KR102463877B1 - Butyric acid separation equipment and separation method using octyl acetate extraction solvent - Google Patents

Abstract

The present invention relates to butyric acid separation equipment using an octyl acetate extraction solvent and a separation method of butyric acid using the equipment, and by separating the butyric acid from the extract obtained by extracting wood-based and marine biomass reforming reaction products with the octyl acetate extraction solvent in an extraction column using a distillation column, the concentration and recovery efficiency of the separated butyric acid are high, and the efficiency of saving energy consumed during the separation operation of butyric acid is high.

Description

Butyric acid separation equipment and butyric acid separation method using octyl acetate extraction solvent

The present invention relates to an apparatus for separating butyric acid using an octyl acetate extraction solvent and a method for separating butyric acid using the apparatus, and more particularly, by separating butyric acid from a lignocellulosic and marine biomass reforming reaction product using an octyl acetate extraction solvent. , It relates to a butyric acid separation apparatus using an octyl acetate extraction solvent, characterized in that the concentration and separation efficiency of butyric acid are high, and the energy consumption during the separation operation of butyric acid is high, and a butyric acid separation method using the apparatus.

Butyric acid, as known in Non-Patent Document 1, is an important biofuel that can provide an alternative to fossil fuels due to several advantages such as high carbon number and oxygen content, low pollution characteristics, and environmental sustainability of the source. , butyric acid can be produced by fermentation of a carbon source.

And as a method of separating butyric acid from the fermentation product, distillation or extraction process, which is a technique widely used in chemical processes, can be adopted, and when only the distillation process is adopted, there is a problem of consuming a large amount of energy, When the extraction solvent is used, the removal of water is not sufficient, so the load of the distillation column is very large, so a large amount of energy is used in the process, and accordingly, there is a problem that the operation cost of the separation process is high.

On the other hand, looking at the patents related to the technology for producing butyric acid from a carbon source, Patent Document 1 uses a novel Clostridium spp. strain for producing butyric acid from galactose of seaweed biomass to produce butyric acid from galactose of seaweed biomass A method for producing butyric acid from a saccharification liquid for fermentation of microorganisms containing a carbon source and glycerol is known in Patent Document 2.

However, Patent Documents 1 and 2 are limited to the technology for producing butyric acid by fermenting a carbon source using a fermentation strain, and the technology for separating only butyric acid from the mixture of the fermentation broth and butyric acid of the carbon source. is not specified as

Therefore, the present inventors have completed the present invention by developing a butyric acid separation device with high separation efficiency of butyric acid by an octyl acetate extraction solvent and a method for separating butyric acid using this device in order to improve the above problems.

Domestic Patent Publication No. 10-1401413 (Announced on June 02, 2014) Clostridium sp. strain, butyric acid production method using the strain, and method for isolating the strain Domestic Patent Publication No. 10-2053330 (Announced December 06, 2019) Composition for fermentation of microorganisms containing glycerol and production method of butyric acid using the same

Esteban-Gutirrez M, Garcia-Aguirre J, Irizar I, Aymerich E. From sewage sludge and agri-food waste to VFA: Individual acid production potential and up-scaling. Waste Manage. 2018;77:203-12. Reyhanitash E, Brouwer T, Kersten SRA, Ham AGJvd, Schuur B. Liquid-liquid extraction-based process concepts for recovery of carboxylic acids from aqueous streams evaluated for dilute streams. Chem Eng Res Des. 2018;137:510-33. Ning P, Yang GF, Hu LH, Sun JX, Shi LN, Zhou YH, et al. Recent advances in the valorization of plant biomass. Biotechnol Biofuels. 2021;14:102.

Esteban-Gutirrez M, Garcia-Aguirre J, Irizar I, Aymerich E. From sewage sludge and agri-food waste to VFA: Individual acid production potential and up-scaling. Waste Management. 2018;77:203-12. Reyhanitash E, Brouwer T, Kersten SRA, Ham AGJvd, Schuur B. Liquid-liquid extraction-based process concepts for recovery of carboxylic acids from aqueous streams evaluated for dilute streams. Chem Eng Res Des. 2018;137:510-33.

As a method for improving the above problems, the present invention separates the lignocellulosic and marine biomass reforming reaction products using an extraction solvent in an extraction column to separate a large amount of mixed water, thereby consuming in the separation operation of butyric acid by distillation. An object of the present invention is to provide an apparatus for separating butyric acid using an octyl acetate extraction solvent, characterized in that the energy saving efficiency is high, and a method for separating butyric acid using the apparatus.

A butyric acid separation device using an octyl acetate extraction solvent according to a preferred embodiment of the present invention for achieving the above object is a waste solution from a mixture of the raw material (F) and the circulating fluid (RL) and the circulating extraction solvent (SR) flowing into the tower. an extraction column (Ex) for separating (Ww) from the lower end, and transferring the mixture (C1) from which the waste liquid (Ww) is separated from the upper end to the first distillation column (DC I); The mixture (C1) transferred from the upper end of the extraction column (Ex) and introduced into the tower is distilled to separate the circulating extraction solvent (SR) from the bottom of the column, and the mixture (C2) from which the circulating extraction solvent (SR) is separated is placed at the top. a first distillation column (DC I) separated from and transferred to a second distillation column (DC Ⅱ); The mixture (C2) transferred from the first distillation column (DC I) and introduced into the column is distilled to separate the circulating liquid (RL) at the top of the column, and the mixture (C3) from which the circulating liquid (RL) is separated is separated at the bottom of the column. a second distillation column (DC Ⅱ) transferred to the third distillation column (DC Ⅲ); and a third distillation column (DC Ⅲ) in which the mixture (C3) transferred from the second distillation column (DC Ⅱ) and introduced into the column is distilled to separate the by-product (Sp) at the top of the column and the product (P) at the bottom of the column, respectively; Inclusion is a means of solving the problem.

And the butyric acid separation method using the octyl acetate extraction solvent according to another preferred embodiment of the present invention is a waste solution (Ww) from the mixture of the raw material (F), the circulating fluid (RL) and the circulating extraction solvent (SR) flowing into the tower. an extraction step (P100) of separating at the stage and separating the mixture (C1) from which the waste liquid (Ww) is separated from the upper stage; The mixture (C1) transferred from the upper end of the extraction column (Ex) and introduced into the tower is distilled to separate the circulating extraction solvent (SR) from the bottom of the column, and the mixture (C2) from which the circulating extraction solvent (SR) is separated is placed at the top. In the first distillation step (P200) to separate: the mixture (C2) transferred from the first distillation column (DC I) and introduced into the column is distilled to separate the circulating liquid (RL) at the top of the column, and the circulating liquid (RL) is a second distillation step of separating the separated mixture (C3) from the bottom of the column (P300); And, a third distillation step (P400) of distilling the mixture (C3) transferred from the second distillation column (DC II) and flowing into the tower to separate the by-product (Sp) at the top of the column and the product (P) at the bottom of the column, respectively; Inclusion is another means of solving the problem.

The raw material (F) is a lignocellulosic or marine biomass reforming reaction product, the circulating extraction solvent (SR) is octyl acetate, and the by-product (Sp) separated at the top of the third distillation column (DC Ⅲ) is acetic acid (Acetic acid), and the product (P) separated from the bottom is characterized in that it is butyric acid.

In addition, the circulating extraction solvent (SR) separated from the bottom of the first distillation column (DC I) is circulated to the extraction column (Ex), and the circulating liquid (RL) separated from the top of the second distillation column (DC II) is It is characterized in that it is circulated to the extraction column (Ex).

The present invention separates butyric acid from the lignocellulosic and marine biomass reforming reaction product with an octyl acetate extraction solvent in an extraction column by using a distillation column to separate butyric acid, the concentration and recovery efficiency of the separated butyric acid are high, and consumption during the separation operation of butyric acid There is a high effect of energy saving efficiency.

1 is a diagram schematically showing an apparatus for separating butyric acid from lignocellulosic and marine biomass reforming reaction products according to a preferred embodiment of the present invention;
2 is a diagram specifically showing an apparatus for separating butyric acid from lignocellulosic and marine biomass reforming reaction products according to a preferred embodiment of the present invention;
3 is a process block diagram showing the flow of a manufacturing process for separating butyric acid from lignocellulosic and marine biomass reforming reaction products according to a preferred embodiment of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail based on the accompanying drawings. On the other hand, in each drawing and detailed description, the illustration and description of the configuration and action that can be easily understood by those in the field of general butyric acid separation process are simplified or omitted. And the present invention is to present the design result of the butyric acid separation process, and to compare it with the conventional process and explain it as follows.

Raw material (F) among the terms described in the specification of the present invention is a lignocellulosic or marine biomass reforming product, It is a mixture of a small amount of butyric acid and acetic acid in a large amount of water, and the product (P) is a mixture of butyric acid as the main component and acetic acid as a small component, The circulating extraction solvent (SR) is a mixture of octyl acetate, an extraction solvent, and butyric acid, a small component, as the main component. It is a mixture of peracetic acid, and the waste solution (Ww) is a mixture of a small amount of butyric acid, acetic acid and octyl acetate in a large amount of water.

In order to make the flow of context natural in the description of the specification of the present invention, the above mixtures are respectively prepared as raw material (F), product (P), by-product (Sp), circulating extraction solvent (SR), circulating fluid (RL) and It is called waste liquid (Ww), and the term 'small amount' refers to an amount in which the amount of a component in the mixture is smaller than that of a 'large amount' or a 'main component'.

For reference, in the specification of the present invention, 'top top' and 'top bottom' mean 'top of the tower' and 'bottom side of the tower', respectively, and 'upper end' and 'lower end' are among the stages configured inside the tower. It means the part corresponding to the upper part or the lower part of the tower, and 'middle end' means the stage located in the middle part of the tower located between the upper end and the lower end.

The butyric acid separation device (hereinafter referred to as 'butyric acid separation device') for separating by the octyl acetate extraction solvent according to the present invention, as shown in FIG. An apparatus for separating butyric acid as a product (P) and acetic acid as a by-product (Sp), comprising one extraction column (Ex) and three distillation columns, a first distillation column (DC I) to a third distillation column (DC Ⅲ) characterized in that

And the extract obtained by treating the lignocellulosic and marine biomass reforming reaction product as the raw material (F) in the extraction column (Ex) is treated in the first distillation column (DC I) to separate and reuse the circulating extraction solvent (SR), The circulating liquid (RL) circulated from the second distillation column (DC Ⅱ) to the extraction column (Ex) contains a small amount of butyric acid and acetic acid, and the product (P) butyric acid and by-product (Sp) in the third distillation column (DC Ⅲ) Recover phosphorous acetic acid.

Therefore, the butyric acid separation device according to the present invention has a high concentration and separation efficiency of butyric acid that is separated from the raw material (F), which is a lignocellulosic or marine biomass reforming product, and has a high efficiency of saving energy consumed in the separation operation of butyric acid and will be described in detail below.

Hereinafter, the butyric acid separation device according to the present invention has a structure as shown in FIGS. 1 and 2, and the extraction column (Ex) and the first distillation column (DC I) to the third distillation column (DC Ⅲ) will be described in detail. If you do, it will look like the following:

The extraction column (Ex) separates the waste liquid (Ww) from the mixture of the raw material (F), the circulating liquid (RL), and the circulating extraction solvent (SR) flowing into the tower at the lower end, and the waste liquid (Ww) is separated from the mixture ( C1) is separated from the upper stage and transferred to the first distillation column (DC I).

The raw material (F) applied to the present invention is a lignocellulosic or marine biomass reforming reaction product, and is a mixture of a small amount of butyric acid and acetic acid in a large amount of water, and the circulating fluid (RL) is It is a mixture of a large amount of butyric acid and a small amount of acetic acid in water, and the circulating extraction solvent (SR) is characterized in that the main component is octyl acetate.

The octyl acetate acts to separate a large amount of water contained in the raw material (F) and remove it as a waste solution (Ww).

Therefore, the extraction column (Ex) is a waste liquid (Ww) at the lower end by octyl acetate (SR), a circulating extraction solvent (SR), in which water contained in a large amount in the raw material (F) of the lignocellulosic or marine biomass reforming reaction product (F) The mixture (C1) from which the waste liquid (Ww) is separated is transferred from the upper stage to the first distillation column (DC I).

The first distillation column (DC I) separates the circulating extraction solvent (SR) from the bottom of the column by distilling the mixture (C1) transferred from the upper end of the extraction column (Ex) and flowing into the column, and the circulating extraction solvent (SR) is It is a column that serves to separate the separated mixture (C2) at the top and transfer it to the second distillation column (DC II).

At this time, the circulating extraction solvent (SR) separated from the bottom of the column is circulated to the extraction column (Ex), and the circulating circulating extraction solvent (SR) is contained in a small amount in the waste liquid (Ww) separated at the lower end of the extraction column (Ex) Since the loss is caused by the circulating extraction solvent (SR), the circulating extraction solvent (SR) transferred to the extraction tower (Ex) supplies the supplemental extraction solvent (Mu) in an amount corresponding to the loss to circulate the extraction solvent (SR) to compensate for the loss of

The second distillation column (DC II) separates the circulating liquid (RL) at the top by distilling the mixture (C2) transferred from the first distillation column (DC I) and flowing into the column, and the circulating liquid (RL) is separated from the mixture (C3) is separated from the bottom of the column and transferred to the third distillation column (DC Ⅲ).

In the above, the circulating liquid (RL) separated from the top of the second distillation column (DC II) is a mixture of a small amount of butyric acid as a product (P) and acetic acid as a by-product (Sp) in a large amount of water. As a mixture, it is circulated to the extraction column (Ex).

The third distillation column (DC Ⅲ) distills the mixture (C3) transferred from the second distillation column (DC Ⅱ) and introduced into the column to separate the by-product (Sp) at the top of the column and the product (P) at the bottom of the column, respectively. is the top

The by-product (Sp) separated at the top of the third distillation column (DC Ⅲ) is acetic acid (Acetic acid), and the product (P) separated from the bottom of the column is butyric acid as a main component and acetic acid as a minor component This is a mixed mixture.

Therefore, the butyric acid separation apparatus according to a preferred embodiment of the present invention extracts the lignocellulosic and marine biomass reforming reaction product using octyl acetate in the extraction column by the technical configuration as described above, and the butyric acid as the product (P) in the distillation column (Butyric acid) and acetic acid as a by-product (Sp) are separated and recovered.

For reference, in the butyric acid separation device according to the present invention, as shown in FIG. 2 , a condenser is installed at the upper portion of the extraction column Ex, and the first distillation column (DC I) to the third distillation column (DC Ⅲ) have a condenser on the upper portion , a reboiler is installed in the lower part, respectively.

Hereinafter, a method of separating butyric acid using a butyric acid separation apparatus according to a preferred embodiment of the present invention will be described in detail with reference to FIG. 3, which is the accompanying drawing.

Since the description of the constituent devices and compounds of each process according to the present invention has been described in detail during the description of the butyric acid separation device, detailed descriptions of the constituent devices, compounds and mixtures of each process will be omitted below.

The separation method of butyric acid according to the present invention consists of an extraction step (P100) and a first distillation step (P200) to a third distillation step (P400).

In the extraction step (P100), the waste liquid (Ww) is separated from the mixture of the raw material (F), the circulating liquid (RL), and the circulating extraction solvent (SR) flowing into the tower at the lower end, and the waste liquid (Ww) is separated from the mixture ( This is the step of separating C1) from the upper end.

In the first distillation step (P200), the mixture (C1) transferred from the upper end of the extraction column (Ex) and introduced into the column is distilled to separate the circulating extraction solvent (SR) from the bottom of the column, and the circulating extraction solvent (SR) is It is a step of separating the separated mixture (C2) at the top.

At this time, the circulating extraction solvent (SR) separated from the bottom of the tower is circulated to the extraction column (Ex), and the circulating extraction solvent (SR) is contained in a small amount in the waste solution (Ww) discharged during the extraction process and discharged to the outside. The amount of supplemental extraction solvent (Mu) corresponding to

In the second distillation step (P300), the mixture (C2) transferred from the first distillation column (DC I) and introduced into the column is distilled to separate the circulating liquid (RL) at the top of the column, and the circulating liquid (RL) is separated from the mixture. (C3) is a step of separating from the bottom.

The third distillation step (P400) is a step of separating the by-product (Sp) at the top of the column and the product (P) at the bottom by distilling the mixture (C3) transferred from the second distillation column (DC II) and flowing into the column, respectively.

As described above, in the butyric acid separation apparatus and separation method according to a preferred embodiment of the present invention, the lignocellulosic and marine biomass reforming reaction products are extracted using octyl acetate in an extraction column, and butyric acid is separated using a distillation column. By doing so, there is an effect of high separation efficiency by extraction, characterized in that the concentration and separation efficiency of the butyric acid to be separated is high, and the efficiency of saving energy consumed during the separation operation of butyric acid is high.

Hereinafter, the method for separating butyric acid using the octyl acetate extraction solvent according to the present invention will be described in detail through the following examples, and the present invention is not necessarily limited only by the following examples.

1. Composition of raw material (F)

The lignocellulosic or marine biomass product, which is the raw material (F) used in this example, was used as a main component of butyric acid as shown in [Table 1] below.

Ingredients Composition (kg/h) water 9,691 Acetic acid 42 Butyric acid 267

2. Separation of butyric acid using extractive distillation

This embodiment uses a lignocellulosic or marine biomass reforming reaction product, which is a raw material (F) having the condition of 1 above, and octyl acetate as an extraction solvent in a separation device for butyric acid as shown in FIG. Octyl acetate) was used to separate butyric acid from the raw material (F).

[Table 2] below presents the process design results of the separation device for butyric acid according to the present invention.

And in order to produce butyric acid together with the composition of the raw material (F), the operating conditions of the device were calculated. In order to calculate the operating conditions, the extraction column (Ex) and the first distillation column (DC I) to the third distillation column (DC Ⅲ) as shown in [Table 2] are operated in various ways in the separation device of butyric acid The distillation calculation was repeated when the conditions were used to find the condition with the lowest energy consumption while producing the required product. For this calculation, the present invention used Aspen Plus, a commercial calculation program, and the required product is obtained under the operating conditions of [Table 2] below.

division extraction tower first distillation column second distillation column 3rd distillation column rescue singular 32 35 48 Raw material (F) injection end One 14 18 14 Extraction solvent (SR) injection stage 32 - - - Circulating fluid (RL) injection end 2 - - - manipulated variable Pressure (MPa)- top 0.1 0.1 0.1 0.1 Temperature (℃) top 25 141.8 100.0 130.1 top bottom 25 214.0 164.7 162.7 F (kg/h) 10,000 8,831 343 269 SR (kg/h) 8,501 - - - Mu (kg/h) 13.0 - - - RL(kg/h) 74.0 - - - Product (kg/h) top 8,831 343 74 4.0 top bottom 9,744 8,488 269 265 Reflux flow (kg/h) - 789 259 296 Steam flow (kg/h) - 7,491 1,284 188 Cooling capacity (MW) - -0.17 -0.14 -0.03 Heating capacity (MW) - 0.14 0.02 Recovered heat capacity (MW) -0.98 0.62 0.004 0.01 Raw material composition (mass frac.) butyric acid 0.0267 0.0311 0.8001 0.9849 product Ovhd. Ovhd. btm btm butyric acid 0.0311 0.8001 0.9849 0.9977

The economic evaluation of the investment and operating cost of the butyric acid separation process according to the present invention was calculated using the following procedure. The cost of the separation system consists of the manufacturing cost and operating cost of the tower and related equipment. The process operation was based on operating 10 tons of raw material per hour for 8,000 hours per year. [Table 3] below shows the calculated equipment cost, operating cost, and economic evaluation of the conventional system for the butanol separation process.

(Unit: 1,000,000 U.S. Dollars) division extraction tower first distillation column second distillation column 3rd distillation column investment cost column 0.247 0.128 0.094 0.055 inner end 0.015 0.006 0.004 0.002 cooler - 0.078 0.032 0.009 reboil - 0.069 0.061 0.022 Intermediate heater/cooler 0.123 0.083 0.003 0.001 subtotal 0.385 0.364 0.194 0.089 Sum 1.032 driving cost steam cost - 0.209 0.052 0.007 coolant cost - 0.002 0.002 0.001 subtotal - 0.211 0.054 0.008 Sum 0.273

According to the contents of [Table 3], the butyric acid separation device according to the present invention has a typical service life of 20 years or more of the butyric acid separation device according to the present invention, which saves fuel cost by 80% with an initial investment cost similar to that of the conventional butyric acid separation device Considering the point, it can be confirmed that it is economical.

As described above, the butyric acid separation apparatus using the octyl acetate extraction solvent and the butyric acid separation method using the apparatus according to the preferred embodiment of the present invention have been described, but this is merely an example and does not depart from the technical spirit of the present invention. It will be well understood by those skilled in the art that various changes and modifications are possible without departing from the scope of the present invention.

Ex: extraction column DC I: first distillation column
DC Ⅱ: second distillation column DC Ⅲ: third distillation column
F : Raw material RL : Circulating fluid
SR : Circulating extraction solvent Mu : Supplemental extraction solvent
P : product Sp : by-product
Ww: waste fluid

Claims (12)

The waste liquid (Ww) is separated from the mixture of the raw material (F), which is a lignocellulosic or marine biomass reforming reaction product, and the circulating liquid (RL) and the circulating extraction solvent (SR), which are octyl acetate, introduced into the tower at the lower stage. and an extraction column (Ex) for separating the mixture (C1) from which the waste liquid (Ww) is separated from the upper end and transferring it to the first distillation column (DC I);
The mixture (C1) transferred from the upper end of the extraction column (Ex) and introduced into the tower is distilled to separate the circulating extraction solvent (SR) from the bottom of the column, and the mixture (C2) from which the circulating extraction solvent (SR) is separated is placed at the top. a first distillation column (DC I) separated from and transferred to a second distillation column (DC Ⅱ);
The mixture (C2) transferred from the first distillation column (DC I) and introduced into the column is distilled to separate the circulating liquid (RL) at the top of the column, and the mixture (C3) from which the circulating liquid (RL) is separated is separated at the bottom of the column. a second distillation column (DC Ⅱ) transferred to the third distillation column (DC Ⅲ); and,
The mixture (C3) transferred from the second distillation column (DC II) and introduced into the column is distilled to separate acetic acid as a by-product (Sp) at the top of the column, and butyric acid as a product (P) at the bottom of the column, respectively. a third distillation column (DC Ⅲ);
Butyric acid separation device using an octyl acetate extraction solvent, characterized in that it comprises a.
delete delete According to claim 1,
The circulating extraction solvent (SR) separated from the bottom of the first distillation column (DC I) is a butyric acid separation device using an octyl acetate extraction solvent, characterized in that it is circulated to the extraction column (Ex).
According to claim 1,
The circulating liquid (RL) separated from the top of the second distillation column (DC II) is circulated to the extraction column (Ex).
delete delete The waste liquid (Ww) is separated from the mixture of the raw material (F), which is a lignocellulosic or marine biomass reforming reaction product, and the circulating liquid (RL) and the circulating extraction solvent (SR), which are octyl acetate, introduced into the tower at the lower stage. and an extraction step (P100) of separating the mixture (C1) from which the waste liquid (Ww) is separated from the upper end;
The mixture (C1) transferred from the upper end of the extraction column (Ex) and introduced into the tower is distilled to separate the circulating extraction solvent (SR) from the bottom of the column, and the mixture (C2) from which the circulating extraction solvent (SR) is separated is placed at the top. The first distillation step (P200) to separate from:
Distilling the mixture (C2) transferred from the first distillation column (DC I) and flowing into the tower to separate the circulating fluid (RL) at the top of the column, and separating the circulating fluid (RL) from the separated mixture (C3) at the bottom of the column a second distillation step (P300); and,
The mixture (C3) transferred from the second distillation column (DC II) and introduced into the column is distilled to separate acetic acid as a by-product (Sp) at the top of the column and butyric acid as a product (P) at the bottom of the column, respectively. a third distillation step (P400);
Butyric acid separation method using an octyl acetate extraction solvent, characterized in that it comprises a. delete delete delete delete

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