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TWI631218B - Fabricating method of maltitol - Google Patents

Fabricating method of maltitol Download PDF

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TWI631218B
TWI631218B TW106105103A TW106105103A TWI631218B TW I631218 B TWI631218 B TW I631218B TW 106105103 A TW106105103 A TW 106105103A TW 106105103 A TW106105103 A TW 106105103A TW I631218 B TWI631218 B TW I631218B
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maltitol
maltose
section
retention
producing
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TW106105103A
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TW201831695A (en
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梁明在
王詩涵
蕭介夫
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義守大學
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Abstract

本發明的麥芽糖醇的製造方法包括以下步驟。提供麥芽糖。在10℃至80℃的溫度範圍內以及1 atm至10 atm的壓力範圍內,利用電極使麥芽糖進行氫化反應而產生混合物,混合物包括麥芽糖與麥芽糖醇。以模擬移動床層析法將混合物中的麥芽糖與麥芽糖醇分離。The method for producing maltitol of the present invention comprises the following steps. Provide maltose. The maltose is hydrogenated by an electrode in a temperature range of 10 ° C to 80 ° C and a pressure range of 1 atm to 10 atm to produce a mixture including maltose and maltitol. The maltose in the mixture was separated from the maltitol by simulated moving bed chromatography.

Description

麥芽糖醇的製造方法Method for producing maltitol

本發明是有關於一種糖醇的製造方法,且特別是有關於一種麥芽糖醇的製造方法。The present invention relates to a method for producing a sugar alcohol, and more particularly to a method for producing maltitol.

社會進步所衍生的糖尿病,使得社會對低升糖指數產品的需求急速增加,其中從天然物萃取的甜菊糖、從麥芽糖經酵素轉化的海藻糖、以及從澱粉水解後氫化得到的各種糖醇(諸如木糖醇、山梨糖醇、以及麥芽糖醇等)已逐漸被市場所接受。Diabetes derived from social progress has led to a rapid increase in the demand for low-glycemic index products, including stevioside extracted from natural sources, trehalose converted from maltose by enzymes, and various sugar alcohols obtained by hydrogenation after hydrolysis of starch ( Such as xylitol, sorbitol, and maltitol, etc., have gradually been accepted by the market.

然而,前述糖類在推廣上仍遭遇許多困難。舉例來說,甜菊糖具有帶苦味或製作成本過高的缺點,而藉由金屬催化在高溫高壓下進行氫化反應所製作的海藻糖則存在糖降解的問題。因此,本領域亟須發展低升糖指數產品的其他製造方法。However, the aforementioned sugars still encounter many difficulties in the promotion. For example, stevioside has the disadvantage of having a bitter taste or being too expensive to produce, and trehalose produced by metal catalyzed hydrogenation under high temperature and high pressure has a problem of sugar degradation. Therefore, there is an urgent need in the art to develop other manufacturing methods for low glycemic index products.

本發明提供一種麥芽糖醇的製造方法,以降低製造成本或提高操作安全性。The present invention provides a method for producing maltitol to reduce manufacturing cost or improve operational safety.

本發明的麥芽糖醇的製造方法包括以下步驟。提供麥芽糖。在10℃至80℃的溫度範圍內以及1 atm至10 atm的壓力範圍內,利用電極使麥芽糖進行氫化反應而產生混合物,混合物包括麥芽糖與麥芽糖醇。以模擬移動床層析法將混合物中的麥芽糖與麥芽糖醇分離。The method for producing maltitol of the present invention comprises the following steps. Provide maltose. The maltose is hydrogenated by an electrode in a temperature range of 10 ° C to 80 ° C and a pressure range of 1 atm to 10 atm to produce a mixture including maltose and maltitol. The maltose in the mixture was separated from the maltitol by simulated moving bed chromatography.

在本發明的一實施例中,上述的電極包含碳電極或銅電極。In an embodiment of the invention, the electrode comprises a carbon electrode or a copper electrode.

在本發明的一實施例中,上述的電極上塗佈有觸媒層。In an embodiment of the invention, the electrode is coated with a catalyst layer.

在本發明的一實施例中,上述的觸媒層為鎳基觸媒。In an embodiment of the invention, the catalyst layer is a nickel-based catalyst.

在本發明的一實施例中,上述的鎳基觸媒是使用NiSO 4或Ni(NO 3) 2作為前驅物,在活性碳載體表面合成鎳化合物。 In an embodiment of the invention, the nickel-based catalyst is a nickel compound synthesized on the surface of the activated carbon support using NiSO 4 or Ni(NO 3 ) 2 as a precursor.

在本發明的一實施例中,上述的鎳化合物包括Ni、NiO、Ni(OH) 2或Ni(NO 3) 2In an embodiment of the invention, the nickel compound includes Ni, NiO, Ni(OH) 2 or Ni(NO 3 ) 2 .

在本發明的一實施例中,上述的溫度範圍為15℃至22℃。In an embodiment of the invention, the temperature range is from 15 ° C to 22 ° C.

在本發明的一實施例中,上述的模擬移動床層析法包括:(i)提供包含至少三區段的模擬移動床,其由移動相及固定相所組成,三區段依序為第一區段、第二區段及第三區段,其分別具有第一相對流速比值m 1、第二相對流速比值m 2及第三相對流速比值m 3,移動相於模擬移動床中朝同一方向流經三區段,固定相相對於移動相朝反方向模擬移動;(ii)將混合物注入模擬移動床的第二區段與第三區段之間,混合物中的麥芽糖與麥芽糖醇分別具有第一滯留常數K A與第二滯留常數K B,第二滯留常數K B大於第一滯留常數K A;(iii)第一區段的第一相對流速比值m 1大於第一滯留常數K A;以及(iv)第二區段及第三區段的第二相對流速比值m 2及第三相對流速比值m 3介於第一滯留常數K A及第二滯留常數K B之間,以分離麥芽糖及麥芽糖醇。 In an embodiment of the invention, the simulated moving bed chromatography method comprises: (i) providing a simulated moving bed comprising at least three segments, which is composed of a moving phase and a stationary phase, and the three segments are sequentially a section, a second section and a third section respectively having a first relative flow velocity ratio m 1 , a second relative flow velocity ratio m 2 and a third relative flow velocity ratio m 3 , the moving phase being the same in the simulated moving bed The direction flows through the three sections, the stationary phase simulates moving in the opposite direction with respect to the mobile phase; (ii) the mixture is injected between the second section and the third section of the simulated moving bed, and the maltose and maltitol in the mixture respectively have a first retention constant K A and a second retention constant K B , the second retention constant K B being greater than the first retention constant K A ; (iii) the first relative flow velocity ratio m 1 of the first segment is greater than the first retention constant K A And (iv) the second relative flow rate ratio m 2 and the third relative flow rate ratio m 3 of the second and third sections are between the first retention constant K A and the second retention constant K B to separate Maltose and maltitol.

在本發明的一實施例中,上述的第一區段、第二區段及第三區段各包含至少兩根管柱,每根管柱內填充顆粒內部具有孔隙的固定相。In an embodiment of the invention, the first section, the second section and the third section each comprise at least two columns, each of which is filled with a stationary phase having pores inside the particles.

在本發明的一實施例中,上述的第一滯留常數K A為0.03,第二滯留常數K B為0.10,而固定相的顆粒內部的孔隙度為0.2~0.8。 In an embodiment of the invention, the first retention constant K A is 0.03, the second retention constant K B is 0.10, and the porosity inside the particles of the stationary phase is 0.2 to 0.8.

在本發明的一實施例中,上述的移動相包括沖滌液,所述沖滌液為去離子水。In an embodiment of the invention, the mobile phase comprises a flushing liquid, and the flushing liquid is deionized water.

基於上述,本發明的麥芽糖醇的製造方法是在常溫常壓下,利用電極將麥芽糖進行氫化反應來產生麥芽糖醇,並藉由模擬移動床層析法來使麥芽糖醇與麥芽糖分離以純化麥芽糖醇。因此,相較於傳統採高溫高壓的氫化技術,本發明具有耗能低、設備需求低、操作安全或純化效率高的優點。Based on the above, the maltitol of the present invention is produced by hydrogenating maltose by an electrode at normal temperature and pressure to produce maltitol, and separating maltitol from maltose by simulated moving bed chromatography to purify maltitol. . Therefore, compared with the conventional high temperature and high pressure hydrogenation technology, the invention has the advantages of low energy consumption, low equipment demand, safe operation or high purification efficiency.

為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。The above described features and advantages of the invention will be apparent from the following description.

本發明的麥芽糖醇的製造方法包括在常溫與常壓下進行電化學反應獲得,而麥芽糖醇的純化方法包括以模擬移動床層析法將麥芽糖醇與麥芽糖分離,藉此有效提升分離效率及麥芽糖醇純度。詳細地說,首先,提供麥芽糖。接著,在10℃至80℃的溫度範圍內以及1 atm的壓力下,利用電極使麥芽糖進行氫化反應而產生混合物,混合物包括麥芽糖與麥芽糖醇。然後,以模擬移動床層析法將混合物中的麥芽糖與麥芽糖醇分離。在本發明一實施例中,利用超臨界水熱法將鎳化合物附載於活性碳粉(即活性碳載體)表面,獲得鎳基觸媒,並將鎳基觸媒塗佈於碳電極或銅電極之上,再利用電氫化將麥芽糖還原成麥芽糖醇。本發明在低溫下以高選擇性的方式進行麥芽糖醇的合成,並藉由搭配離子交換樹脂的模擬移動床,將未反應的麥芽糖與反應生成的麥芽糖醇予以分離,以完全將麥芽糖轉化成為高純度麥芽糖醇。在一實施例中,上述溫度範圍為15℃至22℃。在一實施例中,上述溫度範圍為18℃至20℃。The method for producing maltitol of the present invention comprises obtaining an electrochemical reaction at normal temperature and normal pressure, and the method for purifying maltitol comprises separating maltitol from maltose by simulated moving bed chromatography, thereby effectively improving separation efficiency and maltose. Alcohol purity. In detail, first, maltose is provided. Next, a maltose is hydrogenated by an electrode at a temperature ranging from 10 ° C to 80 ° C and a pressure of 1 atm to produce a mixture including maltose and maltitol. The maltose in the mixture was then separated from the maltitol by simulated moving bed chromatography. In one embodiment of the present invention, a nickel compound is attached to the surface of an activated carbon powder (ie, an activated carbon carrier) by a supercritical hydrothermal method to obtain a nickel-based catalyst, and a nickel-based catalyst is applied to a carbon electrode or a copper electrode. Above, the electrical hydrogenation is used to reduce the maltose to maltitol. The invention performs the synthesis of maltitol in a highly selective manner at a low temperature, and separates the unreacted maltose from the maltitol formed by the reaction by a simulated moving bed with an ion exchange resin to completely convert the maltose into a high Purity maltitol. In one embodiment, the above temperature range is from 15 °C to 22 °C. In one embodiment, the above temperature range is from 18 ° C to 20 ° C.

以下列舉實施例以說明本發明製作方法與純化方法之細節或條件,並且下述實施例主要分成兩大部分,其中第一部分是關於麥芽糖醇的製作方法,並且第二部分是關於麥芽糖醇與麥芽糖的分離。但這些實施例非用以限制本發明保護範圍。所繪圖式係為示意圖僅為說明方便而繪製,並非代表限制其實際之方法、條件或裝置等。The following examples are given to illustrate the details or conditions of the preparation method and purification method of the present invention, and the following examples are mainly divided into two parts, the first part relates to the preparation method of maltitol, and the second part relates to maltitol and maltose. Separation. However, these examples are not intended to limit the scope of the invention. The drawings are schematic for the convenience of description and are not intended to limit the actual methods, conditions, or devices.

[[ 實施例Example 1]1] 麥芽糖氫化反應Maltose hydrogenation

[[ 電極製備Electrode preparation ]]

[NiC/C電極的製備][Preparation of NiC/C electrode]

首先,分別使用NiSO 4與Ni(NO 3) 2作為前驅物,以超臨界水熱方式於活性碳粉表面合成鎳化合物,形成鎳基觸媒(稱為NiC)。接著,將包括NiC、聚乙烯亞胺及去離子水攪拌混合均勻形成一混和溶液。然後,以一次100μl的方式將上述溶液均勻滴於碳片上並陰乾,而後以50℃烘烤上述碳片10分鐘。重複上述步驟5次。接著,以110℃烘烤上述碳片60分鐘,再以200℃烘烤上述碳片120分鐘,以完成NiC/C電極的製作。 First, NiSO 4 and Ni(NO 3 ) 2 were used as precursors, respectively, and a nickel compound was synthesized on the surface of the activated carbon powder by supercritical hydrothermal method to form a nickel-based catalyst (referred to as NiC). Next, the mixture including NiC, polyethyleneimine and deionized water is stirred and mixed to form a mixed solution. Then, the above solution was uniformly dropped on the carbon sheet in a 100 μl manner and dried in the air, and then the above carbon sheet was baked at 50 ° C for 10 minutes. Repeat the above steps 5 times. Next, the carbon sheet was baked at 110 ° C for 60 minutes, and the carbon sheet was baked at 200 ° C for 120 minutes to complete the production of the NiC/C electrode.

圖1A與圖1B為分別使用NiSO 4與Ni(NO 3) 2作為前驅物所形成的鎳基觸媒的掃描式電子顯微鏡結果。由圖1A與圖1B可知,無論使用NiSO 4或Ni(NO 3) 2作為前驅物,均可以在活性碳粉表面形成均勻的鎳基觸媒。圖2A與圖2B為分別使用NiSO 4與Ni(NO 3) 2作為前驅物於水熱法中合成之鎳基觸媒的XRD分析結果。如圖2A顯示,若以NiSO 4作為前驅物,則所得之觸媒晶粒較小,且所得之鎳化合物以包含有Ni(OH) 2、Ni及NiO三種。相反地,如圖2B顯示,若以Ni(NO 3) 2作為前驅物,則所得之鎳化合物則以氧化鎳為主,其結晶性較佳且具有較大的晶粒。 1A and 1B are scanning electron microscope results of a nickel-based catalyst formed using NiSO 4 and Ni(NO 3 ) 2 as precursors, respectively. 1A and 1B, a uniform nickel-based catalyst can be formed on the surface of the activated carbon powder regardless of whether NiSO 4 or Ni(NO 3 ) 2 is used as a precursor. 2A and 2B are XRD analysis results of a nickel-based catalyst synthesized by hydrothermal method using NiSO 4 and Ni(NO 3 ) 2 as precursors, respectively. As shown in FIG. 2A, when NiSO 4 is used as a precursor, the obtained catalyst crystal grains are small, and the obtained nickel compound contains three kinds of Ni(OH) 2 , Ni and NiO. Conversely, as shown in Fig. 2B, when Ni(NO 3 ) 2 is used as a precursor, the obtained nickel compound is mainly nickel oxide, and its crystallinity is preferable and has large crystal grains.

[Cu/C電極的製備][Preparation of Cu/C electrode]

將1g的碳膠均勻塗抹於銅片上,並使用鍛燒爐於120℃下進行鍛燒1小時,以完成Cu/C電極的製作。1 g of the carbon glue was uniformly applied to the copper sheet, and calcined at 120 ° C for 1 hour using a calciner to complete the production of the Cu/C electrode.

[[ 鹽橋製備Salt bridge preparation ]]

[洋菜膠鹽橋][洋菜胶盐桥]

將洋菜膠加入Na 2SO 4水溶液中並加熱至洋菜膠溶解,而後將其倒入U型管中,並冰浴使其凝固。 The agar extract was added to an aqueous Na 2 SO 4 solution and heated to dissolve in the acacia gum, which was then poured into a U-tube and allowed to solidify in an ice bath.

[Nafion薄膜][Nafion film]

使用DuPont™ Nafion ®系列的Nafion薄膜,且將NiSO 4與Ni(NO 3) 2還原於Nafion薄膜上,分別製得Nafion/NiSO 4薄膜與Nafion/Ni(NO 3) 2薄膜。 Nafion/NiSO 4 film and Nafion/Ni(NO 3 ) 2 film were prepared by using a Nafion film of DuPontTM Nafion ® series and reducing NiSO 4 and Ni(NO 3 ) 2 on Nafion film.

[[ 麥芽糖醇的分析Analysis of maltitol ]]

使用HPLC/RI(pump:2130, Hitachi;RI:RID-20A, Shimadzu)進行成份分析,其中管柱為YMC-Pack Polyamine II(YMC股份有限公司,S-5 μm),管柱尺寸為4.6 × 250 mm,並以乙腈(HPLC級,友和貿易股份有限公司)及去離子水比例為77.5:22.5的溶液作為移動相,流速為0.5 mL/min,分析時管柱溫度設定為30℃,所使用的注射環圈體積為20 μL。同時,以麥芽糖(食品級,新糖城生化科技有限公司)與3、7.5、15、22.5、30 g/L的麥芽糖醇(食品級,新糖城生化科技有限公司)建立檢量線。The composition was analyzed by HPLC/RI (pump: 2130, Hitachi; RI: RID-20A, Shimadzu), wherein the column was YMC-Pack Polyamine II (YMC Co., Ltd., S-5 μm), and the column size was 4.6 × 250 mm, with acetonitrile (HPLC grade, Youhe Trading Co., Ltd.) and a deionized water ratio of 77.5:22.5 as the mobile phase, the flow rate is 0.5 mL / min, the column temperature is set to 30 ° C during analysis, used The injection loop volume is 20 μL. At the same time, maltose (food grade, New Sugar City Biochemical Technology Co., Ltd.) and 3, 7.5, 15, 22.5, 30 g / L of maltitol (food grade, New Sugar City Biochemical Technology Co., Ltd.) to establish a check line.

麥芽糖與麥芽糖醇的HPLC/RI分析圖譜如圖6所示,其中麥芽糖與麥芽糖醇的滯留時間分別為38.6分鐘以及34.9分鐘,可達基線分離的程度。再者,若採用體積為20 μL的注射環圈,則麥芽糖標準品的檢量線(A maltose)與麥芽糖醇標準品的檢量線(A maltitol)分別如下: 式(1) 式(1)中,A為吸光值,c為溶質濃度。 The HPLC/RI analysis of maltose and maltitol is shown in Figure 6, where the residence time of maltose and maltitol was 38.6 minutes and 34.9 minutes, respectively, to the extent of baseline separation. Further, if using an injection volume of 20 μL loop, the standard calibration curve of maltose (A maltose) and maltitol standard calibration curve (A maltitol) are as follows: In the formula (1), A is an absorbance value, and c is a solute concentration.

[[ 氫化反應Hydrogenation reaction ]]

在一實施例中,以碳片作為陽極,以NiC/C作為陰極,以及使用0.1M麥芽糖(食品級,新糖城生化科技有限公司)與0.1M Na 2SO 4作為反應溶液。同時,以洋菜膠鹽橋連接陽極與陰極,並施加不同電位,每一小時取一次產物,共取4次產物。 In one embodiment, a carbon sheet was used as an anode, NiC/C was used as a cathode, and 0.1 M maltose (food grade, New Sugar City Biochemical Technology Co., Ltd.) and 0.1 M Na 2 SO 4 were used as a reaction solution. At the same time, the anode and the cathode were connected by a rubber salt bridge, and different potentials were applied, and the product was taken once every hour, and the product was taken 4 times in total.

在一實施例中,以Cu/C電極作為陽極與陰極,以及使用0.1M麥芽糖與0.1M Na 2SO 4作為反應溶液。同時,將Nafion薄膜夾固於陽極與陰極之間,並施加不同電位,每一小時取一次產物,共取9次產物。 In one embodiment, a Cu/C electrode was used as the anode and cathode, and 0.1 M maltose and 0.1 M Na 2 SO 4 were used as the reaction solution. At the same time, the Nafion film was sandwiched between the anode and the cathode, and different potentials were applied, and the product was taken once every hour for a total of 9 times.

接著,以傳統鹽橋的裝置架構進行麥芽糖氫化反應測試。在施加不同電壓之後,取樣以HPLC分析其中麥芽糖以及麥芽糖醇的含量,進而可計算出其轉化率,結果如圖3所示。從圖3可知,持續反應4小時後,轉化率仍然偏低,主要是因為麥芽糖溶液的導電度低,導致反應器內電阻太高所致。再者,使用NiSO 4製備的NiC/C電極與使用Ni(NO 3) 2製備的NiC/C電極進行麥芽糖的氫化反應後,兩者的轉化率皆小於5%。 Next, the maltose hydrogenation reaction test was carried out using the conventional salt bridge apparatus architecture. After applying different voltages, the samples were analyzed by HPLC for the content of maltose and maltitol, and the conversion was calculated, and the results are shown in FIG. It can be seen from Fig. 3 that after 4 hours of continuous reaction, the conversion rate is still low, mainly because the conductivity of the maltose solution is low, resulting in too high resistance in the reactor. Further, after the NiC/C electrode prepared using NiSO 4 and the NiC/C electrode prepared using Ni(NO 3 ) 2 were subjected to hydrogenation reaction of maltose, both conversion rates were less than 5%.

本實施例進一步採用Nafion薄膜取代鹽橋,並以Cu/C電極進行麥芽糖的氫化反應,並取樣分析,結果在HPLC的圖譜中明顯發現麥芽糖醇的訊號,如圖4所示。藉由檢量線可算出樣品中麥芽糖以及麥芽糖醇的含量,並可據以計算出兩種電極在不同電壓下的麥芽糖醇轉化率,結果如圖5所示。由圖5可知,當反應時間為6小時,相較於以NiSO 4為前驅物,若以Ni(NO 3) 2為前驅物(亦即以NiO為主)來合成觸媒,則所生成之觸媒具有較佳的催化能力。此外,以Ni(NO 3) 2合成的觸媒在4小時的反應後,此觸媒的轉化率即可達22%。然而,轉化率雖然會隨施加的電壓增加而上升,但是當電壓超過1.4V時,反應逐漸趨緩,可能是因為高電壓會導致副產物產生。 In this example, the Nafion film was used to replace the salt bridge, and the hydrogenation reaction of maltose was carried out by Cu/C electrode, and the sample was analyzed. As a result, the signal of maltitol was clearly found in the HPLC map, as shown in FIG. 4 . The content of maltose and maltitol in the sample can be calculated by the calibration curve, and the conversion of maltitol at different voltages of the two electrodes can be calculated, and the results are shown in FIG. 5. 5 shows that, when the reaction time was 6 hours, as compared to the precursor NiSO 4, if the Ni (NO 3) 2 as precursor (i.e. mainly as NiO) catalyst was synthesized, then the generation of The catalyst has a better catalytic ability. In addition, the catalyst synthesized by Ni(NO 3 ) 2 can achieve a conversion of 22% after 4 hours of reaction. However, although the conversion rate increases as the applied voltage increases, when the voltage exceeds 1.4 V, the reaction gradually slows down, possibly because a high voltage causes by-products to be produced.

[[ 實施例Example 2]2] 單一管柱層析及三角理論Single column chromatography and trigonometry

本實施例中,先篩選出適合的離子交換樹脂,以進行麥芽糖及麥芽糖醇的分離。以濕式填充方式填充UBK555於尺寸1 x 25 cm的管柱之中,並以水作為沖滌液(流速3.0 mL/min)後,提供麥芽糖及麥芽糖醇作為分析樣品(流速3.0 mL/min),則得到麥芽糖及麥芽糖醇於區段內流動相的濃度相對於滯留時間的貫穿曲線(breakthrough curve)。In this example, a suitable ion exchange resin is first screened for separation of maltose and maltitol. The UBK555 was filled in a 1 x 25 cm column with a wet filling method, and water was used as a flushing solution (flow rate 3.0 mL/min) to provide maltose and maltitol as analytical samples (flow rate 3.0 mL/min). Then, a breakthrough curve of the concentration of the mobile phase in the section of maltose and maltitol relative to the residence time is obtained.

請參見圖7的貫穿曲線圖,其中C/C 0為相對濃度,時間為滯留時間。在圖7中,由於NaCl的滯留時間比麥芽糖與麥芽糖醇更短,因此可將NaCl視為不滯留成分,來進行管柱參數以及等溫吸附行為的調查。由於麥芽糖醇的滯留性高於麥芽糖,因此易於分離兩者。 See the through graph of Figure 7, where C/C 0 is the relative concentration and time is the residence time. In Fig. 7, since the residence time of NaCl is shorter than that of maltose and maltitol, NaCl can be regarded as a non-retention component for investigation of column parameters and isothermal adsorption behavior. Since maltitol has higher retention than maltose, it is easy to separate the two.

當溶質開始注入填充床後,其在填充床出口的應答可以表示成: (式2) 式(2)中,c為管柱出口的濃度,c o代表進料濃度,z為管柱軸向座標,t為進料進入管柱後的時間,ε e為粒子間孔隙度,D為溶質的軸擴散係數或軸向分散係數(axial dispersion coefficient),G為等溫吸附常數,u = Q/A cε e為流動相的線性流速,其中Q為流動相的體積流速,而A c為空管柱的截面積。如果把NaCl當作不滯留成分,則麥芽糖與麥芽糖醇的滯留常數分別為0.03以及0.10,顆粒間的孔隙度為0.36,顆粒內的孔隙度是0.532,而填充管柱的總孔隙度為0.7。在一實施例中,固定相的顆粒內部的孔隙度為0.2~0.8。 When the solute begins to be injected into the packed bed, its response at the packed bed outlet can be expressed as: (Formula 2) In equation (2), c is the concentration at the outlet of the column, c o is the concentration of the feed, z is the axial coordinate of the column, t is the time after the feed enters the column, and ε e is the interparticle pore Degree, D is the axial diffusion coefficient or axial dispersion coefficient of the solute, G is the isothermal adsorption constant, u = Q/A c ε e is the linear flow velocity of the mobile phase, where Q is the volume flow velocity of the mobile phase And A c is the cross-sectional area of the empty pipe string. If NaCl is used as a non-retention component, the retention constants for maltose and maltitol are 0.03 and 0.10, respectively, the porosity between particles is 0.36, the porosity within the particles is 0.532, and the total porosity of the packed column is 0.7. In one embodiment, the porosity of the particles of the stationary phase is from 0.2 to 0.8.

[[ 實施例Example 3]3] 麥芽糖與麥芽糖醇的分離Separation of maltose from maltitol

[[ 模擬移動床的使用Simulated use of moving beds ]]

在本實施例中,模擬移動床層析法包含:(i)提供包含至少三區段的模擬移動床,其由移動相及固定相所組成,所述三區段依序為第一區段、第二區段及第三區段,其分別具有第一相對流速比值m 1、第二相對流速比值m 2及第三相對流速比值m 3,所述移動相於模擬移動床中朝同一方向流經所述三區段,所述固定相相對於所述移動相朝反方向模擬移動;(ii)將混合物注入模擬移動床的所述第二區段與所述第三區段之間,所述混合物中的成分A及成分B分別具有第一滯留常數K A與第二滯留常數K B,第二滯留常數K B大於第一滯留常數K A;(iii)所述第一區段的所述第一相對流速比值m 1大於所述第一滯留常數K A;以及(iv)所述第二區段及所述第三區段的所述第二相對流速比值m 2及所述第三相對流速比值m 3介於所述第一滯留常數K A及所述第二滯留常數K B之間,以分離成分A及成分B。在一實施例中,所述第一區段、所述第二區段及所述第三區段各包含至少兩根管柱。 In the present embodiment, the simulated moving bed chromatography method comprises: (i) providing a simulated moving bed comprising at least three segments, which is composed of a mobile phase and a stationary phase, the three segments being sequentially the first segment a second section and a third section respectively having a first relative flow rate ratio m 1 , a second relative flow rate ratio m 2 , and a third relative flow rate ratio m 3 , wherein the moving phase is in the same direction in the simulated moving bed Flowing through the three sections, the stationary phase simulates movement in a reverse direction relative to the moving phase; (ii) injecting a mixture between the second section of the simulated moving bed and the third section, The component A and the component B in the mixture respectively have a first retention constant K A and a second retention constant K B , and the second retention constant K B is greater than the first retention constant K A ; (iii) the first segment The first relative flow rate ratio m 1 is greater than the first retention constant K A ; and (iv) the second relative flow rate ratio m 2 of the second segment and the third segment and the first 3 interposed between the first and the retentate constant K A constant K B three second retention ratio relative flow rates m, to separate Component A and component B. In an embodiment, the first section, the second section, and the third section each comprise at least two tubular strings.

更詳細而言,以包含至少三區段的模擬移動床層析法(Simulated Moving Bed Chromatography,SMBC)為例,其是藉由固定相(Stationary phase,簡稱SP)及移動相(Mobile phase,簡稱MP)於四區段之間的相對流動,以分離混合物中的物質。固定相填充於各區段之數個管柱中,移動相於管柱中朝同一方向流動,並藉由進料口切換裝置改變混合物之進料位置,以模擬固定相與移動相之相對流動方向。混合物進入層析管柱(進料)後,混合物所包含的成分A及成分B會依照各物質的亨利常數H(或滯留常數K)分別被固定相滯留或隨著移動相移動,進而分離或純化成分A及成分B。由於排拒層析的滯留常數並不會隨著濃度而改變,故根據三角理論(“Optimization of a SMB based on an approximated Langmuir Model”AIChE J. 48,2240-2246)所定義,欲以模擬移動床層析法分離成分A及成分B,則在每一區段當中,其液體與固體的相對體積流速須滿足以下的條件: 式(2) 式(3)中,K A與K B則為成分A與成分B的滯留常數;m j為在j區段內流動相體積相對流速與固體體積相對流速的比值,並且m j定義成: 式(3) 式(3)中,Q j為液體在第j區段的流速,t sw為管柱切換時間,V C為空管柱體積, ε為管柱總孔隙度,V D為每一根管柱的無感體積。 More specifically, a simulated moving bed chromatography (SMBC) including at least three sections is taken as an example of a stationary phase (Stationary phase, SP for short) and a mobile phase (Mobile phase). MP) The relative flow between the four segments to separate the material in the mixture. The stationary phase is filled in a plurality of columns of each section, the moving phase flows in the same direction in the column, and the feeding position of the mixture is changed by the inlet switching device to simulate the relative flow of the stationary phase and the moving phase direction. After the mixture enters the chromatography column (feed), the components A and B contained in the mixture are respectively retained by the stationary phase according to the Henry's constant H (or retention constant K) of each substance or separated by the mobile phase. Purification of component A and component B. Since the retention constant of the exclusion chromatography does not change with concentration, it is intended to be simulated by the triangle theory ("Optimization of a SMB based on an approximated Langmuir Model" AIChE J. 48, 2240-2246). Separation of component A and component B by bed chromatography requires that the relative volumetric flow rates of liquid and solid in each zone satisfy the following conditions: In the formula (3), K A and K B are the retention constants of the component A and the component B; m j is the ratio of the relative flow velocity of the mobile phase volume to the relative flow velocity of the solid volume in the j segment, and m j Defined as: In equation (3), Q j is the flow velocity of the liquid in the j-th segment, t sw is the column switching time, V C is the empty column volume, ε is the total column porosity, and V D is per The non-inductive volume of a column.

圖8顯示模擬移動床層析法依照三角形理論中可分離溶質的操作條件座標圖。如圖8所示,若以第二區段的m 2為橫軸,第三區段的m 3為縱軸,則可以完全分離的操作條件正好座落於三角形內,也就是說可分離的操作範圍為此座標圖中的三角形。在三角形的頂點則具有最佳的分離效果以及分離效率。除了第二區段與第三區段的相對流速需要滿足座落於三角形內之條件外,第一區段與第四區段的相對流速也必須同時滿足式(2)的條件。 Figure 8 is a graph showing the operating conditions of simulated moving bed chromatography in accordance with the theory of separable solutes in the theory of triangles. As shown in FIG. 8, if m 2 of the second section is the horizontal axis and m 3 of the third section is the vertical axis, the operating conditions that can be completely separated are located within the triangle, that is, separable. The operating range is the triangle in this coordinate plot. At the apex of the triangle there is an optimum separation and separation efficiency. In addition to the condition that the relative flow rates of the second and third sections need to satisfy the conditions of being located within the triangle, the relative flow rates of the first and fourth sections must also satisfy the condition of equation (2).

據此,本實施例使用搭載UBK555樹脂的模擬移動床,來分離麥芽糖與麥芽糖醇。圖9顯示三區段的模擬移動床層析之管柱配置示意圖,其管柱組態為分為2管/3管/3管的8管柱(C1~C8)所組成。具體而言,第一區段由兩根管柱串聯而成,以及第二區段以及第三區段分別由三根管柱串聯而成。第二區段以及第三區段的主要功能在進行麥芽糖與麥芽糖醇的分離,而第一區段則在進行沖提。每一根管柱的直徑為2.5 cm而長度為25 cm。Accordingly, this example uses a simulated moving bed equipped with UBK555 resin to separate maltose and maltitol. Figure 9 shows a schematic diagram of a three-section simulated moving bed chromatography column configuration, the column configuration is composed of 2 tubes / 3 tubes / 3 tubes of 8 tubes (C1 ~ C8). Specifically, the first section is formed by connecting two columns in series, and the second section and the third section are respectively formed by connecting three columns in series. The primary function of the second and third sections is to separate the maltose from the maltitol while the first section is being stripped. Each column has a diameter of 2.5 cm and a length of 25 cm.

請參照圖9,麥芽糖與麥芽糖醇(進料成分A/B)透過位於在第二區段與第三區段之間(亦即管柱C5與管柱C6之間)的進料端以0.1 mL/min的流速注入模擬移動床,而去離子水則以18 mL/min的流速從管柱C1注入。同時,在第一區段與第二區段間(亦即管柱C2與管柱C3之間)的萃出端(萃取液出口端)則計量引出6.0 mL/min的溶液(即萃出液),並讓多餘的溶液(亦即萃餘液,12.1 mL/min)從管柱C8出口(萃餘端)流出。在本實施例的模擬移動床中,是以麥芽糖與麥芽糖醇兩種成分作為進料,萃出端主要收集麥芽糖醇(成分B),萃餘端主要收集麥芽糖(成分A)。Referring to Figure 9, maltose and maltitol (feed component A/B) are passed through the feed end between the second section and the third section (i.e., between the column C5 and the column C6) at 0.1. The flow rate of mL/min was injected into the simulated moving bed, while the deionized water was injected from the column C1 at a flow rate of 18 mL/min. At the same time, the extraction end (extract outlet end) between the first section and the second section (that is, between the column C2 and the column C3) is metered to extract a solution of 6.0 mL/min (ie, the extract ) and let the excess solution (ie, raffinate, 12.1 mL/min) flow out of the column C8 outlet (the raffinate end). In the simulated moving bed of the present embodiment, maltose and maltitol are used as feeds, and the extraction end mainly collects maltitol (ingredient B), and the raffinate mainly collects maltose (ingredient A).

當使用上述的方式操作一段時間以後,如5分鐘,便將所有的出口以及入口,同時往下一根管柱切換。再持續一段相同時間後,再一次將所有出入口移往下一根管柱,如此持續的切換管柱,便可模擬固體沿著圖9的左手方向移動,而形成與液體逆向流動的行為。本發明實施例測試了不同切換時間,幫助確認出適合分離麥芽糖與麥芽糖醇的操作條件。When operating for a period of time using the above method, such as 5 minutes, all the outlets and inlets are switched to the next column. After continuing for a similar period of time, all the inlets and outlets are moved to the next column again. Thus, by continuously switching the column, the solid can be simulated to move in the left-hand direction of FIG. 9 to form a reverse flow with the liquid. Embodiments of the present invention tested different switching times to help identify operating conditions suitable for separating maltose and maltitol.

表1為進料總濃度為100.0 g/L (麥芽糖及麥芽糖醇各為50.0 g/L)時,不同管柱切換時間所得分離實驗結果。Table 1 shows the results of separation experiments obtained with different column switching times when the total feed concentration is 100.0 g/L (maltose and maltitol are each 50.0 g/L).

表1中的純度定義如下: (式5-1) (式5-2) 式(5-1)及式(5-2)中, P E 為麥芽糖醇的純度, C E 麥芽糖醇為萃出端的麥芽糖醇濃度, C E 麥芽糖為萃出端的麥芽糖濃度, P R 為麥芽糖的純度, C R 麥芽糖醇為萃餘端的麥芽糖醇濃度,而 C R 麥芽糖為萃餘端的麥芽糖濃度。 The purity in Table 1 is defined as follows: (Formula 5-1) In (Formula 5-2) (5-1) and formula (5-2), P E is the purity of maltitol, C E maltitol maltitol concentration extracted out terminated, C E maltose extracted out end maltose concentration , P R is the purity of maltose, C R maltitol is the concentration of maltitol at the raffinate end, and C R maltose is the concentration of maltose at the raffinate end.

表1中的回收率定義如下: (式6-1) (式6-2) 式(6-1)及式(6-2)中, R E 為麥芽糖醇的回收率, R R 為麥芽糖的回收率, Q E 為萃出端的流速,而 Q R 為萃出端的流速。 The recovery rates in Table 1 are defined as follows: (Formula 6-1) (Formula 6-2) In the formulae (6-1) and (6-2), R E is the recovery rate of maltitol, R R is the recovery rate of maltose, Q E is the flow rate at the extraction end, and Q R is The flow rate at the end of the extraction.

表2 <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 切換時間(分) </td><td> 濃度(g/L) </td><td> 純度(%) </td><td> 回收率(%) </td></tr><tr><td> 萃餘液 </td><td> 萃出液 </td></tr><tr><td> 麥芽糖 </td><td> 麥芽糖醇 </td><td> 麥芽糖 </td><td> 麥芽糖醇 </td><td> 萃餘液 </td><td> 萃出液 </td><td> 萃餘液 </td><td> 萃出液 </td></tr><tr><td> 4.50 </td><td> 0.218 </td><td> 0.148 </td><td> 0.870 </td><td> 1.082 </td><td> 59.5 </td><td> 55.5 </td><td> 33.6 </td><td> 78.4 </td></tr><tr><td> 4.75 </td><td> 0.277 </td><td> 0.109 </td><td> 0.271 </td><td> 1.002 </td><td> 71.7 </td><td> 78.7 </td><td> 67.3 </td><td> 82.0 </td></tr><tr><td> 5.00 </td><td> 0.462 </td><td> 0.140 </td><td> 0 </td><td> 0.983 </td><td> 76.7 </td><td> 100.0 </td><td> 100.0 </td><td> 77.6 </td></tr><tr><td> 6.00 </td><td> 0.637 </td><td> 0.160 </td><td> 0 </td><td> 0.665 </td><td> 79.9 </td><td> 100.0 </td><td> 100.0 </td><td> 67.4 </td></tr></TBODY></TABLE>Table 2  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Switching time (minutes) </td><td> concentration (g/L) </td ><td> Purity (%) </td><td> Recovery (%) </td></tr><tr><td> Raffinate</td><td> Extract</td ></tr><tr><td> Maltose</td><td> Maltitol</td><td> Maltose</td><td> Maltitol</td><td> Raffinate </ Td><td> extractant</td><td> raffinate</td><td> extractant</td></tr><tr><td> 4.50 </td><td> 0.218 </td><td> 0.148 </td><td> 0.870 </td><td> 1.082 </td><td> 59.5 </td><td> 55.5 </td><td> 33.6 < /td><td> 78.4 </td></tr><tr><td> 4.75 </td><td> 0.277 </td><td> 0.109 </td><td> 0.271 </td> <td> 1.002 </td><td> 71.7 </td><td> 78.7 </td><td> 67.3 </td><td> 82.0 </td></tr><tr><td> 5.00 </td><td> 0.462 </td><td> 0.140 </td><td> 0 </td><td> 0.983 </td><td> 76.7 </td><td> 100.0 < /td><td> 100.0 </td><td> 77.6 </td></tr><tr><td> 6.00 </td><td> 0.637 </td><td> 0.160 </td> <td> 0 </td><td> 0.665 </td><td> 79.9 </td><td> 100.0 </td><td> 100.0 </td><td> 67.4 </td></ Tr></TBODY></TABLE>

由表2可知,當切換時間為5分鐘時,能有效分離麥芽糖與麥芽糖醇,麥芽糖醇的純度可達100%,回收率亦達到77.6%。當切換時間為6分鐘時,雖純度及回收率不及切換時間為5分鐘的實驗成果,但亦能獲高純度的麥芽糖醇。It can be seen from Table 2 that when the switching time is 5 minutes, maltose and maltitol can be effectively separated, the purity of maltitol can reach 100%, and the recovery rate is also 77.6%. When the switching time is 6 minutes, although the purity and recovery rate are less than the experimental results of the switching time of 5 minutes, high-purity maltitol can also be obtained.

綜上所述,本發明的麥芽糖醇的製造方法是在常溫常壓下進行,因此相較於傳統採高溫高壓的氫化技術,本發明具有耗能低、設備需求低或操作安全的優點。此外,相較於傳統批次式的純化製程,由於模擬移動床層析法為連續式製程,因此藉由模擬移動床層析法來分離麥芽糖醇與未反應的麥芽糖,能大幅提昇麥芽糖醇的純化效率。In summary, the method for producing maltitol of the present invention is carried out at normal temperature and pressure, so that the present invention has the advantages of low energy consumption, low equipment demand or safe operation compared to conventional high temperature and high pressure hydrogenation technology. In addition, compared to the traditional batch-type purification process, since the simulated moving bed chromatography is a continuous process, the separation of maltitol and unreacted maltose by simulated moving bed chromatography can greatly enhance the maltitol. Purification efficiency.

雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

無。no.

圖1A與圖1B為分別使用NiSO 4與Ni(NO 3) 2作為前驅物製備的鎳基觸媒的掃描式電子顯微鏡結果。 圖2A與圖2B為分別使用NiSO 4與Ni(NO 3) 2作為前驅物製備的鎳基觸媒的XRD分析結果。 圖3為使用不同NiC/C電極進行麥芽糖氫化反應之轉化率結果。 圖4為NiC/C電極採用不同Nafion薄膜進行麥芽糖氫化反應之轉化率結果。 圖5為NiC/C電極採用不同Nafion薄膜進行麥芽糖氫化反應之轉化率結果。 圖6為麥芽糖與麥芽糖醇的HPLC/RI分析圖譜。 圖7是麥芽糖、麥芽糖醇及不滯留物質的貫穿曲線圖。 圖8顯示模擬移動床層析法依照三角形理論中可分離溶質的操作條件座標圖。 圖9顯示三區段的模擬移動床層析之管柱配置示意圖。 1A and 1B are scanning electron microscope results of a nickel-based catalyst prepared using NiSO 4 and Ni(NO 3 ) 2 as precursors, respectively. 2A and 2B are XRD analysis results of a nickel-based catalyst prepared using NiSO 4 and Ni(NO 3 ) 2 as precursors, respectively. Figure 3 shows the results of conversion of maltose hydrogenation using different NiC/C electrodes. Figure 4 shows the conversion results of the maltose hydrogenation reaction of NiC/C electrodes using different Nafion films. Figure 5 shows the conversion results of the maltose hydrogenation reaction using different Nafion films on the NiC/C electrode. Figure 6 is a HPLC/RI analysis of maltose and maltitol. Figure 7 is a cross-sectional graph of maltose, maltitol, and non-retained material. Figure 8 is a graph showing the operating conditions of simulated moving bed chromatography in accordance with the theory of separable solutes in the theory of triangles. Figure 9 is a schematic view showing the configuration of a three-section simulated moving bed chromatography column.

Claims (10)

一種麥芽糖醇的製造方法,包括:提供麥芽糖;在10℃至80℃的溫度範圍內以及1atm至10atm的壓力範圍內,利用電極使麥芽糖進行氫化反應而產生混合物,所述混合物包括麥芽糖與麥芽糖醇;以及以模擬移動床層析法將所述混合物中的所述麥芽糖與所述麥芽糖醇分離,其中所述模擬移動床層析法包括:(i)提供包含至少三區段的模擬移動床,其由移動相及固定相所組成,所述三區段依序為第一區段、第二區段及第三區段,其分別具有第一相對流速比值m1、第二相對流速比值m2及第三相對流速比值m3,所述移動相於所述模擬移動床中朝同一方向流經所述三區段,所述固定相相對於所述移動相朝反方向模擬移動;(ii)將所述混合物注入所述模擬移動床的所述第二區段與所述第三區段之間,所述混合物中的所述麥芽糖與所述麥芽糖醇分別具有第一滯留常數KA與第二滯留常數KB,所述第二滯留常數KB大於所述第一滯留常數KA;(iii)所述第一區段的所述第一相對流速比值m1大於所述第一滯留常數KA;以及(iv)所述第二區段及所述第三區段的所述第二相對流速比值m2及所述第三相對流速比值m3介於所述第一滯留常數KA及所述第二滯留常數KB之間,以分離所述麥芽糖及所述麥芽糖醇。 A method for producing maltitol, comprising: providing maltose; and hydrolyzing a maltose to produce a mixture by using an electrode in a temperature range of 10 ° C to 80 ° C and a pressure ranging from 1 atm to 10 atm, the mixture comprising maltose and maltitol And separating the maltose in the mixture from the maltitol by simulated moving bed chromatography, wherein the simulated moving bed chromatography comprises: (i) providing a simulated moving bed comprising at least three segments, It consists of a mobile phase and a stationary phase, which are sequentially a first segment, a second segment and a third segment, respectively having a first relative flow rate ratio m 1 and a second relative flow rate ratio m 2 and a third relative flow rate ratio m 3 , the moving phase flows through the three segments in the same direction in the simulated moving bed, and the stationary phase simulates moving in a reverse direction with respect to the moving phase; (ii) Causing the mixture between the second section of the simulated moving bed and the third section, the maltose and the maltitol in the mixture having a first retention constant K A and a second retention constant K B , the second retention constant K B being greater than the first retention constant K A ; (iii) the first relative flow velocity ratio m 1 of the first segment is greater than the first retention a constant K A ; and (iv) the second relative flow velocity ratio m 2 of the second segment and the third segment and the third relative flow velocity ratio m 3 are between the first retention constant K A between the A and the second retention constant K B to separate the maltose and the maltitol. 如申請專利範圍第1項所述的麥芽糖醇的製造方法,其中所述電極包含碳電極或銅電極。 The method for producing maltitol according to claim 1, wherein the electrode comprises a carbon electrode or a copper electrode. 如申請專利範圍第1項所述的麥芽糖醇的製造方法,其中所述電極上塗佈有觸媒層。 The method for producing maltitol according to claim 1, wherein the electrode is coated with a catalyst layer. 如申請專利範圍第3項所述的麥芽糖醇的製造方法,其中所述觸媒層為鎳基觸媒。 The method for producing maltitol according to the third aspect of the invention, wherein the catalyst layer is a nickel-based catalyst. 如申請專利範圍第4項所述的麥芽糖醇的製造方法,其中所述鎳基觸媒是使用NiSO4或Ni(NO3)2作為前驅物,於活性碳載體表面合成鎳化合物。 The method for producing maltitol according to the fourth aspect of the invention, wherein the nickel-based catalyst is a nickel compound synthesized on the surface of the activated carbon support by using NiSO 4 or Ni(NO 3 ) 2 as a precursor. 如申請專利範圍第5項所述的麥芽糖醇的製造方法,其中所述鎳化合物包括Ni、NiO、Ni(OH)2或Ni(NO3)2The method for producing maltitol according to claim 5, wherein the nickel compound comprises Ni, NiO, Ni(OH) 2 or Ni(NO 3 ) 2 . 如申請專利範圍第1項所述的麥芽糖醇的製造方法,其中所述溫度範圍為15℃至22℃。 The method for producing maltitol according to claim 1, wherein the temperature ranges from 15 ° C to 22 ° C. 如申請專利範圍第1項所述的麥芽糖醇的製造方法,其中所述第一區段、所述第二區段及所述第三區段各包含至少兩根管柱,每根管柱內填充顆粒內部具有孔隙的所述固定相。 The method for producing maltitol according to claim 1, wherein the first section, the second section, and the third section each comprise at least two columns, each of the columns The stationary phase having pores inside the filler particles. 如申請專利範圍第1項所述的麥芽糖醇的製造方法,其中所述第一滯留常數KA為0.03,所述第二滯留常數KB為0.10,而所述固定相的顆粒內部的孔隙度介於0.2~0.8之間。 The method for producing maltitol according to the first aspect of the invention, wherein the first retention constant K A is 0.03, the second retention constant K B is 0.10, and the porosity of the internal phase of the stationary phase Between 0.2 and 0.8. 如申請專利範圍第1項所述的麥芽糖醇的製造方法,其中所述移動相包括沖滌液,所述沖滌液為去離子水。 The method for producing maltitol according to claim 1, wherein the mobile phase comprises a flushing liquid, and the flushing liquid is deionized water.
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CN102413890A (en) * 2009-02-25 2012-04-11 丹尼斯克有限公司 Separation method

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CN101336313B (en) * 2006-02-08 2012-01-04 动力食品配料公司 Methods for the electrolytic production of erythrose or erythritol
CN102413890A (en) * 2009-02-25 2012-04-11 丹尼斯克有限公司 Separation method

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