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油脂分提工艺发展史
 The development history of oil fractionation technology

 

油脂的主要成份是脂肪酸甘油三酯,甘油三酯中脂肪酸的碳链长度各异,同时不饱和程度也不尽相同,这就使得油脂含有相当数量的低熔点及高熔点的甘油三酯,低熔点的以液体形态存在称为“油”,而高溶点的以固体、半固体形态存在,通常称为“脂肪”。分提工艺是通过控制油脂的冷却结晶过程把油脂分成低熔点液相(液油)及高熔点固脂(硬脂)并将“油”与“脂”分开的油脂加工方法。

The main component of oil is fatty acid triglyceride. The carbon chain length of fatty acid in triglyceride is different, and the degree of unsaturation is also different. This makes the oil contains a considerable amount of triglyceride with low melting point and high melting point , low melting point triglyceride in liquid form is referred to as the "oils", while the high melting point triglyceride in solid or semi-solid form, usually called "fats." The fractionation process is oil and fat processing method that divides the triglyceride into low-melting liquid phase (olein) and high melting point solid fat (stearin) by controlling the cooling and crystallization process, and separates "olein" from "stearin".

一、分提工艺的早期历史

Ⅰ.Early history of the fractionation process

油脂分提工艺已经应用了近150年。油脂分提技术的发明归功于法国人希伯利特•麦加•莫利哀  Hippolyte Mège-Mouriès,希伯利特是他母亲的娘家姓。麦加•莫利哀(1817-1880),出生于法国南部的德拉吉尼昂。1867年麦加•莫利哀正忙于在巴黎附近帝国农场从事乳品研究,他发现瘦小的奶牛尽管减少了牛奶的产出, 仍然在牛奶中产生脂肪。因此, 他开创了一个工艺以人工方法生产奶油,因此成为生物技术的先驱, 这给他带来了持久的名声, 即人造黄油的发明。

The oil fractionation process has been used for nearly 150 years. The invention of oil fractionation technology is attributed to the French Hippolyte Mège-Mouriès, Hippolyte is his mother's maiden name. Mège-Mouriès(1817-1880), born in Draguignan, southern France. Mège-Mouriès was busy doing dairy research on the imperial farm near Paris in 1867,he found that even though thin cows reduced milk production, they still produced fat in milk.Therefore, he created a process to produce butter by artificial methods, and thus became a pioneer in biotechnology, which gave him lasting reputation, namely the invention of margarine.

1869年7月15日, 法国农业和贸易部授予麦加•莫利哀 15 年的专利,用于加工和生产某些动物来源油脂,该专利1873年也在英国获得注册。到 1873年麦加•莫利哀获得美国专利 (146012; 1-1-1873)专利名为 "动物脂肪的改性",不久后他的美国专利由纽约市的美国乳品公司获得,用于生产人造奶油。

On July 15, 1869, the French Ministry of Agriculture and Trade granted Mecca Molière with 15-year patent for processing and producing some animal fats,the patent was also registered in the United Kingdom in 1873. In 1873, Mecca Molière received U.S. patent (146012; 1-1-1873) entitled "Modification of Animal Fat". Soon after this, his US patent was obtained by the American Dairy Company in New York City for the production of margarine.

专利方法中的油脂来源于动物脂牛油和羊油,通过温和冷却后将液态成分从普通牛油中分离出来。但是,只有温差作为驱动力,脂肪的分步结晶是完全自然的自发现象。所以它也被观察到在热带地区收获的棕榈(仁)油,装在木桶中运送到寒冷的西欧途中,冷却后形成的晶体悬浮在木桶中。这些少量的致密固体最终沉淀,这样的成份可以有效地取代人造黄油中的硬化油脂。我们可以因此认为这些木制油桶是第一台油脂分提结晶器,海浪提供混合悬浮物必要的搅拌。此外,棕榈油在冬季自然结晶,这是油脂分提的一个经济的方式。

The fat in the patented method came from animal fat, tallow and mutton fat, after moderate cooling, the liquid components are separated from ordinary tallow. However, only the temperature difference is the driving force, and the step-by-step crystallization of fat is a completely natural phenomenon. Therefore, it was also observed that palm (kernel) oil harvested in tropical regions was transported to cold Western Europe in wooden barrels, and the crystals formed after cooling were suspended in the wooden barrels. These small amounts of dense solids eventually settled, and such components can effectively replace the hardened fat in margarine.Therefore, we can consider these wooden oil barrels as the first oil fractionation crystallizer, and the waves provided the necessary stirring for mixed suspension. In addition, palm oil naturally crystallizes in winter, which is an economical way of oil fractionation.

二、分提工艺的发展

II. The development of fractionation technology

直到二十世纪六十年代, 分提技术才得以蓬勃发展, 当时东南亚棕榈油的生产大量增加, 加工棕榈油的出口税也减少了。然而, 当时的技术边界主要是由相分离来决定的。在分提技术的早期阶段, 油与脂仅依靠重力力量导致较重的固相和较轻的液相之间的分离, 固相包含大量液体油夹带,几乎超过 75% 。在过去的几十年中, 从真空带过滤到离心机和膜压力过滤器等分离技术的不断发展, 使分提成为一种通用的经济改性技术。虽然一些特定的技术依赖表面活性剂适用于非常特殊的生产, 实际上只有两个主要的分提技术是在第二十一世纪的食用油工业中使用:干法分提和溶剂分提。

The technology of fractionation did not take off until the 1960s, when palm oil production in Southeast Asia surged and export taxes on processed palm oil were reduced. However, the technical boundary at that time was mainly determined by the phase separation.In the early stages of the fractionation technology, oil and fat rely solely on gravitational forces to cause the separation between the heavier solid phase and the lighter liquid phase, which contains a large amount of liquid oil, almost over 75%. In the past few decades, the continuous development of separation technology from vacuum filtration to centrifuge and membrane filter press makes fractionation become a general economic modification technology. Although some specific technologies rely on surfactants for very specific production, actually there are only two kinds of main fractionation technology used in the 21st century edible oil industry: dry fractionation and solvent fractionation.

三、影响分提的因素

III Factors affecting fractionation

 影响棕榈油结晶工艺的因素有油脂的组成、同质多晶体和冷却条件等。

The factors affecting the palm oil crystallization process include the oil grease composition, homogeneous polycrystals and cooling conditions.

(1)油脂组成  棕榈油中含有4%~8%的甘油三酯,它会与甘油三酯形成共晶混合物,从而降低固相含量,且导致油脂结晶速率减慢。棕榈油中甘油一酯的含量不到1%,因此它对棕榈油结晶过程没有明显的影响。

Grease composition

Palm oil contains 4% to 8% triglycerides, which will form eutectic mixture with triglycerides, thereby reducing the solid content and slowing down the crystallization rate of oils. The content of monoglycerides in palm oil is less than 1%, so it has no obvious effect on the crystallization process of palm oil.

(2) 同质多晶体  棕榈油的甘油三酯存在同质多晶现象,故其有不同形式的结晶形态,即α型、β’型和β型晶体。这些晶型的稳定性及熔点依次递增,在将棕榈油冷却时,首先得到的是α型晶体,然后依次转化为β’型和β型晶体。为了能得到良好的分离效果,结晶过程中希望能得到β’和β型晶体,因为β’型晶体具有晶体大而且硬的特点,有利于后续的过滤分离。

Homogeneous polycrystals

The triglycerides of palm oil have homogeneity and polymorphism, so they have different forms of crystals, namely α-type, β'-type and β-type crystals. The stability and melting point of these crystal forms gradually increase. When palm oil is cooled, α-type crystals are obtained first, and then they are converted into β'-type and β-type crystals in turn. In order to obtain a good separation effect, it is desirable to obtain β'and β-type crystals during the crystallization process, because β'-type crystals have characteristics of large and hard crystals, beneficial to subsequent filtration and separation.

(3)冷却速率  冷却速率会影响到晶核的形成及晶体的成长。当温度足够低(32~36℃)时,饱和甘油酯就会产生结晶。这些晶体成为低熔点甘油酯进一步结晶的晶核,进而形成大晶体。缓慢的冷却速率和适当的搅拌速率是获得理想晶体的必要条件。

Cooling rate

The cooling rate will affect the formation of crystal nucleus and crystal growth. When the temperature is low enough (32~36℃), saturated glycerides will crystallize. These crystals become crystal nucleus for further crystallization of low-melting glycerides, and then form large crystals. Slow cooling rate and proper stirring rate are necessary conditions for obtaining ideal crystals.

四、分提工艺的应用与发展

IV The application and development of oil fractionation technology 

 

棕榈油干法分提的第一步是在10℃以下的结晶。液体组分被用作油炸、烹调和沙拉油中的替代品, 或进一步分提。随着单级棕榈油分提技术的进一步发展,有一种增加的倾向, 执行双重或三重组份的棕榈油, 以产生具有特定特征的组份,如高碘价超级油酸 (iv > 65) 和超硬棕榈硬脂以及中间组分。

The first step of dry fractionation of palm oil is crystallization below 10°C. The liquid component is used in frying, cooking and as a substitute of salad oils, or is being further separated. With the further development of single-stage palm oil fractionation technology, there is a tendency to increase, perform double or triple components of palm oil to produce components with specific characteristics, such as high iodine number super oleic acid (iv> 65) and super hard palm stearin and intermediate components.

中间组分可以用作生产典型的可可脂 (CBE) 的原料, 它们在物理和化学性质上与可可脂相似, 是非月桂脂。

Intermediate components can be used as raw materials for the production of typical cocoa butter (CBE), which are similar in physical and chemical properties to cocoa butter and are non-laurel butter.

另一个技术领域是使用塞流式反应器(简称PFR) ,它允许连续的分步结晶,从而大大降低操作成本(如蒸汽使用和冷却功率)。不断追求经济和过程最优化,热回收系统、晶种装置、优化的混合程序和优雅的工厂布局都有助于最大限度地提高干法分提装置的容量和成本。

Another technical field is the use of plug flow reactor (Plug Flow Reactor, PFR), which allows continuous step crystallization, thereby greatly reducing operating costs (such as steam usage and cooling power). In fact, just like other edible oil processing technologies, we constantly pursue economic and process optimization. The heat recovery system, feed crystal device, optimized mixing procedure and elegant plant layout help to maximize the capacity and cost of the dry fractionation device.

分提过程产生两种产品,因此,两种组分的总和应该始终超过处理成本和原料成本。这就是为什么多级分提的可行性不仅是技术诀窍的问题,而且是一个对所有“副产品”都有市场的问题。

The fractionation process produces two products, so the sum of two components should always exceed the processing cost and raw material cost. This is why the feasibility of multi-stage fractionation is not only a question of technical know-how, but also a question there is market for all "by-products".

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