WO2019080017A1 - 一种制备高纯度低危害的番茄红素晶体的方法 - Google Patents

一种制备高纯度低危害的番茄红素晶体的方法

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Publication number
WO2019080017A1
WO2019080017A1 PCT/CN2017/107703 CN2017107703W WO2019080017A1 WO 2019080017 A1 WO2019080017 A1 WO 2019080017A1 CN 2017107703 W CN2017107703 W CN 2017107703W WO 2019080017 A1 WO2019080017 A1 WO 2019080017A1
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WIPO (PCT)
Prior art keywords
lycopene
alkane
crystals
solvent
lower alcohol
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PCT/CN2017/107703
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English (en)
French (fr)
Inventor
卢庆国
连运河
张志明
安晓东
李乾丽
高伟
Original Assignee
晨光生物科技集团股份有限公司
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Application filed by 晨光生物科技集团股份有限公司 filed Critical 晨光生物科技集团股份有限公司
Priority to EP17929720.5A priority Critical patent/EP3702412A4/en
Priority to CN201780096223.4A priority patent/CN111315830B/zh
Priority to PCT/CN2017/107703 priority patent/WO2019080017A1/zh
Priority to US16/758,899 priority patent/US11499052B2/en
Publication of WO2019080017A1 publication Critical patent/WO2019080017A1/zh
Priority to IL274216A priority patent/IL274216A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0096—Purification; Precipitation; Filtration
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources

Definitions

  • the invention relates to the field of industrial production of natural plant extracts, in particular to a method for preparing high purity and low hazard lycopene crystals.
  • Lycopene is a natural pigment contained in plants. It is mainly found in the mature fruits of the tomato family Solanaceae. At present, lycopene is mostly extracted from tomato pulp, and tomato skin with high lycopene content is used as waste material for ketchup production. If it can be used, it can not only become waste. Treasure, and can create huge social benefits.
  • Lycopene is a fat-soluble pigment and is not easily absorbed by the human body. At present, it is often used as a health product such as a capsule, a water-dispersible preparation, or a tablet. All need to protect the tomato red from being oxidized by embedding, and at the same time convert the fat-soluble lycopene into water-soluble, which is convenient for human body to absorb and utilize, but in order to ensure the stability of the embedded product, the raw material used for embedding Generally, crystals with relatively high purity are used, so that there is enough space to add wall materials. Currently, most of the lycopene sold on the market is about 15% lycopene oleoresin. Therefore, the preparation method of simple and feasible lycopene crystals needs to be developed. ,to satisfy the market's needs.
  • lycopene crystals In general, in the preparation method of lycopene crystals, most of them adopt single solvent, multiple crystals of trans, repeated recrystallization, and the process is long, which is not conducive to the preservation of lycopene, and most of the crystallization processes are obtained.
  • the purity of the lycopene crystal is too low, and it is difficult to reach more than 80%; and in the existing crystallization process, no one considers the removal of the benzopyrene which is a hazard.
  • the tomato red with low harm Crystals are not the demand of market development.
  • high-purity, low-hazard lycopene crystals need to be developed, and the process needs to be simple and easy to industrialize.
  • the method provided by the invention has the advantages of simple preparation process, high crystal purity, low hazard content, and the like, and is easy to realize industrial production.
  • the method provided by the present invention includes the following specific steps:
  • the method provided by the invention uses the mixed solvent to carry out crystallization, and the lycopene crystal can be obtained only by one-step crystallization; on the basis of obtaining the crystal, the multi-step washing method of washing with different solvents can not only improve the crystal purity, but also It can reduce the content of harmful substances in the crystal and prepare lycopene crystals with high purity and low harm.
  • the present invention employs a mixed solvent crystallization technique which is a mixture of an alkane and a lower alcohol Made up. Due to the complex composition of lycopene oleoresin, crystallization by a single solvent cannot ensure complete removal of impurities, and lycopene obtained by crystallization from a single solvent exhibits a paste shape due to the presence of other impurities, resulting in difficulty in separating crystals from solvents. It is necessary to use a centrifugal device with high separation factor to ensure complete separation of crystal and solvent. Further, in order to improve the purity of lycopene crystal, it takes 2 to 3 times to recrystallize in a single solvent to be able to convert most of lycopene oleoresin.
  • the removal of impurities not only takes a long time, but also requires a low temperature for crystallization, and consumes a large amount of energy. Moreover, since lycopene crystals are easily oxidized, a large amount of lycopene is oxidized and lost during multiple crystallization.
  • the present invention has found through a large number of practices that crystals of a mixed solvent composed of an alkane and a lower alcohol can dissolve most impurities and harmful substances in the crystal in a solvent, and the obtained crystals are in a powder form, and can be simply filtered. The crystals are completely separated from the impurities, and the crystals can be obtained by only one-step method, which not only shortens the time (the crystallization time is only 6 to 10 h), but also crystallizes at 15 to 25 °C.
  • the alkane used in the present invention is preferably one or more of n-hexane, cyclohexane, and No. 6 extracting solvent oil, and more preferably n-hexane.
  • the lower alcohol of the present invention specifically means an alcohol having 1 to 5 carbon atoms, preferably one or more of methanol, ethanol and isopropanol, and more preferably methanol.
  • the volume ratio of the alkane to the lower alcohol is preferably from 2:1 to 4:1, more preferably from 3:1 to 4: 1.
  • the present invention preferably has a mass to volume ratio of the lycopene oleoresin to the mixed solvent of from 4:1 to 8:1. More preferably, it is 6:1 - 8:1.
  • the temperature at which the heat is dissolved is preferably 35 to 60 ° C, and more preferably 55 to 60 ° C.
  • the heat is dissolved for 15 to 40 minutes, more preferably 30 to 40 minutes.
  • the temperature of the temperature-lowering crystallization is preferably 15 to 25 ° C, more preferably 20 to 25 ° C.
  • the time for the temperature-lowering crystallization is 6 to 10 hours, more preferably 6 to 8 hours.
  • the filter cake and the filtrate were obtained by filtration.
  • the filter cake is subjected to two-step washing and drying to obtain a desired product, and the filtrate is concentrated to obtain a low-content lycopene oleoresin.
  • the invention adopts a stepwise washing method to increase the purity of the crystal and reduce the content of the hazardous substance. Since tomato skin is a food skin, it itself contains benzopyrene which is much higher than tomato pulp, and the alkane solvent used for extracting lycopene is easy to dissolve benzopyrene, thus causing lycopene oleoresin extracted from tomato skin residue. Containing more benzopyrene, the present invention uses a mixed solvent to crystallize, and on the basis of ensuring that the crystal is crystallized from the oleoresin only by one step, most of the benzopyrene is left in the low-content oleoresin, and further different solvents are used. The method of multi-step washing is carried out to further reduce the content of benzopyrene in the lycopene after crystallization.
  • the present invention firstly washes the crystals with a polar alcohol solvent, and removes a part of the fatty impurities of the fatty acids, so that the washed crystals are no longer sticky and more loose, which is beneficial to the late alkane solvent to take away.
  • Benzopyrene in the crystal After the alcohol solvent is washed, the filter cake is washed with an alkane solvent of 15 to 25 ° C, preferably 20 to 25 ° C, which can not only take away the benzopyrene hazardous substances, but also does not cause the dissolution of the lycopene crystals.
  • the benzoxanthene content in the washed lycopene crystal can be reduced from about 100 ppm to less than 10 ppm, and the product purity can reach 80% to 95%.
  • the lower alcohol solvent used in the washing is preferably a lower alcohol aqueous solution within four carbons, preferably an aqueous ethanol solution; and the volume fraction of the lower alcohol aqueous solution is preferably 75 to 95%.
  • the alkane-based solvent used in the washing is preferably one or more selected from the group consisting of n-hexane, cyclohexane, and No. 6 solvent oil, and more preferably n-hexane.
  • the present invention preferably uses a filter cake wet weight of 2 to 5 times the volume of lower alcohol to rinse the filter cake to increase the crystal content, and then use the filter cake. 3 to 8 times the wet weight of 15 ⁇ 25 ° C alkane rinse filter cake, Further increase the crystal content while removing impurities such as benzopyrene.
  • Each solvent can be washed several times, that is, washed several times with an alcohol solvent and then washed several times with an alkane to ensure an optimum washing effect.
  • the drying according to the present invention is preferably carried out under vacuum at 30 to 60 °C.
  • the drying time is preferably 5 to 10 hours.
  • the whole crystallization route of the steps (1) to (3) is preferably completed in a fully enclosed device, that is, dissolved and crystallized. Washing and drying the "four-in-one" equipment, which can avoid contact with the outside world during the crystallization process, cause lycopene oxidation, and prevent harmful substances such as microorganisms in the air from constantly coming into contact with crystals.
  • the existing tomato red In the preparation process of crystals since the crystals are relatively viscous and have many impurities, it is necessary to use centrifugal or long-term static stratification to complete the whole process. Therefore, the successful application of "four-in-one" equipment in lycopene crystallization is Great progress in the overall process of lycopene crystals.
  • the lycopene oleoresin as a raw material of the present invention means a lycopene oleoresin which is well known in the art and which is commercially available or can be prepared by itself.
  • the lycopene oleoresin may be prepared by a method comprising the steps of: dehydrating dried tomato skin in a composite consisting of an alkane such as n-hexane and a ketone such as acetone.
  • the solvent is sufficiently extracted, and after recovering the solvent, it is obtained.
  • the volume ratio of the alkane to the ketone in the complex solvent is preferably from 2:1 to 5:1.
  • the extraction temperature is preferably from 35 to 60 °C.
  • tomato skin residue can be used as raw material, after dehydration and drying, dry tomato skin residue can be obtained; dried tomato skin residue seed can be separated, tomato seed can be used for tomato seed oil extraction, and dried tomato skin processing can be obtained.
  • Dried tomato skin granules eg, 3 to 7 mm in diameter and 0.7 to 2 cm in length
  • the method provided by the invention can obtain lycopene crystal by one-step crystallization of a mixed solvent, and further adopts a two-step washing method to further increase the crystal content, reduce the hazard in the crystal, and obtain lycopene crystal with high purity and low hazard, and the whole production Process closed
  • the four-in-one equipment is faster and easier to produce, and produces lycopene crystals with high purity, low hazard, health and safety, suitable for industrial production.
  • the lycopene oleoresin can be prepared by the following method:
  • step C The tomato granules obtained in the step B were extracted using a composite solvent having a ratio of n-hexane and acetone of 5:1 at a temperature of 60 ° C, and the extraction time was 120 min. The solvent was concentrated under reduced pressure to obtain a lycopene oleoresin.
  • This embodiment provides a method for preparing high-purity, low-harm lycopene crystals, specifically:
  • step D The uniform solution dissolved in step D is cooled to 15 ° C, crystallized for 6 h, and after crystallization is completed, the lycopene crystal filter cake is directly filtered in the apparatus;
  • the purity of lycopene crystal obtained by the method is 85%, and the content of benzopyrene in the crystal ⁇ 10ppm.
  • This embodiment provides a method for preparing high-purity, low-harm lycopene crystals, specifically:
  • the lycopene crystal obtained by the method has a purity of 90%, and the benzopyrene content in the crystal is ⁇ 10 ppm.
  • This embodiment provides a method for preparing high-purity, low-harm lycopene crystals, specifically:
  • the purity of the lycopene crystal obtained by the method was 93.7%, and the content of benzopyrene in the crystal was ⁇ 10 ppm.
  • Example 3 Compared with Example 3, the only difference is that petroleum ether is used instead of the mixed solvent of the n-hexane and methanol.
  • the purity of the lycopene crystal obtained by the present comparative method was 55%, and the content of benzopyrene in the crystal was 200 ppm.

Abstract

本发明涉及一种制备高纯度低危害番茄红素晶体的方法，包括以下步骤：(1)将番茄红素油树脂与由烷烃和低级醇组成的混合溶剂混合，加热搅拌溶解，形成均一溶液；(2)将所述均一溶液降温结晶，过滤，得滤饼；(3)将所述滤饼依次用低级醇和烷烃洗涤，干燥，即得。本发明提供的方法采用混合溶剂一步结晶就能够得到番茄红素晶体，又采用二步洗晶法进一步提高晶体含量降低晶体中危害物而得到高纯度低危害物的番茄红素晶体，快捷、简便，生产得到纯度高、危害物低、卫生安全的番茄红素晶体，适于工业化生产。

Description

一种制备高纯度低危害的番茄红素晶体的方法 技术领域
本发明涉及天然植物提取物工业化生产领域，具体涉及一种制备高纯度低危害的番茄红素晶体的方法。
背景技术
番茄红素是植物中所含的一种天然色素。主要存在于茄科植物番茄的成熟果实中,目前番茄红素多从番茄果肉中提取，而番茄红素含量较高的番茄皮作为番茄酱生产的废料,如果能够加以利用，不仅能够变废为宝，而且能够创造巨大的社会效益。
但由于环境污染日益严重，造成番茄外皮中苯并芘等危害物含量极高，而直接造成番茄皮渣中提取得到的番茄红素苯并芘含量远高于番茄果肉中提取得到的番茄红素油树脂。
番茄红素为脂溶性色素，不易被人体直接吸收，而目前多采用制成胶囊、水分散型的制剂、片剂等保健品使用。均需通过包埋的方式，保护番茄红不被氧化，同时将脂溶性的番茄红素转化为水溶性的，便于人体吸收利用，但是为了保证包埋产品的稳定性，用于包埋的原料一般选用纯度比较高的晶体，使有足够空间添加壁材，而目前市场上大多销售的番茄红素为含量15％左右的番茄红素油树脂，因此，简洁可行的番茄红素晶体制备方法亟待开发，满足市场需求。
目前关于番茄红素晶体制备方面的专利还比较少，且制备方法均比较复杂，耗时较长，晶体纯度较低。
公开号为CN1775867A的专利中，将番茄红素油树脂与醇溶液混合后，过滤得到番茄红晶体，本专利中仅采用极性醇溶剂给番茄红素除杂只能出去一部分杂质，得到的晶体仍含有大量杂质，而且粘度较大，过滤极为艰难，产品纯度也较低，其含量仅能达到19-65％；公 开号为CN1687239A的专利中，采用了多级纯化步骤，涉及到皂化、分离、重新溶解结晶，不仅步骤繁琐，而且用到酸碱和高温，其对番茄红素极为不利，虽然晶体纯度较高，但可想而知，晶体得率绝不会太高；公开号为CN1807410A的专利中，番茄红三次重复结晶得到高纯度晶体，重结晶是损失高含量组分的过程，其得率难以保证，生产效率也可想而知。
总体来说，目前番茄红素晶体的制备方法中，大都采用了单溶剂，多次结晶的反式，反复重结晶，过程较长，不利于番茄红素的保存，且大多数结晶工艺中得到的番茄红素晶体纯度偏低，很难达到80％以上；而且现有结晶工艺中，无人考虑到危害物苯并芘的去除，目前随着食品安全的大力宣传，低危害物的番茄红素晶体不是市场发展的需求，总之高纯度、低危害物的番茄红素晶体亟待开发，且需保证工艺的简洁易工业化生产。
发明内容
本发明的目的是克服现有技术的缺陷，提供一种制备高纯度、低危害性番茄红素晶体的方法。本发明提供的方法具有制备工艺简单、晶体纯度高、危害物含量低等优点，且易于实现工业化生产。
具体而言，本发明提供的方法包括以下具体步骤：
(1)将番茄红素油树脂与由烷烃和低级醇组成的混合溶剂混合，加热搅拌溶解，形成均一溶液；
(2)将所述均一溶液降温结晶，过滤，得滤饼；
(3)将所述滤饼依次用低级醇和烷烃洗涤，干燥，即得。
本发明提供的方法使用混合溶剂进行结晶，仅通过一步结晶即可得到番茄红素晶体；在得到晶体的基础上，采用不同溶剂进行洗涤的多步洗晶的方式，不仅能够提高晶体纯度，而且能够降低晶体中危害物的含量，制备得到高纯度低危害物的番茄红素晶体。
本发明采用混合溶剂结晶技术，所述混合溶剂由烷烃和低级醇混 合而成。由于番茄红素油树脂中成分复杂，采用单一溶剂结晶无法保证杂质的完全除去，而且采用单一溶剂结晶后得到的番茄红素中由于仍然含有其它杂质而呈现膏状，造成晶体与溶剂难以分离，必须采用分离因素较高的离心设备才能保证晶体与溶剂的彻底分离；进一步而言，为了提高番茄红素晶体纯度，采用单一溶剂结晶需要2～3次重结晶才能够将番茄红素油树脂的大部分杂质去除，不仅耗时长，结晶所需温度也较低，能耗较大，而且由于番茄红素晶体容易氧化，在多次结晶过程中会有大量的番茄红素被氧化损失。本发明通过大量实践发现，采用由烷烃和低级醇组成的混合溶剂结晶，能够将晶体中的绝大多数杂质以及有害物质溶解于溶剂中，得到的晶体为粉末状，仅采用简单的过滤就能够将晶体与杂质彻底分离，且仅通过一步法即可获得结晶，不仅能够缩短时间(结晶时间仅为6～10h)，而且在15～25℃就能够结晶。
具体而言，本发明采用的烷烃优选为正己烷、环己烷、6号抽提溶剂油中的一种或几种，更优选为正己烷。本发明所述低级醇具体是指碳原子数为1～5的醇类，优选为甲醇、乙醇、异丙醇中的一种或几种，更优选为甲醇。
为了确保所述混合溶剂充分溶解杂质的同时使番茄红素晶体容易于析出，本发明优选所述烷烃和低级醇的体积比为2:1～4:1，更优选为3:1～4:1。
在实际操作中，为了确保晶体以合适的速度析出继而具有较高的纯度，且易于工业化控制，本发明优选所述番茄红素油树脂与混合溶剂的质量体积比比为4:1～8:1，更优选为6:1～8:1。
所述步骤(1)中，加热溶解的温度优选为35～60℃，更优选为55～60℃。作为本发明的优选方案，所述加热溶解的时间为15-40min，更优选为30～40min。
所述步骤(2)中，降温结晶的温度优选为15～25℃，更优选为 20～25℃。作为本发明的优选方案，所述降温结晶的时间为6～10h，更优选为6～8h。
经步骤(2)结晶后，过滤得到滤饼和滤液。所述滤饼进行两步洗涤、干燥后可得到目的产品，而所述滤液经浓缩后可得到低含量番茄红素油树脂。
所述步骤(3)中，本发明采用分步洗晶的方式提高晶体纯度，降低危害物含量。由于番茄皮为食物外皮，其本身就含有远高于番茄果肉的苯并芘，而提取番茄红素所用的烷烃类溶剂又易于溶解苯并芘，因此造成番茄皮渣提取得到的番茄红素油树脂含有较多的苯并芘，本发明采用混合溶剂结晶，在确保晶体从油树脂中仅通过一步结晶出来的基础上，使大部分的苯并芘留在低含量油树脂中，进一步采用不同溶剂进行多步洗晶的方法，进一步降低结晶后的番茄红素中苯并芘的含量。
具体而言，本发明首先使用具有极性的醇溶剂洗涤晶体，带走一部分脂肪酸类的极性杂质，使洗涤后的晶体不再具有粘性，更加松散，有利于后期烷烃类溶剂带走裹藏于晶体中的苯并芘。醇溶剂洗涤结束后，采用15～25℃、优选为20～25℃的烷烃类溶剂冲洗滤饼，不仅能够带走苯并芘危害物，而且不会造成番茄红素晶体的溶解，经过二步洗涤得到的番茄红素晶体中的苯并芘含量能够从100ppm左右降低至10ppm以下，产品纯度能够达到80％～95％。其中，洗涤时所用的低级醇溶剂优选为四碳以内的低级醇水溶液，优选为乙醇水溶液；所述低级醇水溶液的体积分数以75～95％为宜。洗涤时所用的烷烃类溶剂优选自正己烷、环己烷、6号抽提溶剂油中的一种或几种，更优选为正己烷。
在实际操作时，为了确保充分洗涤，同时节约溶剂用量以便于工业化生产和环保，本发明优选用滤饼湿重2～5倍体积的低级醇冲洗滤饼，以提高晶体含量，再用滤饼湿重3～8倍的15～25℃烷烃冲洗滤饼， 进一步提高晶体含量的同时去除苯并芘等危害物。每种溶剂均可进行多次洗涤，即用醇溶剂洗涤多次后再用烷烃类洗涤多次，以确保最佳的洗涤效果。
为了确保所述番茄红素晶体的品质，本发明所述干燥优选在真空、30～60℃条件下进行。干燥时间优选为5～10h。
本发明为了保证产品更加安全、卫生，减少番茄红素晶体的氧化，优选将所述步骤(1)～(3)的整条结晶工艺路线完全在全封闭式的设备中完成，即溶解、结晶、洗涤、干燥“四合一”设备，既能够避结晶过程中不断与外界接触，引起番茄红素氧化，又能够避免空气中的微生物等有害物质与晶体不断接触，而目前现有的番茄红素晶体制备工艺中，由于晶体比较粘稠，杂质较多，均需采用离心或者长时间静止分层的方式才能完成整个工艺，因此“四合一”设备在番茄红素结晶中的成功应用是番茄红素晶体整体工艺的巨大进步。
本发明作为原料的番茄红素油树脂是指本领域熟知的番茄红素油树脂，既可通过市售购得，也可自行制备。
作为本发明的一种优选方案，所述番茄红素油树脂可由包括如下步骤的方法制备而成：将脱水的干番茄皮在由烷烃类(如正己烷)和酮类(如丙酮)组成的复合溶剂中充分提取，回收溶剂后，即得。其中，所述复合溶剂中烷烃类与酮类的体积比优选为2:1～5:1。所述提取温度优选为35～60℃。
在实际生产中，可以以番茄皮渣为原料，经脱水、干燥后，得到干番茄皮渣；将干番茄皮渣皮籽分离，番茄籽用于番茄籽油的提取，得到的干番茄皮加工成干番茄皮颗粒(如：直径3～7mm、长度0.7～2cm)，再加入溶剂提取，可确保番茄红素的充分提取。
本发明提供的方法采用混合溶剂一步结晶就能够得到番茄红素晶体，又采用二步洗晶法进一步提高晶体含量降低晶体中危害物而得到高纯度低危害物的番茄红素晶体，而且整个生产工艺采用封闭式的 四合一设备，生产更加快捷、简便，生产得到纯度高、危害物低、卫生安全的番茄红素晶体，适于工业化生产。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实例用于说明本发明，但不用来限制本发明的范围。
以下各实施例中，所述番茄红素油树脂可采用如下方法制备而成：
A：将15吨水分含量为90％的番茄皮渣用螺旋压榨设备挤压脱水，滚筒烘干，得到干番茄皮渣；
B:将番茄皮渣皮籽分离，得到的番茄皮加工为直径为7mm，长度为2cm的颗粒，分离得到的番茄籽用于番茄籽油的提取；
C:将步骤B得到的番茄颗粒使用正己烷和丙酮比例为5:1的复合溶剂在温度为60℃条件下提取，提取时间为120min。减压浓缩回收溶剂后得到番茄红素油树脂。
实施例1
本实施例提供了一种制备高纯度、低危害性番茄红素晶体的方法，具体为：
(1)将番茄红素油树脂在“四合一”设备中用正己烷和甲醇比例为3:1的混合溶剂按照油树脂与溶剂比例4:1，在温度为35℃条件下溶解15min，得到均一溶液；
(2)将步骤D溶解后的均一溶液降温至15℃，结晶6h，结晶结束后，在设备中直接过滤得到番茄红素晶体滤饼；
(3)先用所述滤饼湿重2倍体积的80％乙醇水溶液冲洗滤饼，提高晶体含量；再用滤饼湿重3倍的15℃的正己烷冲洗滤饼，进一步提高晶体含量的同时去除苯并芘等危害物，在40℃条件下真空干燥10h，即得番茄红素晶体。
采用本方法得到的番茄红素晶体纯度为85％，晶体中苯并芘含量 ＜10ppm。
实施例2
本实施例提供了一种制备高纯度、低危害性番茄红素晶体的方法，具体为：
(1)将番茄红素油树脂在“四合一”设备中用正己烷和甲醇比例为2:1的混合溶剂按照油树脂与溶剂比例6:1，在温度为55℃条件下溶解30min，得到均一溶液；
(2)溶解后的均一溶液降温至20℃，结晶8h，结晶结束后，在设备中过滤得到番茄红素晶体滤饼；
(3)先用滤饼湿重4倍体积的75％乙醇水溶液冲洗滤饼，提高晶体含量，再用滤饼湿重6倍的20℃的环己烷冲洗滤饼，进一步提高晶体含量的同时去除苯并芘等危害物，在30℃条件下真空干燥8h，即得番茄红素晶体。
采用本方法得到的番茄红素晶体纯度为90％,晶体中苯并芘含量＜10ppm。
实施例3
本实施例提供了一种制备高纯度、低危害性番茄红素晶体的方法，具体为：
(1)将番茄红素油树脂在“四合一”设备中用正己烷和甲醇比例为4:1的混合溶剂按照油树脂与溶剂比例8:1，在温度为60℃条件下溶解40min，得到均一溶液；
(2)溶解后的均一溶液降温至25℃，结晶6h，结晶结束后，在设备中过滤得到番茄红素晶体滤饼；
(3)先用滤饼湿重5倍体积的95％的乙醇水溶液冲洗滤饼，提高晶体含量，再用滤饼湿重8倍的25℃的6#抽提溶剂冲洗滤饼，进一步提高晶体含量的同时去除苯并芘等危害物，在60℃条件下真空干燥10h，即得番茄红素晶体。
采用本方法得到的番茄红素晶体纯度为93.7％,晶体中苯并芘含量＜10ppm。
对比例1
与实施例3相比，区别仅在于，用石油醚代替所述正己烷和甲醇组成的混合溶剂。
经检测，用本对比例方法得到的番茄红素晶体纯度为55％,晶体中苯并芘含量200ppm。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种制备高纯度低危害的番茄红素晶体的方法，其特征在于，包括以下步骤：
    (1)将番茄红素油树脂与由烷烃和低级醇组成的混合溶剂混合，加热溶解，形成均一溶液；
    (2)将所述均一溶液降温结晶，过滤，得滤饼；
    (3)将所述滤饼依次用低级醇和烷烃洗涤，干燥，即得。
  2. 根据权利要求1所述的方法，其特征在于，步骤(1)所述烷烃选自正己烷、环己烷、6号抽提溶剂油中的一种或几种，优选为正己烷；
    和/或，所述低级醇选自甲醇、乙醇、异丙醇中的一种或几种，优选为甲醇。
  3. 根据权利要求1或2所述的方法，其特征在于，所述混合溶剂中烷烃和低级醇的体积比为2:1～4:1，优选为3:1～4:1。
  4. 根据权利要求1～3任意一项所述的方法，其特征在于，步骤(1)中所述番茄红素油树脂与混合溶剂的质量体积比为4:1～8:1，优选为6:1～8:1。
  5. 根据权利要求1～4任意一项所述的方法，其特征在于，步骤(1)所述加热溶解的温度为35～60℃，优选为55～60℃。
  6. 根据权利要求1或5所述的方法，其特征在于，步骤(2)所述降温结晶的温度为15～25℃，优选为20～25℃。
  7. 根据权利要求1～6任意一项所述的方法，其特征在于，步骤(3)低级醇为四碳以内的体积分数为75～95％的低级醇水溶液，优选为乙醇水溶液；
    和/或，所述烷烃温度为15～25℃，优选为20～25℃；选自正己烷、环己烷、6号抽提溶剂油中的一种或几种。
  8. 根据权利要求1～7任意一项所述的方法，其特征在于，所述 干燥为在真空、30～60℃条件下干燥。
  9. 根据权利要求1所述的方法，其特征在于，所述步骤(1)～(3)的全过程在一个全封闭式的溶解、结晶、洗涤以及干燥“四合一”设备中进行。
  10. 根据权利要求1所述的方法，其特征在于，所述番茄红素油树脂由包括如下步骤的方法制备而成：将脱水的干番茄皮在由烷烃类和酮类组成的复合溶剂中充分提取，回收溶剂后，即得；
    优选地，所述复合溶剂中烷烃类与酮类的体积比2:1～5:1；和/或，所述提取温度为35～60℃。
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