WO2015026138A1

WO2015026138A1 - Method for removing limonene and device for removing limonene in biomass saccharification liquid, and bioethanol production method using the removal method

Info

Publication number: WO2015026138A1
Application number: PCT/KR2014/007693
Authority: WO
Inventors: 배현종; 신한기; 최인성
Original assignee: 전남대학교산학협력단
Priority date: 2013-08-22
Filing date: 2014-08-19
Publication date: 2015-02-26
Also published as: CN105473621A; KR101498213B1; KR20150023104A

Abstract

The present invention relates to a method for removing limonene in biomass. More specifically, the present invention relates to: a method for removing limonene and a device for removing limonene in a biomass saccharification liquid, whereby it is possible to effectively remove the limonene present in biomass such as mandarin peel, orange peel, grapefruit peel, lemon peel and lime peel, and it is possible to improve the production yield of bioethanol; and a bioethanol production method using the removal method.

Description

Limonene removal method, limonene removal device of biomass saccharification liquid and bioethanol production method using the removal method

The present invention relates to a method for removing limonene of biomass, and more particularly, to efficiently remove limonene present in biomass such as citrus fruit, orange, grapefruit, lemon and lime, and to improve bioethanol production yield. It relates to a limonene removal method, limonene removal device and bioethanol production method using the removal method of the biomass saccharification solution.

In order to solve the greenhouse effect and petroleum depletion problem caused by the recent global warming, much attention and research is focused on the production of bioethanol using saccharified liquid, and sugar cane or starch is used as biomass for bioethanol production. Has been used.

Raw materials for the production of these first-generation bioethanol face many problems such as competition with food and livestock feed, saturation of cultivated area. In order to overcome this, research is being conducted to produce bioethanol using waste resources.

In general, in order to produce bioethanol from biomass including waste resources, it is subjected to saccharification and fermentation. The saccharification process converts biomass into sugar components by acid and enzyme treatment, and the fermentation process refers to a process of converting ethanol and carbon dioxide by using microorganisms such as yeast and E. coli using the saccharification liquid generated through saccharification process. . At this time, in the fermentation process, the presence of a fermentation inhibitor to inhibit the fermentation of microorganisms is very low efficiency of conversion of sugar components to ethanol. Biomass such as citrus, orange, grapefruit, lemon and lime are attracting attention as a raw material for bioethanol production because they contain high sugar content, but they contain fermentation inhibitors called limonene. There is a difficulty. Therefore, effective removal of limonene for bioethanol production is recognized as an important task.

Steam explosion has been developed and used as a method of removing limonene. However, when steam explosion is used, a separate process device and high energy for generating steam are required, and limonene can be removed to a certain level or less. There is no problem that the efficiency of conversion to ethanol during fermentation is low.

The present inventors have completed the present invention by solving the problems of the limonene removal method and apparatus using the conventional steam aeration as a result of research efforts to solve this problem.

Therefore, an object of the present invention, by using activated carbon and cellulose fibers, limonene known as fermentation inhibitors can be removed to a level that will not affect the fermentation process, the biomass saccharification liquid which can improve the fermentation efficiency converted to ethanol It is to provide a method for removing limonene.

Another object of the present invention is to provide a separate process apparatus, such as a steam decay apparatus, and a limonene removal method of biomass saccharified liquid which can be usefully used because high energy for generating steam is not required.

Another object of the present invention is to separate the limonene from the activated carbon and cellulose fiber after the limonene removal process, can reduce the waste of resources, the activated carbon and cellulose fiber can be easily reused, significantly reducing the processing cost The present invention provides a method for removing limonene from a biomass saccharified solution.

The objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object of the present invention, firstly, the present invention comprises the steps of preparing a saccharified liquid obtained from the biomass containing limonene; And it provides a limonene removal method of biomass saccharified liquid comprising the step of contacting any one or more of the saccharified liquid and activated carbon and cellulose fiber.

In a preferred embodiment, the contacting step is used 0.3 to 0.5g of activated carbon based on the limonene content of 0.8411g / cm ³ of the saccharified solution when using activated carbon.

In a preferred embodiment, the step of contacting the cellulose fiber is used 0.125 to 0.2g based on the limonene content of 0.8411g / cm ³ of the saccharified solution when using the cellulose fiber.

The present invention also provides a saccharified liquid obtained from limonene-containing biomass, wherein the limonene content is less than 0.025% by weight.

In addition, the present invention is a hollow housing therein; And it provides a limonene removal device comprising any one or more of activated carbon and cellulose fiber inserted into the hollow at a predetermined thickness.

In a preferred embodiment, at least one of the activated carbon and cellulose fiber is contacted with saccharified liquid obtained from limonene containing biomass to remove limonene.

In another aspect, the present invention comprises the steps of preparing a saccharified solution in which the limonene removal method is performed; And it provides a method of producing a bioethanol comprising a fermentation step of fermenting using any one or more of yeast and E. coli in the saccharification liquid.

The present invention has the following excellent effects.

First, according to the present invention, using activated carbon and cellulose fiber, limonene, known as a fermentation inhibitor, can be removed to a level that will not affect the fermentation process, thereby improving the fermentation efficiency converted to ethanol.

In addition, according to the present invention, a separate process apparatus, such as a steam attenuating device, and high energy for generating steam can be usefully used.

In addition, according to the present invention, after the limonene removal process, limonene can be separated from the activated carbon and the cellulose fiber, thereby reducing the waste of resources, and the activated carbon and the cellulose fiber can be easily reused, thereby significantly reducing the processing cost.

In Figure 1 (a) is a graph analyzing the limonene content before limonene removal using GC (Gas Chromatography), (b) is a graph analyzing the result after limonene removal using the limonene removal method using GC to be.

In Figure 2 (a) is a schematic diagram of a limonene removal apparatus according to an embodiment of the present invention, (b) is a schematic diagram of a limonene removal apparatus according to another embodiment of the present invention, (c) is another of the present invention It is a schematic diagram of a limonene removal apparatus which concerns on an Example.

Figure 3 is a graph showing the fermentation efficiency before and after limonene removal using the limonene removal method of the present invention.

The terms used in the present invention were selected as general terms as widely used as possible, but in some cases, the terms arbitrarily selected by the applicant are included. In this case, the meanings described or used in the detailed description of the present invention are considered, rather than simply the names of the terms. The meaning should be grasped.

Hereinafter, with reference to the accompanying drawings and preferred embodiments will be described in detail the technical configuration of the present invention.

However, the present invention is not limited to the embodiments described herein and may be embodied in other forms.

The technical feature of the present invention is a new limonene removal method that can improve the fermentation efficiency of converting limonene, known as a fermentation inhibitor, to a level that will not affect the fermentation process by using activated carbon and cellulose fiber to convert to ethanol.

Therefore, the limonene removal method of the biomass saccharification liquid of the present invention includes preparing a saccharification liquid obtained from the biomass containing limonene and contacting any one or more of the saccharification liquid with activated carbon and cellulose fiber. At this time, the biomass is not limited to biomass containing limonene, but any one or more selected from the group consisting of peels of tangerines, oranges, grapefruits, lemons, limes, and mixtures thereof, which are discarded as waste after being used. This is preferably used. This is because waste resources that are discarded can be used as biomass, thereby reducing the cost of treating waste resources and producing value-added resources such as bioethanol and limonene from waste resources. In addition, the step of secreting the saccharification liquid may be prepared in general through the saccharification process of acid hydrolysis and enzymatic hydrolysis from the biomass. At this time, as long as the saccharification liquid contains a sugar component capable of fermentation, the method of hydrolysis is not limited.

In Figure 1 (a) is a graph of the saccharified solution analyzed by GC, showing that the saccharin contains limonene. In Figure 1 (b) is a result of analyzing the saccharified solution after removing the limonene using the limonene removal method of the present invention using GC. As shown in (a) and (b) of FIG. 1, limonene contained in the saccharified solution is contacted with activated carbon, contacted with cellulose fiber, and contacted with a mixture prepared by mixing the activated carbon and cellulose fiber. Limonene may be removed through one or more of the step of making.

In this case, the contacting step is preferably 0.3 to 0.5 g of activated carbon based on the limonene content of 0.8411 g / cm ³ of the saccharified solution when activated carbon is used. If less than 0.3 g of activated carbon is used, the content of limonene that is not removed is higher than the concentration causing the inhibition of fermentation, which causes fermentation inhibition in the fermentation process using microorganisms, thereby lowering the production efficiency of bioethanol. In addition, when using more than 0.5g of activated carbon exceeds the amount necessary to remove limonene is a waste of resources, because it does not affect the fermentation efficiency.

In addition, when using the cellulose fiber in the contacting step, it is preferable that 0.125 to 0.2g of the cellulose fiber is used based on the limonene content 0.8411g / cm ³ of the saccharified solution. When using cellulose fiber of less than 0125g as in the case of using the activated carbon, the content of limonene, which is not removed, is higher than the concentration causing the inhibition of fermentation, which induces the inhibition of fermentation in the fermentation process using microorganisms. The production efficiency of is lowered, and when using the cellulose fiber in excess of 0.2g, it exceeds the amount necessary to remove limonene, wastes resources, and does not affect the fermentation efficiency.

Also provided is a saccharified liquid obtained from a limonene-containing biomass, wherein the limonene content is less than 0.025% by weight. When the limonene content of the saccharified liquid obtained from the biomass falls below 0.025% by weight, the sugar component contained in the saccharified liquid may be converted into bioethanol by the microorganism. At this time, more preferably, the limonene content of the saccharified solution may be used by removing it to 0.020% by weight or less. If the limonene content of the saccharified solution is removed to 0.020% by weight or less, limonene does not affect the fermentation process at all, and bioethanol can be produced efficiently.

In addition, a hollow housing therein; And there is provided a limonene removal device comprising any one or more of activated carbon and cellulose fiber inserted into the hollow at a predetermined thickness. As shown in (a) of FIG. 2, a hollow is formed therein, so that the activated carbon is inserted into the hollow at a predetermined thickness to provide a device capable of removing limonene. In addition, as shown in (b) of FIG. 2, the cellulose fiber may be inserted into the hollow at a predetermined thickness to remove limonene, and as shown in (c) of FIG. 2, the activated carbon and the cellulose fiber of the hollow may be removed. The mixture can be inserted to a certain thickness to remove limonene. That is, at least one of the activated carbon and the cellulose fiber is contacted with the saccharification liquid obtained from the limonene-containing biomass to remove limonene. At this time, the limonene removal device is not limited as long as it is manufactured containing any one or more of activated carbon and cellulose fiber.

In addition, the activated carbon and cellulose fiber to which limonene is adsorbed after contact with the saccharification solution to remove limonene can be reused by separating limonene using an organic solvent, wherein the separated limonene is a food additive, a perfume of perfume, a known detergent It can be used as a car article, a cleaning agent, and the like.

In addition, preparing a saccharified solution in which the limonene removal method according to the present invention was performed; And it provides a method of producing a bioethanol comprising a fermentation step of fermenting using any one or more of yeast and E. coli in the saccharification liquid. At this time, saccharomyces cerevisiae ( saccharomyces cerevisiae ), which can convert sugar components to ethanol, can be used. Any of the conventional strains known in the art may be used, such as convertible heat resistant strains, recombinant strains that can simultaneously perform glycosylation and fermentation.

Example 1

Limonene was removed by contacting the saccharified solution containing 1% by weight of limonene using 0 mg, 50 mg, 100 mg, 150 mg, 200 mg, 250 mg, 300 mg, 500 mg of each activated carbon, and the results are shown in Table 1 below.

Table 1

Activated Carbon Usage (mg)	Residual Limonene (wt%)
0	One
50	0.88
100	0.71
150	0.55
200	0.31
250	0.12
300	0.02
500	0.08

Example 2

Limonene was removed by contacting the saccharified solution containing 1% by weight of limonene using 0 mg, 5 mg, 15 mg, 25 mg, 50 mg, 75 mg, 100 mg, 125 mg, and 150 mg of each of the cellulose fibers. Shown in

TABLE 2

Cellulose Fiber Usage (mg)	Residual Limonene (wt%)
0	One
5	0.8
15	0.73
25	0.5
50	1.38
75	0.26
100	0.12
125	0.02
150	0.01

Example 3

In order to remove the limonene component contained in the citrus sac solution, a limonene removal device was prepared in which 25 mg of cellulose fiber and 150 mg of activated carbon were mixed.

Example 4

Limonene was removed from the saccharification solution containing 1% by weight of limonene by using the limonene removing apparatus prepared in Example 3, and as a result, all limonene was removed as shown in Table 3 below.

TABLE 3

Activated Carbon Usage (mg)	Cellulose Fiber Usage (mg)	Residual Limonene (wt%)
0	0	One
0	25	0.5
150	0	0.55
25	150	0

Example 5

Bioethanol was prepared from the saccharification liquid from which the components of limonene were removed from each of Examples 1 to 4 by less than 0.025% by weight. At this time, the strain using a known Saccharomyces cerevisiae , the pH was maintained at 5.0, the fermentation process was carried out in a fermentation tank of 30 under the conditions of rpm 200, to obtain a bioethanol.

Experimental Example 1

In order to confirm the inhibition of limonene fermentation using a saccharification solution containing 0.5% by weight of limonene and a saccharification solution in which limonene was removed to less than 0.025% by weight according to the limonene removal method of the present invention, Under the same conditions, a fermentation process for conversion to ethanol was performed, and the results are shown in FIG. 3. As a result, the saccharified solution containing limonene of 0.5% by weight showed the maximum efficiency of 48%, but the saccharified liquid removed to less than 0.025% by weight of limonene showed 91%. From this result, it can be confirmed that limonene causes a fermentation inhibition phenomenon, and it can be confirmed that the fermentation efficiency can be improved by the limonene removal method of the present invention.

Although the present invention has been shown and described with reference to preferred embodiments as described above, it is not limited to the above-described embodiments and those skilled in the art without departing from the spirit of the present invention. Various changes and modifications will be possible.

Claims

Preparing a saccharified solution obtained from limonene-containing biomass; And

Limonene removal method of the biomass saccharification liquid comprising the step of contacting any one or more of the saccharification liquid and activated carbon and cellulose fiber.
The method of claim 1,

Wherein the step of contacting limonene removal of biomass saccharification liquid, characterized in that the activated carbon is used 0.3 to 0.5g based on the limonene content 0.8411g / cm3 of the saccharification liquid when using activated carbon.
The method of claim 1,

Wherein the step of contacting limonene removal of biomass saccharification liquid, characterized in that when using a cellulose fiber, the cellulose fiber is used 0.125 to 0.2g based on the limonene content 0.8411g / cm3 of the saccharified solution.
A saccharified liquid obtained from a limonene-containing biomass, wherein the limonene content is less than 0.025% by weight.
A hollow housing formed therein; And

Limonene removal device comprising any one or more of activated carbon and cellulose fiber inserted into the hollow at a predetermined thickness.
The method of claim 5,

At least one of the activated carbon and cellulose fiber is in contact with the saccharified liquid obtained from limonene-containing biomass, limonene removal apparatus characterized in that the removal of limonene.
Preparing a saccharified solution in which the limonene removing method of claim 1 is performed; And

Bioethanol production method comprising the step of fermentation using any one or more of yeast and E. coli in the saccharification liquid.