US 2011 0065939A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2011/0065939 A1
Teles et al. (43) Pub. Date: Mar. 17, 2011
(54) METHOD FOR THE SEPARATION OF Related U.S. Application Data
ACETONTRILE FROM WATER
(60) Provisional application No. 61/226,116, filed on Jul.
16, 2009.
(75) Inventors: Joaquim Henrique Teles, Publication Classification
Otterstadt (DE); Hans-Georg
Göbbel, Kallstadt (DE); Peter (51) Int. Cl.
Ba?ler, Viernheim (DE); Philip C07D 301/2 (2006.01)
Kampe, Lorsch (DE); Kai C07C 255/03 (2006.01)
Gumlich, Mannheim (DE); (52) U.S. Cl. ......................................... 549/531; 558/.435
Christian Bartosch, Mannheim (57) ABSTRACT
(DE); Ulrich Miller, Neustadt
(DE); Richard Jacubinas, A method for separating acetonitrile from water, comprising
Bloomfield, NJ (US); Natalia (i) providing a stream S1 containing at least 95 wt.-%, based
Trukhan, Ludwigshafen (DE); on the total weight of S1, acetonitrile and water, wherein the
MeinolfWeidenbach, Stade (DE): weight ratio of acetonitrile:Water is greater than 1; (ii) adding
Martin Cogswell, Camlachie (CA) a stream P. comprising at least 95 wt.-% C3, based on the total
weight of stream P. to S1 to obtain a mixed stream S2, C3
(73) Assignees: BASF SE, Ludwigshafen (DE); The being propene optionally admixed with propane with a mini
Dow Chemical Company, mum weight ratio of propene: propane of 7:3; (iii) Subjecting
Midland, MI (US) S2 to a temperature of 92°C. at most and a pressure of at least
10 bar, obtaining a first liquid phase L1 essentially consisting
of C3, acetonitrile, and water, and a second liquid phase L2
(21) Appl. No.: 12/837,962 essentially consisting of water and acetonitrile wherein the
weight ratio of acetonitrile:water in L2 is less than 1; (iv)
(22) Filed: Jul. 16, 2010 separating L1 from L2.
US 2011/0065939 A1 Mar. 17, 2011

METHOD FOR THE SEPARATION OF distillation wherein unreacted diallyl ether and methanol are
ACETONTRILE FROM WATER recovered at the top of the distillation column. Recycling of
the solvent is not mentioned in EP 1 580 190A1.
0006 EP 1602 651 A1 describes a process for producing
0001. The present invention relates to a method for the propylene oxide, wherein the reaction mixture obtained from
separation of acetonitrile from water wherein a stream S1 the epoxidation, containing propylene oxide, consists of two
which contains at least 95 wt.-% acetonitrile and water with a different phases, namely a water layer and an oil layer. These
weight ratio of acetonitrile:Water of greater than 1 is admixed phases are Subsequently separated into the water layer and the
with a stream P which comprises at least 95 wt.-% of C3 C3 oil layer. The oil layer contained the organic solvent used in
either being propene or a mixture of propene with propane, the epoxidation reaction. By separating the reaction mixture
the weight ratio of propene:propane being at least 7:3. The into these layers, the propylene oxide contained in the reac
mixed stream is then Subjected to temperature and pressure tion mixture was separated from the water layer into the oil
conditions such that two liquid phases are obtained. The first layer. Therefore, EP 1602 651 A1 is strictly limited to pro
liquid mixture, L1, essentially consists of C3, acetonitrile and cesses wherein the oil layer separated from the water layer
water. Preferably, the water content of L1 is 12 wt.-% at most, primarily contains the organic solvent and the propylene
more preferably in the range of from 1 to 5 wt.-%. The second oxide. Although nitriles are generally disclosed as conceiv
liquid phase, L2, essentially consists of water and acetonitrile able solvents, acetonitrile is disclosed as solvent which
with a weight ratio of acetonitrile: water of greater than 1. results in a uniform reaction solution which was not sepa
Preferably, the C3 content of L2 is 5 wt.-% at most. According rable. In this context, it has to be noted that comparative
to the invention, the two liquid phases L1 and L2 are suitably example 3 of EP 1 602 651 A1 erroneously states that the
separated. obtained reaction solution was uniform and separable which
0002. According to a preferred embodiment, the present should certainly read “uniform and not separable'.
invention relates to a method wherein the stream S1 is 0007 EP 2014 654 A1 describes a method for producing
obtained from an oxidation process or a downstream workup propylene oxide, wherein an vent gas stream which is
stage thereof, in particular an epoxidation process or a down obtained from the reactor in which the epoxidation reaction is
stream workup stage thereof, and even more preferably from carried, which vent gas stream contains recyclable com
the epoxidation of propene with hydrogen peroxide in the pounds such as propylene or propylene oxide, is contacted
presence of acetonitrile as solvent or a downstream workup with a solvent containing a nitrile. By absorption in this
stage thereof. As far as this embodiment is concerned, the solvent, the recyclable compounds can be recovered. Further,
present invention is characterized by several possibilities of EP 2014 654 A1 discloses that, if a mixed solvent such as
providing a highly integrated process as far as the recycling of acetonitrile and water and water is used as solvent in the
streams obtained during the overall process is concerned. epoxidation reaction, a portion of the nitrile to be employed in
Thus, the present invention in particular relates to a highly the absorption process can be recovered from the nitrile/water
integrated process for the production of propylene oxide. mixture. Explicit methods for recovering said portion of the
0003 WO 01/57009 A1 relates to a process for the cata nitrile solvent, disclosed in EP 2014 654A1, are the use of a
lytic epoxidation of olefins. From the epoxidation reaction, an molecular sieve or Zeolite as adsorption agent, or distillation.
exit gas stream is obtained which contains olefin oxide, unre In FIG. 2, a process is described wherein the solvent recov
acted olefin and oxygen. This exit gas stream is brought into ering encompasses a distillation wherein, at the top of the
contact in an absorption unit with the same solvent as used in column, acetonitrile and water are obtained, wherein this gas
the reaction stage. mixture is Subsequently subjected to a pressure Swing stage
wherefrom water with an acetonitrile content of less than 1
0004 U.S. Pat. No. 6,350,888 B1 relates to a process for wt.-% and acetonitrile with a water content of less than 1
making an epoxide, in which process a mixture of reaction wt.-% are obtained.
products comprising the epoxide, the diluent and water, and
possibly also unconverted reactants is obtained. This mixture 0008 Generally, it was an object of the present invention
is contacted with an extraction solvent so as to obtain two to provide a novel method for the separation of acetonitrile
from water.
distinct liquid phases wherein the extract contains at least
some of the extraction solvent and at least 10% of the epoxide 0009. It was a further object of the present invention to
produced in the epoxidation reaction. provide an efficient work-up stage in the production of pro
0005 EP 1580 190 A1 discloses a method of oxidizing a pylene oxide wherein acetonitrile is used as solvent and
carbon-carbon double bond of a compound A, which method hydrogen peroxide is used as oxidizing agent for the epoxi
comprises, as a first step, the oxidation of the carbon-carbon dation of propene.
double bond of the compound A using a peroxide as an 0010. It was a further object of the present invention to
oxidizing agent in a presence of a titanosilicate catalyst to provide a highly economical method for the production of
obtain an oxidation reaction mixture, as a second step, the propylene oxide wherein acetonitrile is used as solvent and
separation of the compound Afrom said reaction mixture, and hydrogen peroxide is used as oxidizing agent for the epoxi
as a third step the returning of the separated compound A to dation or propene.
the first step. As particularly preferred compounds A, com 0011. The present invention relates to a method for sepa
pounds are disclosed which have at least two or more func rating acetonitrile from water, comprising
tional groups with at least one functional group being a car 0012 (i) providing a stream S1 containing at least 95
bon-carbon double bond. Especially preferred compounds A wt.-%, based on the total weight of S1, acetonitrile and
are diallyl ether orallyl alcohol. The separation of solvent is water, wherein the weight ratio of acetonitrile:water is
only briefly mentioned in EP 1580 190A1. Concerning this greater than 1;
separation of solvent, example 1 and comparative example 4 0013 (ii) adding a stream P. comprising at least 95 wt.-%
of EP 1 580 190 A1 describes the separation via fractional C3, based on the total weight of stream P. to S1 to obtain a
US 2011/0065939 A1 Mar. 17, 2011

mixed stream S2, C3 being propene optionally admixed range of from 92 to 98 wt.-%, preferably in the range of from
with propane with a minimum weight ratio of propene: 94 to 97 wt.-%, and the content of C3 regarding propane is in
propane of 7:3; the range of from 2 to 8 wt.-%, preferably in the range of from
0014 (iii) subjecting S2 to a temperature of 92 C. at most 3 to 6 wt.-%.
and a pressure of at least 10 bar, obtaining a first liquid 0021 Generally, P is added to S1 in (ii) in an amount so
phase L1 essentially consisting of C3, acetonitrile, and that the weight ratio of C3:acetonitrile in S2 is in the range of
water, and a second liquid phase L2 essentially consisting from 0.2:1 to 5:1. According to preferred embodiments of the
of water and acetonitrile wherein the weight ratio of aceto present invention, P is added to S1 in (ii) in an amount so that
nitrile:water in L2 is less than 1; the weight ratio of C3:acetonitrile in S2 is in the range of from
00.15 (iv) separating L1 from L2. 0.5:1 to 2:1, more preferably in the range of from 1.0:1 to
0016 Generally, it is conceivable to admix a gaseous 1.5:1.
stream S1 and a gaseous stream P. or a liquid stream S1 and a
gaseous stream P. or a gaseous stream S1 and a liquid stream 0022. According to the present invention, the stream S2 is
P. or a liquid stream S1 and a liquid stream P. It is preferred Subjected in (iii) to temperature and pressure conditions so
that in (ii), a liquid stream P is added to a liquid stream S1. that two liquid phases L1 and L2 are obtained. It was found
0017. According to the present invention, at least 95 wt.-% that it is beneficial for the breakup into these phases L1 and L2
of the stream S1 consist of acetonitrile and water, wherein the to Subject the stream S2 to as low a temperature as possible
weight ratio of acetonitrile: water is greater than 1. Preferably, with the proviso that the temperature is still suitable; for
at least 96 wt.-%, more preferably at least 97 wt.-%, more example, the temperature shall not be so low that a solid phase
preferably at least 98 wt.-%, and more preferably at least 99 such as ice is formed. Typically, S2 will be brought to a
wt.-% of the stream S1 consist of acetonitrile and water, temperature of 92 C. at most. According to the present inven
wherein the weight ratio of acetonitrile:water is greater than tion, it is preferred to bring S2 to a temperature in the range of
1 from 5 to 90° C., preferably from 10 to 80° C., more prefer
0018. As far as this weight ratio of acetonitrile: water is ably from 15 to 70° C., more preferably from 20 to 60° C., and
concerned, preferred ratios are at least 1.5:1, even more pre more preferably from 25 to 45° C. Accordingly, S2 is typi
ferred ratios at least 2:1. In particular, S1 contains from 60 to cally subjected to a pressure of at least 10 bar so that S2 will
85 wt.-%, preferably from 65 to 80 wt.-%, more preferably be present essentially or completely in its liquid form. The
from 70 to 80 wt.-% acetonitrile, and from 10 to 35 wt.-%, term “essentially in its liquid form as used in this context of
preferably from 15 to 30 wt.%, more preferably from 15 to the present invention relates to an embodiment according to
25 wt.-% water, in each case based on the total weight of S1. which at least 95 wt.-%, more preferably at least 99 wt.-% and
Therefore, according to a particularly preferred embodiment more preferably at least 99.9 wt.-% of S2 are present in liquid
of the present invention, at least 99 wt.-% of stream S1 consist form after being Subjected to above-mentioned temperatures
of acetonitrile and water, and S1 contains from 70 to 80 wt.-% and pressures. According to the present invention, it is pre
acetonitrile and from 15 to 25 wt.-% water.
0019. According to a specific embodiment of the present ferred to subject S2 to a pressure of at least 15 bar, more
invention, stream S1 comprises at least one glycol, preferably preferably to a pressure in the range of from 15 to 50 bar, more
at least one propylene glycol, Such as monopropylene glycol, preferably from 15 to 40 bar, more preferably from 15 to 30
referred to as propylene glycol, and/or dipropylene glycol, bar, and more preferably from 15 to 25 bar.
and/or tripropylene glycol. In particular, S1 comprises the at 0023 Bringing S2 to above-mentioned temperature can be
least one glycol, preferably the at least one propylene glycol, accomplished by any Suitable method. According to the
if S1 is obtained from an epoxidation process wherein pro present invention, it is preferred to use one or more Suitable
pylene is reacted with hydrogen peroxide in the presence of heat transfer media, e.g. water, in a suitable apparatus, e.g. a
acetonitrile as solvent. Preferably, S1 contains the at least one shell and tube heat exchanger.
glycol, preferably the at least one propylene glycol which is 0024 Subjecting S2 to above-mentioned pressure can be
preferably selected from the group consisting of propylene accomplished by any Suitable method. According to the
glycol, dipropylene glycol, tripropylene glycol, and a mixture present invention, it is preferred to use a suitable pump, e.g. a
of two or three thereof, in an amount of 1 wt.-% or less. centrifugal pump or a radial pump.
0020. According to (ii), a stream P comprising C3, pref 0025. According to the present invention, temperatures
erably a liquid stream P. is added to S1. Generally, at least 95 and pressures as described above allow for the existence of
wt.-% of stream P consist of propene or a mixture of propene two distinct liquid phases L1 and L2. According to (iv), the
with propane. If P contains such mixture of propene and two distinct liquid phases L1 and L2 are Suitably separated
propane, the weight ratio of propene:propane will be at least from each other. Generally, for this separation of the two
7:3. Therefore, propene streams can be employed as P or C3 liquid phases, every conceivable method can be applied. Pos
which have varying contents of propane. For example, com sible apparatuses used for the separation of L1 from L2 are,
mercially available propene can be employed as P or C3 for example, gravity settlers, settlers with coalescing aids
which may be either a polymer grade propene or a chemical Such as weirs, inclined plates separator, coalescers such as,
grade propene. Typically, polymer grade propene will have a for example, mats, beds, layers of porous or fibrous Solids, or
propene content of 99 to 99.8 wt.-% and a propane content of membranes, stagewise mixer-settler equipments, hydrocy
0.2 to 1 wt.-%. Chemical grade propene will typically have a clones, centrifuges, Suitable columns with or without energy
propene content of 92 to 98 wt.-% and a propane content of 2 input. Generally, batch mode or continuous mode is conceiv
to 8 wt.-%. According to a preferred embodiment of the able. Preferably, a gravity settler such as vertical or horizontal
present invention, a stream P is employed, at least 95 wt.-% gravity settler is employed. Still more preferably, a horizontal
thereof consisting of C3, wherein C3 is a mixture of propene gravity settler is employed. It was found that due to the
and propane and the content of C3 regarding propene is in the considerable density difference and low viscosities achieved
US 2011/0065939 A1 Mar. 17, 2011

for the liquid phases L1 and L2 according to the inventive prises Subjecting the liquid phase L1 to a distillation stage.
method, the gravity settler, one of the simplest apparatus, may Preferably, distillation is carried out in a suitable manner so
be employed. that a stream TL1 is obtained which contains at least 90
0026. According to one embodiment of the present inven wt.-%, preferably at least 95 wt.-% C3, based on the total
tion, at least one liquid phase separation improving agent weight of TL1.
Such as at least one Suitable anti-emulsifying, demulsifying or 0034. It is also preferred for said separation that a stream
emulsion breaking agent can be added. Generally, it is pos BL1 is obtained 95 wt.-%, preferably at least 98 wt.-% of
sible to add said liquid phase separation improving agent to which consist of C3, acetonitrile and water, wherein the C3
S1 in (i) or to S2 in (ii) or to S1 in (i) and to S2 in (ii). The content of BL1 is in the range of from 7 to 18 wt.-%, prefer
amount of liquid phase separation improving agent added is ably from 10 to 15 wt.-%, in each case based on the total
preferably at most 1 wt.-% based on the total weight of S1 weight of BL1.
and/or S2. Typically, the amount will be less than 1 wt.-% 0035 Generally, this distillation of L1 can be carried out
such as, for example, below 0.5 wt.-% or below 0.1 wt.-%. according to any suitable method. For example, one, two or
Suitable agents will be known by the skilled person. Refer more distillation towers can be employed provided that
ence is made, e.g., to K. J. Lissant, Making and Breaking above-mentioned streams TL1 and BL1 are obtained. Prefer
Emulsions, Res. Lab., Petrolite Corp., St. Louis, Mo., USA, ably, in said distillation stage, one distillation tower is
in: K. J. Lissant (ed.), Emulsion Technology (1974), chapter employed. More preferably, said distillation is carried out at a
2, pp 111-124, Dekker, New York; and to S. E. Taylor, Chem. dew-point at the top of said distillation tower of at least 40°C.,
Ind. (1992), pp 770-773. preferably in the range of from 40 to 80°C., more preferably
0027. According to another embodiment of the present in the range of from 40 to 70° C. Typically, the number of
invention, the separation of L1 from L2 is performed without theoretical trays is in the range of from 10 to 20. Typical reflux
the addition of Such additional liquid phase separation ratios are in the range of from 0.01 to 0.2 such as, for example,
improving agent. from 0.05 to 0.15.
0028. From the process of the present invention, a liquid 0036 While it is generally possible to use the liquid phase
phase L1 is obtained which essentially consists of C3, aceto L1 as such, as described above, it is an especially preferred
nitrile, and water. The term “essentially consists of C3, aceto embodiment of the present invention to subject L1 to above
nitrile and water as used in this context of the present inven mentioned separation stage, preferably to above-mentioned
tion refers to a liquid phase L1 wherein at least 90 wt.-% of L1 distillation stage. It was found that combining the inventive
consist of C3, acetonitrile and water. separation of L1 from L2 and the downstream separation of
0029. According to a preferred embodiment, at least 95 TL1 from BL1 allows for a highly integrated design of the
wt.-%, more preferably at least 98 wt.-% and still more pref process of the present invention. On the one hand, streamTL1
erably at least 99 wt.-% of L1 consist of the C3, acetonitrile, is especially suitable for being recycled into (ii) of the inven
and water, wherein the water content of L1 is less than 10 tive process as at least a portion of P. If, in addition to at least
wt.-% preferably 9 wt.-% at most, more preferably 5 wt.-% at a portion of TL1, further C3 is added to S1, this further source
most, based on the total weight of L1. More preferably, the of C3 may be suitably chosen. For example, additional C3 can
water content of L1 is in the range of from 1 to 9 wt.-%, more be added as fresh propene, for example as chemical grade
preferably in the range of from 1 to 5 wt.-%, based on the total propene containing about 95 wt.-% propene and about 5
weight of L1. wt.-% propane; certainly, all other suitable sources of addi
0030 Generally, the liquid phase L1 can be used in any tional C3 are conceivable. Such as, for example, a C3 stream
Suitable process. According to a preferred embodiment of the obtained from a supplier in a Verbund site or the like. Further,
present invention, the liquid phase L1 may be employed as it was found that the more C3 is recycled to (ii) via TL1, the
stream which is passed to an oxidation reaction wherein more effective the phase separation according to (ii) to (iv) of
acetonitrile is used as solvent and wherein propene is oxi the inventive process works in terms of as complete a sepa
dized. Still more preferably, the liquid phase L1 may be ration of S1 as possible. Therefore, it is preferred that at least
employed as stream which is passed to an epoxidation reac a portion of TL1, preferably all of TL1 is recycled into (ii).
tion wherein acetonitrile is used as solvent and wherein pro Moreover, in particular as far as a further preferred embodi
pene is oxidized by hydrogen peroxide to obtain propylene ment of the present invention is concerned according to which
oxide. S1 is obtained downstream in an oxidation reaction wherein
0031. According to a preferred embodiment of the present propene is preferably reacted with hydrogen peroxide in the
invention, the liquid phase L.1, prior to being employed in a presence of acetonitrile as solvent, stream BL1 has an ideal
Suitable process, is Subjected to at least one further separation composition allowing for direct recycling, without any other
stage. Preferably, this at least one further separation stage intermediate treatment, to the epoxidation reaction.
serves for separating C3, preferably a portion of C3, from 0037. Further, from the process of the present invention, a
acetonitrile. liquid phase L2 is obtained which essentially consists of
0032. A conceivable method is, for example, evaporation water and acetonitrile wherein the weight ratio of acetonitrile:
of the liquid phase L1 by decompression at a suitable pres water in L2 is less than 1. The term “essentially consists of
sure. Preferably, the temperature of the liquid phase is kept acetonitrile and water as used in this context of the present
essentially constant during decompression. By this decom invention refers to a liquid phase L2 wherein at least 90 wt.-%
pression, C3 is obtained in gaseous form. Thereafter, it is of L2 consist of acetonitrile and water.
possible to recycle at least a portion of this gaseous C3 stream, 0038 According to a preferred embodiment, at least 95
after Suitable compression to obtain a liquid stream, as at least wt.-%, more preferably at least 97 wt.-% and still more pref
a portion of stream Pinto (ii) of the inventive process. erably at least 98 wt.-% of L2 consist of the C3, acetonitrile,
0033. A preferred method for said separation of C3 from and water, wherein the C3 content of L2 is 5 wt.-% at most,
acetonitrile in the at least one further separation stage com preferably 3 wt.-% at most, and more preferably 2 wt.-% at
US 2011/0065939 A1 Mar. 17, 2011

most based on the total weight of L2. As far as the acetonitrile acetonitrile' refers to an embodiment according to which the
is concerned, the respective content of L2 is preferably less acetonitrile content of the bottoms stream of the first distilla
than 45 wt.-%, more preferably in the range of from 10 to 40 tion tower is 500 weight-ppm at most, preferably 300 weight
wt.-%, more preferably from 10 to 35 wt.%, based on the total ppm at most, more preferably 100 weight-ppm at most, based
weight of L2. on the total weight of the bottoms stream of the first distilla
0039 Generally, the liquid phase L2 can be used in any tion tower. In the following, said bottoms stream obtained
suitable process. For example, it is conceivable that the liquid from said first distillation tower, optionally admixed with the
phase L2 is employed as a stream which is passed to an bottoms stream obtained from the second distillation tower as
oxidation reaction or a work-up stage downstream of said described hereinunder, is referred to as stream BL2.
oxidation reaction wherein acetonitrile is used as solvent and 0044. In the context of the two-pressure distillation pro
wherein propene is oxidized, such as an epoxidation reaction cess, at least a portion of preferably all of VTL2 is suitably
whereinacetonitrile is used as solvent and wherein propene is condensed, and this condensed stream is introduced into the
oxidized by hydrogen peroxide to obtain propylene oxide. second distillation tower from which a second bottoms stream
0040. According to a preferred embodiment of the present and a second top stream are obtained. Preferably, said second
invention, the liquid phase L2, prior to being employed in a distillation tower is operated at conditions which allow for
Suitable process, is Subjected to at least one further separation obtaining a top stream TL2 which contains of from 75 to 95
stage. A preferred method for said separation comprises Sub wt.-%, preferably from 80 to 85 wt.-% of acetonitrile, based
jecting the liquid phase L2 to a distillation stage. Preferably, on the total weight of TL2. Typically, said second distillation
distillation is carried out in a suitable manner so that a stream tower is operated at pressures at the top of the tower in the
TL2 is obtained which contains from 75 to 95 wt.-%, prefer range of from 1 to 5 bar, preferably from 1 to 2 bar. Generally,
ably from 80 to 85 wt.-% acetonitrile, based on the total the second distillation tower has from 8 to 20, preferably from
weight of TL2. 10 to 15 theoretical trays. Generally, the reflux ratio of said
0041 Generally, distillation of L2 can be carried out in second distillation tower is in the range of from 0.5 to 5,
one, two, or more distillation towers. If this distillation is preferably of from 1 to 3. The respective bottoms stream
carried out in one distillation tower, the dew-point at the top of obtained from the second distillation tower is preferably
said distillation tower is typically at least 40°C., preferably in essentially free of acetonitrile. In this context, the term
the range of from 40 to 80°C., more preferably in the range of “essentially free of acetonitrile' refers to an embodiment
from 40 to 65°C. Typically, the number of theoretical trays is according to which the acetonitrile content of the bottoms
in the range of from 10 to 25. Typical reflux ratios are in the stream of the second distillation tower is 500 weight-ppm at
range of from 0.5 to 3. By such process, stream TL2 is most, preferably 300 weight-ppm at most, more preferably
obtained as top stream from the distillation tower. The respec 100 weight-ppm at most, based on the total weight of the
tive bottoms stream, BL2, is preferably essentially free of bottoms stream of the second distillation tower.
acetonitrile. In this context, the term “essentially free of 0045 Preferably,TL2 obtained from the respective distil
acetonitrile' refers to an embodiment according to which the lation tower is at least partially, preferably completely
acetonitrile content of BL2 is 500 weight-ppm at most, pref recycled into the inventive process. More preferably, TL2 is
erably 300 weight-ppm at most, more preferably 100 weight either combined with S1 or with S2 or with P.
ppm at most, based on the total weight of BL2. 0046. If stream S1 contains the at least one propylene
0042 Surprisingly, it was found that it is possible to sub glycol, as described above, the stream BL2 obtained from
ject liquid phase L2 to an especially designed distillation said distillation preferably contains the at least one propylene
stage which allows for a highly heat-integrated distillation glycol in an amount of from 1 to 5 wt.-%, more preferably in
process. Thus, it was found that separation of L2 is advanta an amount of from 2 to 5 wt.-%, based on the total weight of
geously carried out using a two pressure distillation process, BL2, whereas streamTL2 is essentially free of the at least one
whereinina first distillation tower, distillation is carried out at propylene glycol. In this context of the present invention, the
a top pressure which is higher than the top pressure of a term “TL2 is essentially free of the at least one propylene
second distillation tower coupled with said first distillation glycol refers to an embodiment according to which the con
tower, wherein the condenser used to condense the top stream tent of TL2 as to the at least one propylene glycol is 500
of the first distillation tower is used simultaneously as the weight-ppm at most TL2 is essentially free of the at least one
vaporizer of the second distillation tower. propylene glycol, preferably 200 weight-ppm at most.
0043. According to this preferred embodiment, liquid 0047. If BL2 contains no or essentially no propylene gly
stream L2 is preferably introduced in said first distillation col, it is preferred to pass BL2 directly to a suitable waste
tower from which a first bottoms stream and a first top stream water treatment plant such as, e.g. a biological waste water
are obtained. Preferably, said first distillation tower is oper treatment plant. It was found that no specific treatment for the
ated at conditions which allow for obtaining a vapor top waste water produced by the inventive process is required,
stream VTL2 which contains of from 50 to 70 wt.-%, prefer rendering the process even more cost-efficient and environ
ably from 55 to 65 wt.-% of acetonitrile, based on the total ment-friendly.
weight of VTL2. Typically, said first distillation tower is 0048 If BL2 contains the at least one propylene glycol in
operated at pressures at the top of the tower in the range of significant amounts, such as in an amount of from 1 to 5
from 10 to 20 bar, preferably from 10 to 15 bar. Generally, the wt.-%, more preferably in an amount of from 2 to 5 wt.-%,
first distillation tower has from 10 to 25, preferably from 15 to based on the total weight of BL2, it can be a preferred embodi
20 theoretical trays. Generally, the reflux ratio of said first ment of the present invention to pass BL2 to a suitable pro
distillation tower is in the range of from 0.25 to 2, preferably pylene glycol separation stage wherein the at least one pro
of from 0.25 to 1. The respective bottoms stream obtained pylene glycol is suitably separated from water and/or wherein
from the first distillation tower is preferably essentially free of two or more different propylene glycols are separate from
acetonitrile. In this context, the term “essentially free of each other. This process for the separation of the at least one
US 2011/0065939 A1 Mar. 17, 2011

propylene glycol from BL2 can be carried out, for example, process, more preferably a process for the production of
by evaporating the mixture in at least two, preferably three propylene oxide, more preferably a process for the production
evaporation and/or distillation stages, preferably three evapo of propylene oxide in the presence of acetonitrile as solvent,
ration stages, at decreasing operating pressures, preferably in more preferably a process for the production of propylene
the ranges of 1.5 to 5.5 bar at a temperature of 111 to 155° C. oxide wherein propene is reacted with hydrogen peroxide in
followed by 1.3 to 5.0 bar at a temperature of 107 to 152°C., the presence of acetonitrile as solvent, still more preferably a
followed in turn by 0.7 to 4.0 bar at a temperature of 90 to highly integrated process for the production of propylene
144° C., thus obtaining mixture BL2 and mixture BL2"; and oxide wherein propene is reacted with hydrogen peroxide in
separating the mixture BL2 in at least one further distillation the presence of acetonitrile as solvent, said process compris
step, obtaining a mixture BL2-I comprising at least 70 wt.-% ing above-described method for separating acetonitrile from
of water and a mixture BL2-II comprising less than 30 wt.-% water or any preferred embodiment of this method for sepa
of water. It is especially preferred to further separate mixture rating acetonitrile from water.
BL2" into a mixture BL2-la comprising at least 90 wt.-% of 0054 According to a preferred embodiment, in said
water and a mixture BL2-Ib comprising less than 95 wt.-% of epoxidation process, propene is reacted with hydrogen per
water by means of reverse osmosis. According to a preferred oxide in a reaction apparatus in the presence of acetonitrile as
embodiment, the at least one propylene glycol is separated solvent, wherefrom a stream S0 is obtained leaving the reac
from the mixture BL2-II, preferably admixed with mixture tion apparatus, S0 containing acetonitrile, water, propylene
BL2-Ib, in at least one further distillation step. According to oxide, and optionally non-reacted propene, oxygen, and fur
a still further preferred embodiment, mixtures BL2" and ther optionally propane. In particular, stream S0 contains
BL2-I are combined and further separated into mixture BL2 propane if propene used as starting material for the epoxida
Ia comprising at least 90 wt.-% of water and mixture BL2-Ib tion reaction is contained in a mixture which, in addition to
comprising less than 95 wt.-% of water by means of reverse propene, also contains propane. If such mixture of propene
osmosis. and propane is used as stream Subjected to epoxidation, the
0049. Therefore, the present invention also relates to a weight ratio of propene:propane will be at least 7:3. For
method as described above wherein example, commercially available propene can be employed
0050 (aa) L2 is introduced into the first distillation tower as which may be eitherapolymer grade propene or a chemical
from which a vapor top stream VTL2 is obtained contain grade propene. Typically, polymer grade propene will have a
ing from 50 to 70 wt.-% acetonitrile, based on the total propene content of 99 to 99.8 wt.-% and a propane content of
weight of top stream VTL2, the distillation preferably 0.2 to 1 wt.-%. Chemical grade propene will typically have a
being carried out at a top pressure of from 10 to 20 bar; and propene content of 92 to 98 wt.-% and a propane content of 2
0051 (bb) at least partially condensing VTL2 obtained in to 8 wt.-%. According to a preferred embodiment of the
(aa) and introducing the condensed stream into the second present invention, a mixture of propene and propane is Sub
distillation tower wherefrom TL2 is obtained as top stream, jected to epoxidation which has a propene content in the range
the distillation preferably being carried out at a top pres of from 92 to 98 wt.-%, preferably in the range of from 94 to
sure of from 1 to 5 bar, 97 wt.-%, and a propane content in the range of from 2 to 8
wherein the condenser used to condense VTL2 is simulta wt.-%, preferably in the range of from 3 to 6 wt.-%.
neously used as vaporizer of the second distillation tower. 0055. Therefore, the present invention also relates to the
0052. It was surprisingly found that this concept wherein method as described above, wherein according to (i), S1 is
most of the water is separated under pressure in a first tower provided by a process comprising
and wherein a comparatively small stream is distilled at lower 0056 (a) reacting propene, optionally admixed with pro
pressures. In total, this concept leads to a lesser energy pane, with hydrogen peroxide in a reaction apparatus in the
demand of the separation problem. presence of acetonitrile as solvent, obtaining a stream S0
0053 According to a preferred embodiment of the present leaving the reaction apparatus, S0 containing acetonitrile,
invention, stream S1 subjected to the process of the present water, propylene oxide, and optionally non-reacted pro
invention is provided by an oxidation process or a down pene, oxygen, and further optionally propane.
stream workup stage thereof. More preferably, stream S1 is 0057 According to a preferred embodiment of the present
obtained from an epoxidation process or a downstream invention, the reaction in (a) is carried out in the presence of
workup stage thereof. More preferably, stream S1 is obtained at least one Suitable catalyst, preferably in the presence of at
from the epoxidation of propene or a workup stage thereof. least one Suitable heterogeneous catalyst. Even more prefer
More preferably, stream S1 is obtained from the epoxidation ably, the at least one Suitable catalyst comprises at least one
of propene wherein hydrogen peroxide is used as oxidizing Zeolite. Specific mention may be made of titanium-, germa
agent, or a workup stage thereof. Even more preferably, nium-, tellurium-, Vanadium-, chromium-, niobium-, Zirco
stream S1 is obtained from the epoxidation of propene in the nium-containing Zeolites having a pentasil Zeolite structure,
presence of acetonitrile as a solvent wherein hydrogen per in particular the types which can be assigned by X-ray-crys
oxide is used as oxidizing agent, or a downstream workup tallography to the structures ABW. ACO, AEI, AEL, AEN,
stage thereof. Most preferably, stream S1 is obtained from a AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY.
workup stage of the epoxidation of propene in the presence of AHT ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT,
acetonitrile as a solvent wherein hydrogen peroxide is used as ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE,
oxidizing agent. Therefore, according to these preferred CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO, CON,
embodiments, the method for separating acetonitrile from CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT,
water, as described hereinabove, can be seen as a specific EPI, ERI, ESV, ETR, EUO, FAU, FER, FRA, GIS, GIU,
workup stage of said oxidation process, in particular of said GME, GON, GOO, HEU, IFR, ISV, ITE, ITH, ITW, IWR,
epoxidation process. Therefore, the present invention also IWW, JBW, KFI, LAU, LEV. LIO, LOS, LOV, LTA, LTL,
relates to an oxidation process, preferably an epoxidation LTN, MAR, MAZ, MEI, MEL, MEP MER, MMFI, MFS,
US 2011/0065939 A1 Mar. 17, 2011

MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAB, epoxidation is carried out is typically in the range of from 2 to
NAT, NEES, NON, NPO, OBW, OFF, OSI, OSO, PAR, PAU, 20 wt.-%, preferably from 5 to 12 wt.-%, based on the total
PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, weight of the overall stream.
RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, 0059. According to especially preferred embodiments
SFG, SFH, SFNSFO, SGT, SOD, SSY, STF, STI, STT, TER, according to the present invention, the overall stream passed
THO, TON, TSC, UEI, UFI, UOZ, USI, UTL, VET, VFI, to the at least one epoxidation reactor. i.e. the reactor feed,
VNI, VSV, WEI, WEN,YUG and ZON, and mixed structures contains of from 50 to 80, preferably from 60 to 70 wt.-%
of two or more of the abovementioned structures. For the acetonitrile, of from 7 to 14, preferably from 8 to 11 wt.-%
purposes of the present invention, preference is given to using propene, of from 5 to 12, preferably from 6 to 10 wt.-%
Ti Zeolites having an MFI structure, an MEL structure, an hydrogen peroxide, and of from 10 to 25, preferably from 12
MFI/MEL mixed structure or an MWW structure. Particular to 20 M-96 water.
preference is given to using zeolite catalysts of the Ti-MWW 0060. In a likewise preferred embodiment of the process of
structure. The catalysts, especially preferably the titanium the present invention, the reaction of the propene can be
Zeolite catalysts and still more preferably the catalysts having carried out in two or more stages. A two-stage reaction takes
Ti-MWW structure, can be employed as powder, as granules, place, for example, as follows:
as microspheres, as shaped bodies having, for example, the
shape of pellets, cylinders, wheels, stars, spheres and so forth, 0061 (A) propene, optionally admixed with propane, is
or as extrudates Such as extrudates having, for example, a reacted with hydrogen peroxide in the presence of aceto
length of from 1 to 10, more preferably of from 1 to 7 and still nitrile as solvent to give a mixture comprising propylene
more preferably of from 1 to 5 mm, and a diameter of from 0.1 oxide, oxygen, and unreacted hydrogen peroxide, and
to 5, more preferably of from 0.2 to 4 and especially prefer optionally propane;
ably of from 0.5 to 2 mm. The preparation of such preferred 0062 (B) the unreacted hydrogen peroxide is separated
catalysts is described, e.g., in US2007043226A1, in particu off from the mixture resulting from (A):
lar in Examples 3 and 5 of US2007043226A1. 0063 (C) the hydrogen peroxide which has been separated
0058 Generally, the reaction in (a) can be carried out in off according to (B) is reacted with propene, optionally
any appropriate way. Thus, for example, it can be carried out admixed with propane.
in a batch reactor or in at least one semi-continuously oper 0064. As far as the preferred epoxidation reaction condi
ated reactor or in at least one continuously operated reactor. tions of stage (A) are concerned, reference is made to the
Particularly, the continuous mode of operation is preferred. In preferred epoxidation reaction as discussed above. The
this particularly preferred embodiment, the reaction is pref hydrogen peroxide can be separated off according to (B) by
erably carried out at from -10 to 120° C., more preferably any suitable methods. The hydrogen peroxide is preferably
from 30 to 90° C. and particularly preferably from 30 to 65° separated off by distillation using one or more distillation
C. Typically, the temperature at which the reaction is carried towers, preferably one distillation tower. This distillation
out is not kept constant but continuously or step-wise adjusted tower is preferably operated at conditions allowing for
to allow for a constant hydrogen peroxide conversion as obtaining a top stream which contains hydrogen peroxide in
determined in stream S0 leaving the reactor in which the an amount of 100 weight-ppm at most, based on the total
epoxidation is carried out. If the epoxidation is carried out in weight of the top stream, preferably containing essentially no
a at least one continuously operated reactor Such as a tube hydrogen peroxide. Additionally this distillation tower is
reactor or a tube bundle reactor which contains at least one preferably operated at conditions allowing for obtaining a top
cooling jacket Surrounding the at least one tube, the term stream which contains at least 80%, preferably at least 90%
“reaction temperature' as used herein refers to the tempera and most preferably at least 95% of the propylene oxide
ture of the cooling medium when entering the cooling jacket. contained in the feed. Typically, this distillation tower has of
Generally, due to catalyst deactivation, the reaction tempera from 15 to 45, preferably from 20 to 40 theoretical trays and
ture is continuously or step-wise increased. Typically, the is operated at a pressure at the top of the tower in a range of
reaction temperature is continuously or step-wise increased from 0.5 to 1.2 bar, preferably from 0.7 to 1.1 bar. The reflux
of by 1° C./day at most. Preferred hydrogen peroxide conver ratio of this distillation tower is typically in the range of from
sion is at least 80%, more preferably at least 85%. The prin 0.05 to 0.5, preferably from 0.1 to 0.2. The bottoms stream
ciple of a preferred hydrogen peroxide conversion determi obtained from the distillation tower in (B), containing essen
nation is described in U.S. Pat. No. 7,351,587 B2, in tially all of the unreacted hydrogen peroxide from (A) and
particular in Examples 1, 2 and 3 of U.S. Pat. No. 7,351,587 further containing acetonitrile, water and optionally at least
B2. The pressures in the at least one reactor are generally in one propylene glycol, is passed to stage (C). As far as stage
the range from 3 to 100 bar, preferably from 15 to 45 bar. In (C) is concerned, it is preferred to use an adiabatic reactor,
particularly preferred embodiments of the process of the preferably an adiabatic shaft reactor. Epoxidation conditions
present invention, the reaction is carried out at temperatures in (C) are preferred allowing for a hydrogen peroxide conver
and pressures at which the reaction mixture is liquid and no sion at the outlet of (C) of at least 99%, preferably at least
gas phase is present in the at least one reactor. The molar ratio 99.5% based on the hydrogen peroxide fed to (A). In (C), it is
of propene: hydrogen peroxide with regard to the starting preferred to use the same catalyst as in (A). As far as the
materials passed into the at least one reactor in which epoxi propene is concerned which is introduced into the reactor
dation is carried is typically in the range of from 0.9:1 to 3.0:1, used in (C), reference is made to the propene already dis
with a range of from 0.98:1 to 1.6:1 being preferred and a cussed hereinabove in the context of (a). Thus, for example,
range of from 1.0 to 1.5 being especially preferred. The chemical grade propene or polymer grade propene can be
amount of acetonitrile passed to the at least one reactor is used, with chemical grade propene being preferred. If stages
adjusted so that the hydrogen peroxide concentration of the (A) and (C) are used in the present invention, the reactors are
overall stream passed to the at least one reactor in which the preferably operated so that the overall propene conversion,
US 2011/0065939 A1 Mar. 17, 2011

taking into account conversion in (A) and conversion in (C), the bottom stream of the distillation tower employed in stage
is at least 80%, more preferably at least 85%. (c) is used. It is also conceivable that stream TL2 or a portion
0065. As described hereinabove, a preferred embodiment thereof is used as stripping agent. Typically, the amount of
of the present invention includes separating acetonitrile from TL2 will not be sufficient, and another stream will be added.
C3 in at least one further separation stage by Subjecting the Typically, the weight ratio of the amount of acetonitrile fed as
liquid phase L1 to a distillation stage wherefrom a streamTL1 external reflux to the top of the distillation tower: weight of the
is obtained which contains at least 90 wt.-%, preferably at stream S0 fed into and to be separated in the distillation tower
least 95 wt.-% C3, based on the total weight of TL1 and is in the range of from 1:1 to 4:1 preferably from 1.5:1 to 3:1.
wherefrom a stream BL1 is obtained 95 wt.-%, preferably at The temperature of the external reflux is generally in the
least 98 wt.-% of which consist of C3, acetonitrile and water, range of from 2 to 20°C., preferably in the range of from 5 to
wherein the C3 content of BL1 is in the range of from 7 to 18 150 C.
wt.-%, preferably from 10 to 15 wt.-%, in each case based on 0070 According to the present invention, at least 95 vol.-
the total weight of BL 1. Surprisingly, it was found that BL1 %, preferably at least 90 vol.-% and still more preferably at
thus obtained can be recycled into the epoxidation process, least 70 vol.-% of the top stream of the distillation column
most preferably without any intermediate workup of BL 1. according to (b) consist of propene, oxygen, and optionally
due to the preferred composition of the overall stream passed propane. Depending on its oxygen content, this top stream
into the at least one epoxidation reactor and the preferred can be passed to a further Suitable workup stage wherein the
composition of BL 1. Therefore, according to a preferred oxygen content is Suitably decreased in order to allow, e.g.,
embodiment, at least a portion of BL1 as described herein for recycling the oxygen-depleted stream to be recycled to
above is recycled into (a). Therefore, the preferred inventive one or more stages of the present invention, such as a starting
method for separating acetonitrile from water allows for an material for stage (a) of the inventive process like stage (A) or
integrated epoxidation process including the economic stage (C), or as portion of stream P. If the oxygen content of
advantages of reusing the epoxidation solvent acetonitrile said top stream is reduced, it is preferred to reduce the oxygen
separated from water in the workup stages and, further, Suit by reaction with hydrogen in the presence of a suitable cata
ably making use of propene employed for said separation of lyst. Such catalysts are, for example, catalysts comprising tin
the solvent acetonitrile from water. and at least one noble metal as described in WO 2007/000396
0066 Generally, it is conceivable that, apart from BL1, A1, in particular in Example 1 of WO 2007/000396A1. It is
additional fresh acetonitrile is needed. This may be due to also conceivable to use catalysts comprising copper in
losses of acetonitrile throughout the overall process. As addi elemental and/or oxidic form on a support, wherein copper is
tional acetonitrile, pure or essentially pure acetonitrile may be present on the support in an amount of 30 to 80 wt.-% based
added, e.g. to the stream BL1 and/or at other suitable point or on the whole catalyst and calculated as CuO. Such catalysts
points upstream the reactor inlet. It is also conceivable to add can be prepared, for example, according to the example of EP
crude acetonitrile Such as an azeotrope of acetonitrile and 0427062 A2, catalyst 2, page 4, lines 41 to 50 (corresponding
water, probably also containing impurities, wherein Such to U.S. Pat. No. 5,194,675). However, in order to reduce the
crude acetonitrile is typically obtainable, for example, by the oxygen content, also other Suitable methods are conceivable.
acrylonitrile process. In this latter case, it would be preferred Optionally, said top stream, prior to be subjected to hydroge
to add the acetonitrile, namely the crude acetonitrile, nation, can be compressed and partially condensed wherein a
upstream the phase separation. liquid stream is obtained which essentially consists of C3 and
0067. According to a preferred embodiment of the present acetonitrile and which contains minor amounts of water. The
invention, the stream S0 obtained from (a), in particular SO non-condensed portion essentially consists of C3 and oxygen
consisting of the top stream obtained from the distillation and contains a minor amount of water wherein, compared to
tower used in (B) combined with the reactor effluent obtained the basic stream, the oxygen content is increased while still
from (C), is passed to a suitable downstream workup stage. being in a range so that the mixture is not ignitable. This
Preferably, in this downstream workup stage, propene, oxy oxygen-enriched is then Subjected to hydrogenation.
gen, and propane are separated from S0 to obtain a stream 0071. Further according to the present invention, at least
essentially consisting of acetonitrile, water, and propylene 98 wt.-%, preferably at least 98.5 wt.-% and still more pref
oxide. This workup stage is referred to as stage (b) in the erably at least 99 wt.-% of the bottoms stream of the distilla
context of the present invention. tion column according to (b) consist of propylene oxide,
0068 Separation according to stage (b) can be conducted acetonitrile, water, and optionally at least one propylene gly
by every suitable method. Most preferably, separation is con col. Prior to feeding this bottoms stream as stream S1 to the
ducted by distillation. Separation according to stage (b) is method according to the present invention, it is especially
preferably carried out in at least one distillation tower, more preferred to separate propylene oxide from said bottoms
preferably in one distillation tower. Preferably, this column stream according to a stage (c) of the inventive process in
has of from 10 to 30, more preferably of from 15 to 25 order to obtain a stream which is essentially free of propylene
theoretical trays. The distillation tower is preferably operated oxide, which stream can be partially used as stripping agent
at a top pressure of from 0.5 to 1.2 bar, more preferably of for stage (b).
from 0.7 to 1.1 bar. 0072 Separation according to stage (c) can be conducted
0069. In order to facilitate said separation task, it was by every suitable method. Most preferably, separation is con
found that it is advantageous to add either acetonitrile or a ducted by distillation. Separation according to stage (c) is
mixture of acetonitrile with water to the top of the column. It preferably carried out in at least one distillation tower, more
is believed that this external reflux serves as stripping agent preferably in one distillation tower. Preferably, this tower has
which, among others, prevents propylene oxide from being of from 50 to 80, more preferably of from 60 to 70 theoretical
separated via the top of the distillation tower. According to a trays. The distillation tower is preferably operated at a top
preferred embodiment of the present invention, a portion of pressure of from 0.2 to 2 bar, more preferably of from 0.4 to
US 2011/0065939 A1 Mar. 17, 2011

1 bar. Preferably, at least one suitable polar solvent such as either individually or as a mixture of two or more thereof, as
preferably water is added in the upper part of the column as active metal on a Suitable Support material. An especially
extractive agent. According to a preferred embodiment, sepa Suitable catalyst, namely a Supported catalyst comprising 5%
ration according to stage (c) can be carried out by by weight of Pd on activated carbon is, described in Example
0073 introducing said bottoms stream into an extrac E2 of US 2004.0068.128A1. The pressure during hydrogena
tive distillation column; tion is typically in the range of from 1 to 100 bar(abs), pref
0074 additionally introducing a polar extracting sol erably from 1 to 10 bar(abs), and the temperature during
vent into said extractive distillation column; hydrogenation is typically in the range of from 0 to 180°C.,
0075 distilling propylene oxide overhead from said preferably from 25 to 120° C., more preferably from 65 to 85°
C. The hydrogen partial pressure during hydrogenation is
extractive distillation column as top stream, the top preferably in the range of from more than 1 to 20 bar, more
stream comprising only minor amounts of acetonitrile preferably from 2 to 15 bar and still more preferably from 3 to
such as 500 ppm or less; 13 bar. If the hydrogenation is carried out in a fixedbed, which
0076 compressing the top stream obtained overhead in is preferred, the residence time of the liquid passed through
the previous step by means of at least one compressor to the hydrogenation reactor is generally in the range of from 1
give a compressed vapor, second (s) to 1 hour (h), preferably from 10s to 20 minutes
0077 condensing the compressed vapor obtained in in (min), in particular from 30 to 5 min.
the previous step and returning at least part of the heat of I0081. Depending on the reaction conditions employed for
condensation to at least one reboiler employed in the reducing, preferably hydrogenating the bottoms stream
extractive distillation column. obtained from the distillation tower according to (c), it may be
0078 From this distillation tower according to (c), a top necessary to the separate the resulting stream from the cata
stream is obtained which contains at least 90 wt.-%, prefer lyst, preferably hydrogenation catalyst and/or non-reacted
ably at least 95 wt.-% of propylene oxide. Depending on the reducing agent, preferably hydrogen and/or by-products from
requirements on the propylene oxide quality, it is conceivable the hydrogenation, preferably CO and/or methane.
to use this propylene oxide fraction without any further puri I0082 In particular, the stream resulting from reduction,
fication. It is, however, also conceivable to further purify said preferably hydrogenation, contains at least 95 wt.-% aceto
propylene oxide fraction, for example in at least one further nitrile and water, based on the total weight of the bottoms
distillation stage. From Such further distillation stage, a pro stream, wherein the weight ratio of acetonitrile:water is
pylene oxide stream may be obtained wherein at least 99.5 greater than 1. Generally, it is conceivable to use the bottoms
wt.-%, more preferably at least 99.9 wt.-% of said stream stream obtained from the distillation tower according to (c) as
consist of propylene oxide. stream S1 of the present invention.
007.9 Further from this distillation tower according to (c), I0083. Depending on the specific conditions during the
a bottoms stream is obtained which typically contains 500 upstream stages of the present invention, i.e. stages (a),
weight-ppm at most, preferably 100 weight-ppm at most, and optionally (b), and/or (c) and/or the reduction, preferably the
more preferably 60 weight-ppm at most of propylene oxide, hydrogenation stage, the stream obtained from reduction,
based on the weight of the bottoms stream. In particular, at preferably hydrogenation may contain certain amounts of
least 98 wt.-%, more preferably at least 98.5 wt.-% and more acetaldehyde and optionally further low boilers such as, for
preferably at least 99 wt.-% of the bottoms stream consist of example, propionaldehyde and acetone. Typically, this
acetonitrile, water, and optionally at least one propylene gly stream may contain up to 2000 weight-ppm, preferably up to
col. 1000 weight-ppm, more preferably up to 300 weight-ppm of
0080 Depending on the specific conditions during the acetaldehyde and other lowboilers in total, based on the total
upstream stages of the present invention, i.e. stages (a), weight of this stream. In order to reduce the acetaldehyde
optionally (b), and/or (c), this bottoms stream obtained from content and optionally the content with respect to the other
the distillation tower according to (c) may also contain certain low boilers and, thus, to avoid the build-up of these com
amounts of hydroperoxides Such as certain amounts of hydro pounds which especially occurs if the inventive highly inte
gen peroxide and/or certain amounts of organic hydroperoX grated process is realized, it is preferred to Subject this stream
ides, for example, 1-hydroperoxypropanol-2 and/or 2-hydro to at least one further process stage. While every suitable
peroxypropanol-1. Typically, the bottoms stream obtained method for at least partially removing acetaldehyde is con
from the distillation tower according to (c) may contain up to ceivable, it is especially preferred to separate acetaldehyde
2 wt.-%, preferably up to 1 wt.-% of these hydroperoxides in from the stream by distillation. Separation according to this
total, based on the weight of the bottoms stream. In order to stage is preferably carried out in at least one distillation tower,
reduce the hydroperoxide content and, thus, to avoid the more preferably in one distillation tower. Preferably, this
build-up of the hydroperoxides which are believed to have a tower has of from 15 to 40, more preferably of from 15 to 30
detrimental influence as far as the formation of undesirable theoretical trays. The distillation tower is preferably operated
by-products and safety aspects based on the decomposition of at a top pressure of from 0.7 to 2 bar, more preferably of from
the hydroperoxides are concerned, it is preferred to subject 1.1 to 1.5 bar.
the bottoms stream obtained from the distillation tower 0084. From this distillation tower, a bottoms stream is
according to (c) to at least one further process stage. Said obtained which typically contains 200 weight-ppm at most,
build-up especially occurs if the inventive highly integrated preferably 100 weight-ppm at most, and more preferably 50
process is realized. While every suitable method for at least weight-ppm at most of acetaldehyde, other low boilers as
partially removing these hydroperoxides is conceivable, it is described above, in total, based on the weight of the bottoms
especially preferred to catalytically reduce, preferably to stream. In particular, at least 99 wt.-%, more preferably at
catalytically hydrogenate the hydroperoxides. As Suitably least 99.5 wt.-% and more preferably at least 99.7 wt.-% of
catalyst, a catalyst may be mentioned which is described in the bottoms stream consist of acetonitrile, water, and option
US 2004.0068.128 A1, in particular in paragraphs 0053 to ally at least one propylene glycol. In particular, the bottoms
0076. Preferred catalysts are selected from the group con stream contains at least 95 wt.-% acetonitrile and water, based
sisting of heterogeneous catalysts comprising Ru, Ni, Pd, Pt, on the total weight of the bottoms stream, wherein the weight
US 2011/0065939 A1 Mar. 17, 2011

ratio of acetonitrile:water is greater than 1. Preferably, this mixed stream S2, C3 being propene optionally admixed
bottoms stream is used as stream 51 in the process of the with propane with a minimum weight ratio of propene:
present invention. According to a conceivable embodiment of propane of 7:3;
the present invention, no such distillation stage is needed. 0097 (e) subjecting S2 to a temperature of 92° C. at most
0085. Therefore, the present invention also relates to the and a pressure of at least 10 bar, obtaining a first liquid
method as described above, further comprising phase L1 essentially consisting of C3, acetonitrile, and
I0086 (y) subjecting the stream obtained from (c) to a water, and a second liquid phase L2 essentially consisting
hydrogenation stage, preferably to a catalytical hydroge of water and acetonitrite wherein the weight ratio of aceto
nation stage, the catalyst preferably being a heterogeneous nitrile:water in L2 is less than 1;
catalysts comprising Ru, Ni, Pd, Pt, either individually or 0.098 (f) separating L1 from L2:
0099 (g) subjecting L1 to a distillation stage wherefrom a
as a mixture of two or more thereof, as active metal on a stream TL1 is obtained which contains at least 90 wt.-%
Suitable Support material, in particular Pd on activated C3, based on the total weight of TL1; and wherefrom a
carbon; said hydrogenation preferably being carried out at further stream BL1 is obtained, at least 95 wt.-% of BL1
a pressure during hydrogenation in the range of from 1 to consisting of C3, acetonitrile and water, wherein the C3
100 bar(abs), preferably from 1 to 10 bar(abs), and a tem content of BL1 is in the range of from 7 to 18 wt.-% based
perature during hydrogenation in the range of from 0 to on the total weight of BL1;
180° C., preferably from 25 to 120° C., more preferably 0100 (h) subjecting L2 to a distillation stage wherefrom a
from 65 to 85°C.: stream TL2 is obtained which contains from 75 to 95
0087 (Z) subjecting the stream obtained from (y) to a wt.-%, preferably from 80 to 85 wt.-% acetonitrile, based
distillation stage, preferably carried out in a distillation on the total weight of TL2:
column operated at a top pressure of from 0.7 to 2 bar, more wherein at least a portion of stream BL1 is recycled into (a):
preferably of from 1.1 to 1.5 bar, to obtained stream S1 and and/or
Subjecting S1 to step (d) as discussed hereinunder. wherein at least a portion of TL1 is recycled into (d); and/or
0088 Generally, the present invention relates to the wherein at least a portion of TL2 is recycled into (d).
method as described above, wherein according to (i), S1 is 0101. It is especially preferred to recycle BL1 into (a) and
provided by a process comprising TL1 into (d) and TL2 into (d).
0089 (a) reacting propene with hydrogen peroxide in a 0102 Above-described process stages, including stages
reaction apparatus in the presence of acetonitrile as sol (y) and (Z), may be carried out either in continuous mode, in
vent, obtaining a stream S0 leaving the reaction apparatus, semi-continuous mode or in batch mode. Preferably, all
S0 containing acetonitrile, water, propylene oxide, and stages are carried out in continuous mode.
optionally non-reacted propene, oxygen, and further 0103) As far as preferred compositions of said streams,
optionally propane; preferred reaction conditions, preferred separation condi
0090 (b) optionally separating propene, oxygen, and pro tions, preferred distillation conditions, or the like, and further
pane from S0 to obtain a stream essentially consisting of preferred embodiments as far, for example, preferred and/or
acetonitrile, water, and propylene oxide; optional additional intermediate and/or workup stages are
0091 (c) separating propylene oxide from S0 or the concerned, reference is made to the respective disclosure
hereinabove.
stream obtained from (b), thus obtaining stream S1. 0104. The present invention is further illustrated in the
0092. As described hereinabove, the inventive method of following examples.
separating acetonitrile from water is preferably integrated as
workup stage in a process for the preparation of propylene EXAMPLES
oxide. Especially as part of this epoxidation process, the
inventive method allows for a highly integrated process. Example 1
Therefore, the present invention also relates to a highly inte Epoxidation of Propene
grated process for the preparation of propylene oxide, the
process comprising 0105. The epoxidation was performed in a continuous
0093 (a) reacting propene, optionally admixed with pro tubular reactor having a cooling jacket and a catalytic bed.
pane, with hydrogen peroxide in a reaction apparatus in the The reactor had a length of 1440 mm and an inner diameter of
presence of acetonitrile as solvent, obtaining a stream S0 7 mm and was built of stainless steel (specification 1.4571).
leaving said reaction apparatus, S0 containing acetonitrile, The reaction tube was Surrounded by a cooling jacket through
water, propylene oxide, and optionally non-reacted pro which a cooling medium (water/glycol mixture) was circu
pene, oxygen, and optionally propane; lated. The reactor was operated in an up-flow mode. Suitable
0094 (b) optionally separating propene, optionally thermoelements were located just above and below the cata
together with propane, and oxygen from S0 to obtain a lytic bed axially centered in the tube in order to measure the
catalytic bed entry and exit temperatures. The reactor was
stream, at least 99 wt.-% thereof consisting of acetonitrile, operated at a constant pressure of 20 bar by using a pressure
water, and propylene oxide; regulating valve at the reactor exit. The temperature was
0095 (c) separating propylene oxide from S0 or the controlled by circulating the cooling medium (fluid) in the
stream obtained from (b), thus obtaining a stream S1 con reactor mantle in concurrent mode relative to the product. The
taining at least 95 wt.-% acetonitrile and water, based on cooling medium entrance temperature is measured by a ther
the total weight of S1, wherein the weight ratio of aceto moelement and used to regulate the thermostat. This tempera
nitrile:Water is greater than 1, ture is referred to as the “reaction temperature' and was held
0096] (d) adding a stream P. comprising at least 95 wt.-% constant at 63°C. throughout the experiment. The flow rate of
C3, based on the total weight of stream P. to S1 to obtain a the cooling medium is adjusted so that the exit temperature of
US 2011/0065939 A1 Mar. 17, 2011

the cooling medium is no more than 1 C. above the cooling

medium entrance temperature. TABLE 1-continued
0106. The reactor was the filled from below with a layer of Component Concentration
glass beads (80 mm), then with the catalyst and any remaining
room was filled up with glass beads. As catalyst, 15 g of a propylene oxide 849 wt.-%
propionitrile O.O23 wt.-%
catalyst were used which were produced by mixing 100 parts hydroxyacetone b)
of a Ti-MWW powder containing 1.5 wt.-% of Ti with 40 1,2-propylene glykol O.052 wt.-%
parts of pyrogenic silica and with water, kneading and extrud dipropylene glykols trace amounts
detected in GC
ing to form cylindrical extrudates with a diameter of 1.5 mm as a mixture of 3
and a length between 3 and 5 mm, and calcining the extru isomers
dates at 450° C. before use. The extrudates had a Ti concen hydroperoxypropanols O.27 wt.-96
tration of 1.1 wt.-%. The length of the catalyst bed layer was O.O8 wt.-96
approximately 950 mm.
0107 The reagents were placed in suitable tanks and con 0109 The liquid stream obtained in the previous step was
tinuously metered to the reactor by using standard metering submitted to distillation in a rotary evaporator with a bath
pumps. Tank 1 contained chemical grade acetonitrile with a temperature and a pressure of 200 mbar until the concentra
purity of 99.98% (containing 0.01% water, 150 wt.-ppm pro tion of propylene oxide in the residue was below 1 wt.-%.
pionitrile and 1 wt.-ppm acrylonitrile as impurities). Tank 2 0110. The residue obtained was analyzed as above, with
contained a standard grade crude, washed hydrogen peroxide the difference that all non-peroxidic organic components
solution with a concentration of 40 wt.-% to which 175 wt.- were determined by quantitative GC with 1,4-dioxane as the
ppm of (NH)HPO were added. Tank 3 contained pressur internal standard. Water was determined using the Carl-Fis
ized liquefied polymer grade propylene. The acetonitrile cher method. The composition of the residue stream is given
metering pump was started first at a feed rate of 60.9 g/h, and in Table 2 below.
the reaction temperature was set to 63°C., and the pressure
regulator was set to 20 bar. When the reactor had been filled TABLE 2
with liquid and the system had been equilibrated, the meter Component Concentration wt-%
ing pump for propylene was started at a feed rate of 8.5 g/h. A
few minutes later the hydrogen peroxide pump was started at acetonitrile 83.8
a feed rate of 11.5 g/h (this point in time was defined as t-0). Water 14.7
The three streams were mixed at room temperature before acetic aldehyde O.O2
propylene oxide 0.7
they were passed into the reactor. The temperatures measured propionitrile O.O24
within the reactor just before and just after the catalytic bed hydroxyacetone O.O12
differed by less than 1° C. from the reaction temperature, thus 1,2-propylene glycol
dipropylene glycols
O.12
O.O2
demonstrating that the layer of glass beads was Sufficient to (mixture of 3 isomers)
heat the reactants to the reaction temperature before they hydroperoxypropanols 0.4
came into contact with the catalyst. H2O2 O.2
0108. The product stream leaving the reactor was decom
pressed to ambient pressure into a vessel where gas and liquid 0111. This stream was used as feed stream S1 for the
phases were separated. The amount of gas was determined process according to Example 2 below.
Volumetrically and its composition analyzed by gas chroma
tography. The liquid phase was gathered for the entire run Example 2
(about 300 h) and analyzed. The total concentration of per
oxides was determined iodometrically. The concentration of Workup of the Stream Obtained According to
H2O, was determined colorimetrically using the titanyl Sul Example 1
fate method. The difference between the two values is gener 0112 50 g of mixture as described in Table 2 was intro
ally a good measure for the concentration of hydroperoxypro duced into an evacuated, tempered autoclave (volume: 315
panols (1-hydroperoxy-2-propanol and 2-hydroperoxy-1- ml) equipped with two opposite Sapphire windows. After
propanol); this was confirmed by determining the amount of equilibration, 40 g of propene (polymer grade, containing 0.1
propylene glycol by GC before and after reducing the mixture wt-% of propane) were introduced into the autoclave. The
with excess triphenylphosphine). All other organic compo temperature was held constant at 40°C. The measured pres
nents were determined by GC using a FID detector. With the sure was 14.3 bar.
exception of acetonitrile, for which only the area-% is given,
all other components were determined quantitatively using 0113. The content of the autoclave was thoroughly mixed
1,4-dioxane as an internal standard. The composition of the by a magnetic stirrer. After the stirrer had been stopped, the
liquid reactor output is given in Table 1 below. mixture immediately separated into two liquid phases. The
lower aqueous phase was removed through an outlet at the
TABLE 1. bottom of the autoclaved and weighed. The aqueous phase
weighed 6.12 g, corresponding to 6.8% of the total contents of
Component Concentration the autoclave (90 g). Both the aqueous and the organic phase
acetonitrile 87.5 (area %)
were analysed as described above, and the composition of
Water not measured both phases is given in Table 3 below. As can be seen from the
acetic aldehyde trace amounts results in Table 3, the ratio of acetonitrile to water (12.1:1) is
detected in GC much lower than the weight ratio in the acetonitrile/water
azeotrope (5.7:1) obtainable by simple distillation.
US 2011/0065939 A1 Mar. 17, 2011
11

described, the compositions disclosed in detail are to be

TABLE 3 understood as mean values determined over the entire con
Aqueous Organic
tinuous process which was carried out for 507 hours.
Component (wt-%) phase phase 0118. From a continuously operated process for the prepa
ration of propylene oxide, essentially carried out according to
C3 (propane + propene) 1.3 42.8 Example 1, using the same starting materials, catalyst, and
acetonitrile 24.8 52.1
Water 71.2 4.3
also comprising the downstream work-up stage of distilling
acetic aldehyde O.04 O.OO9 off the propylene oxide, however, said distillation carried
propylene oxide O.1 O46 being carried in a distillation tower, a stream was obtained
propionitrile O.O3 O.O14 with a flow rate of 102 kg/h and having, with respect to the
hydroxyacetone O.04 O.OOS
1,2-propylene glycol O.48 O.042 main components, a composition as given in Table 5 below.
dipropylene glycols O.O2 O.O13
hydroperoxypropanols 1.4 O.14 TABLE 5
H2O2 O.63 O.O6
Component Concentration wt-%
acetonitrile 78.O
Example 3 Water 21.5
Separation of Acetonitrile from Water
0114. In a second experiment, again, an amount of 50 g of 0119. This stream was used as feed stream S1 for the
the stream obtained according to Example 1 was introduced separation process according to invention.
into an evacuated and tempered autoclave, as described in
Example 2. Subsequently, 50g of propene (chemical grade, I0120 Before stream S1 was passed to the separation
containing 0.1 wt-% of propane) were introduced into the device, it was combined with 3 other streams:
autoclave. The temperature was held constant at 40°C., the 0.121. The first stream 1 was a stream of (fresh) chemi
measured pressure was 14.8 bar. cal grade propene (about 95 wt.-% propene, about 5
0115 The content of the autoclave was thoroughly mixed wt.-% propane) (flow rate of stream 1; 11.4 kg/h).
by a magnetic stirrer. After the stirrer was stopped, the mix 0.122 The second stream 2 was a stream having a pro
ture immediately separated into two liquid phases. The lower pene content of about 95 wt.-%, obtained from a down
aqueous phase was removed through an outlet at the bottom stream work-up stage as described hereinunder. Said
of the autoclaved and weighed. The aqueous phase weighed stream 2 corresponds to stream TL1 as discussed in the
6.8 g. corresponding to 6.8% of the total contents of the context of the present invention. Together with stream 1.
autoclave (100 g). Both the aqueous and the organic phase stream 2 formed stream Pas discussed in the context of
were analysed as described above, and the composition of the present invention. (Flow rate of stream 2: 50 kg/h).
both phases is given in Table 4 below. As can be seen from the 0123. The third stream 3 was a stream which essentially
results in Table 4, the ratio of acetonitrile to water (13.9:1) is consisted of acetonitrile and water (70.5 wt.-% acetoni
again much lower than the weight ratio in the acetonitrile/ trile, 29.3 wt.-% water), obtained from a downstream
water azeotrope (5.7: 1) obtainable by simple distillation. work-up stage as described hereinunder. Said stream 3
corresponds to streamTL2 as discussed in the context of
TABLE 4 the present invention. (Flow rate of stream 3: 6.4 kg/h).
Aqueous Organic 0.124. Together with said streams 1, 2, and 3, stream S1
Component (wt-%) phase phase formed stream S2 having a flow rate of 169.6 kg/hand having,
C3 (propane + propene) 1.O 53.2
with respect to the main components, a composition as given
acetonitrile 23.1 43.1 in Table 6 below.
Water 73.1 3.1
acetic aldehyde O.OS O.OO6 TABLE 6
propylene oxide O.O7 0.4
propionitrile O.O3 O.O1 Component Concentration wt-%
hydroxyacetone O.04 O.OO)4
1,2-propylene glycol O.S O.O3 acetonitrile 49.5
dipropylene glycols O.04 O.OO9 Water 13.9
hydroperoxypropanols 1.4 O.1 propene 34.5
H2O2 O.S O.OS

0116. The results in Examples 2 and 3 show that by adding 0.125. This stream was fed in the separation device, a hori
a propene mixture, in particular a propene/propane, to a mix Zontal gravity settler with a capacity of 2 L.
ture of water and acetonitrile, the mass ratio of acetonitrile: 4.2 Separation According to the Invention
water can be considerably reduced. The effect of increasing
the ratio acetonitrile:Water is increased when more propene is I0126. In the horizontal gravity settler, phase separation
used. was achieved at a temperature in the range of from 30 to 40°
Example 4 C. and at a pressure of 18 bar. The obtained upper layer was
Separation of Acetonitrile from Water fed as a stream with a flow rate of 148 kg/h to a distillation
column A, the obtained lower phase as a stream with a flow
4.1 Providing Stream S2 rate of 21.6 kg/h to a distillation column B1. The upper layer
0117 Since in the following, an entirely continuously had a composition, with respect to the main components, as
operated process according to the present invention is given in Table 7 below:
US 2011/0065939 A1 Mar. 17, 2011

0.135 The top stream obtained from column B1 at a tem

TABLE 7 perature at the top of the column in the range of from 176
Component Concentration wt-%
185°C. had a composition, with respect to the main compo
nents, according Table 10
acetonitrile 53.8
Water 4.5 TABLE 10
propene 39.5
Component Concentration wt-%
0127. The lower layer had a composition, with respect to acetonitrile 45.0
the main components, as given in Table 8 below: Water 55.0

TABLE 8 i.e. essentially the composition of the acetonitrile/wateraZeo

Component Concentration wt-% trope. This top stream of column B1 was fed with a flow rate
of 10.0 kg/h to a downstream distillation column B2.
acetonitrile 20.4 0.136 Distillation column B2 was configured as packed
Water 78.3
column (DN80*9500) (DN 80–Diameter Nominal 80
according to standard EN 10255; length=9500 mm) made of
stainless steel of quality 1.4541 with integrated bottom
4.3 Work-Up of the Upper Layer reboiler. Column B2 was operated at a top pressure of 1.5 bar
0128. The stream obtained as upper layer from the phase and a bottom temperature of 111-112°C. As packing mate
rial, Kühni RombopakR 9m was used (height of the packing:
separation device was passed, as mentioned, to a distillation 6500 mm). The reflux ratio of column B2 was 0.7.
column A.
0129. Distillation column A was configured as bubble-tray 0.137 The bottoms stream having a flow rate of 3.6 kg/h
had a water content of 99.9 wt.-%.
column (internal diameter: 200 mm; length: 10000 mm) 0.138. The top stream obtained from column B2 at a tem
made of stainless steel of quality 1.4541, 40 trays and inte perature at the top of the column in the range of from 74-85
grated bottom reboiler. Column A was operated at a pressure C. had a composition, with respect to the main components,
of 18 bar and a bottom temperature of 105-107°C. The reflux according Table 11
ratio of column A was 0.2.
0130. The top stream obtained from column A at a tem TABLE 11
perature at the top of the column in the range of from 44-45°
C. and having a propene content of 95 wt.-%, was recycled Component Concentration wt-%
with a flow rate of 50 kg/has starting material to the continu acetonitrile 70.5
ously operated epoxidation reaction. Water 29.3
0131 The bottoms stream obtained from column A, hav
ing a composition, with respect to the main components,
according Table 9 0.139. This top stream of column B2 was recycled with a
flow rate of 6.4 kg/h into the separation device as stream 3 to
TABLE 9 be admixed with stream S1 and streams 1 and 2 to obtain
stream S2.
Component Concentration wt-%
acetonitrile 81.2 SUMMARY
Water 6.8
propene 11.2 0140. The major advantage of the inventive process of
separating acetonitrile from water is particularly evident in
was recycled into the separation device as stream 2 to be case the separated acetonitrile is recycled as starting material
admixed with stream S1 and streams 1 and 3 to obtain stream
of an highly integrated process for the epoxidation of pro
S2.
pene, in particular with aqueous hydrogen peroxide. In Such
integrated process, the inventive process allows for big sav
4.4 Work-Up of the Lower Layer ings in energy while at the same time a ratio of acetonitrile:
water can be achieved which is higher than the ratio of aceto
0132) The stream obtained as lower layer from the phase nitrile: water achievable by simple distillation at ambient
separation device was passed, as mentioned, to a distillation pressure. Presently, without wanting to be bound to any
column B1. theory, it is believed that in order to separate and recycle
0.133 Distillation column B1 was configured as bubble acetonitrile from the reaction mixture obtained from such
tray column (internal diameter: 100 mm; length: 9500 mm) epoxidation reaction or a suitable mixture obtained from one
made of stainless steel of quality 1.4541, 50 trays and inte or more work-up stages by distillation at ambient pressure, all
grated bottom reboiler. Column A was operated at a top the acetonitrile plus the amount of water contained in the
pressure of 14 bar and a bottom temperature of 190-196° C. azeotrope would have to be evaporated. However, if a lower
The reflux ratio of column B1 was 1.0. amount of water in the acetonitrile is desired, then a two
0134. The bottoms stream obtained from distillation col pressure distillation set-up would be needed, but this would
umn B1 with a flow rate of 11.6 kg/h had a water content of imply that the complete amount of acetonitrile would have to
97.1 wt.-% and further contained non-specified high boilers. be evaporated twice, necessarily leading to a large energy
The acetonitrile content of the bottoms stream was less than consumption. Thus, using the method of the present inven
0.1 wt.-%. tion, only a fraction of the energy is needed when compared to
US 2011/0065939 A1 Mar. 17, 2011
13

the above mentioned method due to our finding that the liq 0154 8. The method of any of embodiments 1 to 7,
uid/liquid separation required very little energy. Further, it wherein at least 95 wt.-%, preferably at least 98 wt.-% of
was possible to design the desired separation apparatus in the L1 consist of C3, acetonitrile and water, the water content
form a comparatively simple setup. The only significant con of L1 being less than 10 wt.-%, preferably in the range of
tribution to the energy consumption is needed to recover the from 1 to 5 wt.-%, based on the total weight of L1.
low amount of acetonitrile present in the aqueous phase after (O155 9. The method of any of embodiments 1 to 8,
the phase separation. The present invention clearly offers a wherein at least 95 wt.-%, preferably at least 98 wt.-% of
big advantage, both from the point of view of energy con L2 consist of C3, acetonitrile and water, the C3 content of
Sumption and from the point of view of required investment. L2 being 5 wt.-% at most, based on the total weight of L2.
01.41 Example 4 further clearly illustrates a highly inte and the acetonitrile content of L2 being less than 45 wt.-%,
grated embodiment of the separation process of the present preferably in the range of from 10 to 35 wt.%, based on the
invention wherein downstream of the separation process, the total weight of L2.
layers obtained from the separation device are recycled to the 0156 10. The method of any of embodiments 1 to 9,
process, either to the separation process or to the upstream further comprising Subjecting L1 to a distillation stage
epoxidation process, to a maximum extent, thus providing a wherefrom a streamTL1 is obtained which contains at least
highly desirable process setup, both from an economical and 90 wt.-%, preferably at least 95 wt.-% C3, based on the
an ecological point of view. total weight of TL1.
0142. In particular, the present invention relates to the 0157 11. The method of embodiment 10, wherein, from
following embodiments, including the specific combinations said distillation stage, a further stream BL1 is obtained, at
of these embodiments resulting from the back-references in least 95 wt.-%, preferably at least 98 wt.-% of BL1 con
the individual embodiments, as indicated: sisting of C3, acetonitrile and water, wherein the C3 con
0143 1. A method for separating acetonitrile from water, tent of BL1 is in the range of from 7 to 18wt.-%, preferably
comprising from 10 to 15 wt.-%, in each case based on the total weight
0144 (i) providing a stream S1 containing at least 95 of BL1.
wt.-%, based on the total weight of S1, acetonitrile and 0158 12. The method of embodiment 10 or 11, wherein in
water, wherein the weight ratio of acetonitrile:water is said distillation stage, one distillation tower is employed
greater than 1; and wherein said distillation is carried out at a dew-point at
0145 (ii) adding a stream P. comprising at least 95 the top of said distillation tower of at least 40°C., prefer
wt.-% C3, based on the total weight of stream P. to S1 to ably in the range of from 40 to 80°C.
obtain a mixed stream S2, C3 being propene optionally 0159) 13. The method of any of embodiments 10 to 12,
admixed with propane with a minimum weight ratio of wherein at least a portion of TL1 is recycled into (ii).
propene:propane of 7:3; 0160 14. The method of any of embodiments 1 to 13,
0146 (iii) subjecting S2 to a temperature of 92° C. at further comprising Subjecting L2 to a distillation stage
most and a pressure of at least 10 bar, obtaining a first wherefrom a stream TL2 is obtained which contains from
liquid phase L1 essentially consisting of C3, acetoni 75 to 95 wt.-%, preferably from 80 to 85 wt.-%acetonitrile,
trile, and water, and a second liquid phase L2 essentially based on the total weight of TL2.
consisting of water and acetonitrile wherein the weight 0.161 15. The method of embodiment 14, wherein at least
ratio of acetonitrile:water in L2 is less than 1; a portion of TL2 is recycled into (ii).
0147 (iv) separating L1 from L2. (0162. 16. The method of embodiment 14 or 15, wherein
0148 2. The method of embodiment 1, wherein in (ii), a said distillation stage is a two pressure distillation process,
liquid stream P is added to a liquid stream S1. wherein in a first distillation tower, distillation is carried
out at a top pressure which is higher than the top pressure
0149. 3. The method of embodiment 1 or 2, wherein S1 of a second distillation tower and wherein the condenser
contains from 60 to 85 wt.-%, preferably from 65 to 80 used to condense the top stream of the first distillation
wt.-% acetonitrile, and from 10 to 35 wt.-%, preferably tower is used simultaneously as the vaporizer of the second
from 15 to 30 wt.-% water, in each case based on the total distillation tower.
weight of S1. (0163. 17. The method of embodiment 16, wherein
0150. 4. The method of any of embodiments 1 to 3, 0.164 (aa) L2 is introduced into the first distillation
wherein in (ii), P is added to S1 in an amount so that the tower from which a vapor top stream VTL2 is obtained
weight ratio of C3:acetonitrile in S2 is in the range of from containing from 50 to 70 wt.-% acetonitrile, based on the
0.2:1 to 5:1, preferably from 0.5:1 to 2:1. total weight of top stream VTL2, the distillation prefer
0151. 5. The method of any of embodiments 1 to 4, ably being carried out at a top pressure of from 10 to 20
wherein in (iii), S2 is subjected to a temperature of from 5 bar; and
to 90°C., in particular from 25 to 45°C., and to a pressure 0.165 (bb) at least partially condensing VTL2 obtained
in the range of from 15 to 50 bar, in particular from 15 to 25 in (aa) and introducing the condensed stream into the
bar. second distillation tower wherefrom TL2 is obtained as
0152 6. The method of any of embodiments 1 to 5, top stream, the distillation preferably being carried out at
wherein at least one liquid phase separation improving a top pressure of from 1 to 5 bar,
agent is added to S1 in (i) and/or to S2 in (ii), preferably in 0166 wherein the condenser used to condense VTL2 is
an amount of 1 wt.-% at most, based on the total weight of simultaneously used as vaporizer of the second distilla
S1 and/or S2. tion tower.
0153. 7. The method of any of embodiments 1 to 6, (0167 18. The method of any of embodiments 1 to 17,
wherein in (iv), L1 is separated from L2 in a gravity settler, wherein according to (i), S1 is provided by a process com
preferably in a horizontal gravity settler. prising
US 2011/0065939 A1 Mar. 17, 2011

0168 (a) reacting propene, optionally admixed with obtain a mixed stream S2, C3 being propene optionally
propane, with hydrogen peroxide in a reaction apparatus admixed with propane with a minimum weight ratio of
in the presence of acetonitrile as solvent, obtaining a propene:propane of 7:3;
stream S0 leaving the reaction apparatus, S0 containing 0183 (e) subjecting S2 to a temperature of 92 C. at
acetonitrile, water, propylene oxide, and optionally non most and a pressure of at least 10 bar, obtaining a first
reacted propene, oxygen, and further optionally pro liquid phase L1 essentially consisting of C3, acetoni
pane; trile, and water, and a second liquid phase L2 essentially
0169 (b) optionally separating propene, oxygen, and consisting of water and acetonitrile wherein the weight
propane from S0 to obtain a stream essentially consist ratio of acetonitrile:water in L2 is less than 1;
ing of acetonitrile, water, and propylene oxide; 0.184 (f) separating L1 from L2:
0170 (c) separating propylene oxide from S0 or the 0185 (g) subjecting L1 to a distillation stage where
stream obtained from (b), thus obtaining stream S1. from a streamTL1 is obtained which contains at least 90
0171 19. The method of embodiment 18, wherein in (a), wt.-% C3, based on the total weight of TL1; and where
propene is reacted with hydrogen peroxide in the presence from a further stream BL1 is obtained, at least 95 wt.-%
of a heterogeneous catalyst, said catalyst preferably com of BL1 consisting of C3, acetonitrile and water, wherein
prising a Zeolite, preferably a titanium Zeolite, more pref the C3 content of BL1 is in the range of from 7 to 18
erably a titanium zeolite of the structure type MWW. wt.-% based on the total weight of BL1;
0172. 20. The method of embodiment 18 or 19, wherein in 0186 (h) subjecting L2 to a distillation stage where
(b), a distillation tower is used and at the top of said distil from a streamTL2 is obtained which contains from 75 to
lation tower, acetonitrile, optionally admixed with water, is 95 wt.-%, preferably from 80 to 85 wt.-% acetonitrile,
added as a stripping agent. based on the total weight of TL2:
(0173 21. The method of any of embodiments 18 to 20, 0187 wherein at least a portion of stream BL1 is
wherein at least a portion of stream BL1 according to recycled into (a); and/or
embodiment 11 is recycled into (a). 0188 wherein at least a portion of TL1 is recycled into
0.174 22. The method of any of embodiments 18 to 21, (d); and/or
wherein prior to (ii), S1 is Subjected to a hydrogenation 0189 wherein at least a portion of TL2 is recycled into
stage, the resulting hydrogenated stream optionally being (d).
Subjected to a distillation stage. (0190. 27. The process of embodiment 26, wherein BL1 is
(0175 23. The method of any of embodiments 1 to 22, recycled into (a) and TL1 is recycled into (d) and TL2 is
wherein S1 additionally contains at least one glycol, pref recycled into (d).
erably in an amount of 1 wt.-% or less, based on the total (0191) 28. The process of embodiment 26 or 27, further
weight of S1. comprising
0176 24. The method of embodiment 23, wherein the at 0.192 (y) subjecting the stream obtained from (c) to a
least one glycol is selected from the group consisting of hydrogenation stage;
propylene glycol, dipropylene glycol, tripropylene glycol, 0193 (Z) subjecting the stream obtained from (y) to a
and a mixture of two or three thereof. distillation stage to obtained stream S1 and Subjecting
0177. 25. The method of embodiment 23 or 24, the bot S1 to (d).
toms stream obtained from the first distillation tower
according to embodiment 16 or 17 containing at least a
portion of the at least one glycol, wherein said bottoms 1. A method for separating acetonitrile from water, com
stream, optionally after combining with the bottoms prising
stream obtained from the second distillation tower accord (i) providing a stream S1 containing at least 95 wt.-%,
ing to embodiment 18 or 19, is Subjected to a glycol sepa based on the total weight of S1, acetonitrile and water,
ration stage. wherein the weight ratio of acetonitrile:water is greater
0.178 26. A highly integrated process for the preparation than 1;
of propylene oxide, the process comprising (ii) adding a stream P. comprising at least 95 wt.-% C3,
0179 (a) reacting propene, optionally admixed with based on the total weight of stream P. to S1 to obtain a
propane, with hydrogen peroxide in a reaction apparatus mixed stream S2, C3 being propene optionally admixed
in the presence of acetonitrile as solvent, obtaining a with propane with a minimum weight ratio of propene:
stream S0 leaving said reaction apparatus, S0 containing propane of 7:3;
acetonitrile, water, propylene oxide, and optionally non (iii) subjecting S2 to a temperature of 92° C. at most and a
reacted propene, oxygen, and optionally propane; pressure of at least 10 bar, obtaining a first liquid phase
0180 (b) optionally separating propene, optionally L1 essentially consisting of C3, acetonitrile, and water,
together with propane, and oxygen from S0 to obtain a and a second liquid phase L2 essentially consisting of
stream, at least 99 wt.-% thereof consisting of acetoni water and acetonitrile wherein the weight ratio of aceto
trile, water, and propylene oxide; nitrile: water in L2 is less than 1;
0181 (c) separating propylene oxide from S0 or the (iv) separating L1 from L2.
stream obtained from (b), thus obtaining a stream S1 2. The method of claim 1, wherein in (ii), a liquid stream P
containing at least 95 wt.-% acetonitrile and water, is added to a liquid stream S1.
based on the total weight of S1, wherein the weight ratio 3. The method of claim 1, wherein S1 contains from 60 to
of acetonitrile:Water is greater than 1; 85 wt.-%, preferably from 65 to 80 wt.-% acetonitrile, and
0182 (d) adding a stream P. comprising at least 95 from 10 to 35 wt.-%, preferably from 15 to 30 wt.% water, in
wt.-% C3, based on the total weight of stream P. to S1 to each case based on the total weight of S1.
US 2011/0065939 A1 Mar. 17, 2011

4. The method of claim 1, wherein in (ii), P is added to S1 (bb) at least partially condensing VTL2 obtained in (aa)
in an amount so that the weight ratio of C3:acetonitrile in S2 and introducing the condensed stream into the second
is in the range of from 0.2:1 to 5:1, preferably from 0.5:1 to distillation tower wherefrom TL2 is obtained as top
2:1. stream, the distillation preferably being carried out at a
5. The method of claim 1, wherein in (iii), S2 is subjected top pressure of from 1 to 5 bar,
to a temperature of from 5 to 90° C., in particular from 25 to wherein the condenser used to condense VTL2 is simulta
45° C., and to a pressure in the range of from 15 to 50 bar, in neously used as vaporizer of the second distillation
particular from 15 to 25 bar. tOWer.
6. The method of claim 1, wherein at least one liquid phase 18. The method of claim 1, wherein according to (i), S1 is
separation improving agent is added to S1 in (i) and/or to S2 provided by a process comprising
in (ii), preferably in an amount of 1 wt.-% at most, based on (a) reacting propene, optionally admixed with propane,
the total weight of S1 and/or S2. with hydrogen peroxide in a reaction apparatus in the
7. The method of claim 1, wherein in (iv), L1 is separated presence of acetonitrile as solvent, obtaining a stream S0
from L2 in a gravity settler, preferably in a horizontal gravity leaving the reaction apparatus, S0 containing acetoni
settler. trile, water, propylene oxide, and optionally non-reacted
8. The method of claim 1, wherein at least 95 wt.-%, propene, oxygen, and further optionally propane;
preferably at least 98 wt.-% of L1 consist of C3, acetonitrile (b) optionally separating propene, oxygen, and propane
and water, the water content of L1 being less than 10 wt.-%, from S0 to obtain a stream essentially consisting of
preferably in the range of from 1 to 5 wt.-%, based on the total acetonitrile, water, and propylene oxide;
weight of L1. (c) separating propylene oxide from S0 or the stream
9. The method of claim 1, wherein at least 95 wt.-%, obtained from (b), thus obtaining stream S1.
preferably at least 98 wt.-% of L2 consist of C3, acetonitrile 19. The method of claim 18, wherein in (a), propene is
and water, the C3 content of L2 being 5 wt.-% at most, based reacted with hydrogen peroxide in the presence of a hetero
on the total weight of L2, and the acetonitrile content of L2 geneous catalyst, said catalyst preferably comprising a Zeo
being less than 45 wt.-%, preferably in the range of from 10 to lite, preferably a titanium zeolite, more preferably a titanium
35 wt.-%, based on the total weight of L2. Zeolite of the structure type MWW.
10. The method of claim 1, further comprising subjecting 20. The method of claim 18, wherein in (b), a distillation
L1 to a distillation stage wherefrom a streamTL1 is obtained tower is used and at the top of said distillation tower, aceto
which contains at least 90 wt.-%, preferably at least 95 wt.-% nitrile, optionally admixed with water, is added as a stripping
C3, based on the total weight of TL1. agent.
11. The method of claim 10, wherein, from said distillation 21. The method of claim 18, wherein at least a portion of
stage, a further stream BL1 is obtained, at least 95 wt.-%, stream BL1 according to claim 11 is recycled into (a).
preferably at least 98 wt.-% of BL1 consisting of C3, aceto
nitrile and water, wherein the C3 content of BL1 is in the 22. The method of claim 18, wherein prior to (ii), S1 is
range of from 7 to 18 wt.-%, preferably from 10 to 15 wt.-%, Subjected to a hydrogenation stage, the resulting hydroge
in each case based on the total weight of BL1. nated Stream optionally being Subjected to a distillation stage.
12. The method of claim 10, wherein in said distillation 23. The method of claim 1, wherein S1 additionally con
stage, one distillation tower is employed and wherein said tains at least one glycol, preferably in an amount of 1 wt.-% or
distillation is carried out at a dew-point at the top of said less, based on the total weight of S1.
distillation tower of at least 40°C., preferably in the range of 24. The method of claim 23, wherein the at least one glycol
from 40 to 80° C. is selected from the group consisting of propylene glycol,
13. The method of claim 10, wherein at least a portion of dipropylene glycol, tripropylene glycol, and a mixture of two
TL1 is recycled into (ii). or three thereof.
14. The method of claim 1, further comprising Subjecting 25. A highly integrated process for the preparation of pro
L2 to a distillation stage wherefrom a streamTL2 is obtained pylene oxide, the process comprising
which contains from 75 to 95 wt.-%, preferably from 80 to 85 (a) reacting propene, optionally admixed with propane,
wt.-% acetonitrile, based on the total weight of TL2. with hydrogen peroxide in a reaction apparatus in the
15. The method of claim 14, wherein at least a portion of presence of acetonitrile as solvent, obtaining a stream S0
TL2 is recycled into (ii). leaving said reaction apparatus, S0 containing acetoni
16. The method of claim 14, wherein said distillation stage trile, water, propylene oxide, and optionally non-reacted
is a two pressure distillation process, wherein in a first distil propene, oxygen, and optionally propane;
lation tower, distillation is carried out at a top pressure which (b) optionally separating propene, optionally together with
is higher than the top pressure of a second distillation tower propane, and oxygen from S0 to obtain a stream, at least
and wherein the condenser used to condense the top stream of 99 wt.-% thereof consisting of acetonitrile, water, and
the first distillation tower is used simultaneously as the vapor propylene oxide;
izer of the second distillation tower. (c) separating propylene oxide from S0 or the stream
17. The method of claim 16, wherein obtained from (b), thus obtaining a stream S1 containing
(aa) L2 is introduced into the first distillation tower from at least 95 wt.-% acetonitrile and water, based on the
which a vapor top stream VTL2 is obtained containing total weight of S1, wherein the weight ratio of acetoni
from 50 to 70 wt.-% acetonitrile, based on the total trile:Water is greater than 1;
weight of top stream VTL2, the distillation preferably (d) adding a stream P. comprising at least 95 wt.-% C3,
being carried out at a top pressure of from 10 to 20 bar; based on the total weight of stream P. to S1 to obtain a
and mixed stream S2, C3 being propene optionally admixed
US 2011/0065939 A1 Mar. 17, 2011
16

with propane with a minimum weight ratio of propene: (h) subjecting L2 to a distillation stage wherefrom a stream
propane of 7:3; TL2 is obtained which contains from 75 to 95 wt.-%,
(e) subjecting S2 to a temperature of 92 C. at most and a preferably from 80 to 85 wt.-% acetonitrile, based on the
pressure of at least 10 bar, obtaining a first liquid phase total weight of TL2:
L1 essentially consisting of C3, acetonitrile, and water, wherein at least a portion of stream BL1 is recycled into
and a second liquid phase L2 essentially consisting of (a); and/or
water and acetonitrile wherein the weight ratio of aceto wherein at least a portion of TL1 is recycled into (d); and/or
nitrile: water in L2 is less than 1; wherein at least a portion of TL2 is recycled into (d).
26. The process of claim 25, wherein BL1 is recycled into
(f) separating L1 from L2; (a) and TL1 is recycled into (d) and TL2 is recycled into (d).
(g) Subjecting L1 to a distillation stage wherefrom a stream 27. The process of claim 25, further comprising
TL1 is obtained which contains at least 90 wt.-% C3, (y) Subjecting the stream obtained from (c) to a hydroge
based on the total weight of TL1; and wherefrom a nation stage;
further stream BL1 is obtained, at least 95 wt.-% of BL1 (Z) Subjecting the stream obtained from (y) to a distillation
consisting of C3, acetonitrile and water, wherein the C3 stage to obtained stream S1 and Subjecting S1 to (d).
content of BL1 is in the range of from 7 to 18 wt.-% c c c c c
based on the total weight of BL 1: