中国苦水玫瑰精油加工过程废水中玫瑰红色素的回收工艺研究

发布时间：2018-09-13 07:59

【摘要】：中国苦水玫瑰又称为刺玫花、徘徊花。蔷薇科,蔷薇亚科,蔷薇属,落叶灌木,奇数复叶,卵形,有毛边刺,花叶表面多皱纹,花叶底部和花叶柄合生。花朵单个生长,单个枝干可结花骨朵多个,紫红色或粉红色,花蕊及花瓣有浓郁玫瑰香。玫瑰广泛种植于国内各地,如山东省济南市平阴县的平阴玫瑰、甘肃省兰州市永登县苦水镇的苦水玫瑰。国内玫瑰主要用于食品添加及提炼玫瑰精油,玫瑰精油有液体黄金的美称,比等重量黄金价值高,多用于护肤品添加、食品添加剂、精细化工等工业。国内提炼玫瑰精油多采用传统蒸馏法,因无化学试剂的应用,该方法所生产的玫瑰精油品质较为安全优质。但其工业生产中必然会产生大量废水,目前技术水平尚不能达到国家环保标准要求,各生产厂家乱排乱放现象普遍存在,该问题一直是目前各地玫瑰精油厂家忧待解决的问题。玫瑰精油加工所得废水中有机物质含量很高,直接排放会使自然水体中COD(化学需氧量)、BOD(生物需氧量)值明显增加,继而造成严重的环境污染。通过研究玫瑰加工所得废水的物质成分,发现其中大部分有机物污染物是很值得回收利用的物质,如玫瑰色素、玫瑰黄酮、玫瑰多糖等。本论文以甘肃省永登县苦水玫瑰精油加工后所得废水为试验对象,对废水中色素的提取、纯化及回收利用进行了系统的研究,主要研究内容如下:1.苦水玫瑰精油加工所得废水为原料,利用高效液相色谱法测定玫瑰花色素的提取率,研究不同单因素对玫瑰花色素提取效果的影响,在单因素试验的基础上采用响应面曲线法对影响该工艺的关键因子及其相互作用进行分析,采用SPSS分析软件对玫瑰花色素的提取工艺进行优化,确定玫瑰花色素的最佳提取工艺参数为:存储时间0~7天,浓缩温度60℃,乙醇浓度为80%,pH=3.5,提取3次。结果表明:pH值对苦水玫瑰蒸馏法生产玫瑰精油所产生废水中色素提取率的影响最大,乙醇浓度次之,存储时间影响最小。2.玫瑰色素的粗提取使用有机溶剂和大孔吸附树脂进行纯化,然后通过薄层色谱法,紫外-可见吸收光谱。红外光谱法及高效液相色谱法对纯化后的玫瑰花色素进行了定性及定量分析,其中高效液相色谱条件为:DIONEX Acclaim C18 5μm 120A04.6×150mm,进样体积10μL,柱温35℃,波长范围200nm-700nm,检测波长520nm,流速1.0m L/min,流动相A甲醇(磷酸调p H值至2.5),流动相B:乙腈+水(5:95,V/V;磷酸调p H值至2.5):梯度洗脱。结果表明苦水玫瑰红色素主要成分为锦葵色素-3-O-葡萄糖苷。3.天然色素在保存和使用的过程中,受到环境的影响较大,稳定性也会随之变化。本研究通过对p H、温度、光照强度、食品添加剂、金属离子以及氧化剂和还原剂对苦水玫瑰红色素花色苷稳定性的研究,提供了对其保存和使用的条件的参考值。其中,在p H值较高、温度较高,光照强度较大的条件下,苦水玫瑰废水回收所得色素越容易降解;在研究食品添加剂对苦水玫瑰色素稳定性的研究中发现,食盐、蔗糖、苯甲酸钠对苦水玫瑰色素稳定性影响不大;在研究金属离子对苦水玫瑰色素稳定性的研究中发现,Ca+和AL3+有增加色素稳定性的作用,Zn2+对色素的稳定性影响不大,而Mg2+和Fe3+则可加速其降解,特别是若溶液中存在Fe3+可生成墨绿色沉淀;氧化剂和高浓度的还原剂都可以是色素的稳定性下降,特别是氧化剂的效果更为明显。
[Abstract]:Chinese bitter water rose, also known as Rosa roxburghii, wandering flowers. Rosaceae, Rosaceae, Rosaceae, deciduous shrubs, odd compound leaves, oval, bristly spiny, the surface of the flowers and leaves wrinkled, the bottom of the leaves and petioles connate. Flowers grow single, a single stem can form many flowers and bones, purple or pink, stamens and petals have a strong rose fragrance. It is widely planted in various parts of China, such as Pingyin Rose in Jinan City, Shandong Province, and Kushui Rose in Kushui Town, Yongdeng County, Lanzhou City, Gansu Province. In China, the traditional distillation method is often used to extract rose essential oil. Because there is no chemical reagent, the quality of rose essential oil produced by this method is relatively safe and high quality. This problem has been a problem to be solved by rose essential oil factories all over the world. The organic matter content in the waste water from rose essential oil processing is very high. The direct discharge of the waste water will increase the COD (chemical oxygen demand) and BOD (biological oxygen demand) in the natural water, and then cause serious environmental pollution. In this paper, the extraction, purification and recycling of pigment from the wastewater from the processing of Bitter Water Rose Essential Oil in Yongdeng County of Gansu Province were studied systematically. The main contents are as follows: 1. The extraction rate of rose pigment from bitter water rose essential oil wastewater was determined by high performance liquid chromatography, and the effects of different single factors on the extraction of rose pigment were studied. The extraction process of rose pigment was optimized by SPSS software. The optimum extraction process parameters were determined as follows: storage time 0-7 days, concentration temperature 60 C, ethanol concentration 80%, pH=3.5, extraction 3 times. The results showed that pH value had the most effect on the extraction rate of pigment in the waste water from the distillation of rose essential oil with bitter water. The crude extract of rose pigment was purified by organic solvent and macroporous resin, and then by TLC, UV-Vis absorption spectrum, infrared spectrum and high performance liquid chromatography were used to analyze the purified rose pigment qualitatively and quantitatively. The chromatographic conditions were as follows: DIONEX Acclaim C18.5 micron 120A04.6 *150 mm, sample volume 10 microL, column temperature 35 C, wavelength range 200 nm-700 nm, detection wavelength 520 nm, flow rate 1.0 mL/min, mobile phase A methanol (phosphoric Acid P H-modulated to 2.5), mobile phase B: acetonitrile + water (5:95, V/V; Phosphoric Acid P H-modulated to 2.5): gradient elution. The stability of natural pigment in the process of preservation and use will be greatly affected by the environment, and the stability will change accordingly. This study provides a reference for the study on the stability of anthocyanin in bitter water rose pigment by studying the effects of P H, temperature, light intensity, food additives, metal ions, oxidants and reductants. The results showed that salt, sucrose and sodium benzoate had little effect on the stability of the pigment. It was found that Ca + and AL3 + could increase the stability of pigment, Zn2 + had little effect on the stability of pigment, while Mg2 + and Fe3 + could accelerate the degradation of pigment, especially if Fe3 + existed in solution, it could form dark green precipitation; oxidant and reductant could be pigment. The stability is decreased, especially the effect of oxidant is more obvious.
【学位授予单位】：西北师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X789

【参考文献】