阅读说明：本技术 超临界二氧化碳分段提取花椒油树脂的工艺 (Process for extracting zanthoxylum oil resin by supercritical carbon dioxide section ) 是由 王黔林 陆龙发 米涛 黄涛 杨辉 杨建� 于 2020-12-15 设计创作，主要内容包括：本发明公开了一种超临界二氧化碳分段提取花椒油树脂的工艺,利用薄膜-分子一体化蒸馏设备纯化花椒油树脂工艺研究：根据超临界二氧化碳分段提取花椒油树脂的工艺,研究基于薄膜-分子一体化蒸馏纯化技术的花椒萃取、分离、纯化核心技术集成工艺,实现花椒油树脂的二次分离与纯化,去除难溶物质和降低苦味物质含量,提升贵州花椒油的整体质量,形成完整的花椒提取的技术工艺集成生产线；本发明的超临界二氧化碳分段萃取结合薄膜-分子蒸馏一体化的分离纯化新工艺,可以改善花椒油苦味重、感官差等缺陷,提高花椒油的品质。(The invention discloses a process for extracting zanthoxylum oil resin by supercritical carbon dioxide in a sectional way, which utilizes a film-molecule integrated distillation device to purify the zanthoxylum oil resin and comprises the following steps: according to the process for extracting the zanthoxylum oil resin by stages through supercritical carbon dioxide, researching a zanthoxylum extraction, separation and purification core technology integrated process based on a film-molecule integrated distillation and purification technology, realizing secondary separation and purification of the zanthoxylum oil resin, removing insoluble substances and reducing the content of bitter substances, improving the overall quality of the Guizhou zanthoxylum oil, and forming a complete technological integrated production line for extracting the zanthoxylum oil; the novel separation and purification process integrating supercritical carbon dioxide sectional extraction and film-molecular distillation can overcome the defects of heavy bitter taste, poor sense and the like of the zanthoxylum oil and improve the quality of the zanthoxylum oil.)

1. A process for extracting pepper oleoresin by stages through supercritical carbon dioxide is characterized by comprising the following steps;

step 1, extracting pepper powder, adopting peel and stem of pepper, and crushing to 70-90 meshes; and preparing CO₂，CO₂Gaseous CO in storage tank₂Refrigerating and liquefying;

and 2, extraction: adding fructus Zanthoxyli powder into supercritical extraction tank, introducing CO₂Performing supercritical extraction under 18MPa at 50 deg.C to obtain early-stage extractive solution;

step 3, early separation: the early-stage extraction liquid enters a separation tank, the temperature is raised to 55 ℃, the pressure is reduced to below 6.5Mpa, and CO is introduced₂The flow rate is not less than 140m3/h, and the process products, namely the pepper volatile oil, the primary separated matter and gaseous CO are obtained₂Zanthoxylum bungeanum essential oil channelCentrifuging to remove water to obtain fructus Zanthoxyli volatile oil, and adding gaseous CO₂The liquid is recycled through a cold-heat exchanger;

and 4, later-stage extraction: the preliminary separation product separated in the previous stage is put in an extraction tank again, the pressure is increased to 25Mpa, the temperature is reduced to 50 ℃, and CO is introduced₂Performing supercritical extraction, and discharging slag to obtain later-stage extract;

and 5, later-stage separation: the later-stage extract is fed into a separating tank, the pressure is reduced to less than 6.5Mpa, the temperature is raised to 55 ℃, and CO is added₂The flow rate is more than or equal to 140m³H, separating to obtain separated liquid and gaseous CO₂Gaseous CO₂The liquid is recycled through a cold-heat exchanger;

step 6, core purification technology: the method comprises the following steps of (1) separating and purifying the zanthoxylum oil resin again, wherein a film-molecule integrated distillation device is adopted, the film-molecule integrated distillation device comprises a film treatment system and a molecule distillation system, further purification is carried out through the film treatment system, and oil-water separation is carried out through the molecule distillation system;

step 7, contacting and fusing the separation liquid with carboxymethyl cellulose to realize solid-liquid separation again and remove peculiar smell;

step 8, finished product processing: and (4) centrifuging the separated liquid to remove water, thus obtaining the final product zanthoxylum oil resin finished product.

2. The process for extracting zanthoxylum oil resin by stages through supercritical carbon dioxide as claimed in claim 1, wherein: the early extraction time is 30min, and the later extraction time is 60 min.

3. The process for extracting zanthoxylum oil resin by stages through supercritical carbon dioxide as claimed in claim 1, wherein: the early separation time is 30min, the later separation time is 60min, and the re-separation time of the purification core technology is 60 min.

4. The process for extracting zanthoxylum oil resin by stages through supercritical carbon dioxide as claimed in claim 1, wherein: the contact fusion time of the separation liquid and the carboxymethyl cellulose is 5 h.

5. The process for extracting zanthoxylum oil resin by stages through supercritical carbon dioxide as claimed in claim 1, wherein: the molecular distillation system adopts a rotary scraper film evaporator, and the separation liquid flows in a film shape through a heating pipe wall, so that heat transfer and water vapor evaporation are performed.

Technical Field

The invention belongs to the field of pepper deep processing, and particularly relates to a process for extracting pepper oleoresin by sections through supercritical carbon dioxide.

Background

The pricklyash peel belongs to the deciduous plant of Zanthoxylum of Rutaceae, is widely distributed in China, is a common seasoning and Chinese medicinal materials, and has special numb feeling and strong fragrance. It is widely used in dishes in various parts of China, especially Sichuan dishes. In addition, as a common traditional Chinese medicine, the Chinese medicinal composition has the functions of warming spleen and stomach, relieving pain, killing parasites and relieving itching, and can be used for treating symptoms such as abdominal psychroalgia, vomiting and diarrhea, abdominal pain due to parasitic infestation, eczema and pruritus. The main components of green pricklyash peel comprise volatile oil, alkaloid, amide substances, lignan, coumarin and fatty acid, and also comprise some components with low content such as hydrocarbons, sterols, flavonoids and the like. Wherein the volatile oil and amide substances are flavor substances.

The pepper is used as a general seasoning plant in food and has wide application space, particularly pepper essential oil and pepper oleoresin are common natural seasoning agents, the pepper oleoresin is an oily product which is extracted from the pepper by an extraction method and contains all flavor characteristics of the pepper, each kilogram of the pepper oleoresin is equivalent to 20-30 kilograms of fragrance and numb feeling of the pepper, the pepper oleoresin has stable properties, is uniformly dispersed without residues when used, and is an ideal raw material for modulating the fragrance and the numb taste of the pepper; the product mainly comprises zanthoxylum essential oil, zanthoxylum nummular flavor oil, zanthoxylum oleoresin and the like at present. The essential oil of the zanthoxylum bungeanum has the special fragrance of the zanthoxylum bungeanum, can be directly used for modulating the special fragrance of the zanthoxylum bungeanum or diluted and is an ideal flavoring raw material for food processing enterprises and spice industries. The zanthoxylum oil resin is a mixed extract which is extracted from natural zanthoxylum by using a proper solvent and has fragrance, fragrance and numb taste, and is inconvenient for meeting different requirements of users. The zanthoxylum bungeanum sesame oil has the peculiar sesame taste of zanthoxylum bungeanum and is a main substance component of zanthoxylum bungeanum with the effects of anesthesia, excitation, bacteriostasis, wind dispelling, dehumidification, disinsection, analgesia and the like. Various products have different flavors, different nutritional values and different purposes.

The existing extraction process of zanthoxylum oil resin has the problems of low ephedrine content, heavy bitter taste, more precipitates and the like.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a high-quality supercritical carbon dioxide sectional extraction process for zanthoxylum oil resin, which has high tingling degree, less impurities and reduced bitter taste.

The technical scheme of the invention is as follows: a process for extracting oleum Zanthoxyli Bungeani by supercritical carbon dioxide comprises the following steps;

step 1, extracting pepper powder, adopting peel and stem of pepper, and crushing to 70-90 meshes; preparing CO2, and refrigerating and liquefying gaseous CO2 in a CO2 storage tank;

and 2, extraction: adding fructus Zanthoxyli powder into supercritical extraction tank, introducing CO2, and performing supercritical extraction under 18Mpa at 50 deg.C to obtain early-stage extractive solution;

step 3, early separation: the early-stage extract enters a separation tank, the temperature is raised to 55 ℃, the pressure is reduced to below 6.5Mpa, the flow rate of CO2 is more than or equal to 140m3/h, the process products, namely the pepper volatile oil, the primary isolate and gaseous CO2 are obtained, the pepper volatile oil is subjected to centrifugal dewatering to obtain a finished product of the pepper volatile oil, and the gaseous CO2 is subjected to a cold-heat exchanger to become liquid for recycling;

and 4, later-stage extraction: performing supercritical extraction on the primary separated substance separated in the early stage in an extraction tank again by increasing the pressure to 25Mpa and reducing the temperature to 50 ℃, introducing CO2, and discharging slag to obtain a later-stage extract;

and 5, later-stage separation: the later-stage extract enters a separation tank, the pressure is reduced to be less than 6.5Mpa, the temperature is raised to be 55 ℃, the flow of CO2 is more than or equal to 140m3/h, separation liquid and gaseous CO2 are obtained after separation, and the gaseous CO2 becomes liquid through a cold-heat exchanger for recycling;

step 6, core purification technology: the method comprises the following steps of (1) separating and purifying the zanthoxylum oil resin again, wherein a film-molecule integrated distillation device is adopted, the film-molecule integrated distillation device comprises a film treatment system and a molecule distillation system, further purification is carried out through the film treatment system, and oil-water separation is carried out through the molecule distillation system;

step 7, contacting and fusing the separation liquid with carboxymethyl cellulose to realize solid-liquid separation again and remove peculiar smell;

step 8, finished product processing: and (4) centrifuging the separated liquid to remove water, thus obtaining the final product zanthoxylum oil resin finished product.

Specifically, the early-stage extraction time is 30min, and the later-stage extraction time is 60 min.

Specifically, the early separation time is 30min, the later separation time is 60min, and the re-separation time of the purification core technology is 60 min.

Specifically, the separation liquid is contacted with the carboxymethyl cellulose for 5h for fusion.

Specifically, the molecular distillation system adopts a rotary scraper film evaporator, and separation liquid flows in a film shape through a heating pipe wall, so that heat transfer and water vapor evaporation are performed.

Compared with the prior art, the invention has the beneficial effects that: according to the invention, a novel process of integrated separation and purification of supercritical carbon dioxide sectional extraction and film-molecule-distillation is combined, and then the separation liquid is contacted and fused with carboxymethyl cellulose, so that pollutant impurities and some compounds in the oil are effectively removed, the tingling degree of the zanthoxylum oil deep-processed by zanthoxylum oil is improved, the bitter taste is reduced, the impurities are removed, natural precipitation is reduced, the overall quality of the zanthoxylum oil is improved, and the core technology integrated standard production line of the zanthoxylum oil sectional extraction, separation and purification is built.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

A process for extracting oleum Zanthoxyli Bungeani by supercritical carbon dioxide comprises the following steps;

step 1, extracting pepper powder, adopting peel and stem of pepper, and crushing to 70-90 meshes; preparing CO2, and refrigerating and liquefying gaseous CO2 in a CO2 storage tank;

and 2, extraction: adding fructus Zanthoxyli powder into supercritical extraction tank, introducing CO2, and performing supercritical extraction under 18Mpa at 50 deg.C to obtain early-stage extractive solution;

step 3, early separation: the early-stage extract enters a separation tank, the temperature is raised to 55 ℃, the pressure is reduced to below 6.5Mpa, the flow rate of CO2 is more than or equal to 140m3/h, the process products, namely the pepper volatile oil, the primary isolate and gaseous CO2 are obtained, the pepper volatile oil is subjected to centrifugal dewatering to obtain a finished product of the pepper volatile oil, and the gaseous CO2 is subjected to a cold-heat exchanger to become liquid for recycling;

and 4, later-stage extraction: performing supercritical extraction on the primary separated substance separated in the early stage in an extraction tank again by increasing the pressure to 25Mpa and reducing the temperature to 50 ℃, introducing CO2, and discharging slag to obtain a later-stage extract;

and 5, later-stage separation: the later-stage extract enters a separation tank, the pressure is reduced to be less than 6.5Mpa, the temperature is raised to be 55 ℃, the flow of CO2 is more than or equal to 140m3/h, separation liquid and gaseous CO2 are obtained after separation, and the gaseous CO2 becomes liquid through a cold-heat exchanger for recycling;

step 6, core purification technology: the method comprises the following steps of (1) separating and purifying the zanthoxylum oil resin again, wherein a film-molecule integrated distillation device is adopted, the film-molecule integrated distillation device comprises a film treatment system and a molecule distillation system, further purification is carried out through the film treatment system, and oil-water separation is carried out through the molecule distillation system;

step 7, contacting and fusing the separation liquid with carboxymethyl cellulose to realize solid-liquid separation again and remove peculiar smell; the contact temperature is 60-90 ℃, and the contact fusion time of the separation liquid and the carboxymethyl cellulose is 5 h.

The carboxymethyl cellulose is food-grade, is often used as a thickening agent and contains polysaccharide, so that precipitates such as impurities and the like can be bonded in the contact process with a separation liquid, and the effect of solid-liquid separation can be achieved under the centrifugal force or standing.

Mixing carboxymethyl cellulose with water when contacting with the separation solution to prepare a pasty glue solution for later use; when preparing the carboxymethyl cellulose paste, firstly adding a certain amount of clean water into a mixing cylinder with a stirring device, slowly and uniformly scattering the carboxymethyl cellulose into the mixing cylinder under the condition of starting the stirring device, and continuously stirring to ensure that the carboxymethyl cellulose and the water are completely fused and the carboxymethyl cellulose can be fully dissolved.

When dissolving carboxymethyl cellulose, it is necessary to uniformly spread and continuously stir, so as to prevent the problems of agglomeration and caking, decrease of dissolving amount, and increase of dissolving speed when carboxymethyl cellulose meets water.

Step 8, finished product processing: and (4) centrifuging the separated liquid to remove water, thus obtaining the final product zanthoxylum oil resin finished product.

The early extraction time is 30min, and the later extraction time is 60 min. The separation time in the early stage is 30min, the separation time in the later stage is 60min, and the separation time in the purification core technology is 60min again.

The molecular distillation system adopts a rotary scraper film evaporator, and the separation liquid flows in a film shape through a heating pipe wall, so that heat transfer and water vapor evaporation are carried out.

The working principle of the molecular distillation system is as follows: wherein the molecular distiller is preferably a scraper type molecular distiller.

A molecular still is a distillation apparatus operating under high vacuum where the mean free path of the vapor molecules is greater than the distance between the evaporation and condensation surfaces, thereby allowing the separation of liquid mixtures by differences in the evaporation rates of the components of the feed solution. At a certain temperature, the lower the pressure, the larger the mean free path of the gas molecules. When the liquid mixture flows along the heating plate and is heated, light and heavy molecules can escape from the liquid surface and enter the gas phase, because of different free paths of the light and heavy molecules, the molecules of different substances move for different distances after escaping from the liquid surface, and when meeting a condensing plate properly arranged in the molecular still, the light molecules reach the condensing plate and are condensed and discharged, while the heavy molecules cannot reach the condensing plate and are discharged along mixed liquid. Thus, the purpose of material separation is achieved.

Indexes of the finally obtained zanthoxylum oil are as follows:

(1) the extraction yield of the pepper oleoresin is as follows: 8 to 15 percent of

(2) The content of sanshoamides: 130-140mg/g

(3) Content of pepper flavor substances (essential oil): 3 to 6 percent

(4) Extraction rate of pepper spicy substances: not less than 95 percent

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention.