WO2022052280A1 - 一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺 - Google Patents

一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺 Download PDF

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WO2022052280A1
WO2022052280A1 PCT/CN2020/126920 CN2020126920W WO2022052280A1 WO 2022052280 A1 WO2022052280 A1 WO 2022052280A1 CN 2020126920 W CN2020126920 W CN 2020126920W WO 2022052280 A1 WO2022052280 A1 WO 2022052280A1
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copper
chlorophyll
sodium salt
algae
mentioned
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PCT/CN2020/126920
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English (en)
French (fr)
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丁小强
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江西丹霞生物科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings

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  • the invention relates to the technical field of pigment extraction, in particular to a preparation process for preparing copper chlorophyll sodium salt from cyanobacteria.
  • Cyanobacteria algae are widely distributed and can survive in freshwater and seawater, wet and dry soil and rocks, tree trunks and leaves, hot springs, ice and snow, and even in brine pools, rock crevices, etc., and some can penetrate calcium It lives in rocks or calcareous shells (such as calcareous algae) and has great adaptability. It thrives especially in tropical and subtropical neutral or slightly alkaline environments. There are many species that are universal, such as the terrestrial fungus (Nostoc commune), which exists not only in tropical, subtropical and temperate zones, but also in frigid zones and even Antarctica.
  • the algae of Cyanobacteria are highly resistant to stress and can withstand drought, and some dry specimens can be kept alive for 65 to 106 years.
  • China's nitrogen-fixing Anabaena azotica can grow and fix nitrogen when it has been dried for 19 years and then re-cultivated.
  • Some cyanobacteria can grow and reproduce in hot springs at 76°C, and some can grow and fix nitrogen at 54°C (such as dinoflagellate Mastigocladus laminosum); some are resistant to low temperatures of -35°C (such as fungus); It can also grow in saturated salt water.
  • the development and utilization of cyanobacteria are mainly to prepare health care products.
  • Cyanobacteria are rich in chlorophyll, which can harvest light energy, use water as an electron source for photosynthesis, fix CO 2 , and release oxygen. At present, there are few reports on the utilization of chlorophyll in cyanobacteria.
  • chlorophyll is made into chlorophyll copper sodium salt, it becomes a stable metalloporphyrin structure.
  • metalloporphyrin sodium copper chlorophyll has high stability.
  • the main application range (1) Food additives, which can be added as green natural pigments to frozen drinks, beverages, candy, baked goods, jelly and other foods (2) Dyeing in cosmetics and textiles; (3) Medical application: The paste made of copper chlorophyll sodium salt can accelerate wound healing when treating wounds. It is used as an air freshener in daily life and clinical practice, especially in anti-cancer and anti-tumor applications. (4) As a photosensitizer during photoelectric conversion.
  • the method for extracting copper chlorophyll sodium salt from alfalfa and silkworm sand in the prior art has the defect of complicated process, and in the preparation process, organic solvents such as acetone etc. are to be used to remove impurities, so there are toxic solvent residues in the final product; and
  • the method for extracting copper chlorophyll sodium salt from cauliflower leaves and ginkgo leaves has the advantages that the raw materials are subject to seasonal restrictions, difficult to store, and low yield.
  • the purpose of the present invention is to provide a preparation process for preparing chlorophyll copper sodium salt from cyanobacteria algae.
  • preparing chlorophyll copper sodium salt from cyanobacterial algae it has the advantages of high efficiency, safe operation, low pollution and the like.
  • the present invention adopts following technical scheme:
  • a preparation process for preparing copper chlorophyll sodium salt from cyanobacteria algae comprising the following steps:
  • Step 1 Prepare raw materials: select cyanobacterial algae of a certain quality
  • Step 2 leaching: using 50%-90% ethanol that is 3-15 times the weight of the cyanobacteria algae, and leaching the raw materials in a continuous countercurrent extraction device for 4-6 hours to obtain the leaching solution;
  • Step 3 filtration and separation: after the leaching solution is filtered, use a centrifuge to separate out the solid impurities therein to obtain a filtrate;
  • Step 4 concentration: remove above-mentioned filtrate 40-50 ° vacuum concentration to paste;
  • Step 5 Saponification: add 4-8 times of 60%-90% ethanol to the above paste, then adjust the pH to 11-12 with liquid caustic soda, and heat at 40°C-50°C for 30-60min to obtain a saponified solution;
  • Step 6 acidifying copper generation: after filtering and separating the above saponified liquid, adjust the pH value to 2.5-3.5, and add 20% copper sulfate solution of 1%-10% by weight of cyanobacteria; Heating for 20min-50min;
  • Step 7 Concentrating and removing impurities: the above acidified copper-substituting solution is concentrated in a vacuum at 50°C to paste, washed with petroleum ether, filtered to obtain dark green chlorophyll cupric acid with loose particles of metallic color, and then washed with pure water to The filtrate is colorless, dried at 50°C to remove moisture;
  • Step 8 re-saponification and separation: dissolve the above-mentioned chlorophyll cupric acid with 3 times of acetone, adjust the pH to 11-12 with 1 mol/L KOH-C 2 H 5 OH solution, and filter to obtain chlorophyll copper sodium salt powder;
  • Step 9 removing impurities: the above-mentioned copper chlorophyll sodium salt powder is repeatedly washed with ethanol until the filtrate is light green;
  • Step ten sterilization: sterilize the chlorophyll copper sodium salt powder after the above-mentioned removal of impurities to obtain black powder;
  • Step eleven sieving and removing iron: passing the above-mentioned black powder through a 60-120 mesh screen and an iron remover of 8000-12000GS;
  • Step 12 mixing: placing the above-mentioned sieved and iron-removed powder in a powder mixer for full mixing to obtain a sodium copper chlorophyll product;
  • Step thirteen packaging: vacuum-packing the above-mentioned copper chlorophyll sodium salt product to obtain the finished product of copper chlorophyll sodium salt.
  • the filtration method is plate and frame filtration, diatomaceous earth filtration, bag filtration, chamber pressure filtration, vacuum filtration or tubular filtration.
  • centrifuge is a plate and frame or tube centrifuge.
  • cyanobacterial algae are Coeliococcus, Parallel algae, Rosa rosacea 2, Collar algae, Spirulina algae, Oscillator algae, Cyanobacteria, Microcystis algae, Fasciola sp. at least one of algae.
  • the sterilization method is pasteurization
  • the sterilization temperature is 68-90°C
  • the sterilization time is 30-40min.
  • the present invention Compared with the prior art, the present invention has obvious advantages and beneficial effects. Specifically, the present invention utilizes continuous countercurrent extraction equipment for leaching, mild process conditions, short preparation period, and low equipment investment; It has limited properties and is easy to store. Ethanol is used throughout the preparation process, with safe operation and little pollution. It is suitable for continuous and large-scale industrial production, and has high efficiency and high yield.
  • Step 1 prepare raw materials: select 1000kg of blue fiber algae;
  • Step 2 leaching: using 60% ethanol that is 3.5 times the weight of cyanobacteria, leaching the raw material in a continuous countercurrent extraction device for 4 hours to obtain an leaching solution;
  • Step 3 filtration and separation: after filtering the leachate, use a centrifuge to separate out the solid impurities therein to obtain a filtrate;
  • Step 4 concentration: remove above-mentioned filtrate 45 ° of vacuum concentration to paste;
  • Step 5 Saponification: add 5 times of 60% ethanol to the above paste, then adjust the pH to 11.2 with liquid caustic soda, and heat at 45°C for 35min to obtain a saponified solution;
  • Step 6 acidifying copper generation: after filtering and separating the above saponified solution, adjust the pH value to 2.5, and add 20% copper sulfate solution of 5% by weight of cyanobacteria; heat at 45°C for 30min;
  • Step 7 Concentrating and removing impurities: the above acidified copper-substituting solution is concentrated in a vacuum at 50°C to paste, washed with petroleum ether, filtered to obtain dark green chlorophyll cupric acid with loose particles of metallic color, and then washed with pure water to The filtrate is colorless, dried at 50°C to remove moisture;
  • Step 8 re-saponification and separation: dissolve the above-mentioned chlorophyll cupric acid with 3 times of acetone, adjust the pH to 11 with 1mol/L KOH-C 2 H 5 OH solution, and filter to obtain chlorophyll copper sodium salt powder;
  • Step 9 removing impurities: the above-mentioned copper chlorophyll sodium salt powder is repeatedly washed with ethanol until the filtrate is light green;
  • Step ten sterilization: pasteurize the above-mentioned chlorophyll copper sodium salt powder after impurity removal, the sterilization temperature is 70°C, and the sterilization time is 32min to obtain black powder;
  • Step eleven sieving and removing iron: passing the above-mentioned black powder through an 80-mesh sieve and an iron remover of 9000GS;
  • Step 12 Mixing: placing the above-mentioned sieved and iron-removed powder in a powder mixer for full mixing to obtain 19.28kg of copper chlorophyll sodium salt products;
  • Step thirteen packaging: vacuum-packing the above-mentioned copper chlorophyll sodium salt product to obtain the finished product of copper chlorophyll sodium salt.
  • Step 1 prepare raw materials: choose 1100kg of parallel algae;
  • Step 2 leaching: using 70% ethanol that is 4 times the weight of the algae, and leaching the raw material in a continuous countercurrent extraction device for 5 hours to obtain the leaching solution;
  • Step 3 filtration and separation: after filtering the leachate, use a centrifuge to separate out the solid impurities therein to obtain a filtrate;
  • Step 4 concentration: remove above-mentioned filtrate and concentrate to paste in 47° vacuum;
  • Step 5 Saponification: add 4 times of 70% ethanol to the above paste, adjust the pH to 11.5 with liquid caustic soda, and heat at 45°C for 30min to obtain a saponified solution;
  • Step 6 acidifying copper generation: after filtering and separating the above-mentioned saponification solution, adjust the pH value to 3, and add 20% copper sulfate solution of 7% by weight of the algae; heating at 45°C for 20min;
  • Step 7 Concentrating and removing impurities: the above acidified copper-substituting solution is concentrated in a vacuum at 50°C to paste, washed with petroleum ether, filtered to obtain dark green chlorophyll cupric acid with loose particles of metallic color, and then washed with pure water to The filtrate is colorless, dried at 50°C to remove moisture;
  • Step 8 re-saponification and separation: dissolve the above-mentioned chlorophyll cupric acid with 3 times of acetone, adjust the pH to 11.5 with 1mol/L KOH-C 2 H 5 OH solution, and filter to obtain chlorophyll copper sodium salt powder;
  • Step 9 removing impurities: the above-mentioned copper chlorophyll sodium salt powder is repeatedly washed with ethanol until the filtrate is light green;
  • Step 10 sterilization: pasteurize the above-mentioned chlorophyll copper sodium salt powder after removal of impurities, the sterilization temperature is 75°C, and the sterilization time is 32min to obtain black powder;
  • Step eleven sieving and removing iron: passing the above-mentioned black powder through an 80-mesh sieve and an iron remover of 9000GS;
  • Step 12 Mixing: placing the above-mentioned sieved and iron-removed powder in a powder mixer to fully mix to obtain 19.95kg of copper chlorophyll sodium salt products;
  • Step thirteen packaging: vacuum-packing the above-mentioned copper chlorophyll sodium salt product to obtain the finished product of copper chlorophyll sodium salt.
  • Step 1 prepare raw material: choose 1200kg of spirulina;
  • Step 2 leaching: using 80% ethanol that is 5 times the weight of the spirulina, leaching the raw material in a continuous countercurrent extraction device for 5 hours to obtain the leaching solution;
  • Step 3 filtration and separation: after filtering the leachate, use a centrifuge to separate out the solid impurities therein to obtain a filtrate;
  • Step 4 concentration: remove above-mentioned filtrate 50 ° of vacuum concentration to paste;
  • Step 5 Saponification: add 4.5 times of 80% ethanol to the above paste, then adjust the pH to 11.5 with liquid caustic soda, and heat at 45°C for 30 minutes to obtain a saponified solution;
  • Step 6 acidifying copper generation: after filtering and separating the above-mentioned saponification solution, adjust the pH value to 3.3, and add 20% copper sulfate solution of 5% by weight of spirulina; heat at 45°C for 20min;
  • Step 7 Concentrating and removing impurities: the above acidified copper-substituting solution is concentrated in a vacuum at 50°C to paste, washed with petroleum ether, filtered to obtain dark green chlorophyll cupric acid with loose particles of metallic color, and then washed with pure water to The filtrate is colorless, dried at 50°C to remove moisture;
  • Step 8 re-saponification and separation: dissolve the above-mentioned chlorophyll cupric acid with 3 times of acetone, adjust the pH to 11.5 with 1mol/L KOH-C 2 H 5 OH solution, and filter to obtain chlorophyll copper sodium salt powder;
  • Step 9 removing impurities: the above-mentioned copper chlorophyll sodium salt powder is repeatedly washed with ethanol until the filtrate is light green;
  • Step ten sterilization: pasteurize the above-mentioned chlorophyll copper sodium salt powder after impurity removal, the sterilization temperature is 85°C, and the sterilization time is 31min to obtain black powder;
  • Step eleven sieving and removing iron: passing the above-mentioned black powder through an 80-mesh sieve and an iron remover of 9000GS;
  • Step 12 Mixing: placing the above-mentioned sieved and iron-removed powder in a powder mixer for full mixing to obtain 21.85kg of copper chlorophyll sodium salt product;
  • Step thirteen packaging: vacuum-packing the above-mentioned copper chlorophyll sodium salt product to obtain the finished product of copper chlorophyll sodium salt.
  • Example 1 Example 2
  • Example 3 pH 9.5 ⁇ 11.0 10.16 10.21 9.68 Absorbance [ ⁇ 1% (405nm ⁇ 3nm)] ⁇ 568 586 584 591 Absorbance ratio 3.2 ⁇ 4.0 3.71 3.73 3.68 Total copper (Cu), w/% ⁇ 8 6.78 6.75 6.81 Free copper (Cu), w/% ⁇ 0.025 0.0161 0.0159 0.0158 Drying loss, w/% ⁇ 5 3.45 3.47 3.49 Total arsenic (as As)/(mg/kg) ⁇ 2 ⁇ 2 ⁇ 2 ⁇ 2 Lead(Pb)/(mg/kg) ⁇ 5 ⁇ 5 ⁇ 5 ⁇ 5

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Abstract

本发明提供了一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，将原料蓝藻门藻类进行选材、浸提、过滤及分离、浓缩、皂化、酸化铜代、浓缩去杂、再皂化及分离、去杂、灭菌、过筛除铁、混合、包装等步骤，得到叶绿素铜钠盐成品。本发明利用连续逆流提取设备进行浸提、工艺条件温和，制备周期短，设备投资少；蓝藻门藻类原材料不受季节性限制且易存储，在制取过程中全程使用乙醇，操作安全、污染小，适合连续化、大规模化工业生产，效率高。

Description

一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺 技术领域
本发明涉及色素提取技术领域，尤其是指一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺。
背景技术
随着人们生活水平的提高，对健康意识的增强，人们日趋崇尚天然保健产品，在日美及欧盟等发达国家和地区，天然色素已广泛应用于食品、化妆品和医药行业中，并在儿童食品、饮料食品、烤卤食品中禁用合成色素，天然色素的使用比例占整个着色剂比重的80％以上。在我国因“苏丹红”事件、“毒奶粉”事件等食品安全重大事故的发生，人们越来越关注食品安全。在食品着色领域中，逐渐限制合成色素的使用，如我国在儿童食品中已经限制合成色素的使用。天然色素在食品中的使用正在逐渐的替代合成色素，已经成为消费主流。
蓝藻门藻类分布很广，在淡水和海水中、潮湿和干旱的土壤和岩石上、树干和树叶以及温泉、冰雪，甚至在盐卤池、岩石缝等处都可生存，有些还可穿入钙质岩石或钙质皮壳中(如穿钙藻类)生活，具有极大的适应性。在热带、亚热带的中性或微碱性环境中生长特别旺盛。有许多种类是普生性的，如陆生的地木耳(Nostoc commune)，不仅存在于热带、亚热带和温带，在寒带甚至南极洲亦有发现。蓝藻门藻类的抗逆性很强，能耐干旱，有些干燥标本存贮65～106年还可保持活力。中国的固氮鱼腥藻(Anabaena azotica)干燥保存19年后再重新培育时还能生长和固氮。有些蓝藻能在76℃温泉中生长繁殖，有的在54℃条件下还能生长固氮(如鞭枝藻Mastigocladus laminosum)；有的可抗-35℃的低温(如地木耳)；有一些在过饱和盐水中也可生长。目前对于蓝藻门藻类的开发利用主要是制备保 健品，在生产过程中，只简单的加工或只提取了蓝藻门中的微量元素，往往忽略蓝藻门的综合利用价值。蓝藻门藻类富含丰富叶绿素，它能采收光能，以水作为电子来源进行光合作用，固定CO 2，放出氧气；目前，蓝藻门藻类中叶绿素利用的研究鲜有报道。
其次由于叶绿素不稳定，光、酸、碱、氧、氧化剂等都会使其分解，叶绿素制成叶绿素铜钠盐后，使其变成稳定金属卟啉结构。叶绿素铜钠盐作为金属卟啉的一种有着很高的稳定性，主要应用范围：(1)食品添加剂，可做为绿色天然色素添加至冷冻饮品、饮料类、糖果、焙烤食品、果冻等食品中；(2)在化妆品、纺织品中染色用；(3)在医学上的应用：在处理伤口时用叶绿素铜钠盐制成的膏状物可加速伤口愈合。在日常生活及临床中用作空气清新剂，特别是抗癌症及抗肿瘤方面的应用尤为突出。(4)在光电转换时作光敏剂。
现有技术中从苜蓿、蚕沙中提取叶绿素铜钠盐的方法，存在工艺复杂的缺陷，并且在制备过程中要使用有机溶剂如丙酮等进行除杂，因此最终产品中有有毒溶剂残留；而从花椰菜叶、银杏叶中提取叶绿素铜钠盐的方法，原材料易受季节性限制且不易储存、产率低。
发明内容
(一)要解决的技术问题
本发明目的在于提供一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，通过从蓝藻门藻类中制取叶绿素铜钠盐，其具有效率高、操作安全、污染小等优点。为实现上述之目的，本发明采取如下技术方案：
(二)技术方案
一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，包括以下步骤：
步骤一、准备原料：选取一定质量的蓝藻门藻类；
步骤二、浸提：采用蓝藻门藻类重量的3-15倍的50％-90％乙醇，在连续逆流提取设备中对原料浸提4-6小时，得到浸提液；
步骤三、过滤及分离：将浸提液过滤后，再采用离心机分离出其中的 固体杂质，得到滤清液；
步骤四、浓缩：去除上述滤清液40-50°真空浓缩至膏状；
步骤五、皂化：将上述膏状添加4-8倍60％-90％乙醇，再用液碱调节pH至11-12，40℃-50℃进行加热30-60min，得到皂化液；
步骤六、酸化铜代：将上述皂化液过滤及分离后，将pH值调节至2.5-3.5，并添加蓝藻门藻类重量的1％-10％的20％硫酸铜溶液；40℃-50℃进行加热20min-50min；
步骤七、浓缩去杂：将上述酸化铜代液50℃真空浓缩至膏状，用石油醚洗涤，通过过滤得到呈墨绿色带有金属色泽疏松颗粒状的叶绿素铜酸，再用纯净水洗至滤液无颜色，50℃烘干去除水分；
步骤八、再皂化及分离：将上述叶绿素铜酸用3倍丙酮溶解，用1mol/L KOH-C 2H 5OH溶液调节pH至11-12，过滤得到叶绿素铜钠盐粉末；
步骤九、去杂：将上述叶绿素铜钠盐粉末用乙醇反复洗至滤液淡绿色；
步骤十、灭菌：将上述去杂后的叶绿素铜钠盐粉末进行灭菌处理，得到黑色粉末；
步骤十一、过筛除铁：将上述黑色粉末通过60-120目的筛网及8000-12000GS的除铁器；
步骤十二、混合：将上述过筛除铁后的粉末置于粉体混合机中进行充分混合，得到叶绿素铜钠盐制品；
步骤十三、包装：将上述叶绿素铜钠盐制品进行真空包装，得到叶绿素铜钠盐成品。
进一步，所述过滤的方式是板框过滤、硅藻土过滤、袋式过滤、厢式压滤、真空抽滤或管式过滤。
进一步，所述离心机是板框或管式离心机。
进一步，所述蓝藻门藻类是腔球藻、平列藻、念珠2、项圈藻、螺旋藻、颤藻、蓝纤维藻、微囊藻、束丝藻、束球藻、色球藻、鱼腥藻中的至少一种。
进一步，所述灭菌方式为巴氏灭菌，灭菌温度为68-90℃，灭菌时间 为30-40min。
(三)有益效果
本发明与现有技术相比具有明显的优点和有益效果，具体而言，本发明利用连续逆流提取设备进行浸提、工艺条件温和，制备周期短，设备投资少；蓝藻门藻类原材料不受季节性限制且易存储，在制取过程中全程使用乙醇，操作安全、污染小，适合连续化、大规模化工业生产，效率高、产率高。
具体实施方式
以下结合实施例对本发明进一步以说明。
实施例1：
步骤一、准备原料：选取1000kg的蓝纤维藻；
步骤二、浸提：采用蓝纤维藻重量的3.5倍的60％乙醇，在连续逆流提取设备中对原料浸提4小时，得到浸提液；
步骤三、过滤及分离：将浸提液过滤后，再采用离心机分离出其中的固体杂质，得到滤清液；
步骤四、浓缩：去除上述滤清液45°真空浓缩至膏状；
步骤五、皂化：将上述膏状添加5倍60％乙醇，再用液碱调节pH至11.2，45℃进行加热35min，得到皂化液；
步骤六、酸化铜代：将上述皂化液过滤及分离后，将pH值调节至2.5，并添加蓝纤维藻重量的5％的20％硫酸铜溶液；45℃进行加热30min；
步骤七、浓缩去杂：将上述酸化铜代液50℃真空浓缩至膏状，用石油醚洗涤，通过过滤得到呈墨绿色带有金属色泽疏松颗粒状的叶绿素铜酸，再用纯净水洗至滤液无颜色，50℃烘干去除水分；
步骤八、再皂化及分离：将上述叶绿素铜酸用3倍丙酮溶解，用1mol/L KOH-C 2H 5OH溶液调节pH至11，过滤得到叶绿素铜钠盐粉末；
步骤九、去杂：将上述叶绿素铜钠盐粉末用乙醇反复洗至滤液淡绿色；
步骤十、灭菌：将上述去杂后的叶绿素铜钠盐粉末进行巴氏灭菌，灭菌温度为70℃，灭菌时间为32min，得到黑色粉末；
步骤十一、过筛除铁：将上述黑色粉末通过80目的筛网及9000GS的除铁器；
步骤十二、混合：将上述过筛除铁后的粉末置于粉体混合机中进行充分混合，得到叶绿素铜钠盐制品19.28kg；
步骤十三、包装：将上述叶绿素铜钠盐制品进行真空包装，得到叶绿素铜钠盐成品。
实施例2：
步骤一、准备原料：选取1100kg的平列藻；
步骤二、浸提：采用平列藻重量的4倍的70％乙醇，在连续逆流提取设备中对原料浸提5小时，得到浸提液；
步骤三、过滤及分离：将浸提液过滤后，再采用离心机分离出其中的固体杂质，得到滤清液；
步骤四、浓缩：去除上述滤清液47°真空浓缩至膏状；
步骤五、皂化：将上述膏状添加4倍70％乙醇，再用液碱调节pH至11.5，45℃进行加热30min，得到皂化液；
步骤六、酸化铜代：将上述皂化液过滤及分离后，将pH值调节至3，并添加平列藻重量的7％的20％硫酸铜溶液；45℃进行加热20min；
步骤七、浓缩去杂：将上述酸化铜代液50℃真空浓缩至膏状，用石油醚洗涤，通过过滤得到呈墨绿色带有金属色泽疏松颗粒状的叶绿素铜酸，再用纯净水洗至滤液无颜色，50℃烘干去除水分；
步骤八、再皂化及分离：将上述叶绿素铜酸用3倍丙酮溶解，用1mol/L KOH-C 2H 5OH溶液调节pH至11.5，过滤得到叶绿素铜钠盐粉末；
步骤九、去杂：将上述叶绿素铜钠盐粉末用乙醇反复洗至滤液淡绿色；
步骤十、灭菌：将上述去杂后的叶绿素铜钠盐粉末进行巴氏灭菌，灭菌温度为75℃，灭菌时间为32min，得到黑色粉末；
步骤十一、过筛除铁：将上述黑色粉末通过80目的筛网及9000GS的除铁器；
步骤十二、混合：将上述过筛除铁后的粉末置于粉体混合机中进行充分混合，得到叶绿素铜钠盐制品19.95kg；
步骤十三、包装：将上述叶绿素铜钠盐制品进行真空包装，得到叶绿素铜钠盐成品。
实施例3：
步骤一、准备原料：选取1200kg的螺旋藻；
步骤二、浸提：采用螺旋藻重量的5倍的80％乙醇，在连续逆流提取设备中对原料浸提5小时，得到浸提液；
步骤三、过滤及分离：将浸提液过滤后，再采用离心机分离出其中的固体杂质，得到滤清液；
步骤四、浓缩：去除上述滤清液50°真空浓缩至膏状；
步骤五、皂化：将上述膏状添加4.5倍80％乙醇，再用液碱调节pH至11.5，45℃进行加热30min，得到皂化液；
步骤六、酸化铜代：将上述皂化液过滤及分离后，将pH值调节至3.3，并添加螺旋藻重量的5％的20％硫酸铜溶液；45℃进行加热20min；
步骤七、浓缩去杂：将上述酸化铜代液50℃真空浓缩至膏状，用石油醚洗涤，通过过滤得到呈墨绿色带有金属色泽疏松颗粒状的叶绿素铜酸，再用纯净水洗至滤液无颜色，50℃烘干去除水分；
步骤八、再皂化及分离：将上述叶绿素铜酸用3倍丙酮溶解，用1mol/L KOH-C 2H 5OH溶液调节pH至11.5，过滤得到叶绿素铜钠盐粉末；
步骤九、去杂：将上述叶绿素铜钠盐粉末用乙醇反复洗至滤液淡绿色；
步骤十、灭菌：将上述去杂后的叶绿素铜钠盐粉末进行巴氏灭菌，灭菌温度为85℃，灭菌时间为31min，得到黑色粉末；
步骤十一、过筛除铁：将上述黑色粉末通过80目的筛网及9000GS的除铁器；
步骤十二、混合：将上述过筛除铁后的粉末置于粉体混合机中进行充分混合，得到叶绿素铜钠盐制品21.85kg；
步骤十三、包装：将上述叶绿素铜钠盐制品进行真空包装，得到叶绿素铜钠盐成品。
上述三个实施例中制备的叶绿素铜钠盐的理化指标测定见下表
项目 指表(GB264406-2011) 实施例1 实施例2 实施例3
pH 9.5～11.0 10.16 10.21 9.68
吸光度[Ε1％(405nm±3nm)] ≥ 568 586 584 591
吸光度比值 3.2～4.0 3.71 3.73 3.68
总铜(Cu)，w/％ ≤ 8 6.78 6.75 6.81
游离铜(Cu)，w/％ ≤ 0.025 0.0161 0.0159 0.0158
干燥减量，w/％ ≤ 5 3.45 3.47 3.49
总砷(以As计)/(mg/kg) ≤ 2 ＜2 ＜2 ＜2
铅(Pb)/(mg/kg) ≤ 5 ＜5 ＜5 ＜5
以上所述，仅是本发明较佳实施例而已，并非对本发明的技术范围作任何限制，故凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同变化与修饰，均仍属于本发明技术方案的范围内。

Claims (5)

  1. 一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，其特征在于：包括以下步骤：
    步骤一、准备原料：选取一定质量的蓝藻门藻类；
    步骤二、浸提：采用蓝藻门藻类重量的3-15倍的50％-90％乙醇，在连续逆流提取设备中对原料浸提4-6小时，得到浸提液；
    步骤三、过滤及分离：将浸提液过滤后，再采用离心机分离出其中的固体杂质，得到滤清液；
    步骤四、浓缩：去除上述滤清液40-50°真空浓缩至膏状；
    步骤五、皂化：将上述膏状添加4-8倍60％-90％乙醇，再用液碱调节pH至11-12，40℃-50℃进行加热30-60min，得到皂化液；
    步骤六、酸化铜代：将上述皂化液过滤及分离后，将pH值调节至2.5-3.5，并添加蓝藻门藻类重量的1％-10％的20％硫酸铜溶液；40℃-50℃进行加热20min-50min；
    步骤七、浓缩去杂：将上述酸化铜代液50℃真空浓缩至膏状，用石油醚洗涤，通过过滤得到呈墨绿色带有金属色泽疏松颗粒状的叶绿素铜酸，再用纯净水洗至滤液无颜色，50℃烘干去除水分；
    步骤八、再皂化及分离：将上述叶绿素铜酸用3倍丙酮溶解，用1mol/LKOH-C 2H 5OH溶液调节pH至11-12，过滤得到叶绿素铜钠盐粉末；
    步骤九、去杂：将上述叶绿素铜钠盐粉末用乙醇反复洗至滤液淡绿色；
    步骤十、灭菌：将上述去杂后的叶绿素铜钠盐粉末进行灭菌处理，得到黑色粉末；
    步骤十一、过筛除铁：将上述黑色粉末通过60-120目的筛网及8000-12000GS的除铁器；
    步骤十二、混合：将上述过筛除铁后的粉末置于粉体混合机中进行充分混合，得到叶绿素铜钠盐制品；
    步骤十三、包装：将上述叶绿素铜钠盐制品进行真空包装，得到叶绿素铜钠盐成品。
  2. 根据权利要求1所述一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，其特征在于：所述过滤的方式是板框过滤、硅藻土过滤、袋式过滤、厢式压滤、真空抽滤或管式过滤。
  3. 根据权利要求1所述一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，其特征在于：所述离心机是板框或管式离心机。
  4. 根据权利要求1所述一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，其特征在于：所述蓝藻门藻类是腔球藻、平列藻、念珠2、项圈藻、螺旋藻、颤藻、蓝纤维藻、微囊藻、束丝藻、束球藻、色球藻、鱼腥藻中的至少一种。
  5. 根据权利要求1所述一种从蓝藻门藻类中制取叶绿素铜钠盐的制备工艺，其特征在于：所述灭菌方式为巴氏灭菌，灭菌温度为68-90℃，灭菌时间为30-40min。
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