中石化上海高桥分公司恶臭治理项目设计心得

随着我国重质高硫原油进口量的逐年递增,以及国产原油品质变差、硫含量升高,原油加工深度的提高,石油炼制过程中产生的恶臭污染日益加重,已成为炼油企业亟待解决的重大环保课题。笔者主持设计的《中石化上海高桥分公司恶臭治理项目》中,利用"低温柴油吸收—碱液吸收脱硫"和"膜法化学品回收"两种技术来除臭,现在与大家交流一些设计心得。     

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.     

Refining high-free fatty acid wheat germ oil

Wheat germ oil was refined using conventional degumming, neutralization, bleaching, and continuous tray deodorization, and the effects of processing conditions on oil quality were determined. The crude wheat germ oil contained 1,428 ppm phosphorus, 15.7% free fatty acid (FFA), and 2,682 ppm total tocopherol, and had a peroxide value (PV) of 20 meq/kg. Degumming did not appreciably reduce the phosphorus content, whereas neutralization was effective in removing phospholipid. Total tocopherol content did not significantly change during degumming, neutralization, and bleaching. A factorial experimental design of three deodorization tempeatures and three residence times (oil flow rates) was used to determine quality changes during deodorization. High temperatures and long residence times in deodorization produced oils with less FFA, PV, and red color. Deodorization at temperatures up to 250°C for up to 9 min did not significantly reduce tocopherol content, but, at 290°C for 30-min residence time, the tocopherol content was significantly reduced. Good-quality wheat germ oil was produced after modifying standard oil refining procedures.     

Quality control in edible oil processing

This paper describes a Q.C. program for the manufacture of edible products from crude degummed oil. Tests done at various stages in the production are discussed, including test methods used and what is considered as acceptable results. Processes covered include receiving oil, alkali refining, bleaching, hydrogenation, deodorization, bulk shipping and packaged finished product.     

Fatty Acid,Phytosterol, and Polyamine Conjugate Profiles of Edible Oils Extracted from Corn Germ,Corn Fiber,and Corn Kernels

This study compared the profiles of fatty acids, phytosterols, and polyamine conjugates in conventional commercial corn oil extracted from corn germ and in two “new-generation” corn oils: hexane-extracted corn fiber oil and ethanol-extracted corn kernel oil. The fatty acid compositions of all three corn oils were very similar and were unaffected by degumming, refining, bleaching, and deodorization. The levels of total phytosterols in crude corn fiber oil were about tenfold higher than those in commercial corn oil, and their levels in crude corn kernel oil were more than twofold higher than in conventional corn oil. When corn kernel oil was subjected to conventional degumming, refining, bleaching, and deodorization, about half of the phytosterols was removed, whereas when corn fiber oil was subjected to a gentle form of degumming, refining, bleaching, and deodorization, only about 10% of the phytosterols was removed. Finally, when the levels of polyamine conjugates (diferuloylputrescine and p-coumaroyl feruloylputrescine) were examined in these corn oils, they were only detected in the ethanol-extracted crude corn kernel oil, confirming earlier reports that they were not extracted by hexane, and providing new information that they could be removed from ethanol-extracted corn kernel oil by conventional degumming, refining, bleaching, and deodorizing.     

Steam refining

Steam refining of fatty oils to reduce the partially high free fatty acid content of certain crude oils before conventional refining has been practiced in Europe for many years. Intensive laboratory testing indicated that crude palm oil could be pretreated to remove trace metals and certain heat resistant organic compounds. This pretreated oil could then be steam refined and simultaneously steam deodorized to produce a high quality finished edible oil. Analytical data on crude and finished oil quality and operating yields are presented to illustrate the steam refining/deodorization process. Laboratory results obtained by steam refining a variety of other oils also are presented.     

Physical refining of edible oils

Physical refining of edible oils offers several advantages over alkali refining. The method described for physical refining of rapeseed oil involves several novel factors, including the availability of cold-pressed rapeseed oil low in phosphatide content and deacidification/deodorization in a film molecular evaporator. Parameters are presented from a pilot plant unit with an output of 500 metric tons per year. Further applications of the technology are proposed, including the processing of oils to pharmaceutical-grade products.     

Supercritical CO2 degumming and physical refining of soybean oil

A hexane-extracted crude soybean oil was degummed in a reactor by counter-currently contacting the oil with supercritical CO₂ at 55 MPa at 70°C. The phosphorus content of the crude oil was reduced from 620 ppm to less than 5 ppm. Degummed feedstocks were fed (without further processing,i.e., bleaching) directly to a batch physical refining step consisting of simultaneous deacidification/deodorization (1 h @ 260°C and 1–3 mm Hg) with and without 100 ppm citric acid. Flavor and oxidative stability of the oils was evaluated on freshly deodorized oils both after accelerated storage at 60°C and after exposure to fluorescent light at 7500 lux. Supercritical CO₂-processed oils were compared with a commercially refined/bleached soybean oil that was deodorized under the same conditions. Flavor evaluations made on noncitrated oils showed that uncomplexed iron lowered initial flavor scores of both the unaged commercial control and the CO₂-processed oils. Oils treated with .01% (100 ppm) citric acid had an initial flavor score about 1 unit higher and were more stable in accelerated storage tests than their uncitrated counterparts. Supercritical CO₂-processed oil had equivalent flavor scores, both initially and after 60°C aging and light exposure as compared to the control soybean oil. Results showed that bleaching with absorbent clays may be eliminated by the supercritical CO₂ counter-current processing step because considerable heat bleaching was observed during deacidification/deodorization. Colors of salad oils produced under above conditions typically ran 3Y 0.7R.     

Acephate,methamidophos and monocrotophos residues in a laboratory‐scale oil refining process

Acephate, methamidophos and monocrotophos are insecticides used in oil palm plantations for the control of bagworms and leaf‐eating caterpillars. The main purpose of this study was to determine whether the physical refining process at laboratory scale, which simulated the manufacturing process, could remove the residues of these three insecticides in crude palm oil, in the unlikely event that crude palm oil were contaminated with these organophosphorus insecticides. A series of crude palm oil samples spiked with low (0.1 µg/g) and high (1.0 µg/g) levels of these insecticides were subjected to a laboratory‐scale physical oil refining process. Oil samples drawn at various stages of the refining process, namely, degumming, bleaching and deodorization, were analyzed using an in‐house analytical method. The results obtained from these experiments suggest that the physical refining process is capable of effectively removing residual insecticides from crude palm oil. The final product of crude palm oil refining, the refined, bleached and deodorized palm oil, was found to have no detectable levels of acephate, methamidophos and monocrotophos.     

Chlorophyll removal during earth bleaching of soybean oil

Summary A spectrophotometric procedure for determining and calculating the chlorophyll content of unhardened as well as hardened soybean oil has been given. This procedure has proven satisfactory from a practical standpoint for controlling the greenness imparted to finished shortenings by chlorophyll. The influence of the refining, hydrogenation and deodorization operations on the chlorophyll content has also been reviewed. Isotherms have also been presented which illustrate the complexity encountered in bleaching soybean oil with respect to chlorophyll.     

Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil

The effect of different processing steps of refining on retention or the availability of oryzanol in refined oil and the oryzanol composition of Indian paddy cultivars and commercial products of the rice bran oil (RBO) industry were investigated. Degumming and dewaxing of crude RBO removed only 1.1 and 5.9% of oryzanol while the alkali treatment removed 93.0 to 94.6% of oryzanol from the original crude oil. Irrespective of the strength of alkali (12 to 20° Be studied), retention of oryzanol in the refined RBO was only 5.4–17.2% for crude oil, 5.9–15.0% for degummed oil, and 7.0 to 9.7% for degummed and dewaxed oil. The oryzanol content of oil extracted from the bran of 18 Indian paddy cultivars ranged from 1.63 to 2.72%, which is the first report of its kind in the literature on oryzanol content. The oryzanol content ranged from 1.1 to 1.74% for physically refined RBO while for alkali-refined oil it was 0.19–0.20%. The oil subjected to physical refining (commercial sample) retained the original amount of oryzanol after refining (1.60 and 1.74%), whereas the chemically refined oil showed a considerably lower amount (0.19%). Thus, the oryzanol, which is lost during the chemical refining process, has been carried into the soapstock. The content of oryzanol of the commercial RBO, soapstock, acid oil, and deodorizer distillate were in the range: 1.7–2.1, 6.3–6.9, 3.3–7.4, and 0.79%, respectively. These results showed that the processing steps—viz., degumming (1.1%), dewaxing (5.9%), physical refining (0%), bleaching and deodorization of the oil—did not affect the content of oryzanol appreciably, while 83–95% of it was lost during alkali refining. The oryzanol composition of crude oil and soapstock as determined by high-performance liquid chromatography indicated 24-methylene cycloartanyl ferulate (30–38%) and campesteryl ferulate (24.4–26.9%) as the major ferulates. The results presented here are probably the first systematic report on oryzanol availability in differently processed RBO, soapstocks, acid oils, and for oils of Indian paddy cultivars.     

Polycyclic aromatic hydrocarbons in crude and deodorized vegetable oils

The efficiency of the refining process in removing polycyclic aromatic hydrocarbons (PAH) from crude vegetable oils was studied. Samples of the crude oils (coconut, soybean and rapeseed oils) and the corresponding refined, deodorized oil were taken on-line in three Swedish oil refineries and margarine manufacturing plants and analyzed for 20 different PAHs. Of the crude oils, coconut oil had by far the highest PAH levels. However, the PAH levels in the refined coconut oils were very low. This shows that the activated charcoal treatment used for removing PAHs from coconut oil achieves the desired effect. The crude soybean and rapeseed oils contained relatively low, but varying, amounts of PAH. At present these oils are not purified by activated charcoal. Nevertheless, the PAH levels in the refined oils were considerably lower than those in the corresponding crude oils. This probably is due to evaporation of PAH in the deodorization process, where steam is passed through the hot oil under high vacuum. However, deodorization has only a marginal effect on the high molecular PAHs, of which several are classified as carcinogens.     

Physical refining of coconut oil: Effect of crude oil quality and deodorization conditions on neutral oil loss

In the present study, neutral oil loss (distillative and mechanical carry-over) during physical refining of coconut oil was quantified. Neutral oil loss seems to depend on both the crude oil quality and the process conditions during deodorization. The distillation of volatile glyceridic components (monoand diglycerides), originally present in the crude oil, was confirmed as the major cause for the neutral oil loss. The amount of these volatile components in crude coconut oils cannot be derived as such from the initial free fatty acid content. A lower deodorization pressure with less sparge steam resulted in a larger neutral oil loss than a higher pressure with more steam. A “deodorizability” test on a laboratory scale under standardized conditions (temperature=230°C, pressure=3 mbar, time=60 min, sparge steam=1%), to evaluate crude oil quality and to obtain a more accurate prediction of the expected neutral oil loss and free fatty acid content in the fatty acid distillate, is described.     

Removal of copper from hydrogenated soybean oil

Hydrogenation with a copper-chromite catalyst at 170 C, 30 psi, increased the copper content of a refined, bleached soybean oil from 0.02 to as much as 3.8 ppm. Removing residual copper from soybean oil is essential to the successful use of copper catalysts for selective hydrogenation. Various methods were examined to remove this copper, including alkali refining, bleaching, acid washing, citric acid treatment and cation-exchange resin treatment. Properly conducted, each of the methods except alkali refining gives 95% or higher removal of copper introduced during hydrogenation. Ion exchange appears to be the most economical, but addition of about 0.01% citric acid during deodorization may be needed to inactivate traces of unremoved copper. Soybean oil hydrogenated with a copper-chromite catalyst, bleached or treated with an ion-exchange resin and deodorized with 0.01% citric acid added had low AOM peroxide values and acceptable flavor scores after eight days at 60 C which indicate that removal of residual copper from the oil should be adequate for the production of stable oils low in linolenic acid content. Presented at AOCS Meeting, Chicago, October 1967.     

Canola oil processing in Canada

Canola is the registered trademark of the Canola Council of Canada for the seed, oil and meal derived from rapeseed cultivars low in erucic acid and low in glucosinolates. Conversion to canola cultivars on a commercial scale started in 1976; in 1981, ca. 87% of the brassica-based oil crop in Canada was of canola quality. Canola oil is the most important oil in Canada. Processing of the oil is, in its essentials, conventional. A few problems not usually encountered with other oils are its chlorophyll content which requires extra processing and analytical effort, and certain limitations in crystallization behavior when highly hydrogenated. Advantages are that stable oils can be produced at moderate degree of hydrogenation, and without hydrogenation in the case of salad oil. New developments in processing of the oil have led to the production of acid-degummed, crude oil on a commercial scale. This opens the possibility to apply physical refining to the oil.     

Removal of chlorinated pesticides from crude vegetable oils by simulated commercial processing procedures

Crude soybean and cottonseed oil were processed using simulated commercial processing procedures to determine if oil processing would remove chlorinated pesticide contaminants of either natural or spiked origin. Two crude oil lots were spiked with endrin, DDT, DDE, aldrin, dieldrin, heptachlor and heptachlor epoxide before processing. Representative samples of crude oil and products following each processing step were analyzed for pesticide contamination. Results indicated that alkali-refining or subsequent bleaching did not reduce chlorinated pesticide contamination. Hydrogenation prior to deodorization reduced endrin contamination. Deodorization, with or without hydrogenation, eliminated chlorinated pesticides. The results of this study indicate that normal commercial processing of crude vegetable oils for human consumption effectively removes any chlorinated pesticides which may be present in crude oils. It is hypothesized that chlorinated pesticide removal is achieved by volatilization during deodroization, which is supported by known volatilization characteristics, similarity of behavior in pesticides studied, and absence of the pesticide or its conversion products in the finished oils, or both.     

The effect of processing operations on the total sulphur content in rapeseed oil

The technological difficulties due to the presence of sulphur-containing compounds in rapeseed oil lead to the problem of proper hydrogenation under commercial conditions. The effect of refining operations on the total sulphur content of rapeseed oil was studied. Degumming (phosphoric acid treatment) had an insignificant effect on the sulphur content while deacidification (alkali refining) removed about 30% and bleaching with Fuller's earth removed about 50% of the total sulphur in commercial crude oil. Deodorization affected nearly the complete removal of residual sulphur left after the application of treatments mentioned above.     

Membrane degumming of crude rice bran oil: Pilot plant study

The procedure for the classical chemical refining of vegetable oils consists of degumming, alkali neutralization, bleaching, and deodorization. Conventional refining of rice bran oil using alkali gives oil of acceptable quality, but the refining losses are very high. A critical work has been carried out to study the application of membrane technology in the pretreatment of crude rice bran oil. Oils intended for physical refining should have a low phosphorus content, and this is not readily achievable by the conventional acid/water degumming process. The application of membrane technology for the pretreatment of rice bran oil has been investigated. The process has already been successfully applied to other vegetable oils. Ceramic membranes, which are important from the commercial point of view, were examined for this purpose. The results showed that the membrane‐filtered oils met the requirements of physical refining, with a substantial reduction in color. It was observed that most of the waxy material was also rejected. Experiments were carried out to establish the relationship between permeate flux and rejection with membrane pore size, trans‐membrane pressure and micellar solute concentration.     

Oxidation and quality of soybean oil: A preliminary study of the anisidine test

The anisidine test, a measure of secondary oxidation products in glyceride oils, was applied to a number of soybean salad oils processed from sound and damaged soybeans. A highly significant correlation (−0.68) was found between the anisidine values of salad oils from sound soybeans and their flavor scores. Multiple correlations between flavor scores, anisidine, and peroxide values yielded a correlation of 0.81 and provided a method for predicting the initial flavor scores of sound soybean salad oils. Similar data for oils from damaged beans gave a highly significant, but lower, correlation (−0.65). Comparative studies indicated that sound crude oils usually contain lower levels of oxidation products than damaged crude. Oxidation in both sound and damaged crudes increased roughly in proportion to iron content. Reproducibility of the test and the effects of hydrogenation, accelerated storage, and fluorescent light on anisidine values were studied. Analysis of damaged oils before and after deodorization showed that little, if any, reduction of anisidine value occurred. Deodorization of sound oils, however, lowered anisidine values. In comparison with damaged oils, the anisidine values of sound oils were lower at comparable stages of processing. The poor quality of damaged soybean oil was substantiated by organoleptic evaluations. Flavor scores of oils given special processing treatments increased as anisidine values decreased.     

Chemical and physical effects of processing fats and oils

Soybean oil is processed for a variety of food uses, salad/cooking oil, margarine and shortening. Crude soybean oil is composed mainly of triglycerides but also contains measurable amounts of minor constituents that may have beneficial or detrimental effects on oil characteristics. The nature of these minor constituents, the role they play in oil stability or deterioration and their fate during processing are subjects of this review. Iodine value, fatty acid composition, solid fat index and congeal point are chemical and physical characteristics of oil that are affected by the hydrogenation process. Techniques and effects of degumming, alkali refining, bleaching, hydrogenation, winterization and deodorization are discussed. Utilization or disposal of by-products or wastes from each processing step is reviewed. Presented at Northeast Section, AOCS, Symposium, Newark, N.J., November 5–6, 1979.