Optimization Of Refining Process Of Geniposide And Preparation Of It's Derivatives

In this paper,the purification and deep processing technology of geniposide,the symbolic active ingredient in gardenia jasminoides,was researched and developed.Geniposide crude product?44%?obtained in the extraction process of gardenia yellow pigment was used as raw material to obtain the low cost geniposide refining process meeting the requirements of industrialization and high purity geniposide?>95%?meeting the market demand.At the same time,with the recrystallized mother liquor of geniposide as the raw material,through the coupling of biocatalysis and chemical reaction,the design and development of the related processes of high efficiency and low toxicity biological crosslinking agent genipin,high quality gardenia blue pigment and gardenia red pigment were carried out to realize the deep processing and comprehensive utilization of geniposide.This paper will introduce the relevant content through the following three parts:In the first chapter,the effective components of gardenia,pharmacological action and common separation and purification methods of geniposide,the background and significance of this thesis were discussed.In chapter 2,the components of geniposide crude product were found as follows:acidic polysaccharides accounted for 55.16%,triterpenes 13.2%,total phenols 1.6%,and almost no flavonoids.The aqueous solution was acidic with a pH of 4.57.In combination with the market requirements on the purity of geniposide and the cost-benefit analysis of the relevant preparation process,the preparation of high purity geniposide will be achieved by calcium salt precipitation extraction method.Through optimization,the optimal preparation process was obtained as follows:The crude product of geniposide was prepared into a solution of 10%,and the powder of Ca₃?PO₄?₂ was used as the precipitant.The dosage was 10%,and the mixture was stirred for 10 min.Three times of constant volume water saturated n-butanol extraction,combined with the extraction liquid,activated carbon and basic alumina decolorization,concentrated to obtain the purity of 84.7%,the yield of 83.1%of geniposide.Geniposide was recrystallized with methanol-ethyl acetate as recrystallization solvent,and the purity of geniposide was greater than 95%,with a total yield of 54.1%.After further optimization and pilot production of 20 batches in the cooperative enterprise Zhejiang suichang limin pharmaceutical co.,LTD.,the average refining yield of geniposide was 51.8%,and the purity could reach 96.3%,meeting the requirements of the enterprise.On this basis,in the cooperative enterprises to further expand the study.After batch processing of 100 L geniposide concentrate,the average refining yield was 52.5%and the purity was 96.2%after batch trial production,meeting the market demand and having good economic value.In chapter 3,the preparation of genipin and the synthesis of gardenia blue pigment and gardenia red pigment by the condensation of genipin and amino acids were realized through the enzymatic hydrolysis of geniposide crystal mother liquor as raw materials,and the industrialization process of high-quality gardenia red pigment was realized.Firstly,the process of enzymatic hydrolysis for the preparation of genipin was developed.Using the crystal mother liquor of geniposide as raw material,cellulose 80 W as catalyst,dosage of 10%,the two-phase solvent method was adopted,in pH 4.8 buffer,48?heat for 2 hours,ethyl acetate extraction,can obtain 94.1%purity,yield 78.5%blue genipin,Further in 80?ethanol recrystallization,can get the purity is more than 98%white needle crystal,the overall yield was 75.4%.Subsequently,high quality gardenia blue pigment was prepared by condensation of the obtained high purity genipin with primary ammonia compound.The raw material cost and product quality were integrated.Sodium glutamate was used as the binding agent,and the ratio of sodium glutamate to ginnepin was 2:1.The reaction took place for 7 hours in 60?water solution with oxygen protection,and the high-quality gardenia blue pigment was obtained.The product has bright colors and the color price can reach 101,Mn=4103,Mw=19220.Finally,the preparation technology and refining method of geniposide for gardenia red pigment were studied.Geniposide was hydrolyzed and prepared into geniposide acid,with?-glucosidase as catalyst and glutamate as condensation amino acid.In pH 4.8 aqueous solution,48?oxygen was used to protect it for 25 h,and the color value of gardenia red pigment solution was 13.After adsorption and purification by macroporous resin HPD-100A and elution with pH11 ammonia solution,gardenia red pigment with color value of 91,Mn=14536,Mw=20956,was obtained.In addition,in the preparation process of gardenia pigment,it was found that the condensation of genipin or genipin acid with p-aminobenzoic acid showed a green color,and the alcohol solubility was very good,which could be used as a potential natural green pigment for development.The maximum absorption wavelength was 640⁶50 nm,Mn=1806,Mw=6103.In this paper,the process optimization and comprehensive product development of geniposide,the most abundant component in gardenia,were carried out,and a geniposide refining process line meeting the production requirements of the enterprise was developed to obtain high purity geniposide.Subsequently,the crystallization mother liquor was used as the raw material to study the preparation process of high value-added and promising biological cross-linking agents genipin,gardenia blue pigment and gardenia red pigment.The comprehensive utilization of geniposide,a by-product in the extraction process of gardenia yellow pigment,can reduce the total cost of preparation of gardenia yellow pigment,improve the profit of gardenia yellow pigment extraction and processing industry and reduce waste emissions,which is beneficial to environmental protection and increase production and income of enterprises.