WO2019091194A1 - Procédé de raffinage d'acide carnosique par distillation moléculaire - Google Patents

Procédé de raffinage d'acide carnosique par distillation moléculaire Download PDF

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Publication number
WO2019091194A1
WO2019091194A1 PCT/CN2018/103157 CN2018103157W WO2019091194A1 WO 2019091194 A1 WO2019091194 A1 WO 2019091194A1 CN 2018103157 W CN2018103157 W CN 2018103157W WO 2019091194 A1 WO2019091194 A1 WO 2019091194A1
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WO
WIPO (PCT)
Prior art keywords
carnosic acid
molecular distillation
distillation
purifying
stage
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PCT/CN2018/103157
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English (en)
Chinese (zh)
Inventor
刘智谋
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湖南诺泽生物科技有限公司
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Publication of WO2019091194A1 publication Critical patent/WO2019091194A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/12—Molecular distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation

Definitions

  • the invention relates to a method for purifying and purifying carnosic acid by molecular distillation.
  • Rosemary (Latin name: Rosmarinus officinalis), Labiatae. Sexually warm climate, native to Europe and the Mediterranean coast of northern Africa. As far back as Cao Wei, he introduced China. Antioxidants (carnosic acid and rosmarinic acid) and rosemary essential oils with excellent antioxidant properties can be extracted from the leaves of rosemary. Rosemary antioxidants are widely used in medicine, fried foods, oil-rich foods and various types of oils and fats; while rosemary flavors are used in perfumes, air fresheners, ants, bactericides, insecticides, etc. Chemical industry.
  • the antioxidant carnosic acid has a carboxy hydroxyl group in its structure, and is easily oxidized under conditions of light and alkali, and is easily decomposed or oxidized at a high temperature.
  • industrial production is mainly extracted and separated by organic reagents.
  • the method since the method has a long heating time and is prone to oxidation and polymerization, the product extraction rate is not high and the production cost is high.
  • the technical problem to be solved by the present invention is to provide a method for purifying and purifying carnosic acid by molecular distillation with high purity and low production cost.
  • molecular distillation technology is a new type of liquid-liquid fine separation technology. Since molecular distillation is distilled under low-oxygen inert conditions, the material has a short heating time and a low operating pressure (high vacuum), so the degree of separation, the yield and the product quality are high, and the purified components do not change much before and after distillation. Therefore, molecular distillation is particularly suitable for the separation and purification of high boiling point, heat sensitive and easy oxide materials such as carnosic acid.
  • the technical solution adopted by the present invention to solve the technical problem thereof is: a method for purifying and purifying carnosic acid by molecular distillation, comprising the following steps:
  • Carnosic acid solubilization take a low content of carnosic acid product, and add solvent to dissolve;
  • Three-stage molecular distillation separation The secondary molecular distillation heavy component is pumped into a tertiary molecular distiller for tertiary molecular distillation separation to obtain light and heavy components, and the light component is carnosic acid.
  • the low content of the carnosic acid product means a carnosic acid product having a content of less than 40% by weight.
  • the rosemary is extracted and isolated by a conventional method, and the conventional methods include supercritical extraction, subcritical extraction, extraction with an organic reagent, and the like.
  • the auxiliary solvent is stirred and dissolved at 65 ⁇ 2 ° C.
  • the co-solvent is one or more of propylene glycol, glycerin, vegetable oil (such as soybean oil, etc.) or polyethylene glycol 300-600.
  • the first-stage thin film distillation has a heating temperature of 60 to 120 ° C, a vacuum degree of 20 to 500 Pa, a doctor blade rotation speed of 100 to 300 rpm, and a discharge condensation temperature of 40 to 80 ° C.
  • the heating temperature of the secondary molecular distillation is 120 to 200 ° C
  • the discharge condensation temperature is 40 to 80 ° C
  • the scraping film rotation speed is 100 to 300 rpm
  • the vacuum degree is 20 to 100 Pa.
  • the third-stage molecular distillation has a heating temperature of 160 to 210 ° C, a discharge condensation temperature of 40 to 80 ° C, a doctor blade rotation speed of 100 to 300 rpm, and a vacuum degree of 3 to 10 Pa.
  • the present invention has the following advantages:
  • the present invention provides an optimal separation method for separating high boiling point, heat sensitive and easy oxide materials such as carnosic acid - molecular distillation, because molecular distillation operates at a temperature far below the boiling point of the material, and the residence time of the material is short. Therefore, the damage to the material is small;
  • the invention adopts molecular distillation to effectively remove organic solvents, odors and the like in the material, which is very effective for carnosic acid;
  • the invention adopts multi-stage molecular distillation, and can simultaneously achieve the purpose of degassing, dehydrating, desolvating and refining the target product;
  • the fractionation process of the present invention is a purely physical process, thereby protecting the separated material from contamination and damage;
  • the invention can avoid the rectification tower process operation, and has the characteristics of short operation time, low production intensity, low energy consumption and low production cost compared with other conventional distillations, and the product has high purity and easy realization of continuous industrial production.
  • Example 1 is a liquid phase detection spectrum of carnosic acid prepared in Example 1 of the present invention.
  • Example 2 is a liquid phase detection spectrum of carnosic acid prepared in Example 2 of the present invention.
  • Example 3 is a liquid phase detection spectrum of carnosic acid prepared in Example 3 of the present invention.
  • Example 4 is a liquid phase detection map of carnosic acid prepared in Example 4 of the present invention.
  • a method for molecularly purifying carnosic acid comprising the following steps
  • Carnosic acid solubilization 1 kg of carnosic acid product with a content of 15% which was initially extracted by a conventional method, and 2 kg of polyethylene glycol 400 were stirred and dissolved at 65 ⁇ 2 ° C;
  • the secondary molecular distillation heavy component was pumped into a tertiary molecular distiller at a flow rate of 40 ml/min for tertiary molecular distillation separation to obtain a light component of 0.12 kg and a heavy component of 1.72 kg. It is divided into purity 85% carnosic acid, wherein the heating temperature of the tertiary molecular distillation is 200 ° C, the discharge condensation temperature is 65 ° C, the scraping film rotation speed is 100 rpm, and the vacuum degree is 3-10 Pa. (The map is shown in Figure 1)
  • a method for molecularly purifying and purifying carnosic acid comprises the following steps:
  • Carnosic acid solubilization 1.2 kg of carnosic acid product with a content of 23% preliminarily extracted by a conventional method, and 2 kg of propylene glycol were stirred and dissolved at 65 ⁇ 2 ° C;
  • the secondary molecular distillation heavy component is pumped into a tertiary molecular distiller at a flow rate of 40 ml/min for tertiary molecular distillation separation to obtain a light component of 0.51 kg and a heavy component of 2.20 kg.
  • the composition is a purity of 91% carnosic acid, wherein the heating temperature of the tertiary molecular distillation is 200 ° C, the discharge condensation temperature is 75 ° C, the scraping film rotation speed is 100 rpm, and the vacuum degree is 3 to 5 Pa. (The map is shown in Figure 2)
  • a method for molecularly purifying and purifying carnosic acid comprises the following steps:
  • Carnosic acid solubilization 1 kg of carnosic acid product with a content of 28% which was initially extracted by a conventional method, and 2 kg of glycerin were stirred and dissolved at 65 ⁇ 2 ° C;
  • the secondary molecular distillation heavy component is pumped into a tertiary molecular distiller at a flow rate of 40 ml/min for tertiary molecular distillation separation to obtain a light component of 0.33 kg and a heavy component of 2.02 kg.
  • the composition is purity 80% carnosic acid, wherein the heating temperature of the tertiary molecular distillation is 200 ° C, the discharge condensation temperature is 75 ° C, the scraping film rotation speed is 100 rpm, and the vacuum degree is 3 to 5 Pa. ( Figure 3)
  • a method for molecularly purifying and purifying carnosic acid comprises the following steps:
  • Carnosic acid solubilization 1 kg of carnosic acid product with a content of 28% initially extracted by a conventional method, and 2 kg of olive oil are stirred and dissolved at 65 ⁇ 2 ° C;
  • the secondary molecular distillation heavy component is pumped into a tertiary molecular distiller at a flow rate of 40 ml/min for tertiary molecular distillation separation to obtain a light component of 0.32 kg and a heavy component of 2.13 kg.
  • the composition is purity 87% carnosic acid, wherein the heating temperature of the tertiary molecular distillation is 200 ° C, the discharge condensation temperature is 70 ° C, the scraping film rotation speed is 100 rpm, and the vacuum degree is 3 to 5 Pa. (The map is shown in Figure 4)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

L'invention concerne un procédé de raffinage d'acide carnosique au moyen d'une distillation moléculaire, le procédé comprenant les étapes suivantes : (1) hydrotropie d'acide carnosique : consistant à prendre un produit ayant une faible teneur en acide carnosique et ajouter un agent d'hydrotropie pour dissoudre celui-ci; (2) déshydratation et dégazage au moyen d'une distillation de film mince de premier étage : consistant à ajouter de l'acide carnosique, auquel l'agent d'hydrotropie a été ajouté, dans une colonne de distillation de film mince de premier étage pour déshydratation et dégazage au moyen d'une distillation de film mince de premier étage; (3) distillation moléculaire de second étage et séparation : consistant à pomper un liquide déshydraté et dégazé dans un distillateur moléculaire de second étage pour une distillation moléculaire de second étage et une séparation de façon à obtenir des composants légers et lourds, le composant léger étant une partie contenant une partie de l'acide carnosique; (4) distillation moléculaire de troisième étage et séparation : consistant à pomper le composant lourd de la distillation moléculaire de deuxième étage dans un distillateur moléculaire de troisième étage pour une distillation moléculaire de troisième étage et une séparation de façon à obtenir des composants légers et lourds, le composant léger étant de l'acide carnosique. La présente invention présente des caractéristiques en termes de temps de fonctionnement court, d'une faible intensité de production, d'une faible consommation d'énergie et d'un faible coût de production, et en même temps, le produit présente une pureté élevée et permet de réaliser facilement une production industrielle en continu.
PCT/CN2018/103157 2017-11-13 2018-08-30 Procédé de raffinage d'acide carnosique par distillation moléculaire WO2019091194A1 (fr)

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CN201711117531.9A CN109160878A (zh) 2017-11-13 2017-11-13 一种分子蒸馏精制鼠尾草酸的方法
CN201711117531.9 2017-11-13

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CN111171104B (zh) * 2020-01-09 2021-03-30 湖南德诺健康产业有限公司 一种以迷迭香油膏副产品制备熊果酸的方法
CN111544922A (zh) * 2020-04-03 2020-08-18 广州正明生物科技有限公司 一种迷迭香提取物的制备方法及其在食用油抗氧化中的应用
CN112426739A (zh) * 2020-10-16 2021-03-02 安庆缘启医药科技有限公司 一种分子蒸馏提取抗癌药物的制备工艺

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CN102286059A (zh) * 2011-09-08 2011-12-21 南京泽朗医药科技有限公司 从迷迭香中提取熊果酸、鼠尾草酸和迷迭香酸的方法
CN102617315A (zh) * 2012-02-29 2012-08-01 华南理工大学 一种分子蒸馏精制假性紫罗兰酮的方法

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CN102417447B (zh) * 2011-10-31 2014-04-30 广西亿康药业股份有限公司 十一烯酸的生产方法
CN105601477B (zh) * 2016-01-29 2018-03-06 广东嘉博制药有限公司 一种高纯度丙泊酚的生产方法

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CN102286059A (zh) * 2011-09-08 2011-12-21 南京泽朗医药科技有限公司 从迷迭香中提取熊果酸、鼠尾草酸和迷迭香酸的方法
CN102617315A (zh) * 2012-02-29 2012-08-01 华南理工大学 一种分子蒸馏精制假性紫罗兰酮的方法

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