WO2016149993A1 - 一种以阿拉伯胶为原料提取制备高纯度l-阿拉伯糖的工艺 - Google Patents

一种以阿拉伯胶为原料提取制备高纯度l-阿拉伯糖的工艺 Download PDF

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WO2016149993A1
WO2016149993A1 PCT/CN2015/078439 CN2015078439W WO2016149993A1 WO 2016149993 A1 WO2016149993 A1 WO 2016149993A1 CN 2015078439 W CN2015078439 W CN 2015078439W WO 2016149993 A1 WO2016149993 A1 WO 2016149993A1
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arabinose
purity
raw material
gum arabic
polar
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鲍宗必
黄敏慧
张治国
杨启炜
苏宝根
邢华斌
任其龙
杨亦文
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C07H1/08—Separation; Purification from natural products

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  • the invention belongs to the technical field of chemical engineering, and particularly relates to a process for preparing high-purity L-arabinose from gum arabic. Specifically, a high-purity L-arabinose is extracted and isolated from gum arabic by a reaction separation step such as hydrolysis, neutralization, decolorization, adsorption, and crystallization.
  • a reaction separation step such as hydrolysis, neutralization, decolorization, adsorption, and crystallization.
  • L-arabinose As a new type of functional sugar, L-arabinose can be used as an intermediate in synthetic medicine. It can be used to synthesize anticancer, antiviral and cardiovascular diseases such as cytarabine and L-ribose, and can be used for biochemistry. Preparation of bacterial culture media in the field, as well as perfume synthesis. In addition, in recent years, it has been found that L-arabinose has a strong non-competitive function of inhibiting sucrose absorption, inhibits the increase of serum glucose concentration caused by sucrose absorption, prevents obesity, prevents and treats diseases associated with hyperglycemia, and Its application prospects in weight loss and diabetes control are widely optimistic.
  • L-arabinose has been approved by the US Food and Drug Administration (FDA) and the Japanese Ministry of Health and Welfare for inclusion in health food additives, and the American Medical Association has also included it as a nutritional supplement or over-the-counter for anti-obesity agents. It can be seen that L-arabinose has broad prospects in the pharmaceutical and food industries.
  • Natural L-arabinose is usually present in plant pulp, hemicellulose, pectic acid in the form of L-arabin, L-arabino-xylan and L-arabinan-D-galactose. At this stage, L-arabinose is mainly obtained by hydrolyzing a natural raw material and post-treating. Prior to the present invention, preparation of L-arabinose by hydrolysis of gum arabic has been reported in the following literature.
  • Chinese Patent Publication No. CN102146102A discloses a method for extracting L-arabinose and D-galactose from gum arabic. Acid-catalyzed hydrolysis of gum arabic, the neutralized solution obtained after neutralization of the alkali solution is concentrated, etherified with a ketone organic reagent to form an ether compound, and then the ether compound is extracted with an alcohol, and then ether is removed to obtain pure L-arabinose, respectively. And the yield of D-galactose and L-arabinose is 15% to 24% of the mass of the raw gum arabic.
  • This process can obtain two kinds of monosaccharides at the same time, but the process involves a large amount of organic solvents, which seriously pollutes the environment and is an environmentally unfriendly process. At the same time, the purity of the obtained crystals was not guaranteed.
  • S.Mukher jee and ANS Shrivastava uses Arab SUNDRA gel as a raw material, and after hydrolysis, it is separated by a large amount of semi-saturated aqueous solution of butanol as an eluent to obtain L-arabinose, D-galactose and rhamnose (J Sci. Ind. Research India, 1956, 168, 566-7).
  • the Chinese Patent Publication No. CN1373135A discloses a method for extracting L-arabinose from gum arabic by a two-column method.
  • the gum arabic is used as a raw material, hydrolyzed by a mineral acid, concentrated after alkali neutralization, and initially extracted with alcohol, 4 times the amount of acetic acid.
  • the hydrolysis mixed solution produced by the above method has high requirements for purification extraction technology, large consumption of organic solvent for elution separation, low concentration of L-arabinose after separation, high energy consumption when the fraction is concentrated, high cost, and is not suitable for industrial use. Mass production.
  • the Chinese patent publication No. CN101993826A discloses a selective enzymatic hydrolysis of gum arabic by a new strain produced by acabinase, Fusarium sp. BYB2, followed by a conventional separation and purification process to obtain a pure L.
  • the yield of arabinose and L-arabinose is 18% of the mass of the raw gum arabic.
  • the advantage of enzymatic hydrolysis is that the reaction conditions are mild and the equipment losses are low.
  • this method has the disadvantages that the parameter controllability is not strong and the efficiency of enzyme hydrolysis is low, and it is difficult to industrialize production.
  • the invention provides a process for extracting high-purity L-arabinose by using gum arabic as raw material, and finally purifying L-arabinose with a purity of more than 98%, and the yield is up to 25% of the mass of the original raw gum arabic. ⁇ 29%.
  • the basic principle of the whole process is low cost, green and environmental protection, and the section is simple, reliable and easy to operate, and is suitable for industrial scale production.
  • a process for extracting high-purity L-arabinose by using gum arabic as raw material comprising the following steps:
  • the aqueous alkali solution is sodium hydroxide solution, potassium hydroxide solution, sodium carbonate solution And a combination of one or any combination of potassium carbonate solutions having a molar concentration of 10 to 20 mol/L.
  • sodium hydroxide having a molar concentration of 15 mol/L, which is inexpensive and readily available, and has been widely used in industry.
  • the inorganic acid is one or a combination of sulfuric acid, hydrochloric acid, and phosphoric acid, and the hydrogen ion has a molar concentration of 1 to 6 mol/L.
  • the hydrolysis reaction time is preferably from 1 to 5 hours, more preferably from 1 to 3 hours, and the hydrolysis time is not too long, so as to solve the excessive separation of the sugar, which is disadvantageous for subsequent separation.
  • the solid-liquid ratio solid-liquid ratio when the gum arabic dissolves
  • the dissolution rate of gum arabic is slow, which is not conducive to uniform stirring, and the concentration of arabinose and sugar in the hydrolyzate is increased, which is not conducive to subsequent separation and purification treatment.
  • the solid-liquid ratio is too small, the viscosity of the hydrolyzate is small, which can bring convenience to filtration, stirring, etc., but increases the energy consumption and time of subsequent concentration, and reduces production efficiency. Therefore, when the gum arabic is dissolved, the solid-liquid ratio is preferably 1 kg: (8 to 12) L.
  • the hydrolysis conditions in the step (1) are: sulfuric acid having a hydrogen ion molar concentration of 1 to 2 mol/L is hydrolyzed at 90 to 100 ° C for 1 to 3 hours, and the solid to liquid ratio of the gum arabic is 1:10.
  • the gum arabic is difficult to dissolve in cold water, and should be pulverized to a certain extent. After being dissolved in hot water, the acid solution is added to increase the heat efficiency and shorten the hydrolysis time.
  • the adsorbent A is a granular activated carbon, a nonpolar macroporous polystyrene adsorption resin, a weakly polar macroporous polystyrene adsorption resin, a nonpolar macroporous acrylic adsorption resin, and a weak Polar macroporous acrylic adsorption resin, non-polar gel polystyrene acid adsorption resin, weakly polar gel polystyrene acid adsorption resin, nonpolar gel type acrylic adsorption resin, and weak Any one of polar gel type acrylic adsorption resins.
  • the above adsorbent has good adsorption selectivity to the pigment in the hydrolyzate, has good decolorization effect, and has fast adsorption rate, the target recovery rate is above 95%, and the decolorization rate is above 95%.
  • the above adsorbent itself has stable physical and chemical properties, high mechanical strength, easy regeneration, and high recyclability.
  • the adsorbent A is a granular activated carbon, a non-polar macroporous polystyrene-based adsorption resin, or a non-polar macroporous acrylic-based adsorption resin.
  • the granular activated carbon is preferably activated carbon of 200 to 400 mesh.
  • the cumulative volume of the hydrolysis neutralization solution is 2 to 12 times the volume of the fixed bed.
  • the decoloring condition in this step is: temperature 20-40 ° C, hydrolysis neutralization flow rate is 0.5-3 Bed / hour.
  • the decolorization temperature should not be too high, the rate of pigment adsorption and desorption is increased, and the pigment removal ability is poor.
  • the decoloring conditions in the step (2) are: a temperature of 25 to 30 ° C and a flow rate of 0.8 to 1.5 beds per hour.
  • the decoloring liquid obtained in the step (2) is passed through a microporous membrane to obtain a pretreatment liquid, and the pretreatment liquid is subjected to electrodialysis desalination to obtain a desalting liquid.
  • the electrodialysis desalination process in the step (3) is as follows:
  • the pretreatment liquid and the pure water are respectively used as the dense phase and the dilute phase, and the Na 2 SO 4 solution is used as the polar water.
  • the pretreatment liquid, the pure water and the polar water are respectively in the concentrated chamber, the rare chamber and the polar chamber. Cycle, control flow rate, desalt for 2 to 5 hours at a constant operating voltage.
  • the pore size of the aqueous microfiltration membrane was 0.45 ⁇ m.
  • the concentration of recharge salt should not be too high, which will cause certain corrosion loss to the electrodialysis instrument.
  • the Na 2 SO 4 solution has a mass fraction concentration of 3% to 8%, and the volume ratio of the polar water, the pretreatment liquid, and the pure water is 0.25:1:1 to 3.
  • the electrodialysis conditions in the step are: an operating voltage of 20 to 30 V, and a liquid flow rate of 10 to 30 L/h.
  • the desalination method has the advantages of large processing capacity, high efficiency, low acid-base consumption, small amount of waste water, controllable desalination conditions, and the like, and the device has compact structure, beautiful appearance and reasonable occupation area. This method is clearly superior to conventional ion exchange or reverse osmosis desalination processes.
  • the desalting step is:
  • the desalting liquid obtained in the step (2) is passed through a 0.45 ⁇ m aqueous microporous membrane to obtain a pretreatment liquid, and the mass fraction concentration is 3% to 8%.
  • the Na 2 SO 4 solution is polar water, driven by a pump, pretreatment liquid, pure water.
  • the polar water is circulated in the concentrated chamber, the dilute chamber and the polar chamber respectively, and the flow rate is controlled at 20 L/h.
  • the salt is desalted under a constant operating voltage (25 V) for 2.5 hours, and the volume ratio of the polar water, the pretreatment liquid and the pure water is 0.25:1. : 1 to 3.
  • the adsorbent B is a non-polar macroporous polystyrene-based adsorption resin, a non-polar macroporous acrylic-based adsorption resin, a non-polar gel-type polystyrene acid-based adsorption resin, and a non-polar Any one of a gel type acrylic adsorption resin, granular activated carbon, silica gel bonded with C 18 , and silica gel bonded with C 30 .
  • the above adsorbents have high selectivity to arabinose and other heterosaccharides, and have large adsorption capacity, and the recovery rate of arabinose obtained is above 85%. Moreover, the above adsorbent has high mechanical strength and is easy to regenerate.
  • the adsorbent B is a granular activated carbon, a non-polar macroporous polystyrene-based adsorption resin, or a non-polar macroporous acrylic-based adsorption resin.
  • the concentration of the solid solution (desalting solution) in the step is 75 mg/mL to 120 mg/mL, and the desalting solution obtained in the step (3) is added at a flow rate of 0.5 to 1.5 BV/h to collect the effluent.
  • a desalting solution of 6 to 7 BV is preferred, and the flow rate is 0.8 to 1.5 BV/h.
  • the water content in the syrup obtained by concentrating under reduced pressure in the step (4) is from 60% to 200%.
  • the supersaturated syrup obtained in (4) is thermally dissolved with alcohol, and then gradually cooled to room temperature, and then added to the arabinose seed crystal to induce crystallization, cooled and crystallized for 24 to 72 hours, filtered, and vacuum dried at 50 to 60 ° C to obtain a purity of up to 98. More than % of L-arabinose white powder.
  • the alcohol is methanol or ethanol, and the ratio of the added amount to the supersaturated syrup is (6 to 10) L: 1 kg.
  • the cooling temperature of the gradual cooling is 0.2 to 3 ° C / min, and the crystallization temperature is -5 to 10 ° C.
  • the hot melt process is as follows:
  • the supersaturated syrup is dissolved in a methanol or ethanol solution having a volume percentage of 70% to 90% at 60-85 ° C, and the volume ratio of the methanol or ethanol solution and the super-saturated syrup is 1:6 to 1:10, and heated under reflux. 1 to 3 hours, preferably 70% to 80% of ethanol, and the volume ratio is 1:7 to 1:8.
  • the arabinose seed crystal is added to induce crystallization, and it is allowed to crystallize in the environment of -5 to 10 ° C for 24 to 72 h, further preferably 0 to 5 ° C, and crystallize for 48 to 56 h.
  • the recovery rate and purity in the present invention are calculated as follows:
  • Recovery rate mass of L-arabinose in solution / quality of L-arabinose in solution before treatment
  • Purity mass of L-arabinose in the treatment liquid / total mass of solids in the treatment liquid
  • a solution having a solid concentration of 75 to 120 mg/mL means that each ml of the solution is concentrated to a mass of 75 to 120 mg of solid matter. Since the composition of the solution is complicated, there is a certain insoluble matter, and the total mass is referred to as the whole. The total mass of the system, including the quality of the suspension or precipitation.
  • Bed volume refers to the volume of the bed packed with activated carbon adsorbent in the fixed bed adsorption column in steps (2) and (4).
  • BV/h The mobile phase flows through the bed volume of the fixed bed adsorbent in (2) and (4) per hour.
  • the process of the invention is green and environmentally friendly, and the arabin gum with the highest L-arabinose content and low cost is used as raw material, and by integrating a plurality of high-efficiency separation unit operations, gum arabic is hydrolyzed with inorganic acid to obtain a hydrolyzate containing arabinose.
  • the adsorption capacity of activated carbon on the pigment is stronger than that of arabinose, and the pigment is selectively adsorbed to achieve the decolorization effect. Further electrodialysis desalination facilitates the subsequent separation and purification process.
  • the interaction between the steps makes the high-purity L-arabinose with a purity of more than 98% finally obtained, and the whole process is easy to realize, and the parameters are easy to control.
  • the beneficial effects of the invention are that the provided process route has the advantages of less three wastes, simple process, high yield, low production cost, suitable for large-scale production, etc., and has obvious commercial implementation value and economy. benefit.
  • Figure 1 is an HPLC chromatogram of the product obtained in Example 1 of the present invention.
  • Example 2 is a photograph of a photograph of the prepared high-purity L-arabinose crystals in Example 1 of the present invention.
  • reaction time was counted from the start of the addition of sulfuric acid, and the stirring and heating were stopped after 1 hour of reaction, and then the hydrolyzate was transferred to a 2 liter Erlenmeyer flask and sealed, and then rapidly cooled by a cold water bath to terminate the reaction.
  • a total of 537 mL of the feed liquid was obtained, the arabinose was 23.42 g, and the purity was 51%.
  • Neutralize to pH 7 with 15 M NaOH.
  • reaction time was counted from the addition of sulfuric acid, and the stirring and heating were stopped after 3 hours of reaction, and then the hydrolyzate was transferred to a 2 liter Erlenmeyer flask and sealed, and then rapidly cooled by a cold water bath to terminate the reaction.
  • a total of 523 mL of the feed liquid was obtained, the arabinose was 19.23 g, and the purity was 49%.
  • Neutralize to pH 7 with 15 M NaOH.
  • Adsorption separation The feed liquid was added to a fixed bed of activated carbon containing 200 to 400 mesh (high 25.0 cm, inner diameter 1.0 cm) by wet filling, and compacted with a large flow rate of pure water.
  • the bed volume (BV) of the activated carbon column used was 20 mL, and the flow rate was 0.4 mL/min, that is, 1.2 BV/hr.
  • the effluent of 3-9 BV was collected to obtain 354 mL of solution, and the arabinose was 13.75 g.
  • the recovery rate at this stage was about 86%, and the purity was increased by 88%.
  • UHPLC analysis method was established by using American Dion D3000 ultra performance liquid chromatography
  • the instrument is an electrochemical spray detector (CAD); the column is: GRACE Prevail Carbohydrate ES (250 mm ⁇ 4.6 mm, 5 ⁇ m); the amount of liquid: 5 ⁇ L; the mobile phase is acetonitrile-water (75:25, v/v); Flow rate: 1 mL/min; column temperature: 30 °C.
  • CAD electrochemical spray detector
  • the column is: GRACE Prevail Carbohydrate ES (250 mm ⁇ 4.6 mm, 5 ⁇ m); the amount of liquid: 5 ⁇ L; the mobile phase is acetonitrile-water (75:25, v/v); Flow rate: 1 mL/min; column temperature: 30 °C.

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Abstract

一种以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺：以阿拉伯胶为原料经酸水解、碱中和、吸附脱色、电渗析脱盐、吸附分离去杂质以及结晶，最终纯化得到纯度达98％以上的L-阿拉伯糖，且收率可达最初原料阿拉伯胶质量的25％～29％。整个工艺的基本原则是低成本、绿色环保，且工段简单可靠、易操作，适应于工业规模化生产。

Description

一种以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺 技术领域
本发明属于化学工程技术领域，特别涉及到一种以阿拉伯胶为原料制备高纯度L-阿拉伯糖的工艺。具体而言，是利用水解、中和、脱色、吸附及结晶等反应分离工序，从阿拉伯胶中提取分离得到高纯度的L-阿拉伯糖。
背景技术
L-阿拉伯糖作为一种新型的功能性糖，可作为合成医药的中间体，可用来合成阿糖胞苷、L-核糖等抗癌、抗病毒和治疗心血管疾病的药物，并可用于生化领域中细菌培养基的制备以及香料合成等。此外，近年来发现L-阿拉伯糖具有很强的非竞争性抑制蔗糖吸收的功能，能够抑制吸收蔗糖引起的血清中葡萄糖浓度升高，可以预防肥胖、预防并治疗与高血糖有关的疾病，使得它在减肥、控制糖尿病等方面的应用前景被广泛看好。L-阿拉伯糖已被美国食品药品监督管理局(FDA)和日本厚生省批准列入健康食品添加剂，美国医疗协会也将其列入抗肥胖剂的营养补充剂或非处方药。由此可见，L-阿拉伯糖在医药、食品行业具有广泛的前景。
天然的L-阿拉伯糖通常以L-阿拉伯聚糖、L-阿拉伯-木聚糖和L-阿拉伯聚糖-D-半乳糖等形式存在于植物果浆、半纤维素、果胶酸中。现阶段，L-阿拉伯糖主要通过水解天然原料并进行后处理来获得，在本发明之前，以阿拉伯胶水解制备L-阿拉伯糖有如下文献报道制备方法。
公开号为CN102146102A的中国专利文献公开了一种从阿拉伯胶中提取L-阿拉伯糖和D-半乳糖的方法。用酸催化水解阿拉伯胶，碱液中和后得到的中和液浓缩后用酮类有机试剂醚化生成醚化物，再用醇萃取醚化物，再脱醚，从而分别获得纯的L-阿拉伯糖和D-半乳糖，L-阿拉伯糖的收率为原料阿拉伯胶质量的15％～24％。此工艺能同时得到两种单糖，但工艺过程涉及大量有机溶剂，严重污染环境，是环境非友好型工艺。同时，所得晶体纯度未能达到保证。
S.Mukher jee and A.N.S Shrivastava以阿拉伯SUNDRA胶为原料，水解后用大量丁醇的半饱和水溶液为洗脱液进行柱分离，得到L-阿拉伯糖、D-半乳糖和鼠李糖(J Sci.Ind.Research India,1956,168,566-7)。公开号为CN1373135A中国专利文献公开了利用两柱法从阿拉伯胶提取L-阿拉伯糖的方法，以阿拉伯胶为原料，经无机酸水解，碱中和后浓缩，醇初提取，4倍量乙酸热熔提纯，再用正丁醇、乙酸乙酯、异丙醇、乙酸等有机溶剂结合双柱分离制得纯度为96％～99.5％的L-阿拉伯糖，收率为原料阿拉伯胶质量的16％～18％。EP0115068欧洲专利文献公开了一种以阿拉伯PYCNANTHA胶为原料制备L-阿拉伯糖的工艺，将原料用酸水解，用阴离子IR-4B(OH)树脂中和，乙醇萃取，再用大量乙酸乙酯半饱和液结合柱分离以制备L-阿拉伯糖及其衍生物。上述方法所产生的水解混合溶液对精制提取技术要求高，用于洗脱分离的有机溶剂消耗大，分离后L-阿拉伯糖浓度低，馏分浓缩时的能耗大，成本高，并不适合工业大规模生产。
公开号为CN101993826A的中国专利文献公开了一种以阿拉伯胶酶产生的新菌株-镰刀菌(Fusarium sp.)BYB2进行选择性酶水解阿拉伯胶，后续采用传统的分离纯化工艺，从而得到纯的L-阿拉伯糖，L-阿拉伯糖的收率为原料阿拉伯胶质量的18％。酶催化水解的优点是反应条件温和，对设备损耗较低。但该方法存在参数可控性不强以及酶水解的效率低下的缺点，难以工业化生产。
发明内容
本发明提供了一种以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，最终纯化得到了纯度达98％以上的L-阿拉伯糖，且收率可达最初原料阿拉伯胶质量的25％～29％。整个工艺的基本原则是低成本、绿色环保，且工段简单可靠、易操作，适应于工业规模化生产。
一种以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，包括如下步骤：
(1)水解：将阿拉伯胶溶解后加入无机酸，控制混合溶液的pH值至0.2～1，在70～100℃进行水解反应，反应结束后向反应液中加碱水溶液中和至pH值4～7，得含有阿拉伯糖的水解中和液。
优选地，所述碱水溶液为氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液 和碳酸钾溶液中的一种或任意几种组合，其摩尔浓度为10～20mol/L。进一步优选氢氧化钠，其摩尔浓度为15mol/L，价廉易得，且已广泛应用于工业。
优选地，所述无机酸为硫酸、盐酸、磷酸中的一种或两种组合，氢离子摩尔浓度为1～6mol/L。
所述水解反应时间优选1～5小时，进一步优选为1～3h，水解时间不宜太长，以防水解出过多的杂糖，不利于后续分离。
当固液比(阿拉伯胶溶解时的固液比)过大，阿拉伯胶溶解速度慢，不利于均匀搅拌，水解液中阿拉伯糖和杂糖浓度均提高，不利于后续分离纯化处理。当固液比过小，水解液的粘度小，虽能给过滤、搅拌等操作带来方便，但增加后续浓缩的能耗和时间，降低生产效率。因此，阿拉伯胶溶解时优选固液比为1kg:(8～12)L。
进一步优选，步骤(1)中的水解条件为：氢离子摩尔浓度为1～2mol/L的硫酸在90～100℃下水解1～3h，阿拉伯胶溶解时固液比1:10。
所述的阿拉伯胶较难溶解于冷水，应先进行一定程度的粉碎，用热水溶解后再加入酸溶液，提高热效率，缩短水解时间。
(2)脱色：将步骤(1)所得水解中和液连续通过装有吸附剂A的固定床，收集流出液为脱色液。
优选地，所述吸附剂A为颗粒活性炭、非极性大孔型聚苯乙烯系吸附树脂、弱极性大孔型聚苯乙烯系吸附树脂、非极性大孔型丙烯酸系吸附树脂、弱极性大孔型丙烯酸系吸附树脂、非极性凝胶型聚苯乙烯酸系吸附树脂、弱极性凝胶型聚苯乙烯酸系吸附树脂、非极性凝胶型丙烯酸系吸附树脂和弱极性凝胶型丙烯酸系吸附树脂中的任意一种。
以上吸附剂对水解液中的色素具有良好的吸附选择性，脱色效果好，且吸附速率快，目标物回收率在95％以上，脱色率在95％以上。另外，以上吸附剂本身物化性质稳定，机械强度高，易于再生，可循环利用性高。
进一步优选，所述吸附剂A为颗粒活性炭、非极性大孔型聚苯乙烯系吸附树脂或非极性大孔型丙烯酸系吸附树脂。所述颗粒活性炭优选为200～400目的活性炭。
水解中和液累积通入体积为固定床体积的2～12倍。
优选地，该步骤中脱色条件为：温度20～40℃，水解中和液流速为0.5～3 床层/小时。
脱色温度不宜太高，色素吸附脱附速率均增大，色素脱除能力差。
因此进一步优选，步骤(2)中脱色条件为：温度25～30℃，流速为0.8～1.5床层/小时。
(3)脱盐：将步骤(2)所得脱色液过水系微孔滤膜得预处理液，将所述预处理液进行电渗析脱盐得脱盐液。
步骤(3)中所述电渗析脱盐过程如下：
以预处理液和纯水分别作为浓相和稀相，用Na2SO4溶液作为极水，在泵的驱动下，预处理液、纯水、极水分别在浓室、稀室、极室循环，控制流速，在恒定的操作电压下脱盐2～5小时。
所述水系微孔滤膜的孔径为0.45μm。
补给盐浓度不宜过高，会对电渗析仪器造成一定腐蚀损耗。纯水所用量越大，除盐效率越大，但后续的废水量体积较大，回收处理能耗较大，因此纯水用量不宜太大。优选地，所述Na2SO4溶液质量分数浓度为3％～8％，极水、预处理液和纯水的体积比为0.25:1:1～3。
优选地，该步骤中电渗析条件为：操作电压20～30V，各液体流量为10～30L/h。
此除盐方式具有处理量大、效率高、酸碱消耗少、废水量小、除盐条件可控等优点，同时，设备结构紧凑、美观合理，占地面积小。该方法明显优于传统的离子交换或反渗透脱盐工艺。
最优选地，所述脱盐步骤为：
将步骤(2)所得脱盐液过0.45μm水系微孔膜得预处理液，质量分数浓度为3％～8％Na2SO4溶液为极水、在泵的驱动下，预处理液、纯水、极水分别在浓室、稀室、极室循环，控制流速20L/h，在恒定的操作电压(25V)下脱盐2.5小时，极水、预处理液和纯水的体积比为0.25:1:1～3。
(4)吸附分离：将步骤(3)所得脱盐液在室温下通过装有吸附剂B的固定床，收集洗脱液，将所述洗脱液于45～60℃减压浓缩得过饱和糖浆。
优选地，所述吸附剂B为非极性大孔型聚苯乙烯系吸附树脂、非极性大孔型丙烯酸系吸附树脂、非极性凝胶型聚苯乙烯酸系吸附树脂、非极性凝胶型丙烯酸系吸附树脂、颗粒活性炭、键合有C18的硅胶和键合有C30的硅胶中的任意一种。
以上吸附剂对阿拉伯糖和其他杂糖有很高的选择性，吸附容量大，得到的阿拉伯糖的回收率在85％以上。且以上吸附剂机械强度大，易于再生。
进一步优选，所述吸附剂B为颗粒活性炭、非极性大孔型聚苯乙烯系吸附树脂或非极性大孔型丙烯酸系吸附树脂。
优选地，该步骤中上样液(脱盐液)固形物浓度为75mg/mL～120mg/mL，取步骤(3)所得脱盐液5～8BV以0.5～1.5BV/h的流速加入，收集流出液。优选6～7BV的脱盐液，流速为0.8～1.5BV/h。
步骤(4)中减压浓缩得到的糖浆中的含水量为60％～200％。
(5)结晶：将步骤(4)所得过饱和糖浆经结晶、干燥处理得L-阿拉伯糖白色粉末。
步骤(5)所述结晶、干燥过程如下：
将(4)得到的过饱和糖浆用醇进行热溶，再逐步降温至室温后，加入阿拉伯糖晶种进行诱导结晶，冷却结晶24～72小时后过滤，50～60℃真空干燥得到纯度高达98％以上的L-阿拉伯糖白色粉末。
所述醇为甲醇或乙醇，加入量和过饱和糖浆的比例为(6～10)L:1kg。
逐步降温的降温幅度为0.2～3℃/min，结晶温度为-5～10℃。
所述热熔过程如下：
过饱和糖浆在60～85℃下溶于体积百分浓度为70％～90％的甲醇或乙醇溶液中，甲醇或乙醇溶液和过饱和糖浆体积比例为1:6～1:10，加热回流的1～3h，优选70％～80％的乙醇，体积比例为1:7～1:8。
进一步优选，该步骤中得到溶液自然冷却后，加入阿拉伯糖晶种进行诱导结晶，并放至-5～10℃环境下结晶24～72h，进一步优选0～5℃，结晶48～56h。
本发明中的回收率和纯度的计算方法如下：
回收率＝处理后溶液中L-阿拉伯糖质量/处理前溶液中L-阿拉伯糖质量
纯度＝处理液中L-阿拉伯糖的质量/处理液中固形物的总质量
本发明中所涉及到的术语意义具体解释如下：
固形物浓度为75～120mg/mL的溶液，是指每毫升溶液浓缩至质量不变时含有75～120mg固形物，由于溶液成分复杂，会有一定的不溶物质，计算总质量时指的是整个体系的总质量，包括悬浮或沉淀的质量。
BV：床层体积，指步骤(2)、(4)中固定床吸附柱中活性炭吸附剂装填的床层体积。
BV/h：流动相每小时流过(2)、(4)中固定床吸附剂的床层体积数。
本发明的工艺流程绿色环保，以L-阿拉伯糖含量最高且价廉的天然产物阿拉伯胶为原料，通过集成多种高效的分离单元操作，阿拉伯胶用无机酸水解得到含有阿拉伯糖的水解液，利用活性炭对色素的吸附能力强于阿拉伯糖的特点，选择性吸附色素，达到脱色效果，进一步电渗析脱盐方便后续分离及纯化过程。各步骤间共同作用使最终得到了纯度达98％以上的高纯度L-阿拉伯糖，整个工艺易于实现，参数便于控制。
与现有技术相比，本发明的有益效果是所提供的工艺路线具有产生三废少、工艺简单、收率高、生产成本低、适合大规模化生产等优点，具有明显的商业实施价值和经济效益。
附图说明
图1为本发明实施例1中所得产品的HPLC色谱图；
图2为本发明实施例1提取制备的高纯度L-阿拉伯糖晶体的实物照片。
具体实施方式
下面结合高纯度L-阿拉伯糖的制备方法和测试结果对本发明进一步说明。
实施例1
(1)水解：取1000mL圆底三口烧瓶，加入350mL去离子水。采用油浴加热使温度上升至80℃，加入约50g阿拉伯胶，开动磁力搅拌(转速＝300～400rpm)至阿拉伯胶溶解，并继续加热至90℃，此时加入经预热的150mL H2SO4溶液(浓度1mol/L，即用移液管量取50mL 50％发烟硫酸再加水定容至1L)，上述过程温度会小幅下降，约降至74～78℃，最终反应液中硫酸浓度＝0.3mol/L(pH＝0.51)。反应时间从加入硫酸开始计时，反应1小时即停止搅拌和加热，随后水解液转移至2升锥形瓶中并密封，再用冷水浴迅速冷却以终止反应。共得到537mL料液，阿拉伯糖为23.42g， 纯度为51％。用15M NaOH中和至pH＝7。
(2)脱色：将料液加入到装有200～400目的活性炭固定床中(高30.0cm，内径1.5cm)采用湿法装填，并经大流速纯水压实。所用活性炭柱床层体积(BV)＝53mL，上柱过程，流速为1.32mL/min，即1.5BV/h。收集所有流出液，为506mL脱色液，阿拉伯糖为21.1g，此阶段的回收率高达90％。
(3)脱盐：将得到的脱色液过0.45μm水膜，再加入到电渗析槽中，用5wt％Na2SO4作为极水，电渗析条件为：电压25V、各物料流量为20L/h。其中，极水、预处理液和纯水的体积比为0.25:1:1。电渗析脱盐2.5小时至淡化室电导率由最初的11.2mS/cm降低到340μS/cm，导出料液为481mL，阿拉伯糖为19.51g，此工艺操作回收率约为92％，纯度提高至60％。(4)吸附分离：将料液加入到装有200～400目的活性炭固定床中(高25.0cm，内径1.0cm)采用湿法装填，并经较大流速纯水压实。所用活性炭柱床层体积(BV)＝20mL，上柱过程，流速为0.5mL/min，即1.5BV/hr。收集4～11BV的流出液，得到371mL溶液，阿拉伯糖为16.71g，此阶段回收率约为85％，纯度提高88％。
(5)结晶：取步骤(4)得到的流出液减压蒸馏至糖浆，加入80％的乙醇溶液，糖浆与乙醇溶液固液比为1:8，92℃水浴加热回流3h。自然回流冷却至室温，加入少量阿拉伯胶晶体，放入5℃冰箱中冷却结晶56h后，过滤，滤饼用适量无水乙醇冲洗，滤液经浓缩回收溶剂后循环至步骤(4)加以套用。充分抽干后，放入真空干燥箱中25℃干燥4h，得14.51g，纯度为98.5％，以最初水解液中L-阿拉伯糖为基准，整个工艺L-阿拉伯糖的回收率为62％，质量为最初阿拉伯胶投料量的29％，所得产品的HPLC色谱图如图1所示，实物图片如图2所示。
实施例2
(1)水解：取1000mL圆底三口烧瓶，加入450mL去离子水。采用油浴加热使温度上升至80℃，加入约40g阿拉伯胶，开动磁力搅拌(转速＝300～400rpm)至阿拉伯胶溶解，并继续加热至90℃，此时加入经预热的50mL H2SO4溶液(浓度1mol/L，即用移液管量取50mL 50％发烟硫酸再加水定容至1L)，上述过程温度会小幅下降，约降至74～78℃，最终反应液 中硫酸浓度＝0.1mol/L(pH＝0.70)。反应时间从加入硫酸开始计时，反应3小时即停止搅拌和加热，随后水解液转移至2升锥形瓶中并密封，再用冷水浴迅速冷却以终止反应。共得到523mL料液，阿拉伯糖为19.23g，纯度为49％。用15M NaOH中和至pH＝7。
(2)脱色：将料液加入到装有200～400目的非极性大孔型聚苯乙烯系吸附树脂固定床中(高25.0cm，内径1.5cm)采用湿法装填，并经大流速纯水压实。所用活性炭柱床层体积(BV)＝44mL，上柱过程，流速为0.75mL/min，即1BV/h。收集所有流出液，为502mL脱色液，阿拉伯糖为17.56g，此工艺回收率高达91％。
(3)脱盐：将得到的脱色液过0.45μm水膜，再加入到电渗析槽中，用5wt％Na2SO4作为极水，电渗析条件为：电压25V、各物料流量为15L/h。电渗析脱盐2小时至淡化室电导率由最初的10.05mS/cm降低到278μS/cm，导出料液为475mL，阿拉伯糖为15.94g，此阶段回收率约为91％，纯度提高62％。
(4)吸附分离：将料液加入到装有200～400目的活性炭固定床中(高25.0cm，内径1.0cm)采用湿法装填，并经大流速纯水压实。所用活性炭柱床层体积(BV)＝20mL，上柱过程，流速为0.4mL/min，即1.2BV/hr。收集3～9BV的流出液，得到354mL溶液，阿拉伯糖为13.75g，此阶段回收率约为86％，纯度提高88％。
(5)结晶：取将得到的流出液减压蒸馏至糖浆，加入80％的乙醇溶液，糖浆与乙醇溶液固液比为1:8，92℃水浴加热回流3h。自然回流冷却至室温，加入少量阿拉伯胶晶体，放入5℃冰箱中冷却结晶56h后，过滤，滤饼用适量无水乙醇冲洗,滤液经浓缩回收溶剂后循环至步骤(4)加以套用。充分抽干后，放入真空干燥箱中25℃干燥4h，得11.45g，纯度为98.2％，以最初水解液中L-阿拉伯糖为基准，整个工艺L-阿拉伯糖的回收率为60％，质量为最初阿拉伯胶投料的28％。
L-阿拉伯糖浓度测定方法
以上实施例均采用以下方法测试L-阿拉伯糖、D-半乳糖、鼠李糖等各单糖浓度。
采用美国戴安D3000超高效液相色谱仪建立UHPLC分析方法，检测 器为电化学喷雾检测器(CAD)；色谱柱为：GRACE Prevail Carbohydrate ES(250mm×4.6mm,5μm)；进液量：5μL；流动相为乙腈-水(75:25,v/v)；流速：1mL/min；柱温：30℃。
各单糖线性范围：
阿拉伯糖：0.5～4g/L；半乳糖：0.1～1g/L；鼠李糖：0.1～1.5g/L
各单糖标准曲线：
阿拉伯糖：y＝0.0036x2+0.2665x，R2＝0.9991；半乳糖：y＝0.0017x2+0.1329x，R2＝0.9998；鼠李糖：y＝0.0014x2+0.0331x，R2＝0.9995。x——峰面积，y——浓度。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，包括如下步骤：
    (1)将阿拉伯胶溶解后加入无机酸，控制混合溶液的pH值至0.2～1，在70～100℃进行水解反应，反应结束后向反应液中加碱水溶液中和至pH值4～7，得含有阿拉伯糖的水解中和液；
    (2)将步骤(1)所得水解中和液连续通过装有吸附剂A的固定床，收集流出液为脱色液；
    (3)将步骤(2)所得脱色液过水系微孔滤膜得预处理液，将所述预处理液进行电渗析脱盐得脱盐液；
    (4)将步骤(3)所得脱盐液在室温下通过装有吸附剂B的固定床，收集洗脱液，将所述洗脱液于45～60℃减压浓缩得过饱和糖浆；
    (5)将步骤(4)所得过饱和糖浆经结晶、干燥处理得L-阿拉伯糖白色粉末。
  2. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述无机酸为硫酸、盐酸、磷酸中的一种或两种组合，氢离子摩尔浓度为1～6mol/L。
  3. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述水解反应时间为1～5小时。
  4. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述吸附剂A为颗粒活性炭、非极性大孔型聚苯乙烯系吸附树脂、弱极性大孔型聚苯乙烯系吸附树脂、非极性大孔型丙烯酸系吸附树脂、弱极性大孔型丙烯酸系吸附树脂、非极性凝胶型聚苯乙烯酸系吸附树脂、弱极性凝胶型聚苯乙烯酸系吸附树脂、非极性凝胶型丙烯酸系吸附树脂和弱极性凝胶型丙烯酸系吸附树脂中的任意一种。
  5. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，步骤(2)中脱色条件为：温度20～55℃，水解中和液的流速为0.5～3床层/小时。
  6. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述电渗析脱盐过程如下：
    以预处理液和纯水分别作为浓相和稀相，用Na2SO4溶液作为极水，在泵的驱动下，预处理液、纯水、极水分别在浓室、稀室、极室循环，控制流速，在恒定的操作电压下脱盐2～5小时。
  7. 根据权利要求6所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述Na2SO4溶液质量分数为3％～8％，预处理液和纯水的体积比为1:1～3。
  8. 根据权利要求6所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，电渗析条件为：操作电压20～30V，各液体流量为10～30L/h。
  9. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述吸附剂B为非极性大孔型聚苯乙烯系吸附树脂、非极性大孔型丙烯酸系吸附树脂、非极性凝胶型聚苯乙烯酸系吸附树脂、非极性凝胶型丙烯酸系吸附树脂、颗粒活性炭、键合有C18的硅胶和键合有C30的硅胶中的任意一种。
  10. 根据权利要求1所述以阿拉伯胶为原料提取制备高纯度L-阿拉伯糖的工艺，其特征在于，所述结晶、干燥过程如下：
    将步骤(4)得到的过饱和糖浆用醇热溶，逐步降温至室温后，加入阿拉伯糖晶种进行诱导结晶，冷却结晶24～72小时后过滤，50～60℃真空干燥得到纯度高达98％以上的L-阿拉伯糖白色粉末；
    所述醇为甲醇或乙醇，加入量和过饱和糖浆的比例为(6～10)L:1kg，逐步降温的降温幅度为0.2～3℃/min，结晶温度为-5～10℃。
PCT/CN2015/078439 2015-03-24 2015-05-07 一种以阿拉伯胶为原料提取制备高纯度l-阿拉伯糖的工艺 Ceased WO2016149993A1 (zh)

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CN106589010B (zh) * 2016-12-16 2019-07-19 南京凯通粮食生化研究设计有限公司 一种同时生产l-阿拉伯糖和d-半乳糖的方法
WO2023130594A1 (zh) 2022-01-06 2023-07-13 唐传生物科技（厦门）有限公司 一种阿拉伯糖及其制剂和用途
JP2026502722A (ja) * 2023-02-03 2026-01-23 唐伝生物科技（廈門）有限公司 Ｌ－アラビノースの不純物制御方法及びその使用

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