Effects of Degumming and Bleaching on 3-MCPD Esters Formation During Physical Refining

Crude palm oil (CPO) was physically refined in a 200-kg batch pilot refining plant. A study of the possible role of degumming and bleaching steps in the refining process for a possible critical role in the formation of 3-chloropropane-1,2-diol (3-MCPD) esters was evaluated. For the degumming step, different percentages of phosphoric acid (0.02–0.1%) as well as water degumming (2.0%) were carried out. Six different types of bleaching clays, mainly natural and acid activated clays were used for bleaching process at a fixed dose of 1.0%. Deodorization of the bleached oils was performed at 260 °C for 90 min. Analyses showed that 3-MCPD esters were not detected in the CPO. Phosphoric acid degumming (0.1%) in combination with acid activated clays produced the highest levels (3.89 ppm) of 3-MCPD esters in the refined (RBD) oil. The esters were at the lowest levels (0.25 ppm) when the oil was water degummed and bleached with natural bleaching clays. However, the refined oil qualities were slightly compromised. Good correlation of 0.9759 and 0.9351 was obtained when concentration of the esters was plotted against acidity of the bleaching earths for the respective acid and water degumming processes. The findings revealed the contribution of acidic conditions on the higher formation of 3-MCPD esters. In order to lower the esters formation, it is important to reduce acid dosage based on the crude oil qualities or to find alternatives to acid degumming process. Neutralization of the acidity prior to deodorization was effective in reducing the formation of 3-MCPD esters.     

Effect of processing on the composition and oxidative stability of coconut oil

The effect of various processing procedures on the composition and oxidative stability of coconut oil has been studied. The crude oil is relatively stable but major reductions in oxidative stability occur during the bleaching of oil degummed with phosphoric acid; during alkali refining; during the deodorization of oil degummed with citric acid and bleached; and during the deodorization of oil processed with a combined phosphoric acid degumming and bleaching operation. The reasons for the loss of oxidative stability during processing are discussed with reference to changes in the composition of the oil. Residual traces of citric acid or phosphoric acid play an important role in stabilizing processed oils. The tocopherol content is also important, although no additional stabilization of the oil occurs on adding levels of tocopherol above those present naturally in the crude oil. A combined phosphoric acid degumming and bleaching process leads to smaller losses of tocopherols than sequential treatments.     

The effect of carotene extraction system on crude palm oil quality, carotene composition, and carotene stability during storage

Palm carotene was successfully concentrated from crude palm oil (CPO) by an adsorption process using a synthetic adsorbent followed by solvent extraction. Evaluation of feed CPO and CPO which underwent the carotene extraction process was conducted. The quality of CPO after the extraction process was slightly deteriorated in terms of free fatty acid, moisture content, impurities, peroxide value, anisidine value, discriminant function, and deterioration of bleachability index. However, the CPO still can be refined to produce refined, bleached, deodorized palm oil that meets the Palm Oil Refiners Association of Malaysia specifications. No extra cost was incurred by refining this CPO as the dosage of bleaching earth used was very similar to the refining of standard CPO. The triglyceride carbon number and fatty acid composition of CPO after going through the carotene extraction process were almost the same as CPO data. The major components of the carotene fraction were similar to CPO, which contains mainly α- and β-carotene. The carotene could be stored for at least 3 mon.     

Pretreatment of corn oil for physical refining

Crude corn oil that contained 380 ppm of phosphorus and 5% of free fatty acids was degummed, bleached, and winterized for physical refining. The pretreatment and the steam-refining conditions were studied in pilot plant scale (2 kg/batch). The efficiency of wet degumming and of the total degumming processes, at different temperatures, was evaluated. TriSyl silica was tested as an auxiliary agent in the reduction of the phosphorus content before bleaching. The experimental conditions of the physical refining were: temperature at 240 or 250°C; 8 to 18 mbar vacuum, and distillation time varying from 1 to 3 h. Degumming at 10 or 30°C resulted in the removal of more phosphorus than at 70°C. Water degumming was more efficient than the processes of total degumming or acid degumming. Corn oil, degummed at 10 or 30°C, after bleaching passed the cold test, irrespective of the degumming agent used. Degumming and winterization took place simultaneously at these temperatures. The pretreatment was able to reduce the phosphorus content to less than 5 ppm. The amount of bleaching earth was reduced by carrying out dry degumming or by using silica before bleaching. Corn oil acidity, after physical refining, varied from 0.49 to 1.87%, depending on the residence time. Contrary to alkali refining, physical refining did not promote color removal due to the fixation of pigments present in the crude corn oil.     

The Total Degumming Process – Theory and Industrial Application in Refining and Hydrogenation

The degumming of vegetable oils prior to physical refining is a crucial preliminary step. The degumming process is not only largely responsible for the quality of the final product, but it also determines the amount of bleaching earth to be used, which has a substantial effect on the yield improvement which can be attained by this route. Investigations show clearly that iron, as a pro-oxidant, strongly influences the stability of refined oils, and that oil, degummed before bleaching and physical refining, may contain a maximum of 0.2 ppm Fe, if it is to yield a stable product. The Total Degumming Process has been developed on the basis of these findings, to make it possible to degum oil to a residual Fe-level below 0.2 ppm and a residual phosphorus content below 10 ppm. The principles and industrial application of the process have been considered. The results of industrial production using different raw materials of various qualities have been used to make a comparison between the conventional refining process (neutralization – bleaching – deodorization) and the Total Degumming Process in combination with physical refining. The combination of the Total Degumming Process and a simplified caustic refining process, and the use of Totally Degummed Oil for hydrogenation have also been considered.     

Quality of oil from damaged soybeans

Various processing steps were explored in an at-tempt to improve the quality of oil from field- and storage-damaged soybeans. A crude soybean oil (5.7% free fatty acid) commercially extracted from damaged soybeans was degummed in the laboratory with different reagents: water, phosphoric acid, and acetic anhydride. Two alkali strengths, each at 0.1 and 0.5% excess, were used to refine each degummed oil. After vacuum bleaching (0.5% activated earth) and deodorization (210 C, 3 hr), these oils were un-acceptable as salad oils. A flavor score of 6.0 or higher characterizes a satisfactory oil. Scores of water and phosphoric acid degummed oils ranged from 4.5 to 5.1, while acetic anhydride degummed oils aver-aged 5.6. Flavor evaluations of (phosphoric acid de-gummed) single- and double-refined oils (210 C deodorization) showed that the latter were signifi-cantly better. Flavor scores increased from 5.0 to about 6.0. To study the effects of deodorization tem-perature, the crude commercial oil was alkali-refined, water-washed and bleached with 0.5% activated earth, but the degumming step was omitted. Flavor evalua-tion of oil deodorized at 210, 230, and 260 C showed that each temperature increment raised flavor scores significantly. Further evaluations of specially proc-essed oils (water, phosphoric acid, and acetic anhy-dride degummed oils given single and double refinings and deodorized at 260 C) showed that deodorization temperature is the most important factor affecting the initial quality of oil from damaged beans. Flavor evaluations showed that hydrogenation and hydro-genation-winterization treatments produced oils of high initial quality, but with poorer keeping proper-ties than oils from normal beans. No evidence was found implicating nonhydratable phosphatides in the oil flavor problem. Iron had a deleterious effect in oils not treated with citric acid during deodorization. Presented at AOCS Meeting, Philadelphia, September 1974.     

The total degumming process

A novel degumming process is described that is applicable to both undegummed and water-degummed oils. Such totally degummed oils have residual iron contents below 0.2 ppm Fe and residual phosphorus contents that average below 5 ppm P. Therefore, they can be physically refined to yield a stable refined oil while using the same level of bleaching earth commonly used for alkali refined oils prior to deodorization. They can also be alkali refined with reduced oil loss to yield a soapstock that only requires slight acidification for fatty acid recovery, and thus avoids the strongly polluting soap splitting process. The total degumming process involes dispersing a non-toxic acid such as phosphoric acid or citric acid into the oil, allowing a contact time, and then mixing a base such as caustic soda or sodium silicate into the acid-in-oil emulsion. This keeps the degree of neutralization low enough to avoid forming soaps, because that would lead to increased oil loss. Subsequently, the oil is passed to a centrifugal separator where most of the gums are removed from the oil stream to yield a gum phase with minimal oil content. The oil stream is then passed to a second centrifugal separator to remove all remaining gums to yield a dilute gum phase which is recycled. Washing and drying or in-line alkali refining complete the process. After the adoption of the total degumming process, in comparison with the classical alkali refining process, an overall yield improvement of approximately 0.5% has been realized. It did not matter whether the totally degummed oil was subsequently alkali refined, bleached and deodorized, or bleached and physically refined.     

影响油菜籽毛油脱胶因素的研究

采用市售油菜籽进行压榨制备毛油,并进行脱胶实验,单因素试验表明:菜籽毛油加热温度在50～60℃、磷酸加入量为油重0.1%～0.3%、加水量为4%～6%、水化时间在20～30min时脱胶效果比较好。在单因素试验结果基础上设计L_9(3~4)正交实验,确定菜籽油脱胶工艺的最佳参数为:温度50℃,磷酸添加量0.3%,加水量6%,水化时间30min,在此脱胶条件下,脱胶率可达为97.69%。     

Pretreatment efficiency for physical refining of sunflowerseed oil

The appropriate pretreatment of crude oil is of crucial significance for the application of physical refining. This paper presents a simplified process for the preparation of sunflowerseed oil by applying multistep acid degumming as the only pretreatment step. Amorphous silica hydrogel was used instead of treatment with bleaching earth. The results obtained showed that samples of crude-pressed and extracted sunflowerseed oil differ significantly with respect to the content and composition of phosphatides, which is important for the pretreatment. The proper choice of oil and the application of multistep acid degumming results in an effective pretreatment of sunflowerseed oil for physical refining.     

Optimization of the Degumming Process for Aqueous-Extracted Wild Almond Oil

Wild almond (Amygdalus scoparia) oil is rich in oleic acid and, considering both nutritional and stability points of view, it can be utilized for future food applications. In the current study, acid degumming was investigated based on a method by response surface methodology using four degumming parameters, namely the amount of phosphoric acid (0.0–0.2%, w/w), the amount of water (1.0–5.0%, w/w), degumming temperature (30–70 °C), and degumming time (10–50 min). Optimum conditions for the minimum phosphorus level in the oil were found to be 0.15% phosphoric acid, 3.0% water, 40 °C degumming temperature, and 28 min degumming time, resulting in an almost complete removal of phosphorus. The final degummed wild almond oil had less than 1 mg kg⁻¹ phosphorus (reduced from an original value of 206 mg kg⁻¹). The experimental value of phosphorus reduction at optimum conditions agreed well with that predicted by the model. Peroxide value, anisidine value, iron, copper, and lead contents, phytosterols, unsaponifiable matter, and color of the oil decreased significantly during the degumming process; however, the fatty acid composition did not change. Also, degumming did not significantly impact the free fatty acid level, refractive index, density, iodine value, and the saponification value of the oil. However, tocopherols and the oxidative stability of the oil increased during degumming. Crude wild almond oil contained a trace level of amygdalin, which was completely eliminated during the degumming process.     

Benefits and limitations of a novel chlorophyll adsorbent

Silica hydrogels acidified with strong mineral acids, such as sulfuric acid, are highly effective chlorophyll and phospholipid adsorbents relative to traditional acid-activated bleaching earth (ABE), but they are not effective β-carotene adsorbents. When an acidified silica is used as the only bleaching agent, sulfuric acid leaches into the oil, and after deodorization, Tintometer red and yellow (R/Y) numbers are higher than those for ABE-bleached and deodorized oils. The fixed R/Y colors do not arise solely from the decomposition of β-carotene during deodorization. Sequential treatments of canola oils with sulfuric acid/silica and ABE can be performed to overcome all of the drawbacks associated with sulfuric acid/silica treatment alone, such that finished oils can be produced by lower overall adsorbent dosages.     

Auxiliary Degumming and Pressurized High Temperature Water Washing to Mitigate the Formation of Monochloropropanediols in Palm Oil

This study reports the benefits of auxiliary degumming (Aux.D) and pressurized high temperature (165 °C) water washing (PHTW) to mitigate the formation of monochloropropanediols (MCPD) during labscale physical refining of palm oil. Water-based degumming in combination with bleaching and deodorization are performed as the selected physical refining process. The mitigation concepts Aux.D and PHTW are integrated into the refining protocol and the ultimately observed MCPD levels in the fully refined oils are determined. Aux.D is performed by extracting the hydratable gum from pressed sunflower oil and using it as a degumming agent to further purify palm oil that has been previously subjected to centrifugation and water degumming. This approach enables the mitigation of 3-MCPD from the water washed reference 2.4–0.9 mg kg⁻¹ in ampoules. Even stronger mitigation is obtained when Aux.D is combined with bleaching and executed twice allowing a mitigation from the reference 1.9–0.6 mg kg⁻¹, in ampoules. PHTW is shown to decrease the 3-MCPD content of the refined oil from the reference 2.4–1 mg kg⁻¹, in ampoules and when combined with bleaching and executed twice showing a decrease from the reference 1.9–0.9 mg kg⁻¹. Practical applications: The benefits of these mitigation concepts are confirmed both in sealed ampoule tests and in deodorizer experiments at the lab scale. A combined application of Aux.D or PHTW with physical refining may represent new insights that can help to potentially further mitigate the formation of MCPD in physically refined palm oil beyond the limits achievable with current refining practices.     

Effects of minor compounds on hydrogenation rate of soybean oil

The poisoning effects of minor compounds in soybean oil on the activity of nickel-based catalysts during hydrogenation was investigated. Several soybean oils prepared by different processes were used as the starting oils for hydrogenation. Soybean oil prepared by combining neutralization with degumming and then followed by bleaching leads to a slower hydrogenation rate than an oil prepared by sequential degumming, neutralization and bleaching with activated clay. The selection of bleaching earth used in the bleaching process affected the hydrogenation rate. Soybean oil bleached with neutral clay showed a slower hydrogenation rate. Higher amounts of phosphorus compounds, oxidation products, β-carotene and iron in these oils accounted for the slower hydrogenation rate. Storage of refined and bleached soybean oil greatly affected the hydrogenation rate. An increase in the oxidation products of RB soybean oil during storage was the major reason for the decrease in the hydrogenation rate.     

A kinetic study of phospholipid extraction by degumming process in sunflower seed oil

During the refining process of vegetable oils (degumming), phospholipids are eliminated by thermal treatment with water (hydratable phospholipids, HP) and other degumming agents such as phosphoric acid, citric acid, or acid mixtures (nonhydratable phospholipids, NHP). Samples of pressed crude sunflower oils were degummed with water and acids, and the corresponding pellets (gums) and supernatant oils were obtained by centrifugation. During the water degumming process, a decrease of more than 98% in the phosphatidylcholine (PC) content was achieved in 5 min; phosphatidylethanolamine (PE) was the most difficult compound to be removed. Phosphatidylserine, phosphatidic acid, and phosphatidylinositol (PI) presented an intermediate behavior. The optimal contact time for quantitative extraction of the most important HP (PC, PI, and PE) in crude sunflower oils was 35 min. For acid treatments, a rapid elimination of the residual levels of PC was registered (5 min); the optimal contact times for the quantitative removal of the NHP were 35 min for phosphoric acid und acid mixture, and 25 min for citric acid. Taking into account that PE was the most difficult component to be removed, its level could be used as a monitor to evaluate the efficiency of the degumming process.     

A new analytical method to monitor lipid peroxidation during bleaching

Whereas solid phase microextraction (SPME) combined with gas chromatography is a wide‐spread technique in certain fields of food analysis this technique is quite new for the analysis of vegetable oils. The method is sensitive enough to follow changes in the oxidative state of vegetable oils by measuring the amount of volatile materials produced during storage and the refining process. In the present study degummed rapeseed oil was bleached using different activated bleaching earths applied in four dosages. Their effect on lipid degradation was determined both by traditional methods (e.g. UV absorbance, p‐anisidine value) and by the SPME‐HS method. Although the p‐anisidine value (p‐AV) gives only the concentration of β‐unsaturated aldehydes it correlates well to the amount of total volatile substances as determined by SPME at the headspace of the sample. The extracted volatile materials were separated and identified by gas chromatography combined with mass spectrometry. SPME gives more information about the stage of oxidation and the applied bleaching earth by quantifying the volatile compounds. Additionally SPME does not require any toxic reagent such as p‐methoxy aniline which is used to determine the p‐AV. Although bleaching is very important it was disregarded in recent years. Therefore one of the aims of the present study is to draw back more attention towards bleaching.     

Degumming,refining and bleaching soybean oil

This subject deals with the removal of the fat-soluble impurities from crude soybean oil. These impurities may be present in true solution or in a colloidal state; their effective removal is necessary to achieve quality standards for end-use products. The processing step options for the removal of these impurities in any given situation are easily defined; the conditions and practices used, however, are the primary concern of this paper. International trading of soybean oil mandates the degumming step. The increased use of import/export soybean oil increases the importance of this processing practice. Pretreatment and effective contact time are the critical issues. Refining, as a specific process, deals primarily with free fatty acid removal, with or without simultaneous degumming as a single-step operation. State-of-the-art wet, chemical refining practices are described, and the current limitations and future opportunities for the physical refining of soybean oil are discussed. The importance of the bleaching step cannot be overstated and it should be noted that color reduction is only coincidentally achieved. The primary function of the bleaching process is to remove oxidative breakdown products, and the degree or level of treatment should be consistent with that objective. Underbleaching and thermal decolorization (deodorization) of soybean oil are misguided practices. Once “cleaned-up” through adequate bleaching, an oil should be guarded against thermal/oxidative abuse.     

Effect of process conditions on the removal of phospholipids from Jatropha curcas oil during the degumming process

This work aims to study the removal of phospholipids from Jatropha oil through a conventional degumming process combined with ultrafiltration membrane separation in a small-scale batch system. The effect of temperature, amount of acid solution added, and speed of centrifugation during the conventional degumming process were analyzed using response surface methodology (RSM). The optimum operating condition was determined to be at 65 °C, with 4 wt% acid solution added and a centrifugation speed of 1600 rpm. After the degumming process, the phospholipid content of Jatropha oil was reduced from 1200 ppm to 60 ppm. This was further reduced to less than 20 ppm by subjecting the oil to ultrafiltration membrane separation. It was found that the entire process not only decreased the phospholipid content of the oil but also improved its fuel properties, especially its kinematic viscosity and carbon residue. The kinematic viscosity was decreased from 30.02 cSt (mm²/s) to 27.20 cSt, while the carbon residue was decreased from 7.8% to 4.0%. Aside from the phospholipid content, the other two properties mentioned above were also considered to be important in the use of pure plant oil as a fuel in diesel engines. Future research could investigate the integration and optimization of the conventional degumming process combined with a membrane separation process.     

Effect of degumming reagents on the recovery and nature of lecithins from crude canola,soybean and sunflower oils

Six reagents (water, citric acid, phosphoric acid, oxalic acid, acetic anhydride and maleic anhydride) were evaluated for their effectiveness in degumming three crude vegetable oils (canola, soybean and sunflower). All chemical reagents tested were found to be significantly more effective than water in removing lecithin material from all three oils except for acetic anhydride degumming of canola. Citric and phosphoric acids were found to be very effective in reducing phosphorus levels in canola oil (91 and 93% removal, respectively). For soybean oil, all reagents except water showed excellent degumming ability by removing 98% phosphorus, while in the case of sunflower oil, maleic anhydride and oxalic acid produced the highest level of phosphorus removal (95 and 90%, respectively). Both citric acid and acetic anhydride were effective in removing Fe from all three oils during degumming (84 to 94%), while phosphoric acid showed slightly lower values (73 to 87%). No significant changes in the phospholipid composition or fatty acid profiles of the phospholipid classes were observed as a result of degumming with the various chemical reagents. In general, canola phospholipids were lowest in palmitic, stearic and linoleic acid and contained the highest levels of oleic acid when compared to soybean and sunflower phospholipids. Both citric and acetic anhydride were found to influence the removal of an unknown glycolipid significantly. Canola lecithin was shown to contain a greater amount of glycolipids than sunflower and soybean lecithins.     

Comparison of oxalic acid and phosphoric acid as degumming agents for vegetable oils

For many years, phosphoric acid has been used for degumming vegetable oils with high phosphatide content prior to alkali refining. One disadvantage of this technique is the resulting undesirable phosphate waste in streams, a problem which has increased substantially in importance in recent times. We have investigated an alternative degumming technique using oxalic acid that alleviates the pollution problem in cases where water purification by means of a chemical treatment process is not possible.     

Deacidification of high FFA rice bran oil by reesterification and alkali neutralization

Rice bran oils of 15 to 30% free fatty acid can be deacidified to low levels by reesterification with glycerol after degumming and dewaxing. The reesterification can by combined with conventional alkali neutralization and bleaching to produce light color edible oil.