WO2020057555A1 - 连续大规模分离制备d-阿洛酮糖的方法和设备 - Google Patents

连续大规模分离制备d-阿洛酮糖的方法和设备 Download PDF

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WO2020057555A1
WO2020057555A1 PCT/CN2019/106472 CN2019106472W WO2020057555A1 WO 2020057555 A1 WO2020057555 A1 WO 2020057555A1 CN 2019106472 W CN2019106472 W CN 2019106472W WO 2020057555 A1 WO2020057555 A1 WO 2020057555A1
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sugar
column
liquid
psicose
chromatographic
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PCT/CN2019/106472
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English (en)
French (fr)
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任世阔
牛志国
韩子明
赵红兵
吴会广
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上海立足生物科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K13/00—Sugars not otherwise provided for in this class
    • C13K13/007—Separation of sugars provided for in subclass C13K

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  • the invention belongs to the field of food raw material processing, and particularly relates to a method and equipment for continuous large-scale separation and preparation of D-psicose.
  • D-psicose is a rare sugar that exists in nature. According to research reports, D-psicose is a new type of functional monosaccharide. Compared with sucrose, it has low calories and pure taste, and will not be affected by the human body. Metabolism can well control blood sugar. In 2011, the FDA of the United States has approved D-psicose as a food ingredient and considered it to be a safe food; therefore, D-psicose is expected to become a substitute for sucrose, as a food or food additive, widely used in diet, health care and Medicine and other fields.
  • the price of starch is lower than that of glucose, fructose and sucrose.
  • the D-psicose-containing solution obtained by using starch as a raw material preparation method has complex components, and there has not been any purification in the art to obtain such a complex solution to obtain D-Axose Industrial Large-Scale Separation of Lactulose.
  • the purpose of the present invention is to provide a method for continuous and large-scale separation and preparation of D-psicose, and the method can be used to separate D-psicose-containing solutions with complex components prepared from sugars such as starch. ; And corresponding separation equipment.
  • a continuous and large-scale separation and preparation method for D-psicose is provided, wherein the method includes the following steps:
  • the sugar-containing mixed solution includes: alloxulose, fructose, glucose and oligosaccharides;
  • the oligosaccharide is a sugar selected from the group consisting of maltose, isomaltose, maltotriose, maltotetraose, polysaccharide, or a combination thereof;
  • the chromatographic separation includes:
  • Elution step the eluent D is passed into a chromatographic column for elution, and the eluent D is water;
  • Discharging step collecting a discharging liquid, wherein the discharging liquid includes a first discharging liquid, and the first discharging liquid is the solution of psicose;
  • the chromatographic separation device includes 2-20 of the chromatographic column and / or column segment, and the filler of the chromatographic column and / or column segment is a cationic resin, and each of the chromatographic column and / or chromatographic column is The column segments are connected in series.
  • the 2-20 chromatographic column segments are divided into a plurality of chromatographic columns, each of which can be fed in and out, and the segments are connected in series with each other, and the liquid can flow through each Paragraphs; and / or
  • the 2-20 chromatographic columns mean that each chromatographic column is connected in series, and materials can be fed and discharged between the columns, and the liquid can flow through each chromatographic column in sequence.
  • a feed port for the sugar-containing mixed liquid, a second output liquid outlet, an eluent inlet, and a first output liquid are sequentially provided. mouth.
  • the material-water ratio is 1: (0.5-3.0); wherein the material-water ratio is the mass ratio of feed F: eluent D; preferably, the material-water ratio is 1: (0.8 -2.5); preferably, 1: (1.0-2.0).
  • the switching time of the chromatographic column and / or the chromatographic column segment of the method is 3-15 minutes; preferably, it is 5-8 minutes.
  • the discharge liquid further includes a second discharge liquid, and the second discharge liquid includes glucose and fructose.
  • the first output liquid refers to a material liquid obtained by collecting slow components in a chromatographic separation
  • the second output liquid refers to a material liquid obtained by collecting fast components in a chromatographic separation
  • steps (2.1), (2.2), and (2.3) are performed sequentially or independently.
  • steps (2.1) and (2.2) are performed sequentially or independently.
  • step (2.1) and step (2.2) are performed intermittently; and / or step (2.3) is performed continuously.
  • the mass ratio of the collected first discharge liquid to the total amount of the feed F is (0.9-1.5): 1; preferably, (1.0-1.3): 1.
  • the mass ratio of the collected second discharge liquid to the total amount of the feed F is (1 to 3): 1; preferably, (1 to 2.4): 1.
  • the mass ratio of the first discharge liquid to the second discharge liquid is 1: (1.0 to 3.0).
  • the feed flow rate of the method is 0.002-0.150 BV (bed volume) / h; preferably, the feed flow rate of the method is 0.005-0.10 BV / h; more preferably, 0.01-0.05 BV / h.
  • the flow rate of the eluent is 0.005-0.375 BV (bed volume) / h; preferably, the flow rate of the feed of the method is 0.0125-0.10 BV / h; More preferably, it is 0.025-0.125 BV / h.
  • step (2.3) the flow rate of the discharge liquid is 0.002-0.150 BV (bed volume) / h.
  • the column temperature of the chromatographic column and / or column segment of the method is 20-80 ° C; preferably, 30-70 ° C; more preferably, 50-65 ° C.
  • the method has one or more of the following features:
  • the particle size of the cationic resin is: 50-500um
  • a density of the cationic resin filled in a single column and / or column segment is 0.85 to 0.95 g / cm 3 ;
  • the single column of the chromatographic column and / or the single segment length of the chromatographic column segment is 50-200cm;
  • the moving bed chromatography comprises 4-12 chromatography columns and / or chromatography column segments; and / or
  • the cationic resin is selected from the group consisting of calcium-type cationic resin, sodium-type cationic resin, potassium-type cationic resin, magnesium-type cationic resin, lithium-type cationic resin, or a combination thereof; preferably, calcium-type cationic resin and magnesium-type cationic resin , Or a combination thereof.
  • the aspect ratio is 1 / 15-1 / 1.
  • the fillers of the respective chromatographic columns and / or column segments are the same or different, the lengths are the same or different, and / or the aspect ratios are the same or different.
  • the packing, length and diameter-to-height ratio of each column and / or column segment are the same.
  • the sugar-containing mixed solution is a sugar-containing mixed solution made from starch; preferably, the sugar-containing mixed solution is obtained by liquefying starch with amylase and saccharifying the saccharifying enzyme to obtain a saccharified solution. After the saccharification solution is catalyzed and converted by glucose isomerase and C-3 epimerase, a mixed solution containing alloxulose, that is, a sugar-containing mixed solution is obtained.
  • the total concentration of the saccharides in the sugar-containing mixed solution is 20-70 wt%; based on the total mass of the mixed solution; preferably, the total concentration is 30-68 wt%; more preferably, It is 50-65 wt%.
  • the purity of the allosene in the sugar-containing mixed solution is greater than 5 wt%, and the purity refers to a percentage of the total mass of the dry matter; preferably, greater than 11 wt%; more preferably, greater than 14 wt %.
  • the sugar-containing mixed solution includes: 5 to 7.5% by weight of alloxulose, 8.6 to 10.5% by weight of fructose, 25 to 29% by weight of glucose, and 2.7 to 6.2% by weight of sugar.
  • the total mass of the mixed liquid is used as a reference.
  • the sugar-containing mixed solution can be obtained after the second output is catalyzed by glucose isomerase and C-3 epimerase.
  • the purity of the psicose isolated by the method is greater than 85% by weight; more preferably, greater than 90% by weight; and most preferably, greater than 95% by weight.
  • the recovery of the psicose by the method is greater than 85% by weight; more preferably, it is greater than 90% by weight.
  • the cationic resin does not require regeneration treatment; it is a physical adsorption process.
  • the step (1) further includes a desalination step; preferably, the desalination step is to pass the sugar-containing mixed solution through a cation exchange resin to remove metal ions in the sugar-containing mixed solution.
  • the metal ions removed in the recycling desalination step are recovered.
  • FIG. 1 is a schematic diagram of a continuous chromatography separation process of the present invention.
  • the inventors have developed a method for the separation of allosexose. Based on moving bed chromatography, the method realizes the complex sugar-containing solution produced from the preparation of allosexose from starch and other raw materials. Continuous and large-scale separation of psicose. Psicose isolated by this method has high purity, high concentration, and high recovery rate of psicose. In addition, this method obtains a unit of mass of psicose The amount of mobile phase required is small. Based on this, the inventors have completed the present invention.
  • dry matter refers to the sum of all substances except water.
  • concentration refers to the percentage of the mass of a particular substance to the total mass of a solution, for example, the concentration of psicose is the mass of psicose / total solution * 100%.
  • the term "purity” refers to the percentage of the mass of a specific substance to the total mass of substances other than water, for example, the purity of psicose is the mass of psicose / the mass of dry matter in the solution * 100%.
  • saccharide substance is a molecular compound composed of three elements of C, H, and O.
  • the saccharide substance is ptoseose, fructose, glucose, and the like.
  • mass ratio is the average mass ratio between materials over a period of time or when a certain amount of material is separated.
  • fast component refers to a component with a shorter retention time, first-in (first-out chromatographic separation).
  • slow component refers to a component with a longer retention time and a later-out (slower leaving the chromatographic separation).
  • the purpose of the present invention is to be able to further reduce the production cost of D-psicose and promote the industrialization of D-psicose.
  • starch is liquefied by amylase and saccharified by saccharifying enzyme to obtain saccharified liquid (composition: about 95.4% glucose, about 1.9% maltose, about 0.9% isomaltose, about 0.5% maltotriose, and more than maltotetraose (About 1.4%);
  • the saccharified solution is directly isomerized with glucose isomerase and C-3 epimerase, and the starch-containing saccharified solution is converted into a mixture of alloxone sugar after glucose isomerase and C-3 epimerase conversion.
  • the C-3 epimerase is D-psicose-3-epimerase, and the mixed solution is specifically for:
  • the dry matter (mainly sugars) concentration of the mixed solution is 50-60% by weight, based on the total mass of the mixed solution;
  • the components of the mixed liquid 5.5-7.5 wt% of ptoseose, 18.6-20.5 wt% of fructose, 20.5-25.9 wt% of glucose, 1.5-2.0 wt% of maltose, 0.5-1.2 wt% of isomalt, and maltotriose 0.1 to 1.0% by weight and 0.6 to 2.0% by weight of maltotetraose or higher polysaccharides, based on the total mass of the mixed solution;
  • Starch liquefaction and saccharification Mix (starch and water, concentration 25-35% (starch concentration in water), add amylase 10-25U / g starch, adjust pH), liquefaction (100-130 ° C liquefaction and maintain 30 -60 minutes), neutralization (adjusting pH), saccharification (adding saccharifying enzyme 80-150U / g starch, saccharification at 58-62 ° C) to obtain the "saccharified solution”
  • the components are: about 90.0-96.0% glucose, 1.5-2.0% maltose , Isomaltose 0.5-1.5%, maltotriose 0.1-1.0%, maltotetraose or more polysaccharide 1.4-2.0%.
  • the columnoose-containing mixed solution is obtained after column transformation, and its material components are: allosexose 5.5-7.5%, fructose 18.6% -20.5%, glucose 20.5-25.9%, maltose 1.5-2.0%, and isomalt 0.5 ⁇ 1.2%, maltotriose 0.1-1.0%, maltotetraose or more polysaccharide 0.6-2.0%.
  • Desalination uses a cation exchange column, and the above-converted material (that is, a mixture containing alloxone sugar) is passed through the cation exchange column, which can remove metal ions added during the reaction and can be recovered by ion replacement. The metal ions are repeatedly used in the reaction, thereby completing the process of desalting or recycling the metal ions.
  • the above-converted material that is, a mixture containing alloxone sugar
  • FIG 1 is a schematic diagram of the separation and purification of alloxulose (Psi) and the recovery of glucose and fructose.
  • the discharge is performed continuously (divided into the fast component discharge phase and the slow component discharge phase, and the group is discharged). Separate discharge and slow component discharge are performed alternately), intermittent feeding (feeding interval time such as 30-60min, which is related to the amount of resin and packing density, etc.) and elution (elution interval time such as 30-60min , Related to the amount of resin and filling density, etc., collect the fast component (that is, the second output liquid, the main components are glucose and fructose) and the slow component (that is, the first output liquid, the main component is polozone) sugar).
  • feed interval time such as 30-60min, which is related to the amount of resin and packing density, etc.
  • elution interval time elution interval time such as 30-60min
  • chromatographic columns are connected in series, and the mobile phase flows in sequence (the flow rate is 0.002 to 0.150 BV / h, in which the flow rates in the four columns are the same or different).
  • the four columns can flow to the mobile phase Move in the direction.
  • First feed feed flow 0.002-0.150BV / h
  • elute with water and move the chromatographic column so that the water inlet point (the position where the eluent is added) is located at the fast component.
  • the column switching time t is 5-8min.
  • the switching time means that the chromatographic column is at a certain position, and at time t, the chromatographic column starts to move in the opposite direction of the mobile phase flow direction and moves to the next position in the opposite direction of the mobile phase flow direction; for example, As shown in FIG. 1, after a chromatographic column is moved to the position of chromatographic column 1, and after time t has elapsed, the chromatographic column is rapidly moved from the position of chromatographic column 1 to the position of chromatographic column 4 in the figure.
  • the total mass of the psicose solution (the first discharge solution) is 0.25Kg, the purity is greater than 95%, the psicose solution contains 0.018Kg or more, and the yield is greater than 90%;
  • the total mass of the "fructose + glucose” mixed solution (second output liquid) is 0.31-0.54Kg (including about 0.11Kg of fructose and glucose, and the recovery rate is greater than 90%), in which the purity of fructose is 30-55% 3. Glucose purity is 40-70%; Fructose and glucose can also be collected separately.
  • this material can also be used (mixed solution of starch saccharified solution after glucose isomerization and C-3 epimerization), and the pleose is separated by chromatographic separation method.
  • the material-water ratio is 1.0: 0.5 -1.0: 3.0, fast component (glucose + fructose) / slow component (psicose) is 1.0 to 3.0 (mass).
  • the parameters of the chromatographic separation are:
  • Aspect ratio 1 / 20-1 / 0.4, preferably 1 / 15-1 / 1;
  • Resin type cation chromatography resin (for example, calcium, sodium, potassium, magnesium, lithium cation chromatography resin);
  • the particle size range of the resin used for chromatographic separation is: 50-500um.
  • the feed flow rate is 0.002-0.150 BV / h, preferably 0.005-0.10 BV / h, and more preferably 0.01-0.05 BV (bed volume) / h;
  • deionized water including various forms of deionized water, such as demineralized water, distilled water, or reverse osmosis water, etc.
  • Material-water ratio 1: (0.5-3.0), preferably 1: (0.8-2.5), more preferably 1: (1.0-2.0);
  • Dry matter concentration 20-70%, preferably 30-68%, more preferably 50-65%;
  • the column can be divided into 3-20 sections, preferably 4-12 sections, and more preferably 5-10 sections.
  • three or more resin columns are used for chromatographic separation.
  • the form of chromatographic separation includes a column of real moving bed chromatography, simulated moving bed chromatography, or batch chromatography.
  • a method for chromatographic separation of alloseneose is performed according to the following steps:
  • Axoseose mixed liquid ie, a sugar-containing mixed liquid
  • starch as a raw material, and the components of the mixed liquid are: allosexose 5 to 14.5%, fructose 8.6 to 10.5%, glucose 25 to 29%, maltose 1.5 ⁇ 2.0%, isomaltose 0.5-1.2%, maltotriose 0.1-1.0%, maltotetraose or more polysaccharide 0.6-2.0%.
  • the first discharge liquid the purity of the psicose reaches 95% or more, the yield is more than 90%, and the concentration is 4 to 7.2%; it is processed into the psicose product through processes such as concentration and crystallization;
  • the second discharge liquid fructose 2.8 to 5.3%, glucose 8.0 to 14.5%;
  • the third component 0.6-1.0% of maltose, 0.3-0.5% of isomaltose, 0.13-0.3% of maltotriose, 0.4-0.7% of maltotetraose or higher polysaccharide, and 0.05-0.3% of phaloseose.
  • the preparation of the mixed solution of apsulose before chromatographic separation includes the steps of: starch is liquefied by amylase, saccharifying enzyme is saccharified, and saccharified solution is obtained; the saccharified solution is epimerized by glucose isomerase and C-3 After the enzyme-catalyzed conversion, a mixed solution containing alloxulose was prepared; the components of the mixed solution were: allosexose 5 to 14.5%, fructose 8.6 to 10.5%, glucose 25 to 29%, maltose 1.5 to 2.0%, and isomalt 0.5 ⁇ 1.2%, maltotriose 0.1-1.0%, maltotetraose or more polysaccharide 0.6-2.0%.
  • the purity of the D-psicose in the prepared D-psicose mixed solution is greater than 5%, usually more than 11%, preferably more than 14%.
  • the process of the present invention can be used to separate a complex solution containing alloxulose.
  • the process of the present invention uses relatively closed, high temperature (55-65 degrees Celsius), high-concentration (50-70%) operations, and is not prone to microbial pollution.
  • the concentration of the psicose in the psicose solution obtained by the method is high, which is conducive to subsequent processing (such as concentration, crystallization, etc.)
  • the process of the present invention is suitable for large-scale production.
  • the separated glucose and fructose can be recycled, and the resin separated by chromatography does not need to be regenerated (belonging to physical adsorption), and can be directly recycled for the next batch of separation. Because this process uses relatively closed, high temperature (55-65 degrees Celsius), high concentration (50-70%) operations, it is not easy to produce microbial pollution as a whole.
  • the total resin is 4Kg
  • the total amount of feed is 1Kg (which contains alloxulose 0.084Kg, glucose 0.252Kg, fructose 0.246Kg, other sugars 0.018Kg)
  • control the column temperature At 60 ° C, the feed flow rate is 0.020 BV / h, eluted with deionized water, the ratio of material to water is 1.0: 2.0, and the elution flow rate is 0.050 BV / h.
  • Allo Ketosugar first output liquid, slow component, 0.076Kg,
  • fructose + glucose second output liquid, fast component, 0.48Kg
  • residual solution maltose + isomaltose + maltotriose + polysaccharide + Axulose in water (0.034 Kg).
  • the aqueous solution of ptoseose obtained by this method has a relatively high concentration, which is beneficial for subsequent operations such as concentration and crystallization.
  • the separation efficiency of the method of the present invention is 76g Psi / (8h * 4Kg resin), that is 2.38g Psi / (h * Kg resin); 76g Psi / (8h * 2Kg water * 1Kg material), among which 1Kg material Containing 84g Psi, that is 4.75g Psi / (h * Kg water), 1kg of water can be separated per hour to obtain 4.75g Psi.
  • Example 1 According to the operation of Example 1, feed 1.0Kg, column length 100cm, adjust the feed temperature, column temperature, feed speed, elution speed, and column diameter-height ratio. The results are shown in Table 1.
  • the particle size of the resin separated by chromatography is 50-500um.

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Abstract

一种连续分离制备D-阿洛酮糖的方法，提供包括阿洛酮糖、果糖、葡萄糖及低聚糖含糖混合液作为进料F，通过基于移动床色谱的色谱分离设备对所述含糖混合液进行分离，得到含阿洛酮糖的溶液，所述含阿洛酮糖的溶液中的阿洛酮糖的纯度＞80wt％。

Description

连续大规模分离制备D-阿洛酮糖的方法和设备 技术领域
本发明属于食品原料加工领域，具体涉及一种连续大规模分离制备D-阿洛酮糖的方法和设备。
背景技术
D-阿洛酮糖是自然界存在的一种稀有糖，据研究报道，D-阿洛酮糖是一种新型功能性单糖，和蔗糖相比，其热量低、口味纯正，不会被人体代谢，可以很好的控制血糖。2011年，美国FDA已批准D-阿洛酮糖作为食品原料，并认为是安全食品；所以D-阿洛酮糖有望成为蔗糖的替代品，作为食品或食品添加剂，广泛用于饮食、保健和医药等领域。
目前D-阿洛酮糖的生产成本还相对较高，作为一种新型甜味剂，要得到普遍的推广和使用，还需进一步降低生产成本。尤其是阿洛酮糖的分离纯化技术需要完美解决，才能够进一步产业化应用。已有很多的专利报道都是以果糖、葡萄糖或蔗糖为底物生产阿洛酮糖，如以果糖为原料通过生物酶转化制备阿洛酮糖的方法，用葡萄糖为原料连续转化制备阿洛酮糖的方法，和以蔗糖为原料通过生物转化制备阿洛酮糖的方法。淀粉比葡萄糖、果糖和蔗糖的价格都更低，然而以淀粉作为原料的制备方法获得的含D-阿洛酮糖的溶液成分复杂，本领域尚未有纯化这种成分复杂的溶液获得D-阿洛酮糖的工业大规模的分离方法。
综上所述，本领域迫切需要开发一种可以连续、大规模分离制备D-阿洛酮糖的方法，且该方法可用于分离由淀粉等糖类制备的具有复杂组分的含D-阿洛酮糖溶液；以及相应的分离设备。
发明内容
本发明的目的就是提供一种可以连续、大规模分离制备D-阿洛酮糖的方法，且该方法可用于分离由淀粉等糖类制备的具有复杂组分的含D-阿洛酮糖溶液；以及相应的分离设备。
在本发明的第一方面，提供了一种连续、大规模分离制备D-阿洛酮糖的方法，其中，所述的方法包括下述步骤：
(1)提供含糖类物质的含糖混合液作为进料F；
其中，所述含糖混合液包括：阿洛酮糖、果糖、葡萄糖及低聚糖；
所述低聚糖为选自下组的糖：麦芽糖、异麦芽糖、麦芽三糖、麦芽四糖、多糖、或 其组合；以及
(2)色谱分离：通过基于移动床色谱的色谱分离设备对所述含糖混合液进行分离，得到含阿洛酮糖的溶液，其中，所述含阿洛酮糖的溶液中的阿洛酮糖的纯度>80wt％，以溶液中干物质的质量为基准；
所述色谱分离包括：
(2.1)进料步骤：将所述的含糖混合液通入的色谱柱中；
(2.2)洗脱步骤：将洗脱液D通入色谱柱中进行洗脱，且所述洗脱液D为水；
(2.3)出料步骤：收集出料液，其中，所述出料液包括第一出料液，且所述第一出料液为所述含阿洛酮糖的溶液；
其中，所述色谱分离设备包括2-20个所述色谱柱和/或色谱柱段，且所述色谱柱和/或色谱柱段的填料为阳离子树脂，所述的各个色谱柱和/或色谱柱段串联连接。
在另一优选例中，所述2-20个色谱柱段为将色谱柱分为若干段，每段之间可以实现进出料的，且段与段之间串联连接，液体可以依次流过各段；和/或
所述2-20个色谱柱是指将各个色谱柱串联，各柱之间可以实现进出料的，液体可以依次流过各个色谱柱。
在另一优选例中，在流动相的流动方向上，依次设有含糖混合液的进料口、第二出料液的出料口、洗脱剂进口及第一出料液的出料口。
在另一优选例中，料水比为1:(0.5-3.0)；其中，所述料水比为进料F:洗脱液D的质量比；优选地，料水比为1:(0.8-2.5)；优选地，为1:(1.0-2.0)。
在另一优选例中，所述方法的色谱柱和/或色谱柱段的切换时间为3～15min；优选地，为5-8min。
在另一优选例中，步骤(2.3)中，所述出料液还包括第二出料液，所述第二出料液包含葡萄糖及果糖。
在另一优选例中，所述的第一出料液是指收集色谱分离中慢组分获得的料液；及第二出料液是指收集色谱分离中快组分获得的料液。
在另一优选例中，步骤(2.1)、(2.2)及(2.3)按次序进行或各自独立地进行。
在另一优选例中，步骤(2.1)及(2.2)按次序进行或各自独立地进行。
在另一优选例中，步骤(2.1)及步骤(2.2)间歇进行；和/或步骤(2.3)连续进行。
在另一优选例中，收集的第一出料液与进料F总量的质量比为(0.9～1.5):1；优选地，(1.0～1.3):1。
在另一优选例中，收集的第二出料液与进料F总量的质量比为(1～3):1；优选地，(1～2.4):1。
在另一优选例中，第一出料液与第二出料液的质量比为1:(1.0～3.0)。
在另一优选例中，步骤(2.1)中，所述方法的进料的流量为0.002-0.150BV(床体积)/h；优选地，所述方法的进料的流量为0.005-0.10BV/h；更优选地，为0.01-0.05BV/h。
在另一优选例中，步骤(2.2)中，洗脱液的流量为0.005-0.375BV(床体积)/h，；优选地，所述方法的进料的流量为0.0125-0.10BV/h；更优选地，为0.025-0.125BV/h。
在另一优选例中，步骤(2.3)中，所述出料液的流量为0.002-0.150BV(床体积)/h。
在另一优选例中，所述方法的色谱柱和/或色谱柱段的柱温为20-80℃；优选地，为30-70℃；更优选地，为50-65℃。
在另一优选例中，所述方法具有下述一个或多个特征：
所述阳离子树脂的粒径为：50-500um；
单个所述色谱柱和/或色谱柱段填充的所述阳离子树脂的密度为0.85～0.95g/cm 3；
所述色谱柱的单柱和/或色谱柱段的单段长度为50-200cm；
所述色谱柱的单柱和/或色谱柱段的单段径高比1/20-1/0.4；
所述的移动床色谱包括4-12个色谱柱和/或色谱柱段；和/或
所述的阳离子树脂选自：钙型阳离子树脂、钠型阳离子树脂、钾型阳离子树脂、镁型阳离子树脂、锂型阳离子树脂，或其组合；优选地，为钙型阳离子树脂、镁型阳离子树脂，或其组合。
在另一优选例中，所述径高比为1/15-1/1。
在另一优选例中，5-10个色谱柱和/或色谱柱段。
在另一优选例中，各个色谱柱和/或色谱柱段的填料相同或不同，长度相同或不同，和/或径高比相同或不同。
在另一优选例中，各个色谱柱和/或色谱柱段的填料、长度及径高比相同。
在另一优选例中，所述的含糖混合液为由淀粉制得的含糖混合液；优选地，所述的含糖混合液，由淀粉经淀粉酶液化、糖化酶糖化，得糖化液；所述糖化液由葡萄糖异构酶和C-3差向异构酶催化转化后，得含有阿洛酮糖混合液即含糖混合液。
在另一优选例中，所述含糖混合液中糖类物质的总浓度为20-70wt％；以含混合液总质量为基准；优选地，总浓度为30-68wt％；更优选地，为50-65wt％。
在另一优选例中，所述含糖混合液中阿洛酮糖纯度大于5wt％，所述的纯度是指占干物质总质量的百分比；优选地，大于11wt％；更优选地，大于14wt％。
在另一优选例中，所述含糖混合液包括：5～7.5wt％的阿洛酮糖、8.6～10.5wt％的果糖、25～29wt％的葡萄糖及2.7～6.2wt％，以含糖混合液的总质量为基准。
在另一优选例中，所述第二出料经过葡萄糖异构酶和C-3差向异构酶催化转化后，可得到所述含糖混合液。
在另一优选例中，通过所述方法分离的阿洛酮糖的纯度大于85wt％；更优选地，大于90wt％；最优选地，大于95wt％。
在另一优选例中，所述方法的阿洛酮糖的回收率大于85wt％；更优选地，大于90wt％。
在另一优选例中，所述阳离子树脂不需再生处理；为物理吸附过程。
在另一优选例中，步骤(1)中还包括脱盐步骤；优选地，所述脱盐步骤为使所述含糖混合液通过阳离子交换树脂以脱去所述含糖混合液中的金属离子。
在另一优选例中，回收再利用脱盐步骤中脱除的金属离子。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
附图说明
图1为本发明的连续色谱分离流程示意图。
具体实施方式
发明人通过广泛而深入的研究，开发了一种阿洛酮糖分离方法，本方法基于移动床色谱，实现了从由淀粉等为原料制备阿洛酮糖时产生的成分复杂的含糖溶液中连续、大规模分离地分离阿洛酮糖，本方法分离出的阿洛酮糖具有高纯度、高浓度、对阿洛酮糖的回收率高，而且本方法获得单位质量的阿洛酮糖所需流动相的量少。基于此发明人完成了本发明。
术语
如本文所用，术语“干物质”是指除去水以外的所有物质的总和。
如本文所用，术语“浓度”是指特定物质质量占溶液总质量的百分比，例如，阿洛酮糖的浓度为阿洛酮糖质量/溶液总质量*100％。
如本文所用，术语“纯度”是指特定物质质量占除水以外物质总质量的百分比，例如，阿洛酮糖的纯度为阿洛酮糖质量/溶液中干物质的质量*100％。
如本文所用，术语“糖类物质”由C、H、O三种元素组成的分子化合物，在本申请中所述糖类物质为阿洛酮糖、果糖、葡萄糖等。
如本文所用，术语“质量比”在一定时间段内或者分离一定量的物料时各物质之间的 平均质量比。
如本文所用，术语“快组分”是指保留时间较短，先出(较快离开色谱分离)的组分。类似地，术语“慢组分”是指保留时间较长，后出(较慢离开色谱分离)的组分。
本发明的目的是为了能够进一步降低D-阿洛酮糖的生产成本，并推动阿洛酮糖的产业化，我们开发了由色谱法分离制备D-阿洛酮糖的方法。
1.原料制取：淀粉经过淀粉酶液化、糖化酶糖化，得糖化液(成分：葡萄糖约95.4％、麦芽糖约1.9％、异麦芽糖约0.9％、麦芽三糖约0.5％、麦芽四糖以上多糖约1.4％)；
将该糖化液直接用葡萄糖异构酶和C-3差相异构酶异构化，淀粉糖化液经葡萄糖异构酶和C-3差向异构酶转化后的含阿洛酮糖混合液(采用固定化酶技术，或已经从反应产物中去除酶)，其中，所述C-3差向异构酶为D-阿洛酮糖-3-差向异构酶，所述混合液具体为：
1)混合液的干物(主要为糖类物质)浓度50-60wt％，按混合液的总质量计；
2)混合液的组分：阿洛酮糖5.5～7.5wt％、果糖18.6～20.5wt％、葡萄糖20.5～25.9wt％、麦芽糖1.5～2.0wt％、异麦芽糖0.5～1.2wt％、麦芽三糖0.1～1.0wt％、麦芽四糖以上多糖0.6～2.0wt％，以混合液的总质量计；
2.进入色谱分离，分离后主要得到三部分溶液，如下：
1)阿洛酮糖，纯度达到95％以上(以溶液中干物质总质量为基准)，收率90％以上，浓度4～7.2％(以溶液总质量为基准)。经过浓缩、结晶等工艺加工成阿洛酮糖产品；
2)果糖2.8～5.3％、葡萄糖8.0～14.5％，以溶液总质量为基准；
3)麦芽糖0.6～1.0％、异麦芽糖0.3～0.5％、麦芽三糖0.13～0.3％、麦芽四糖以上多糖0.4～0.7％、阿洛酮糖0.05～0.3％，葡萄糖0.05-2.0％，果糖0.05-1.0％(以溶液总质量为基准)。
具体操作步骤：
1)淀粉液化与糖化：混合(淀粉与水，浓度25-35％(淀粉于水中的浓度)、加入淀粉酶10～25U/g淀粉、调pH)、液化(100-130℃液化并维持30-60分钟)、中和(调pH)、糖化(加入糖化酶80-150U/g淀粉、58-62℃糖化)得到“糖化液”成分为：葡萄糖约90.0-96.0％、麦芽糖1.5-2.0％、异麦芽糖0.5-1.5％、麦芽三糖0.1-1.0％、麦芽四糖以上多糖1.4-2.0％。
2)将上述糖化液(采用MVR或其它蒸发器)浓缩到干物浓度为45-55％并加入金属离子；按照一定流速通过装有“葡萄糖异构酶”和“C-3果糖差相异构酶”的酶固定化柱子。
过柱转化后得到所述含阿洛酮糖混合液，其物料成分为：阿洛酮糖5.5～7.5％、果 糖18.6～20.5％、葡萄糖20.5～25.9％、麦芽糖1.5～2.0％、异麦芽糖0.5～1.2％、麦芽三糖0.1～1.0％、麦芽四糖以上多糖0.6～2.0％。
3)脱盐：脱盐采用阳离子交换柱，将上述过柱转化好的物料(即含阿洛酮糖混合液)流经该阳离子交换柱，可以除去反应过程中加入的金属离子，通过离子置换可以回收该金属离子并重复用于反应，从而完成脱盐或该金属离子的循环再用过程。
4)色谱分离：采用2-20个装有专用色谱分离树脂的柱子，流程示意如图1所示(以4柱为例)。
如图1为分离纯化阿洛酮糖(Psi)和回收葡萄糖和果糖的示意图，如图1所示，出料连续进行(分为快组分出料阶段和慢组分出料阶段，出组分出料与慢组分出料交替进行)，进行间歇性进料(进料间隔时间比如30-60min，与树脂的量和填充密度等有关)和洗脱(洗脱间隔时间比如30-60min，与树脂的量和填充密度等有关)，分别收集快组分(即第二出料液，主要成分是葡萄糖和果糖)和慢组分(即第一出料液，主要成分是阿洛酮糖)。
具体地，4个色谱柱串联连接，流动相依次流过(流速为0.002-0.150BV/h，其中，4个柱子中流速相同或不同)这4个色谱柱，同时色谱柱可向流动相流动方向移动。
首先进料(进料流量0.002-0.150BV/h)，进料0.01-0.02BV后进水洗脱，且通过移动色谱柱来使进水点(加入洗脱剂的位置)位于快组分出料位置和慢组分出料位置之间，色谱柱的切换时间t为5-8min。其中，所述切换时间是指，色谱柱在某一位置，在t时间时，色谱柱开始沿流动相流动方向的反方向移动并移动到流动相流动方向的反方向上的下一个位置；例如，如图1所示，某一色谱柱移动到色谱柱1位置后，再经过t时间后，该色谱柱由色谱柱1位置快速移动到了图中色谱柱4的位置。
在另一优选例中，色谱分离操作条件：设定进料F＝0.4Kg/h(与树脂量有关，此处所用树脂总量为8.0Kg)、实验温度为60-65摄氏度、处理料液浓度60wt％(溶质(即干物质)的总含量)、阿洛酮糖的纯度为14％(阿洛酮糖与总溶质的质量比，以下纯度值意义相同)、洗脱剂(水)D＝0.6Kg/h、出料BD(慢组分)＝0.33Kg/h、AD(快组分)＝0.66Kg/h、处理量0.240Kg料液(含果糖+葡萄糖+其它糖0.115Kg，含阿洛酮糖0.020Kg)、料水比1:1.5、AD/BD＝2；瞬时操作条件：F→A＝33ml/min(进料时快组分出料)、D→B(洗脱时慢组分出料)＝33ml/min、D→A＝33ml/min(洗脱时快组分出料)，循环流速33ml/min(或者柱内流动相流速33ml/min)，切换时间5-8min。
结果：
(1)得到阿洛酮糖溶液(第一出料液)总质量为0.25Kg，纯度大于95％、含阿洛酮糖0.018Kg以上，收率大于90％；
(2)得到“果糖+葡萄糖”混合液(第二出料液)总质量为0.31-0.54Kg，(含果糖及葡萄糖共约0.11Kg，回收率大于90％)，其中果糖纯度30～55％、葡萄糖纯度40～70％； 也可以分开收集果糖和葡萄糖。
(3)除阿洛酮糖溶液及“果糖+葡萄糖”混合液外的残余溶液，总质量为0.16～0.32Kg，包含：麦芽糖、异麦芽糖、麦芽三糖、多糖、阿洛酮糖、葡萄糖及果糖，干物浓度5.0～10.0％(总溶质约0.016Kg)，其中：麦芽糖纯度3.0～10.0％(0.0005-0.0016Kg)、异麦芽糖纯度3.0～10.0％(0.0005-0.0016Kg)、麦芽三糖纯度1.0～5.0％(0.00016～0.001Kg)、多糖纯度0.5～5.0％(0.0001～0.001Kg)、阿洛酮糖纯度1.0～6.0％(0.00016～0.001Kg)、葡萄糖纯度1.0-5.0％(0.00016～0.001Kg)、果糖纯度1.0-5.0％(0.00016-0.001Kg)。
在更大规模的生产中，同样可以采用该物料(淀粉糖化液经葡萄糖异构和C-3差向异构后混合液)，利用色谱分离方法分离阿洛酮糖，料水比1.0:0.5～1.0：3.0、快组分(葡萄糖+果糖)/慢组分(阿洛酮糖)为1.0～3.0(质量)。
在另一优选例中，色谱分离的参数：
单柱的长度：50-200cm；
径高比：1/20-1/0.4，较佳地1/15-1/1；
树脂类型：阳离子色谱树脂(例如，钙型、钠型、钾型、镁型、锂型阳离子色谱树脂)；
在另一优选例中，色谱分离所用树脂的粒径范围为：50-500um。
温度：20-80℃，较佳地30-70℃，更佳地50-65℃；
进料流量为0.002-0.150BV/h，较佳地0.005-0.10BV/h，更佳地0.01-0.05BV(床体积)/h；
洗脱剂：去离子水(包括各种形式的去离子水，如脱盐水、蒸馏水、或反渗透水等)；
料水比：1:(0.5-3.0)，较佳地1:(0.8-2.5)，更佳地1:(1.0-2.0)；
干物浓度：20-70％，较佳地30-68％，更佳地50-65％；
分节：使用色谱柱可以分为3-20节，较佳地4-12节，更佳地5-10节。
在另一优选例中，色谱分离采用树脂柱3个以上(含3个)。
在另一优选例中，色谱分离所采用的形式包括真实移动床色谱、模拟移动床色谱，或间歇式色谱的色谱柱。
在另一优选例中，可以推广到生产放大。
阿洛酮糖的色谱分离方法
一种阿洛酮糖的色谱分离方法，按照下述步骤进行：
1)用淀粉做原料制备阿洛酮糖混合液(即含糖混合液)，该混合液成分为：阿洛酮糖5～14.5％、果糖8.6～10.5％、葡萄糖25～29％、麦芽糖1.5～2.0％、异麦芽糖0.5～1.2％、麦芽三糖0.1～1.0％、麦芽四糖以上多糖0.6～2.0％。
2)将以上阿洛酮糖混合液，在30-80度条件下，注入装有专用色谱填料的色谱柱，用水做洗脱剂，分别收集含有不同组份的洗脱液；色谱柱的柱温为30-80度、柱径高比为1:(0.4～15)、进料量为0.01BV/h～1.0BV/h、洗脱速度为0.02BV/h～3.0BV/h、及料水比为1:(0.5-3.0)。色谱柱的专用色谱填料为强型阳离子树脂、钙型阳离子树脂、镁型阳离子树脂、钠型阳离子树脂、钾型阳离子树脂或铵型阳离子树脂。
分离后成分
第一出料液：阿洛酮糖纯度达到95％以上，收率90％以上，浓度4～7.2％；经过浓缩、结晶等工艺加工成阿洛酮糖产品；
第二出料液：果糖2.8～5.3％、葡萄糖8.0～14.5％；
第三组分：麦芽糖0.6～1.0％、异麦芽糖0.3～0.5％、麦芽三糖0.13～0.3％、麦芽四糖以上多糖0.4～0.7％、阿洛酮糖0.05～0.3％。
在另一优选例中，色谱分离前的阿洛酮糖混合液制备包括步骤：淀粉经过淀粉酶液化、糖化酶糖化、得糖化液；糖化液由葡萄糖异构酶和C-3差向异构酶催化转化后制得含有阿洛酮糖混合液；该混合液成分为：阿洛酮糖5～14.5％、果糖8.6～10.5％、葡萄糖25～29％、麦芽糖1.5～2.0％、异麦芽糖0.5～1.2％、麦芽三糖0.1～1.0％、麦芽四糖以上多糖0.6～2.0％。
在另一优选例中，所制得D-阿洛酮糖的混合液中，D-阿洛酮糖的纯度大于5％，通常在11％以上，优选14％以上。
本发明的主要优点包括
(a)本发明的工艺可以用于分离成分复杂的含阿洛酮糖溶液。
(b)本发明的工艺适合大规模生产。
(c)分离得到的葡萄糖和果糖可以循环使用，并且色谱分离的树脂不需要进行再生处理(属于物理吸附)，可以直接循环用于下一批次的分离。
(d)本发明的工艺采用相对密闭、高温(55-65摄氏度)、高浓度(50-70％)的操作，不易产生微生物的污染。
(e)通过本方法生产获得阿洛酮糖溶液中阿洛酮糖的浓度高，利于后续处理(如浓缩、结晶等)
本发明的工艺适合大规模生产，分离得到的葡萄糖和果糖可以循环使用，并且色谱分离的树脂不需要进行再生处理(属于物理吸附)，可以直接循环用于下一批次的分离。由于该工艺采用相对密闭、高温(55-65摄氏度)、高浓度(50-70％)的操作，所以整体上不易产生微生物的污染。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规 条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数是质量百分比和质量份数。
实施例1
将由淀粉做原料经过酶催化转化获得的阿洛酮糖水溶液，经离子交换树脂脱盐后，预热至60℃，注入径高比为1:10，填充钙型阳离子色谱树脂的色谱柱(柱长100cm，直径10.0cm，共6根)，树脂总量为4Kg，进料总量为1Kg(其中含阿洛酮糖0.084Kg，葡萄糖0.252Kg，果糖0.246Kg，其他糖分0.018Kg)，控制柱温在60℃，进料流量为0.020BV/h，用去离子水洗脱，料水比为1.0:2.0，洗脱流速为0.050BV/h，分别收集洗脱液和残留液，分别获得阿洛酮糖(第一出料液，慢组分，0.076Kg，)、果糖+葡萄糖(第二出料液，快组分，0.48Kg)和残余溶液(麦芽糖+异麦芽糖+麦芽三糖+多糖+阿洛酮糖的水溶液0.034Kg)。
Figure PCTCN2019106472-appb-000001
通过本方法获得的阿洛酮糖水溶液具有较高的浓度，有利于进行后续浓缩结晶等操作。
分离1Kg物料(含84gPsi，498gGlu+Fru和18g其它糖分杂质)
实施例1中，本发明方法的分离效率为76g Psi/(8h*4Kg树脂)，即2.38g Psi/(h*Kg树脂)；76g Psi/(8h*2Kg水*1Kg物料)，1Kg物料其中含84g Psi，即4.75g Psi/(h*Kg水)，1kg水每小时可分离获得4.75g Psi。
在该试验中，所用水量和进料量都远超出高效液相的分离能力。相比较，水和进料的比例极大降低(高效液相进样20uL，需要流动相9mL，其水料比高达450)。
实施例2到11
按照实例1的操作，进料1.0Kg，色谱柱长度100cm，调整进料温度、柱温、进料速度、洗脱速度和色谱柱径高比等因素，结果见表1所示，表1中色谱分离的树脂粒径为：50-500um。
表1
Figure PCTCN2019106472-appb-000002
对比例单分离柱分离
0.2Kg物料(含16gPsi)，1Kg树脂单节树脂柱分离，用5Kg的水只能分离得到约1g的Psi。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种连续、大规模分离制备D-阿洛酮糖的方法，其特征在于，所述的方法包括下述步骤：
    (1)提供含糖类物质的含糖混合液作为进料F；
    其中，所述含糖混合液包括：阿洛酮糖、果糖、葡萄糖及低聚糖；
    所述低聚糖为选自下组的糖：麦芽糖、异麦芽糖、麦芽三糖、麦芽四糖、多糖、或其组合；以及
    (2)色谱分离：通过基于移动床色谱的色谱分离设备对所述含糖混合液进行分离，得到含阿洛酮糖的溶液，其中，所述含阿洛酮糖的溶液中的阿洛酮糖的纯度>80wt％，以溶液中干物质的质量为基准；
    所述色谱分离包括：
    (2.1)进料步骤：将所述的含糖混合液通入的色谱柱中；
    (2.2)洗脱步骤：将洗脱液D通入色谱柱中进行洗脱，且所述洗脱液D为水；
    (2.3)出料步骤：收集出料液，其中，所述出料液包括第一出料液，且所述第一出料液为所述含阿洛酮糖的溶液；
    其中，所述色谱分离设备包括2-20个所述色谱柱和/或色谱柱段，且所述色谱柱和/或色谱柱段的填料为阳离子树脂，所述的各个色谱柱和/或色谱柱段串联连接。
  2. 如权利要求1所述的方法，其特征在于，料水比为1:(0.5-3.0)；其中，所述料水比为进料F:洗脱液D的质量比。
  3. 权利要求1所述的方法，其特征在于，所述方法的色谱柱和/或色谱柱段的切换时间为3～15min。
  4. 如权利要求1所述的方法，其特征在于，步骤(2.3)中，所述出料液还包括第二出料液，且所述第二出料液包含葡萄糖及果糖。
  5. 如权利要求4所述的方法，其特征在于，步骤(2.3)中，第一出料液与第二出料液的质量比为1:(1.5～3)。
  6. 如权利要求1所述的方法，其特征在于，步骤(2.1)及步骤(2.2)间歇进行；和/或步骤(2.3)连续进行。
  7. 如权利要求1所述的方法，其特征在于，步骤(2.1)中，所述方法的进料的流量为0.002-0.150BV/h；
    步骤(2.2)中，洗脱液的流量为0.005-0.375BV/h；和/或
    步骤(2.3)中，所述出料液的流量为0.002-0.150BV/h。
  8. 如权利要求1所述的方法，其特征在于，所述方法的色谱柱和/或色谱柱段的柱温为20-80℃。
  9. 如权利要求1所述的方法，其特征在于，所述方法具有下述一个或多个特征：
    所述阳离子树脂的粒径为：50-500um；
    单个所述色谱柱和/或色谱柱段填充的所述阳离子树脂的密度为0.85～0.95g/cm 3；
    所述色谱柱的单柱和/或色谱柱段的单段长度为50-200cm；
    所述色谱柱的单柱和/或色谱柱段的单段径高比1/20-1/0.4；
    所述的移动床色谱包括4-12个色谱柱和/或色谱柱段；和/或
    所述的阳离子树脂选自：钙型阳离子树脂、钠型阳离子树脂、钾型阳离子树脂、镁型阳离子树脂、锂型阳离子树脂，或其组合。
  10. 如权利要求1所述的方法，其特征在于，所述含糖混合液具有下述的一个或多个特征：
    所述含糖混合液的糖类物质的总浓度为20-70wt％，以含糖混合液总质量为基准；
    所述含糖混合液中阿洛酮糖的纯度大于5wt％
    所述含糖混合液为由淀粉制得的含糖混合液；和/或
    所述含糖混合液包括：5～7.5wt％的阿洛酮糖、8.6～10.5wt％的果糖、25～29wt％的葡萄糖及2.7～6.2wt％，以含糖混合液的总质量为基准。
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