Patent Application
20240409484
The invention concerns a method for providing a high-purity n-butanol product stream from a crude n-butanol feed stream by fractional distillation in a dividing wall column comprising an upper section, a middle section and a lower section, the middle section comprising an inflow section and an offtake section laterally separated from each other by a dividing wall fixed in the column, the crude n-butanol feed stream being fed to the inflow section and the high-purity n-butanol product stream being withdrawn from the offtake section.
Highly pure n-butanol is typically obtained from a mixture containing more than 90% by weight of n-butanol and further components such as 4-heptanone, dibutyl ether, 2-methylbutanol, 2-ethylhexanal, butyl butyrate, butyl acetal, isobutanol, n-butyraldehydes and water. This so-called “crude n-butanol stream” is typically separated in a distillation column sequence comprising a light-end column, a pure product column and a heavies column. The crude n-butanol stream is fed to the light-end column where components lighter than n-butanol and water are separated off overhead. The remaining mixture including the n-butanol is fed to the pure product column where a highly pure n-butanol stream is obtained as a side draw in the rectifying section of the column. Some lighter components are withdrawn at the top of the pure product column. Components heavier than n-butanol are separated from the bottom of that column and are fed to the heavies column for further separation. This classical process comes along with high investment and operating costs, in particular due to a high energy demand for the three distillation columns.
One possibility to reduce investment and energy costs is to integrate two or even three columns into one column that has a dividing wall in a middle section of the column. A dividing wall column generally has the following segments: an upper column region located above the dividing wall, an inflow section located on the side of the feed point and bounded laterally by a dividing wall, an offtake section located on the side of the side offtake and bounded laterally by the dividing wall and a lower column region located below the dividing wall. Compared to the arrangement of conventional distillation columns, dividing wall columns offer advantages in respect of both energy consumption and capital costs.
Document EP 2 394 723 B1 discloses a process for the purification of n-butanol from a crude n-butanol stream in a dividing wall column where all three columns of the classical sequence are integrated into one dividing wall column. The crude n-butanol stream is fed to the inflow section on one side of the dividing wall, whereas a highly pure n-butanol product stream is withdrawn from the offtake section on the other side of the dividing wall. Lighter components are withdrawn overhead and heavier components are obtained in the bottom of the dividing wall column. The integration of all three separation tasks, i.e. separation of lighter components, heavier components and highly pure n-butanol necessitates a rather high bottom temperature and large internal volumes of liquid and vapor circulating in the column. Consequently, this process also shows a high energy demand and thus operating costs. Furthermore, the high bottom temperature may foster the formation of unwanted byproducts that reduce the yield of the wanted product n-butanol. Unwanted byproducts that are light-boiling enrich in the top of the column which leads to an increase of the stream to be withdrawn from the top of the column and thus to an increase of energy needed to fulfill the specification of the n-butanol side draw.
It was an object of the invention to provide a method for preparing highly pure n-butanol from a crude n-butanol stream that shows a lower energy demand than processes known from prior art without compromising on the quality of the desired product n-butanol.
This task is solved according to the invention by a method according to claim 1. Advantageous variants of the method are presented in claim 2 to 7.
Subject of the invention is a method for providing a high-purity n-butanol product stream from a crude n-butanol feed stream by fractional distillation in a dividing wall column comprising an upper section, a middle section and a lower section. The middle section includes an inflow section and an offtake section laterally separated from each other by a dividing wall fixed in the column, the crude n-butanol feed stream being fed to the inflow section and the high-purity n-butanol product stream being withdrawn from the offtake section. The liquid stream flowing out of the upper section is collected and divided into a first liquid stream and a second liquid stream, the first liquid stream being fed to the upper region of the offtake section and the second liquid stream being fed to the upper region of the inflow section, wherein the split ratio between the mass flow rate of the first liquid stream and the mass flow rate of the second liquid stream is from 2:1 to 5:1. It was found that a split ratio in this range has a double positive effect: The overall energy demand is decreased compared to the prior art, thereby maintaining the flexibility of reacting to disturbances or changing operating conditions, for example variations in the feed composition with respect to the ratio of light and heavy boiling components.
The dividing wall column may be of any type known in the art that is suitable for separating a crude n-butanol feed stream. The column may for example be equipped with trays like sieve trays or valve trays or with structured or random packings. With respect to a desired minimization of the pressure drop along the column height, structured packings are preferred.
The upper section has preferably from 15 to 40 theoretical stages, more preferably from 20 to 30 theoretical stages.
The lower section has preferably from 10 to 30 theoretical stages, more preferably from 12 to 20 theoretical stages.
The inflow section comprises two zones, an upper inflow zone between the upper section and the feed stage and a lower inflow zone between the feed stage and the lower section. The upper inflow zone has preferably from 8 to 22 theoretical stages, more preferably from 10 to 15 theoretical stages. The lower inflow zone has preferably from 10 to 30 theoretical stages, more preferably from 15 to 25 theoretical stages.
The offtake section also comprises two zones, an upper offtake zone between the upper section and the side-draw through with the product stream is withdrawn and a lower offtake zone between the side-draw and the lower section. The upper offtake zone has preferably from 10 to 30 theoretical stages, more preferably from 15 to 25 theoretical stages. The lower offtake zone has preferably from 8 to 25, more preferably from 10 to 15 theoretical stages.
According to the invention, the liquid flowing out of the upper section is collected and fed in two separate streams to the offtake section and the inflow section. Liquid collectors and distributors for distillation columns are known in the art.
Depending on its source, the crude n-butanol feed stream may have varying compositions. In a preferred embodiment the crude n-butanol feed stream comprises more than 96% by weight of n-butanol, less than 2% by weight of water and less than 2% of other organic components, for example isobutanol or butyl butyrate.
In a preferred embodiment the ratio between the cross-sectional area of the inflow section and the cross-sectional area of the offtake section is from 0.9 to 1.1, more preferably from 0.95 to 1.05. Most preferably the cross-sectional areas are equal, apart from tolerances due to manufacturing or installation of the dividing wall. A dividing wall column with equal or nearly equal cross-sectional areas of the two section on either side of the dividing wall is easy to manufacture, to install and to operate.
In a further preferred embodiment of a method according to the invention the temperature in the lower section is from 115° C. to 130° C. The pressure in the lower section is preferably from 1.0 to 1.5 bar (abs), more preferably from 1.1 to 1.3 bar (abs). It has been found that under these conditions at the bottom of the dividing wall column the yield of the desired product n-butanol in the product side-draw is high on the one hand whereas on the other hand the energy demand for heating and cooling the liquid and vapor flows in the column are reasonable. At higher temperatures, for example as in the known prior art, there is an increasing risk that longer-chain components form that increase the temperature in the sump even more. There is also a risk at higher temperatures that high boiling components decompose into lighter boiling components which then flow upwards in the column and may have a detrimental effect on the purity of the product withdrawal in the side-draw.
A relatively low temperature in the lower section of the dividing wall column goes along with a higher percentage of n-butanol in the stream withdrawn from the bottom of the column. However, the advantages in terms of smooth operation of the column and a low energy demand are higher than the potential loss of the product n-butanol via the bottom flow. It is therefore preferred that the n-butanol product stream contains more than 99% by weight of n-butanol, and a bottom product stream taken off from the bottom of the column contains more than 40% by weight of n-butanol.
Depending on the source of the crude n-butanol stream and on the target use of the n-butanol produced by the method according to the invention, more or less side-components are allowed in the final product. In a preferred embodiment the crude n-butanol feed stream contains more than 300 ppm by weight of butyl butyrate, and the n-butanol product stream contains less than 100 ppm by weight of butyl butyrate. In a further preferred embodiment, the crude n-butanol feed stream contains more than 500 ppm by weight of isobutanol, and the n-butanol product stream contains less than 500 ppm by weight of isobutanol. In a further preferred embodiment, the crude n-butanol feed stream contains more than 500 ppm by weight of water, and the n-butanol product stream contains less than 500 ppm by weight of water. This can be achieved by choosing the split ratio in the range according to the invention.
The split ratio between the mass flow rate of the first liquid stream and the mass flow rate of the second liquid stream can be realized by different means. In one embodiment the split ratio is fixed by design, for example by an appropriate dimensioning of the pipes through which the first liquid stream and the second liquid stream flow or by installing respective valves or throttles. In a preferred embodiment the flow rates of the first liquid stream and the second liquid stream are measured and at least one of the two streams is controlled by an actuator to adjust the split ratio to a predefined value between 2:1 and 5:1. This embodiment has the advantage that the split ratio can be adjusted when needed.
In a further preferred embodiment the location of the draw-off of the liquid collected from the upper section and the location of the inlets to the distributors of the inflow section and the offtake section are spaced apart at a vertical distance. Preferably this distance is from 1 to 3 meters, more preferably from 1.5 to 2.5 meters. A vertical distance in that range provides a sufficient compensation of the pressure drop induced by installed equipment like flow meters, flow control valves or piping without compromising too much on installation space needed. No pumps or other means for forced transportation are necessary in that case.
It is further preferred that the pipes connecting the draw-off and the inlets are formed as u-bend, meaning that the pipe from the draw-off extends below the positions of the inlets, are deflected in a u-bend form and lead back upwards to the inlets. In such a configuration, the control instrumentation like flow meters and/or flow control valves is preferably arranged in that part of the pipes that extends below the inlets of the distributors of the inflow section and the offtake section. More preferably, the control instrumentation is arranged in that part of the pipes that is positioned between the u-bend and the inlets. Due to the u-bend form the parts of the pipes that extend below the inlets are constantly filled with liquid. An arrangement of the control instruments in that part of the pipes is advantageous as it enables consistent and proper measurements and liquid distribution control.
It is advantageous to control the quality of the high-purity n-butanol product stream. The quality can be assessed for example by analyzing the composition of the product stream. Indirect methods are also possible, for example measuring temperature and pressure near the product withdrawal and determining the product composition based thereon, e.g. using a mathematical model. There are also different options to influence the product composition, for example by appropriate settings of the reboil ratio or amount of vapor flowing up in the column or the reflux ratio or amount of condensed liquid flowing down in the column.
In a preferred embodiment the quality of the n-butanol product stream is controlled to a predefined setpoint by measuring a process value representing the quality in the product stream, in particular the amount of n-butanol in the product stream, as the controlled variable and adjusting the split ratio between the mass flow rates of the first liquid stream and the second liquid stream as the manipulated variable. It is further preferred to adjust the amount of heat provided to a reboiler, e.g. steam, as a further manipulated variable.
The invention is explained in more detail below with reference to the drawings. The drawings are to be interpreted as in-principle presentation. They do not constitute any restriction of the invention, for example with regard to specific dimensions or design variants. In the figures:
Liquid containing heavier boiling components that collects in the sump of the lower section 110 of the column is withdrawn from the column and is partially fed to a reboiler where it is vaporized and fed back to the lower section 110 of the column.
The vapor outlet at the top of the column is connected to a condenser where the vapor is condensed and partially recycled to the upper section 104 of the column. The remaining part of the condensed stream is withdrawn from the column as a distillate stream. The condenser may be a total condenser that condenses the complete vapor stream or a partial condenser that only condenses a part of the vapor stream. In the latter case, a vaporous stream of non-condensed components can be withdrawn from the condenser. The condenser may further comprise a phase-separation unit wherein an aqueous phase is separated from an organic phase. In such a case, the aqueous phase is withdrawn from the condenser, whereas the organic phase is at least partially recycled to the upper section 104 of the column.
The liquid stream that flows out of the upper section 104 is collected below the upper section 104 and is withdrawn from the column in two separate streams, a first liquid stream 114 and a second liquid stream 116. Both streams are measured, for example by flow meters installed in the respective pipes. The first liquid stream 114 is fed back to the column and is distributed onto the upper region of the offtake section 108 and thus to only one side of the dividing wall 112. The second liquid stream 116 is also fed back to the column and is distributed onto the upper region of the inflow section 106 and thus to the other side of the dividing wall 112. At least one of these two streams can be set to a specified value by an actuator, for example by a control valve, such that the ratio between the mass flow rate of the first liquid stream 114 and the mass flow rate of the second liquid stream 116 can be set from 2:1 to 5:1.
The first liquid stream taken off through the first draw off nozzle 204 is fed through a first pipe 206 to a first distributor 208 that is located on top of the offtake section 108 on one side of the dividing wall 112. The second liquid stream taken off through the second draw off nozzle 210 is fed through a second pipe 212 to a second distributor 214 that is located on top of the inflow section 106 on the other side of the dividing wall 112.
According to the invention, the split ratio between the mass flow rate of the first liquid stream and the mass flow rate of the second liquid stream is set to a value from 2:1 to 5:1. The example according to
Other control schemes and control systems are also possible, both in terms of instrumentation and in terms of the control logic. For example, the flow control valve 218 could also be provided in the second pipe 212 or an additional flow control valve could be provided in the second pipe.
It is preferred that the location of the draw off nozzles and the location of the inlets to the distributors are spaced apart at a vertical distance D of from 1 to 3 meters, preferably from 1.5 to 2.5 meters. A vertical distance D in that range provides a sufficient compensation of the pressure drop induced by the flow meter 216, the flow control valve 218 and piping without compromising too much on installation space needed. No pumps or other means for forced transportation are necessary in that case.
A laboratory-scale dividing wall column according to
The crude n-butanol feed was provided to the inflow section 106 at a flow rate of 2750 g/h and a composition as given in Table 1 below (denoted as “Feed”). All compositions in Table 1 are given in area percent. The compositions were determined using a gas chromatograph without an inner standard. The gas chromatograph was equipped with a CP-Sil 19 CB column (dimensions 25 m×250 μm×0.2 μm). 0.2 μl were injected and the split ratio was 100:1. Detection was done with a flame ionization detector (FID) at at temperature of 300° C.
A distillate stream containing low-boiling components was withdrawn from the condenser at a flow rate of 26 g/h. The reflux from the condenser to the top of the upper section 104 was set to 2850 g/h. A bottom sump stream of 155 g/h containing high-boiling components was withdrawn from the bottom of the lower section 110 at a temperature of about 120° C. The content of n-butanol in the sump stream was about 63%. The side-draw containing the desired high-purity n-butanol was withdrawn at a flow rate of 2568 g/h.
The split ratio between the mass flow rate of the first liquid stream and the mass flow rate of the second liquid stream has been varied between 2:1, 3:1 and 5:1. The results depending on the different operating conditions are given in Table 1 (denoted as “Product side-draw—2:1/3:1/5:1”).
As can be seen from Table 1 a selection of the split ratio in the inventive range from 2:1 to 5:1 yields a high-purity n-butanol product. In all cases the energy demand required for operation the dividing wall column is minimized compared to processes known from prior art. Apart from the energy consumption, a stable mode of operation is an important factor for operating the process. One aspect thereof is a sufficient distribution of liquid on the respective zones, for example onto the top of the inflow section and the offtake section. A split ratio from 2:1 to 5:1 has turned out to fulfill all requirements to evenly and efficiently distribute the liquid stream to guarantee a stable operation.
As a further example, a production-scale dividing wall column according to
A crude n-butanol feed with a composition given in Table 2 below (denoted as “Feed”) is fed to the inflow section at a flow rate of 30033 kg/h. All compositions in Table 2 are given in percent by weight (wt.-%). The vapor phase at the top of the column is withdrawn and is fed to a total condenser where it is totally condensed except for non-condensable components. The condensed liquid is fed to a phase separator (not shown in
The total amount of energy needed for the separation of n-butanol from the crude n-butanol stream is 8161 kW. The specific amount of energy with respect to the high-purity n-butanol product stream is 8161 kW/28750 kg/h*3600 s/h=1022 kJ/kg. The amount of n-butanol recovered as high-purity product in the side draw corresponds to 98.7 percent by weight of the n-butanol fed to the column.
The distillation system used in this simulation is comparable to the system disclosed in the example of the prior art document EP 2 394 723 B1 (Table 3, Table 4,
Compared to the prior art, a selection of the split ratio in the inventive range from 2:1 to 5:1 yields a high-purity n-butanol product at a comparable recovery rate and a significantly lower specific energy demand required for operating the dividing wall column.
| Number | Date | Country | Kind |
|---|---|---|---|
| 21204088.5 | Oct 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/078770 | 10/17/2022 | WO |
