Title of Invention	PROCESS FOR RECOVERING METHANOL
Abstract	Disclosed is a method for recovering methanol from mixtures containing methanol and water. Said method comprises multistage evaporation with the integration of heat, the pressure being decreased from one stage to the next, followed by a series of distillation stages with the integration of heat, the pressure being increased from one stage to the next. The inventive method allows the amount of energy required for recovering methanol to be reduced.

Title of Invention

PROCESS FOR RECOVERING METHANOL

Abstract

Disclosed is a method for recovering methanol from mixtures containing methanol and water. Said method comprises multistage evaporation with the integration of heat, the pressure being decreased from one stage to the next, followed by a series of distillation stages with the integration of heat, the pressure being increased from one stage to the next. The inventive method allows the amount of energy required for recovering methanol to be reduced.

Full Text	Process for recovering methanol The invention relates to an improved process for recovering methanol from mixtures containing methanol and water, which process requires less energy for separation. Propylene oxide may be produced by reacting propylene with hydrogen peroxide in the presence of a titanium-containing zeolite catalyst. Methanol is advantageously used as solvent in this process. When working up the reaction mixture resulting from this process, a mixture is obtained which contains methanol and water. Methanol has to be recovered from this mixture, in order to be able to return it to the epoxidation reaction and to be able to operate the process economically. The water arising from hydrogen peroxide and any water introduced into the process with aqueous hydrogen peroxide, has to be removed from the process. The recovery of methanol from the mixture containing methanol and water consumes a large proportion of the thermal energy expended on the process. To perform the process economically, there is therefore a need for an improved process for recovering methanol from a mixture containing methanol and water, wherein the method exhibits a reduced energy requirement. WO 02/02544 describes a process for the production of propylene oxide, in which working up of the reaction mixture results in a mixture which contains methanol, water and small quantities of hydrogen peroxide. The document describes separating off water from this mixture by distillation performed in two columns, wherein the pressures are so selected that the bottom of the column operated at low pressure is heated using the vapors from the second column, which is operated at high pressure. The coupling of the columns described in WO 02/02544 makes it possible to reduce the energy requirement for recovering methanol from the mixture. However, the need still remains for processes for recovering methanol which require less energy than the prior art. This object is achieved by the process according to the invention. The present invention provides a process for recovering methanol from mixtures containing methanol and water, wherein the process comprises multistage evaporation and a downstream series of distillation stages and wherein the bottoms obtained in the final evaporation stage of the multistage evaporation are supplied to the first distillation stage of the series of distillation stages. The multistage evaporation comprises at least two evaporation stages, wherein each evaporation stage comprises an evaporator and, in the multistage evaporation, the pressure is reduced from each evaporation stage to the next evaporation stage. The evaporator of the second and each subsequent evaporation stage is heated with the vaporous overhead of the in each case previous stage. The series of distillation stages comprises at least two distillation stages, wherein each distillation stage comprises a distillation column and an evaporator and wherein the bottoms from the in each case previous distillation stage are supplied to the second and each subsequent distillation stage. In the series of the distillation stages, the pressure is increased from each distillation stage to the next distillation stage and, with the exception of the final distillation stage, in each distillation stage the evaporator is heated in each case with the vaporous overhead of the distillation column of the subsequent distillation stage. Preferably, each evaporation stage additionally comprises a distillation column with a rectifying section, such that an overhead with a methanol content of more than 90 wt.%, preferably more than 95 wt.%, is obtained in each evaporation stage. The process according to the invention comprises multistage evaporation with at least two evaporation stages, wherein the pressure is reduced from each evaporation stage to the next. Each of the evaporation stages comprises an evaporator, wherein any evaporator may be used for the process according to the invention which is suitable for evaporation of methanol from mixtures containing methanol and water. Preferably, continuous-flow evaporators are used in the evaporation stages, which evaporators may be operated without a circulating pump. In each evaporation stage, the mixture is supplied in liquid form to the evaporator and vaporous vapors and liquid bottoms are obtained as a result of evaporation. The liquid bottoms are supplied in each case to the evaporator of the next evaporation stage. Due to the reduction in pressure from each evaporation stage to the next, no pump is generally necessary for this purpose. The evaporator of the first evaporation stage is heated with a heating medium, preferably with steam. The evaporator of the second and each subsequent condensation stage is heated with the vapors, i.e. the vaporous overhead, of the in each case previous stage. The number of evaporation stages is selected in accordance with the composition of the mixture from which methanol is to be recovered and preferably ranges from 3 to 5 evaporation stages. The pressure gradation between the evaporation stages is so selected that the boiling point of the liquid stream supplied to the second evaporation stage is lower than the condensation temperature of the vapors from the preceding stage, such that the heat of condensation of the vapors is used to heat the evaporator and the vapors are condensed in the evaporator. The same also applies for the pressure gradation in the subsequent evaporation stages. The vapors obtained in the final evaporator of the multistage evaporation process are condensed in a separate cooler, wherein cooling water is preferably used for condensation of the vapors. The pressure in the first evaporation stage is preferably- selected to be in the range from 3 to 10 bar and particularly preferably 4 to 7 bar. The pressure is so selected that a sufficient pressure and temperature gradient is achieved over the series of evaporation stages and an economic heating medium, preferably steam at a pressure of 4 to 8 bar, may be used to heat the first evaporator. The pressure in the final evaporation stage is preferably selected to be in the range from 0.5 to 2 bar and particularly preferably 0.8 to 1.5 bar. The pressure is so selected that a sufficient pressure and temperature gradient is achieved over the series of evaporation stages and the vapors from the final evaporation stage may be condensed in an economic manner using cooling water. In a preferred embodiment of the process according to the invention, each evaporation stage additionally comprises a distillation column with a rectifying section, such that an overhead with a methanol content of more than 90 wt.%, preferably more than 95 wt.%, is obtained in each evaporation stage The vaporous stream produced in the evaporator is supplied to the lower part of the distillation column. The liquid bottoms resulting in the evaporator may optionally also be supplied to the distillation column together with the vaporous stream. The distillation column may take the form of an apparatus separate from the evaporator. Likewise, it is also possible, however, for the evaporator and the associated distillation column to be constructed as one apparatus. At the top of the column, the vapors are removed in vapor form and supplied to the evaporator of the subsequent evaporation stage. A liquid stream of condensed vapors is fed into the upper part of the column, to produce reflux. The stream of condensed vapors used to produce reflux may be taken from the liquid stream which is obtained by- condensation of the vapors in the subsequent evaporation stage. Likewise, however, the vapors of all the evaporation stages may also be combined together and the liquid stream for producing reflux may be taken from the mixture of combined vapors. The liquid stream obtained by reflux in the bottom of the column is supplied together with the bottoms from the evaporator to the next evaporation stage. For the distillation column used in the evaporation stages in this preferred embodiment, the plate number and the reflux ratio are selected in accordance with the composition of the vaporous stream produced in the evaporator and the desired purity of the recovered methanol. The reflux ratio is here defined as the ratio of the mass of the stream fed in in liquid form as reflux to the mass of the vaporous vapors removed at the top of the column. The distillation columns used in the evaporation stages preferably comprise 2 to 10 and particularly preferably 3 to 6 theoretical plates. Preferably, columns are used in the series of evaporation stages which have a plate number which increases over the series. The distillation columns used in the evaporation stages may in principle be of any desired design and may for example take the form of plate columns or of packed columns having regular or irregular packing. The distillation columns in the evaporation stages are preferably operated at a reflux ratio in the range from 0.1 to 1 and particularly preferably 0.2 to 0.6. Preferably, the distillation columns are operated with a reflux ratio which increases over the series of evaporation stages. The process according to the invention additionally comprises a series of at least 2 distillation stages, wherein in this series the pressure is increased from each distillation stage to the next. Each of the distillation stages comprises a distillation column and an evaporator. The liquid bottoms obtained in the final evaporation stage of the multistage evaporation are supplied to the first distillation stage in the middle portion of the distillation column. The bottoms obtained in the distillation column of the preceding distillation stage is in each case supplied to the second distillation stage and each subsequent distillation stage in a middle portion of the distillation column. In the final distillation stage, the evaporator is heated with a heating medium, preferably with steam. The evaporators of the preceding distillation stages are in each case heated with the vaporous vapors of the distillation column of the immediately subsequent distillation stage. The vapors obtained at the top of the distillation column of the first distillation stage are condensed in a separate cooler, wherein cooling water is preferably used for condensation of the vapors. The number of distillation stages is selected in accordance with the composition of the mixture fed into the first distillation stage and the desired residual methanol content in the bottoms, obtained in the distillation column of the final distillation stage, and preferably amounts to two distillation stages. The pressure gradation in the series of distillation stages is so selected that the boiling point at the bottom of the distillation column of the first distillation stage is lower than the condensation temperature of the vapors from the distillation column of the second distillation stage, such that the heat of condensation of the vapors from the second distillation stage is used to heat the evaporator of the first distillation stage and the vapors are condensed in the evaporator. The same applies to the pressure gradation between the further distillation stages. In the first distillation stage, the pressure used is preferably of 0.5 to 2 bar and particularly preferably 0.8 to 1.5 bar, such that a sufficient pressure and temperature gradient is achieved over the series of distillation stages and the vapors arising at the top of the column of the first distillation stage may be condensed economically with cooling water. The pressure in the final distillation stage is preferably selected to be in the range from 3 to 10 bar, particularly preferably 4 to 7 bar, so that a sufficient pressure and temperature gradient is achieved over the series of distillation stages, and an economic heating medium, preferably steam at a pressure of 4 to 16 bar, may be used to heat the evaporator of the final distillation stage. To produce reflux, a liquid stream of condensed vapors is fed in at the top of the column in the case of each distillation column of the distillation stages. The liquid stream may be taken from the condensed vapors obtained by condensation from the same column. Likewise, however, the vapors obtained in the distillation columns of the series of distillation stages may also be combined together and the liquid stream used to produce the reflux may be taken from the mixture of combined condensed vapors. For the distillation columns used in the series of distillation stages, the plate number and the reflux ratio are preferably so selected that an overhead with a methanol content of more than 90 wt.% and preferably more than 95 wt.% is obtained in each column. The distillation columns used in the series of distillation stages preferably exhibit a separation effect of 10 to 40 theoretical plates. In principle, all types of distillation column construction are suitable, for example distillation columns with plates or distillation columns with packing, wherein both regular and irregular packing may be used. The reflux ratio in the columns is preferably so selected that it increases over the series of distillation stages from a reflux ratio in the range from 0.3 to 1 in the first column to a reflux ratio in the range from 0.5 to 3 in the final column. If the mixture containing methanol and water from which methanol is to be recovered still contains intermediate- boiling compounds with a boiling point between the boiling points of methanol and water, the distillation column of the final distillation stage may be provided with a side outlet from which a stream is taken which has an enriched content of the intermediate-boiling compound. For such an embodiment, the distillation column of the final distillation stage may also advantageously take the form of a dividing wall column, in order to obtain a stream with a high concentration of intermediate-boiling compounds. The process according to the invention is particularly suitable for the recovery of methanol from mixtures containing methanol in a concentration of 70 wt.% and above. The process according to the invention may advantageously be used for the recovery of methanol from mixtures which arise during working up of reaction mixtures which arise when epoxidizing propylene with hydrogen peroxide using methanol as solvent. Such mixtures obtained from working up the reaction mixture from propylene epoxidation typically contain 70 to 90 wt.% of methanol, up to 3 wt.% of intermediate-boiling compounds and up to 3 wt.% of high-boiling compounds, the rest being water. Intermediate-boiling compounds are any compounds whose boiling point lies between the boiling points of methanol and water. High-boiling compounds are any compounds whose boiling point lies above the boiling point of water. To separate such mixtures, the process according to the invention is preferably carried out in such a way that, starting from a mixture with a methanol content of 70 wt.% or higher, a mixture with a methanol content in the range from 40 to 60 wt.% is obtained in multistage evaporation and the mixture is supplied to a series of distillation stages. The operating conditions of the evaporation stages and distillation stages are selected in each case such that overheads with a methanol content of more than 90 wt.% and preferably more than 95 wt.% are obtained. Figure 1 shows an embodiment of the method according to the invention with four-stage evaporation and a subsequent series of two distillation stages. The evaporation stages are provided with an in each case separately constructed distillation stage. Figure 1 shows only the evaporators, distillation columns and condensers required in the process. Pumps, intermediate containers and fittings also required for carrying out the process are not illustrated for the sake of clarity and may be added by a person skilled in the art in accordance with his/her specialist knowledge. In the most preferred embodiment, the process according to the invention is carried out in an arrangement corresponding to Figure 1. The process comprises four-stage evaporation, wherein each evaporation stage comprises a continuous flow evaporator and a distillation column with a rectifying section. The first evaporation stage with the evaporator (1) and the distillation column (2), which comprises a rectifying section with 3 theoretical plates, is operated at a pressure of 5 bar. The second evaporation stage with the evaporator (3) and the distillation column (4), which comprises a rectifying section with 3 theoretical plates, is operated at a pressure of 2.8 bar. The third evaporation stage with the evaporator (5) and the distillation column (6), which comprises a rectifying section with 4 theoretical plates, is operated at a pressure of 1.8 bar. The fourth and final evaporation stage with the evaporator (7) and the distillation column (8) with a rectifying section with 6 theoretical plates is operated at a pressure of 1.0 bar. The fourth evaporation stage additionally comprises a vapor condenser (9). Downstream of the four-stage evaporation is a series of two distillation stages. The first distillation stage comprises the distillation column (10) with a separation effect of 18 theoretical plates, an evaporator (11) incorporated into the column and a vapor condenser (12) and is operated at a pressure of 1 bar. The second distillation stage comprises the distillation column (13) with a separation effect of 17 theoretical plates and the evaporator (14) incorporated into the column and is operated at a pressure of 4 bar. The stream (15) from which the methanol is to be recovered and which has a methanol content of 75 to 85 wt.%, an intermediate-boiling compound content of up to 3 wt.% and a high-boiling compound content of up to 1 wt.%, the rest being water, is supplied to the evaporator (1) of the first evaporation stage. The evaporator (1) is heated via the stream (16) by steam under a pressure of 4 bar. The quantity of steam supplied to the evaporator (1) is selected such that approximately 25 wt.% of the stream (15) supplied is evaporated and supplied to the distillation column in vapor form as stream (17). The liquid bottoms arising in the evaporator at a temperature of approx. 118°C are supplied as stream (18) to the evaporator of the second evaporation stage. Vapor condensate in liquid form is fed in via stream (19) at the top of the distillation column (2), such that a reflux ratio of 0.2 is obtained. The vaporous vapors obtained at the top of the distillation column (2) are supplied as stream (20) to the evaporator (3) of the second evaporation stage as a heating medium. The liquid stream (21) arising at the bottom of the distillation column is supplied, together with the stream (18), to the evaporator of the second evaporation stage. In the second evaporation stage, the vaporous vapors of the first evaporation stage are condensed in the evaporator (3) and obtained as a liquid vapor condensate (22). The stream (23) evaporated thereby is supplied to the distillation column (4). The liquid bottoms (24) obtained in the evaporator are supplied at a temperature of approximately 100°C to the evaporator (5) of the third evaporation stage. Liquid vapor condensate is fed in at the top of the distillation column 4 via stream (25) to produce reflux, such that a reflux ratio of 0.25 is obtained. The vaporous vapors obtained at the top of the column 4 are supplied via stream (2 6) to the evaporator (5) of the third evaporation stage as a heating medium. The liquid product arising at the bottom of the column (4) is supplied as stream (27), together with stream (24), to the evaporator (5) of the third evaporation stage. The vaporous vapors obtained in the evaporator of the second evaporation stage are condensed in the evaporator (5) of the third evaporation stage and the liquid condensate is combined with the stream (22). The vaporous stream (28) produced in the evaporator (5) is supplied to the distillation column (6). The liquid bottoms of the evaporator (5) are supplied at a temperature of approx. 87°C to the evaporator (7) of the fourth and final evaporation stage. Liquid vapor condensate is fed in at the top of the distillation column (6) via stream (30), such that a reflux ratio of 0.35 is obtained. The vaporous vapors arising at the top of the column (6) are supplied via stream (31) to the evaporator (7) of the fourth evaporation stage as heating medium. The liquid product obtained at the bottom of the column (6) is supplied as stream (32) together with stream (29) to the evaporator of the fourth evaporation stage. In the evaporator (7) of the fourth evaporation stage, the vaporous vapors (31) from the third evaporation stage are condensed and the condensate is combined with the stream (22). The product stream (33) evaporated in the evaporator (7) is supplied to the distillation column (8). Liquid vapor condensate is fed in as stream (34) at the top of the distillation column (8), such that a reflux ratio of 0.4 is obtained. The vaporous vapors obtained at the top of the column (8) are condensed as stream (35) in the condenser (9) and the liquid condensate is combined with the stream (22). The liquid product (36) obtained at the bottom of the column (8) is combined with the liquid bottoms of the evaporator (7) and supplied as stream (3 8) to the first distillation stage. The liquid stream (38) leaving the multistage evaporation still contains around 45 to 50 wt.% of methanol and is supplied to the distillation column (10) of the first distillation stage. The vaporous vapors (39) obtained at the top of the distillation column (10) are condensed in the condenser (12) and a proportion of the resultant vapor condensate is fed in with stream (40) as reflux at the top of the column (10), such that a reflux ratio of 0.4 is obtained. The remaining proportion of the condensed vapors is combined with stream (22). The liquid bottoms (41) obtained in the distillation column (10) are supplied to the distillation column (13) of the second distillation stage. The evaporator (14) of the second distillation stage is heated via stream (42) by steam under a pressure of 8 bar, such that a bottoms temperature of approx. 143°C is established. The vaporous vapors obtained at the top of the distillation column (13) are supplied as stream (43) to the evaporator (11) of the first distillation stage as a heating medium. Some of the vapors condensed in the evaporator (11) are recycled as stream (44) as reflux to the top of the column (13), such that a reflux ratio of 1.1 is obtained. The remainder of the condensed vapors is combined with stream (22). At the bottom of the column (13) a stream (45) is obtained, which only has a residual methanol content of less than 0.5 wt.%. The vapor streams (20), (26), (31), (35), (39) and (43) arising in the process are combined after condensation and yield a product stream (46) which contains more than 90 wt.% of methanol and less than 4 wt.% of water. In this embodiment, the energy requirement for recovering methanol is around 157 kWh/t of methanol. In contrast, the requirement is around 44 7 kWh/t of methanol for the recovery of methanol in a single column without heat integration. With the process known from WO 02/02544 using two columns with heat integration, the energy requirement is around 246 kWh/t of methanol. The process according to the invention with heat integration both in the multistage evaporation and in the subsequent series of distillation stages thus makes it possible to save approximately 65% of the heating energy required compared with methanol recovery without heat integration. An energy saving of approx. 3 6 % is obtained relative to the method known from WO 02/02544. WE CLAIM: 1. A process for recovering methanol from mixtures containing methanol and water, comprising: a) a multistage evaporation with a series of at least two evaporation stages, wherein each evaporation stage comprises an evaporator (1,3,5,7) and provides a vaporous overhead product, in the multistage evaporation the pressure is reduced along the series of evaporation stages and the evaporator of the second evaporation stage and each subsequent evaporation stage is heated with the vaporous overhead product of the preceding stage, and b) a series of at least two distillation stages, wherein each distillations stage comprises a distillation column (10, 13) and an evaporator (11, 14) and provides a bottoms product (41, 45) and a vaporous overhead product (39, 43), the bottoms product is supplied to the subsequent distillations stage along the series of distillation stages, the pressure is increased along the series of distillation stages and wherein, with the exception of a final distillation stage, in each distillation stage the evaporator is heated by the vaporous overhead product of the subsequent distillation stage, wherein the bottoms product obtained in the final evaporation stage of the multistage evaporation is supplied to the first distillation stage of the series of distillation stages. 2. A process as claimed in claim 1, wherein the multistage evaporation comprises 3 to 5 evaporation stages. 3. A process as claimed in claim 1 or claim 2, wherein the pressure in the first evaporation stage is in the range from 3 to 10 bar, preferably 4 to 7 bar and the pressure in the final evaporation stage is in the range from 0.5 to 2 bar, preferably 0.8 to 1.5 bar. 4. A process as claimed in any one of the preceding claims, wherein each evaporation stage additionally comprises a distillation column (2,4,6,8) with a rectifying section, such that an overhead with a methanol content of more than 90 wt.%, preferably more than 95 wt.%, is obtained in each evaporation stage. 5. A process as claimed in claim 4, wherein the rectifying section exhibits in each case a separation effect of 2 to 10 theoretical plates and is operated with a reflux ratio in the range from 0.1 to 1. 6. A process as claimed in claim 5, wherein in each evaporation stage the rectifying section exhibits a separation effect of 3 to 6 theoretical plates. 7. A process as claimed in claim 5 or claim 6 wherein in each evaporation stage the rectifying section is operated with a reflux ratio in the range from 0.2 to 0.6. 8. A process as claimed in any one of the preceding claims, wherein the series of distillation stages comprises two distillation stages. Disclosed is a method for recovering methanol from mixtures containing methanol and water. Said method comprises multistage evaporation with the integration of heat, the pressure being decreased from one stage to the next, followed by a series of distillation stages with the integration of heat, the pressure being increased from one stage to the next. The inventive method allows the amount of energy required for recovering methanol to be reduced.

Full Text

Process for recovering methanol
The invention relates to an improved process for recovering
methanol from mixtures containing methanol and water, which
process requires less energy for separation.
Propylene oxide may be produced by reacting propylene with
hydrogen peroxide in the presence of a titanium-containing
zeolite catalyst. Methanol is advantageously used as
solvent in this process. When working up the reaction
mixture resulting from this process, a mixture is obtained
which contains methanol and water. Methanol has to be
recovered from this mixture, in order to be able to return
it to the epoxidation reaction and to be able to operate
the process economically. The water arising from hydrogen
peroxide and any water introduced into the process with
aqueous hydrogen peroxide, has to be removed from the
process. The recovery of methanol from the mixture
containing methanol and water consumes a large proportion
of the thermal energy expended on the process. To perform
the process economically, there is therefore a need for an
improved process for recovering methanol from a mixture
containing methanol and water, wherein the method exhibits
a reduced energy requirement.
WO 02/02544 describes a process for the production of
propylene oxide, in which working up of the reaction
mixture results in a mixture which contains methanol, water
and small quantities of hydrogen peroxide. The document
describes separating off water from this mixture by
distillation performed in two columns, wherein the
pressures are so selected that the bottom of the column
operated at low pressure is heated using the vapors from
the second column, which is operated at high pressure. The
coupling of the columns described in WO 02/02544 makes it
possible to reduce the energy requirement for recovering
methanol from the mixture.
However, the need still remains for processes for
recovering methanol which require less energy than the
prior art. This object is achieved by the process according
to the invention.
The present invention provides a process for recovering
methanol from mixtures containing methanol and water,
wherein the process comprises multistage evaporation and a
downstream series of distillation stages and wherein the
bottoms obtained in the final evaporation stage of the
multistage evaporation are supplied to the first
distillation stage of the series of distillation stages.
The multistage evaporation comprises at least two
evaporation stages, wherein each evaporation stage
comprises an evaporator and, in the multistage evaporation,
the pressure is reduced from each evaporation stage to the
next evaporation stage. The evaporator of the second and
each subsequent evaporation stage is heated with the
vaporous overhead of the in each case previous stage. The
series of distillation stages comprises at least two
distillation stages, wherein each distillation stage
comprises a distillation column and an evaporator and
wherein the bottoms from the in each case previous
distillation stage are supplied to the second and each
subsequent distillation stage. In the series of the
distillation stages, the pressure is increased from each
distillation stage to the next distillation stage and, with
the exception of the final distillation stage, in each
distillation stage the evaporator is heated in each case
with the vaporous overhead of the distillation column of
the subsequent distillation stage.
Preferably, each evaporation stage additionally comprises a
distillation column with a rectifying section, such that an
overhead with a methanol content of more than 90 wt.%,
preferably more than 95 wt.%, is obtained in each
evaporation stage.
The process according to the invention comprises multistage
evaporation with at least two evaporation stages, wherein
the pressure is reduced from each evaporation stage to the
next. Each of the evaporation stages comprises an
evaporator, wherein any evaporator may be used for the
process according to the invention which is suitable for
evaporation of methanol from mixtures containing methanol
and water. Preferably, continuous-flow evaporators are used
in the evaporation stages, which evaporators may be
operated without a circulating pump. In each evaporation
stage, the mixture is supplied in liquid form to the
evaporator and vaporous vapors and liquid bottoms are
obtained as a result of evaporation. The liquid bottoms are
supplied in each case to the evaporator of the next
evaporation stage. Due to the reduction in pressure from
each evaporation stage to the next, no pump is generally
necessary for this purpose.
The evaporator of the first evaporation stage is heated
with a heating medium, preferably with steam. The
evaporator of the second and each subsequent condensation
stage is heated with the vapors, i.e. the vaporous
overhead, of the in each case previous stage.
The number of evaporation stages is selected in accordance
with the composition of the mixture from which methanol is
to be recovered and preferably ranges from 3 to 5
evaporation stages. The pressure gradation between the
evaporation stages is so selected that the boiling point of
the liquid stream supplied to the second evaporation stage
is lower than the condensation temperature of the vapors
from the preceding stage, such that the heat of
condensation of the vapors is used to heat the evaporator
and the vapors are condensed in the evaporator. The same
also applies for the pressure gradation in the subsequent
evaporation stages. The vapors obtained in the final
evaporator of the multistage evaporation process are
condensed in a separate cooler, wherein cooling water is
preferably used for condensation of the vapors.
The pressure in the first evaporation stage is preferably-
selected to be in the range from 3 to 10 bar and
particularly preferably 4 to 7 bar. The pressure is so
selected that a sufficient pressure and temperature
gradient is achieved over the series of evaporation stages
and an economic heating medium, preferably steam at a
pressure of 4 to 8 bar, may be used to heat the first
evaporator. The pressure in the final evaporation stage is
preferably selected to be in the range from 0.5 to 2 bar
and particularly preferably 0.8 to 1.5 bar. The pressure is
so selected that a sufficient pressure and temperature
gradient is achieved over the series of evaporation stages
and the vapors from the final evaporation stage may be
condensed in an economic manner using cooling water.
In a preferred embodiment of the process according to the
invention, each evaporation stage additionally comprises a
distillation column with a rectifying section, such that an
overhead with a methanol content of more than 90 wt.%,
preferably more than 95 wt.%, is obtained in each
evaporation stage The vaporous stream produced in the
evaporator is supplied to the lower part of the
distillation column. The liquid bottoms resulting in the
evaporator may optionally also be supplied to the
distillation column together with the vaporous stream. The
distillation column may take the form of an apparatus
separate from the evaporator. Likewise, it is also
possible, however, for the evaporator and the associated
distillation column to be constructed as one apparatus. At
the top of the column, the vapors are removed in vapor form
and supplied to the evaporator of the subsequent
evaporation stage. A liquid stream of condensed vapors is
fed into the upper part of the column, to produce reflux.
The stream of condensed vapors used to produce reflux may
be taken from the liquid stream which is obtained by-
condensation of the vapors in the subsequent evaporation
stage. Likewise, however, the vapors of all the evaporation
stages may also be combined together and the liquid stream
for producing reflux may be taken from the mixture of
combined vapors. The liquid stream obtained by reflux in
the bottom of the column is supplied together with the
bottoms from the evaporator to the next evaporation stage.
For the distillation column used in the evaporation stages
in this preferred embodiment, the plate number and the
reflux ratio are selected in accordance with the
composition of the vaporous stream produced in the
evaporator and the desired purity of the recovered
methanol. The reflux ratio is here defined as the ratio of
the mass of the stream fed in in liquid form as reflux to
the mass of the vaporous vapors removed at the top of the
column. The distillation columns used in the evaporation
stages preferably comprise 2 to 10 and particularly
preferably 3 to 6 theoretical plates. Preferably, columns
are used in the series of evaporation stages which have a
plate number which increases over the series. The
distillation columns used in the evaporation stages may in
principle be of any desired design and may for example take
the form of plate columns or of packed columns having
regular or irregular packing. The distillation columns in
the evaporation stages are preferably operated at a reflux
ratio in the range from 0.1 to 1 and particularly
preferably 0.2 to 0.6. Preferably, the distillation columns
are operated with a reflux ratio which increases over the
series of evaporation stages.
The process according to the invention additionally
comprises a series of at least 2 distillation stages,
wherein in this series the pressure is increased from each
distillation stage to the next. Each of the distillation
stages comprises a distillation column and an evaporator.
The liquid bottoms obtained in the final evaporation stage
of the multistage evaporation are supplied to the first
distillation stage in the middle portion of the
distillation column. The bottoms obtained in the
distillation column of the preceding distillation stage is
in each case supplied to the second distillation stage and
each subsequent distillation stage in a middle portion of
the distillation column. In the final distillation stage,
the evaporator is heated with a heating medium, preferably
with steam. The evaporators of the preceding distillation
stages are in each case heated with the vaporous vapors of
the distillation column of the immediately subsequent
distillation stage. The vapors obtained at the top of the
distillation column of the first distillation stage are
condensed in a separate cooler, wherein cooling water is
preferably used for condensation of the vapors. The number
of distillation stages is selected in accordance with the
composition of the mixture fed into the first distillation
stage and the desired residual methanol content in the
bottoms, obtained in the distillation column of the final
distillation stage, and preferably amounts to two
distillation stages.
The pressure gradation in the series of distillation stages
is so selected that the boiling point at the bottom of the
distillation column of the first distillation stage is
lower than the condensation temperature of the vapors from
the distillation column of the second distillation stage,
such that the heat of condensation of the vapors from the
second distillation stage is used to heat the evaporator of
the first distillation stage and the vapors are condensed
in the evaporator. The same applies to the pressure
gradation between the further distillation stages.
In the first distillation stage, the pressure used is
preferably of 0.5 to 2 bar and particularly preferably 0.8
to 1.5 bar, such that a sufficient pressure and temperature
gradient is achieved over the series of distillation stages
and the vapors arising at the top of the column of the
first distillation stage may be condensed economically with
cooling water. The pressure in the final distillation stage
is preferably selected to be in the range from 3 to 10 bar,
particularly preferably 4 to 7 bar, so that a sufficient
pressure and temperature gradient is achieved over the
series of distillation stages, and an economic heating
medium, preferably steam at a pressure of 4 to 16 bar, may
be used to heat the evaporator of the final distillation
stage.
To produce reflux, a liquid stream of condensed vapors is
fed in at the top of the column in the case of each
distillation column of the distillation stages. The liquid
stream may be taken from the condensed vapors obtained by
condensation from the same column. Likewise, however, the
vapors obtained in the distillation columns of the series
of distillation stages may also be combined together and
the liquid stream used to produce the reflux may be taken
from the mixture of combined condensed vapors.
For the distillation columns used in the series of
distillation stages, the plate number and the reflux ratio
are preferably so selected that an overhead with a methanol
content of more than 90 wt.% and preferably more than 95
wt.% is obtained in each column. The distillation columns
used in the series of distillation stages preferably
exhibit a separation effect of 10 to 40 theoretical plates.
In principle, all types of distillation column construction
are suitable, for example distillation columns with plates
or distillation columns with packing, wherein both regular
and irregular packing may be used. The reflux ratio in the
columns is preferably so selected that it increases over
the series of distillation stages from a reflux ratio in
the range from 0.3 to 1 in the first column to a reflux
ratio in the range from 0.5 to 3 in the final column.
If the mixture containing methanol and water from which
methanol is to be recovered still contains intermediate-
boiling compounds with a boiling point between the boiling
points of methanol and water, the distillation column of
the final distillation stage may be provided with a side
outlet from which a stream is taken which has an enriched
content of the intermediate-boiling compound. For such an
embodiment, the distillation column of the final
distillation stage may also advantageously take the form of
a dividing wall column, in order to obtain a stream with a
high concentration of intermediate-boiling compounds.
The process according to the invention is particularly
suitable for the recovery of methanol from mixtures
containing methanol in a concentration of 70 wt.% and
above. The process according to the invention may
advantageously be used for the recovery of methanol from
mixtures which arise during working up of reaction mixtures
which arise when epoxidizing propylene with hydrogen
peroxide using methanol as solvent. Such mixtures obtained
from working up the reaction mixture from propylene
epoxidation typically contain 70 to 90 wt.% of methanol, up
to 3 wt.% of intermediate-boiling compounds and up to 3
wt.% of high-boiling compounds, the rest being water.
Intermediate-boiling compounds are any compounds whose
boiling point lies between the boiling points of methanol
and water. High-boiling compounds are any compounds whose
boiling point lies above the boiling point of water. To
separate such mixtures, the process according to the
invention is preferably carried out in such a way that,
starting from a mixture with a methanol content of 70 wt.%
or higher, a mixture with a methanol content in the range
from 40 to 60 wt.% is obtained in multistage evaporation
and the mixture is supplied to a series of distillation
stages. The operating conditions of the evaporation stages
and distillation stages are selected in each case such that
overheads with a methanol content of more than 90 wt.% and
preferably more than 95 wt.% are obtained.
Figure 1 shows an embodiment of the method according to the
invention with four-stage evaporation and a subsequent
series of two distillation stages. The evaporation stages
are provided with an in each case separately constructed
distillation stage. Figure 1 shows only the evaporators,
distillation columns and condensers required in the
process. Pumps, intermediate containers and fittings also
required for carrying out the process are not illustrated
for the sake of clarity and may be added by a person
skilled in the art in accordance with his/her specialist
knowledge.
In the most preferred embodiment, the process according to
the invention is carried out in an arrangement
corresponding to Figure 1.
The process comprises four-stage evaporation, wherein each
evaporation stage comprises a continuous flow evaporator
and a distillation column with a rectifying section. The
first evaporation stage with the evaporator (1) and the
distillation column (2), which comprises a rectifying
section with 3 theoretical plates, is operated at a
pressure of 5 bar. The second evaporation stage with the
evaporator (3) and the distillation column (4), which
comprises a rectifying section with 3 theoretical plates,
is operated at a pressure of 2.8 bar. The third evaporation
stage with the evaporator (5) and the distillation column
(6), which comprises a rectifying section with 4
theoretical plates, is operated at a pressure of 1.8 bar.
The fourth and final evaporation stage with the evaporator
(7) and the distillation column (8) with a rectifying
section with 6 theoretical plates is operated at a pressure
of 1.0 bar. The fourth evaporation stage additionally
comprises a vapor condenser (9).
Downstream of the four-stage evaporation is a series of two
distillation stages. The first distillation stage comprises
the distillation column (10) with a separation effect of 18
theoretical plates, an evaporator (11) incorporated into
the column and a vapor condenser (12) and is operated at a
pressure of 1 bar. The second distillation stage comprises
the distillation column (13) with a separation effect of 17
theoretical plates and the evaporator (14) incorporated
into the column and is operated at a pressure of 4 bar.
The stream (15) from which the methanol is to be recovered
and which has a methanol content of 75 to 85 wt.%, an
intermediate-boiling compound content of up to 3 wt.% and a
high-boiling compound content of up to 1 wt.%, the rest
being water, is supplied to the evaporator (1) of the first
evaporation stage. The evaporator (1) is heated via the
stream (16) by steam under a pressure of 4 bar. The
quantity of steam supplied to the evaporator (1) is
selected such that approximately 25 wt.% of the stream (15)
supplied is evaporated and supplied to the distillation
column in vapor form as stream (17). The liquid bottoms
arising in the evaporator at a temperature of approx. 118°C
are supplied as stream (18) to the evaporator of the second
evaporation stage. Vapor condensate in liquid form is fed
in via stream (19) at the top of the distillation column
(2), such that a reflux ratio of 0.2 is obtained. The
vaporous vapors obtained at the top of the distillation
column (2) are supplied as stream (20) to the evaporator
(3) of the second evaporation stage as a heating medium.
The liquid stream (21) arising at the bottom of the
distillation column is supplied, together with the stream
(18), to the evaporator of the second evaporation stage.
In the second evaporation stage, the vaporous vapors of the
first evaporation stage are condensed in the evaporator (3)
and obtained as a liquid vapor condensate (22). The stream
(23) evaporated thereby is supplied to the distillation
column (4). The liquid bottoms (24) obtained in the
evaporator are supplied at a temperature of approximately
100°C to the evaporator (5) of the third evaporation stage.
Liquid vapor condensate is fed in at the top of the
distillation column 4 via stream (25) to produce reflux,
such that a reflux ratio of 0.25 is obtained. The vaporous
vapors obtained at the top of the column 4 are supplied via
stream (2 6) to the evaporator (5) of the third evaporation
stage as a heating medium. The liquid product arising at
the bottom of the column (4) is supplied as stream (27),
together with stream (24), to the evaporator (5) of the
third evaporation stage.
The vaporous vapors obtained in the evaporator of the
second evaporation stage are condensed in the evaporator
(5) of the third evaporation stage and the liquid
condensate is combined with the stream (22). The vaporous
stream (28) produced in the evaporator (5) is supplied to
the distillation column (6). The liquid bottoms of the
evaporator (5) are supplied at a temperature of approx.
87°C to the evaporator (7) of the fourth and final
evaporation stage. Liquid vapor condensate is fed in at the
top of the distillation column (6) via stream (30), such
that a reflux ratio of 0.35 is obtained. The vaporous
vapors arising at the top of the column (6) are supplied
via stream (31) to the evaporator (7) of the fourth
evaporation stage as heating medium. The liquid product
obtained at the bottom of the column (6) is supplied as
stream (32) together with stream (29) to the evaporator of
the fourth evaporation stage.
In the evaporator (7) of the fourth evaporation stage, the
vaporous vapors (31) from the third evaporation stage are
condensed and the condensate is combined with the stream
(22). The product stream (33) evaporated in the evaporator
(7) is supplied to the distillation column (8). Liquid
vapor condensate is fed in as stream (34) at the top of the
distillation column (8), such that a reflux ratio of 0.4 is
obtained. The vaporous vapors obtained at the top of the
column (8) are condensed as stream (35) in the condenser
(9) and the liquid condensate is combined with the stream
(22). The liquid product (36) obtained at the bottom of the
column (8) is combined with the liquid bottoms of the
evaporator (7) and supplied as stream (3 8) to the first
distillation stage.
The liquid stream (38) leaving the multistage evaporation
still contains around 45 to 50 wt.% of methanol and is
supplied to the distillation column (10) of the first
distillation stage. The vaporous vapors (39) obtained at
the top of the distillation column (10) are condensed in
the condenser (12) and a proportion of the resultant vapor
condensate is fed in with stream (40) as reflux at the top
of the column (10), such that a reflux ratio of 0.4 is
obtained. The remaining proportion of the condensed vapors
is combined with stream (22). The liquid bottoms (41)
obtained in the distillation column (10) are supplied to
the distillation column (13) of the second distillation
stage. The evaporator (14) of the second distillation stage
is heated via stream (42) by steam under a pressure of 8
bar, such that a bottoms temperature of approx. 143°C is
established. The vaporous vapors obtained at the top of the
distillation column (13) are supplied as stream (43) to the
evaporator (11) of the first distillation stage as a
heating medium. Some of the vapors condensed in the
evaporator (11) are recycled as stream (44) as reflux to
the top of the column (13), such that a reflux ratio of 1.1
is obtained. The remainder of the condensed vapors is
combined with stream (22). At the bottom of the column (13)
a stream (45) is obtained, which only has a residual
methanol content of less than 0.5 wt.%. The vapor streams
(20), (26), (31), (35), (39) and (43) arising in the
process are combined after condensation and yield a product
stream (46) which contains more than 90 wt.% of methanol
and less than 4 wt.% of water.
In this embodiment, the energy requirement for recovering
methanol is around 157 kWh/t of methanol. In contrast, the
requirement is around 44 7 kWh/t of methanol for the
recovery of methanol in a single column without heat
integration. With the process known from WO 02/02544 using
two columns with heat integration, the energy requirement
is around 246 kWh/t of methanol. The process according to
the invention with heat integration both in the multistage
evaporation and in the subsequent series of distillation
stages thus makes it possible to save approximately 65% of
the heating energy required compared with methanol recovery
without heat integration. An energy saving of approx. 3 6 %
is obtained relative to the method known from WO 02/02544.
WE CLAIM:
1. A process for recovering methanol from mixtures containing methanol and
water, comprising:
a) a multistage evaporation with a series of at least two evaporation stages,
wherein each evaporation stage comprises an evaporator (1,3,5,7) and provides
a vaporous overhead product, in the multistage evaporation the pressure is
reduced along the series of evaporation stages and the evaporator of the second
evaporation stage and each subsequent evaporation stage is heated with the
vaporous overhead product of the preceding stage, and
b) a series of at least two distillation stages, wherein each distillations stage
comprises a distillation column (10, 13) and an evaporator (11, 14) and provides
a bottoms product (41, 45) and a vaporous overhead product (39, 43), the
bottoms product is supplied to the subsequent distillations stage along the series
of distillation stages, the pressure is increased along the series of distillation
stages and wherein, with the exception of a final distillation stage, in each
distillation stage the evaporator is heated by the vaporous overhead product of
the subsequent distillation stage,
wherein the bottoms product obtained in the final evaporation stage of the
multistage evaporation is supplied to the first distillation stage of the series of
distillation stages.
2. A process as claimed in claim 1, wherein the multistage evaporation
comprises 3 to 5 evaporation stages.
3. A process as claimed in claim 1 or claim 2, wherein the pressure in the
first evaporation stage is in the range from 3 to 10 bar, preferably 4 to 7 bar and
the pressure in the final evaporation stage is in the range from 0.5 to 2 bar,
preferably 0.8 to 1.5 bar.
4. A process as claimed in any one of the preceding claims, wherein each
evaporation stage additionally comprises a distillation column (2,4,6,8) with a
rectifying section, such that an overhead with a methanol content of more than
90 wt.%, preferably more than 95 wt.%, is obtained in each evaporation stage.
5. A process as claimed in claim 4, wherein the rectifying section exhibits in
each case a separation effect of 2 to 10 theoretical plates and is operated with a
reflux ratio in the range from 0.1 to 1.
6. A process as claimed in claim 5, wherein in each evaporation stage the
rectifying section exhibits a separation effect of 3 to 6 theoretical plates.
7. A process as claimed in claim 5 or claim 6 wherein in each evaporation
stage the rectifying section is operated with a reflux ratio in the range from 0.2
to 0.6.
8. A process as claimed in any one of the preceding claims, wherein the
series of distillation stages comprises two distillation stages.

Disclosed is a method for recovering methanol from mixtures containing
methanol and water. Said method comprises multistage evaporation
with the integration of heat, the pressure being decreased from one stage
to the next, followed by a series of distillation stages with the integration
of heat, the pressure being increased from one stage to the next. The
inventive method allows the amount of energy required for recovering
methanol to be reduced.

PROCESS FOR RECOVERING METHANOL

Documents:

Inventors:

PCT Conventions: