a Group IIA silicate Such as calcium nol composition. Exemplary finished ethanol compositional
metasilicate, pyrogenic silica, high purity silica, and mixtures ranges are provided below in Table 6.
thereof. Other supports may include, but are not limited to, 40
iron oxide, alumina, titania, Zirconia, magnesium oxide, car TABLE 6
bon, graphite, high Surface area graphitized carbon, activated
carbons, and mixtures thereof. FINISHED ETHANOL COMPOSITIONS
The catalyst Support may be modified with a Support modi Conc. Conc. Conc.
fier. Preferably, the support modifier is a basic modifier that 45
Component (wt.%) (wt.%) (wt.%)
has a low volatility or no volatility. Such basic modifiers, for
example, may be selected from the group consisting of: (i) Ethanol 7S to 96 80 to 96 85 to 96
Water <12 1 to 9 3 to 8
alkaline earth oxides, (ii) alkali metal oxides, (iii) alkaline Acetic Acid <1 O.001 to O.1 O.005 to O.O1
earth metal metasilicates, (iv) alkali metal metasilicates, (v) Ethyl Acetate <5 O.001 to 4 O.O1 to 3
Group IIB metal oxides, (vi) Group IIB metal metasilicates, 50 Acetal <O.OS <0.01 <O.OOS
(vii) Group IIIB metal oxides, (viii) Group IIIB metal meta Acetone <O.OS <0.01 <O.OOS
silicates, and mixtures thereof. In addition to oxides and Isopropanol <O.S <0.1 <O.OS
n-propanol <O.S <0.1 <O.OS
metasilicates, other types of modifiers including nitrates,
nitrites, acetates, and lactates may be used. Preferably, the
Support modifier is selected from the group consisting of 55 The finished ethanol composition of the present invention
oxides and metasilicates of any of Sodium, potassium, mag preferably contains very low amounts, e.g., less than 0.5
nesium, calcium, Scandium, yttrium, and Zinc, as well as wt.%, of other alcohols, such as methanol, butanol, isobu
mixtures of any of the foregoing. Preferably, the support tanol, isoamyl alcohol and other Ca-Co alcohols. In one
modifier is a calcium silicate, and more preferably calcium embodiment, the amount ofisopropanol in the finished etha
metasilicate (CaSiO). If the support modifier comprises cal 60 nol is from 80 to 1,000 wppm, e.g., from 95 to 1,000 wppm,
cium metasilicate, it is preferred that at least a portion of the from 100 to 700 wppm, or from 150 to 500 wppm. In one
calcium metasilicate is in crystalline form. In preferred embodiment, the finished ethanol composition preferably is
embodiments that use a basic Support modifier, the basic Substantially free of acetaldehyde and may comprise less than
support modifier is present in an amount from 0.1 wt.% to 50 8wppm of acetaldehyde, e.g., less than 5 wppm or less than
wt.%, e.g., from 0.2 wt.% to 25 wt.%, from 0.5 wt.% to 15 65 1 wppm.
wt.%, or from 1 wt.% to 8 wt.%, based on the total weight The finished ethanol composition produced by the embodi
of the catalyst. ments of the present invention may be used in a variety of
 US 8,546,622 B2
19 20
applications including fuels, solvents, chemical feedstocks, performed several times under different acetic acid conver
pharmaceutical products, cleansers, sanitizers, hydrogena sion levels. The results are compared in FIG. 4. At lower
tion transport or consumption. In fuel applications, the fin conversions, the SiO Al-O (7 wt.%)-Pt(1.6 wt.%)-Sn(1.0
ished ethanol composition may be blended with gasoline for wt.%) catalyst showed increased selectivity to ethanol. How
motor vehicles Such as automobiles, boats and Small piston ever, at higher conversions, the SiO, TiO, (10 wt.%)-Pt(1.6
engine aircrafts. In non-fuel applications, the finished ethanol wt.%)-Sn(1.0 wt.%) catalyst showed similar selectivity to
composition may be used as a solvent for toiletry and cos ethanol. In addition, Surprisingly and unexpectedly, the pro
metic preparations, detergents, disinfectants, coatings, inks, ductivity of the acidic catalyst at high acetic acid conversion
and pharmaceuticals. The finished ethanol composition may showed a significant improvement.
also be used as a processing solvent in manufacturing pro 10
cesses for medicinal products, food preparations, dyes, pho Example 3
tochemicals and latex processing.
The finished ethanol composition may also be used a The acidic catalyst comprising SiO Al-O (7 wt.%)-
chemical feedstock to make other chemicals such as vinegar, Pt(1.6 wt.%)-Sn(1.0 wt.%) from Example 2 was also used to
ethyl acrylate, ethyl acetate, ethylene, glycol ethers, ethy 15
hydrogenate acetic acid in several runs under the following
lamines, aldehydes, and higher alcohols, especially butanol. different reaction conditions set forth in Table 8.
In the production of ethyl acetate, the finished ethanol com
position may be esterified with acetic acid or reacted with TABLE 8
polyvinyl acetate. The finished ethanol composition may be
dehydrated to produce ethylene. Any of known dehydration Selectivity
catalysts can be employed in to dehydrate ethanol. Such as Tem- HOAC mol%
those described in copending U.S. application Ser. No. Run Pressure perature GHSV Conversion EtOH EtOAc
12/221,137 and U.S. application Ser. No. 12/221,138, the
entire contents and disclosures of which are hereby incorpo 1 200 psig 250° C. 4500 hr' 87.5 65.8 33.4
rated by reference. A zeolite catalyst, for example, may be 25 2 200 psig 250° C. 2200 hr' 93.4 81.4 18.0
employed as the dehydration catalyst. Preferably, the Zeolite 3 250 psig 300° C. 4500 hr' 94.3 754 20.8
4 250 psig 300° C. 1300 hr' 97.3 89.2 7.2
has a pore diameter of at least about 0.6 nm, and preferred
Zeolites include dehydration catalysts selected from the group
consisting of mordenites, ZSM-5, a zeolite X and a zeolite Y. While the invention has been described in detail, modifi
Zeolite X is described, for example, in U.S. Pat. No. 2,882, 30 cations within the spirit and scope of the invention will be
244 and Zeolite Y in U.S. Pat. No. 3,130,007, the entireties of readily apparent to those of skill in the art. In view of the
which are hereby incorporated by reference. foregoing discussion, relevant knowledge in the art and ref
In order that the invention disclosed herein may be more erences discussed above in connection with the Background
efficiently understood, the following examples are provided and Detailed Description, the disclosures of which are all
below. 35
incorporated herein by reference. In addition, it should be
EXAMPLES
understood that aspects of the invention and portions of vari
ous embodiments and various features recited below and/or in
Example 1 the appended claims may be combined or interchanged either
40 in whole or in part. In the foregoing descriptions of the vari
Acetic acid was hydrogenated in the present of an acidic ous embodiments, those embodiments which refer to another
catalyst comprising SiO, TiO (10 wt.%)-Pt(1.6 wt.%)-Sn embodiment may be appropriately combined with other
(1.0 wt.%). There were 2 runs with this catalyst in a reactor at embodiments as will be appreciated by one of skill in the art.
200 psig, 250° C. First run was at 4500 hr' GHSV, and the Furthermore, those of ordinary skill in the art will appreciate
second run was at 2200 hr' GHSV. In FIG. 3, the theoretical 45 that the foregoing description is by way of example only, and
is not intended to limit the invention.
calculations for a K of 4 and for a K of 12. As indicated in
FIG. 3, the amount of ethyl acetate at lower acetic acid con
version is greater than that of ethanol. However, at higher We claim:
acetic acid conversions, the kinetics of the equilibrium reac 1. A process for producing ethanol, comprising
tion Surprisingly drive the ethyl acetate content lower and 50 hydrogenating acetic acid in the presence of a first catalyst
increase the ethanol content. Table 7 summarizes the results. to form an intermediate product comprising ethanol and
unreacted acetic acid; and
TABLE 7 hydrogenating the unreacted acetic acid in the present of a
HOAC Selectivity (mol% 55
second catalyst to form ethanol, wherein the second
catalyst comprises a first metal on an acidic Support
Run GHSV Conversion EtOH EtOAC Selected from the group consisting of
1 4500 hr. 71.9% 58.8% 40.6% an acidic Support material selected from the group con
2 2200 hr. 92.9% 79.2% 20.4% sisting of iron oxide, alumina, Silica/alumina, titania,
60 Zirconia, and mixtures thereof, and
a Support material modified with an acidic modifier.
Example 2 2. The process of claim 1, wherein the first catalyst com
prises a catalyst comprising one or more metals, a silicaceous
Acetic acid was hydrogenated in the present of an acidic Support, and at least one basic Support modifier.
catalyst comprising SiO, TiO (10 wt.%)-Pt(1.6 wt.%)-Sn 65 3. The process of claim 2, wherein the at least one basic
(1.0 wt.%) and an acidic catalyst comprisingSiO Al-O-(7 Support modifier is selected from the group consisting of (i)
wt.%)-Pt(1.6 wt.%)-Sn(1.0 wt.%). Each hydrogenation was alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alka
 US 8,546,622 B2
21 22
line earth metal metasilicates, (iv) alkali metal metasilicates, 8. The process of claim 7, wherein the first catalyst is in a
(v) Group IIB metal oxides, (vi) Group IIB metal metasili first reactor region and the second catalyst is in a second
cates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal reactor region, wherein the first reactor region and the second
metasilicates, and mixtures thereof. reactor region are separated.
4. The process of claim 2, wherein the silicaceous Support
is selected from the group consisting of silica, silica/alumina, 9. The process of claim 7, wherein the first catalyst com
calcium metasilicate, pyrogenic silica, high purity silica and prises a catalyst comprising one or more metals, a silicaceous
mixtures thereof. Support, and at least one basic modifier.
5. The process of claim 1, wherein the hydrogenating acetic
acid is conducted in a first reactor and the hydrogenating of 10. The process of claim 9, wherein the at least one basic
the unreacted acetic acid is conducted in a second reactor. 10 Support modifier is selected from the group consisting of (i)
6. The process of claim 5, wherein at least 10% of the acetic alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alka
acid is converted in the first reactor, and at least 70% of the line earth metal metasilicates, (iv) alkali metal metasilicates,
unreacted acetic acid is converted in the second reactor. (v) Group IIB metal oxides, (vi) Group IIB metal metasili
7. A process for producing ethanol, comprising cates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal
hydrogenating acetic acid in the presence of a first catalyst 15
metasilicates, and mixtures thereof.
and a second catalyst in a reactor to form ethanol,
wherein the second catalyst comprises a first metal on an 11. The process of claim 9, wherein the silicaceous support
acidic Support selected from the group consisting of is selected from the group consisting of silica, silica/alumina,
an acidic Support material selected from the group con calcium metasilicate, pyrogenic silica, high purity silica and
sisting of iron oxide, alumina, silica/alumina, titania, 2O mixtures thereof.
Zirconia, and mixtures thereof, and
a Support material modified with an acidic modifier.