EP0247411B1 - Method for treating caustic refined glyceride oils for removal of soaps and phospholipids - Google Patents

Method for treating caustic refined glyceride oils for removal of soaps and phospholipids Download PDF

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Publication number
EP0247411B1
EP0247411B1 EP87106683A EP87106683A EP0247411B1 EP 0247411 B1 EP0247411 B1 EP 0247411B1 EP 87106683 A EP87106683 A EP 87106683A EP 87106683 A EP87106683 A EP 87106683A EP 0247411 B1 EP0247411 B1 EP 0247411B1
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Prior art keywords
oil
soaps
caustic
silica
phospholipids
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EP87106683A
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German (de)
English (en)
French (fr)
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EP0247411A1 (en
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William Alan Welsh
James Marlow Bogdanor
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WR Grace and Co Conn
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WR Grace and Co Conn
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/10—Refining fats or fatty oils by adsorption

Definitions

  • This invention relates to a method for refining glyceride oils by contacting the oils with an adsorbent capable of removing certain impurities. More specifically, it has been found that amorphous silicas are quite effective in adsorbing both soaps and phospholipids from caustic treated or caustic refined glyceride oils, to produce oil products with substantially lowered concentrations of these impurities.
  • impurities refers to soaps and phospholipids. The phospholipids are associated with metal ions and together they will be referred to as "trace contaminants”.
  • the term "glyceride oils” as used herein is intended to encompass both vegetable and animal oils.
  • oils i.e., oils derived from fruits or seeds of plants and used chiefly in foodstuffs, but it is understood that oils whose end use is as non-edibles are to be included as well.
  • the invention is applicable to oils which have been subjected to caustic treatment, which is the refining step in which soaps are formed in the oil.
  • Crude glyceride oils are refined by a multi-stage process, the first step of which typically is “degumming” or “desliming” by treatment with water or with a chemical such as phosphoric acid, citric acid or acetic anhydrid. This treatment removes some but not all gums and certain other contaminants. Some of the phosphorus content of the oil is removed with the gums.
  • Either crude or degummed oil may be treated in a chemical, or caustic, refining process. The addition of an alkali solution, caustic soda for example, to a crude or degummed oil causes neutralization of free fatty acids to form soaps.
  • the water wash and centrifugation steps must be repeated in order to reduce the soap content of the oil below about 50 ppm.
  • the water-washed oil then must be dried to remove residual moisture to below about 0.1 weight percent.
  • the dried oil is then either transferred to the bleaching process or is shipped or stored as once-refined oil.
  • a significant part of the waste discharge from the caustic refining of vegetable oil results from the water wash process used to remove soaps.
  • a primary reason for refiners' use of the physical refining process is to avoid the wastestream production associated with removal of soaps generated in the caustic refining process: since no caustic is used in physical refining, no soaps are generated.
  • some oil is lost in the water wash process.
  • the dilute soapstock In the caustic refining process to which this invention relates, moreover, the dilute soapstock must be treated before disposal, typically with an inorganic acid such as sulfuric acid in a process termed acidulation. Sulfuric acid is frequently used.
  • phosphorus-containing trace contaminants In addition to removal of soaps created in the caustic refining process, phosphorus-containing trace contaminants must be removed from the oil. The presence of these trace contaminants can lend off colors, odors and flavors to the finished oil product. These compounds are phospholipids, with which are associated ionic forms of the metals calcium, magnesium, iron and copper.
  • references to the removal or adsorption of phospholipids is intended also to refer to removal or adsorption of the associated metal ions.
  • Adsorption of phosphorus on various adsorbents for example, bleaching earth
  • No adsorption process has accomplished the removal of both soaps and phospholipids at an early stage of caustic refining where large quantities of soaps are present.
  • GB-A-599 595 refers to an improved method of refining crude glyceride oils, in which the oil is mist- mixed with water-absorbtive agent selected from the group consisting of salts containing water-absorbtive ions, colloidal silica and mixtures thereof and with a caustic alkali solution which acts to neutralize the fatty acids present in the oil to form a soap-stock.
  • the caustic alkali is used in an amount in such excess of that necessary to neutralize the free fatty acid that some of the caustic alkali is present at the time of separation of the soapstock from the oil and said agent being used in an amount effective to substantially reduce the neutral oil retained by the soapstock and to retard the saponification of the neutral oil.
  • a simple physical adsorption process has been found whereby soaps and phospholipids can be removed from caustic treated or caustic refined vegetable oils in a single unit operation.
  • This unique process completely eliminates the need to subject caustic treated or caustic refined oil to a water washing process in order to remove soaps. It also eliminates the need for a separate adsorption process to reduce the phospholipid content of the oil.
  • the process described herein utilizes amorphous silica adsorbents having an average pore diameter of greater than 6 nm (60 A) which can remove all or substantially all soaps from the oil and which reduce the phospholipid content on the oil to at least below 15 parts per million, preferably below 5 parts per million, most preferably substantially to zero.
  • Adsorption of soaps and phospholipids (together with associated contaminants) onto amorphous silica in the manner described offers tremendous advantage in caustic refining by eliminating the several unit operations required when conventional water-washing, centrifugation and drying are employed to remove soaps from the oils.
  • this method eliminates the need for wastewater treatment and disposal from those operations.
  • Reduction or elimination of an additional bleaching earth step will result in substantial oil conservation as this step typically results in significant oil loss. Moreover, since spent bleaching earth has a tendency to undergo spontaneous combustion, reduction or elimination of this step will yield an occupationally and environmentally safer process.
  • An additional object of the invention is to simplify the recovery costs and processing now associated with preparation of the aqueous soapstock for use in the animal feed industry.
  • the spent silica adsorbent can be used in animal feeds either as is or after acidulation to convert the soaps into free fatty acids.
  • the need in the conventional caustic refining process for drying or concentrating the dilute soapstock is eliminated by this invention.
  • amorphous silicas are particularly well suited for removing both soaps and phospholipids from caustic refined glyceride oils.
  • the process for the removal of these impurities essentially comprises the steps of selecting a caustic treated or caustic refined glyceride oil which comprises soaps and phospholipids, selecting an adsorbent which comprises a suitable amorphous silica, contacting the caustic treated or caustic refined oil and the adsorbent, allowing the soaps and phospholipids to be adsorbed onto the amorphous silica, and separating the adsorbent-treated oil from the adsorbent.
  • soaps and phospholipids can be removed from oils in a single adsorption step.
  • the presence of increasing levels of soap in the oil to be treated actually enhances the capacity of amorphous silica to adsorb phosphorus. That is, the presence of soaps at levels below the maximum adsorbent capacity of the silica makes it possible to substantially reduce phosphorus content at lower silica usage than required in the absence of soaps.
  • the process described herein can be used for the removal of phospholipids from any caustic refined glyceride oil, for example, oils of soybean, peanut, rapeseed, corn, sunflower, palm, coconut, olive, cottonseed, etc.
  • the caustic refining process involves the neutralization of the free fatty acid content of crude or degummed oil by treatment with bases, such as sodium hydroxide or sodium carbonate, which typically are used in aqueous solution.
  • bases such as sodium hydroxide or sodium carbonate
  • the neutralized free fatty acid present as the alkali or alkaline earth salt is defined as soap.
  • the soap content of caustic treated oil will vary depending on the free fatty content of the unrefined oil.
  • the acceptable concentration of phosphorus in the finished oil product should be less than about 15.0 ppm, preferably less than about 5.0 ppm, according to general industry practice.
  • typical phosphorus levels in soybean oil at various stages of chemical refining are shown in Table I.
  • the process of this invention also removes from edible oils ionic forms of the metals calcium, magnesium, iron and copper, which are believed to be chemically associated with phospholipids, and which are removed in conjunction with the phospholipids.
  • These metal ions themselves have a deleterious effect on the refined oil products. Calcium and magnesium ions can result in the formation of precipitates, particularly with free fatty acids, resulting in undesired soaps in the finished oil. The presence of iron and copper ions promote oxidative instability.
  • each of these metal ions is associated with catalyst poisoning where the refined oil is catalytically hydrogenated. Typical concentrations of these metals in soybean oil at various stages of chemical refining are shown in Table I. Throughout the description of this invention, unless otherwise indicated, reference to the removal of phospholipids is meant to encompass the removal of associated metal ions as well.
  • the amorphous silicas described below exhibit very high capacity for adsorption of soaps and phospholipids.
  • the capacity of the silica for phospholipids is improved with increasing soap levels in the starting oil, provided that sufficient silica is used to obtain adsorbent-treated oil with soap levels of approximately 30 ppm or less. It is when the residual soap levels (in the adsorbent-treated oil) fall below about 30 ppm that the increased capacity of the silica for phospholipid adsorption is seen. It is believed that the total available adsorption capacity of amorphous silica is about 50 to 75 wt.% on a dry basis.
  • the silica usage should be adjusted so that the total soap and phospholipid content of the caustic treated or caustic refined oil does not exceed about 50 to 75 wt.% of the silica added on a dry basis.
  • the maximum adsorption capacity observed in a particular application is expected to be a function of the specific properties of the silica used, the oil type and stage of refinement, and processing conditions such as temperature, degree of mixing and silica-oil contact time. Calculations for a specific application are well within the knowledge of a person of ordinary skill as guided by this specification.
  • the adsorption step itself is accomplished by conventional methods in which the amorphous silica and the oil are contacted, preferably in a manner which facilitates the adsorption.
  • the adsorption step may be by any convenient batch or continuous process. In any case, agitation or other mixing will enhance the adsorption efficiency of the silica.
  • the adsorption can be conducted at any convenient temperature at which the oil is a liquid.
  • the caustic refined oil and amorphous silica are contacted as described above for a period sufficient to achieve the desired levels of soap and phospholipid in the treated oil.
  • the specific contact time will vary somewhat with the selected process, i.e., batch or continuous.
  • the adsorbent usage that is, the relative quantity of adsorbent brought into contact with the oil, will affect the amount of soaps and phospholipids removed.
  • the adsorbent usage is quantified as the weight percent of amorphous silica (on a dry weight basis after ignition at 954°C (1750°F), calculated on the basis of the weight of the oil processed.
  • the preferred adsorbent usage is at least about 0.01 to about 1.0 wt.%, dry basis, most preferably at least about 0.1 to about 0.15 wt.%, dry basis.
  • soap content and the phosphorus content of the treated oil will depend primarily on the oil itself, as well as on the silica, usage, process, etc.
  • the initial soap content will vary significantly depending whether the oil is treated by this adsorption method following caustic treatment or following primary centrifugation.
  • the phosphorus content will be somewhat reduced following degumming, caustic treatment and/or primary centrifuge.
  • phosphorus levels of less than 15 ppm, preferably less than 5.0 ppm, and most preferably less than 1.0 ppm, and soap levels of less than 50 ppm, preferably less than about 10 ppm and most preferably substantially zero ppm, can be achieved by this adsorption method.
  • the soap and phospholipid enriched silica is removed from the adsorbent-treated oil by any convenient means, for example, by filtration or centrifugation.
  • the oil may be subjected to additional finishing processes, such as steam refining, bleaching and/or deodorizing.
  • additional finishing processes such as steam refining, bleaching and/or deodorizing.
  • heat bleaching instead of a bleaching earth step, which is associated with significant oil losses.
  • simultaneous or sequential treatment with amorphous silica and bleaching earth provides an extremely efficient overall process.
  • the spent silica may be used in animal feed, either as is, or following acidulation to reconvert the soaps into fatty acids. Alternatively, it may be feasible to elute the adsorbed impurities from the spent silica in order to re-cycle the silica for further oil treatment.
  • silica as used herein is intended to embrace silica gels, precipitated silicas, dialytic silicas and fumed silicas in their various prepared or activated forms. Both silica gels and precipitated silicas are prepared by the destabilization of aqueous silicate solutions by acid neutralization. In the preparation of silica gel, a silica hydrogel is formed which then typically is washed to low salt content. The washed hydrogel may be milled, or it may be dried, ultimately to the point where its structure no longer changes as a result of shrinkage. The dried, stable silica is termed a xerogel.
  • the destabilization is carried out in the presence of polymerization inhibitors, such as inorganic salts, which cause precipitation of hydrated silica.
  • the precipitate typically is filtered, washed and dried.
  • Dialytic silica is prepared by precipitation of silica from a soluble silicate solution containing electrolyte salts (e.g., NaN0 3 , Na 2 S0 4 , KN0 3 ) while electrodialyzing, as described in EP-A-107 142.
  • Fumed silicas are prepared from silicon tetrachloride by high-temperature hydrolysis, or other convenient methods. The specific manufacturing process used to prepare the amorphous silica is not expected to affect its utility in this method.
  • the silica adsorbent will have the highest possible surface area in pores which are large enough to permit access to the soap and phospholipid molecules, while being capable of maintaining good structural integrity upon contact with the oil.
  • the requirement of structural integrity is particularly important where the silica adsorbents are used in continuous flow systems, which are susceptible to disruption and plugging.
  • Amorphous silicas suitable for use in this process have surface areas of up to about 1200 square meters per gram, preferably between 100 and 1200 square meters per gram. It is preferred, as well, for as much as possible of the surface area to be contained in pores with diameters greater than 6 nm (60 A).
  • the method of this invention utilizes amorphous silicas with substantial porosity contained in pores having diameters greater than about 6 nm (60 A), as defined herein, after appropriate activation. Activation typically is accomplished by heating to temperatures of about 232 to 371°C (450 to 700°F) in vacuum.
  • One convention which describes silicas is average pore diameter ("APD"), typically defined as that pore diameter at which 50% of the surface area or pore volume is contained in pores with diameters greater than the stated APD and 50% is contained in pores with diameters less than the stated APD.
  • APD average pore diameter
  • Silicas with a higher proportion of pores with diameters greater than 6 nm (60 A) will be preferred, as these will contain a greater number of potential adsorption sites. The practical upper limit is about 500 nm (5000 A).
  • Silicas which have measured intraparticle APDs within the stated range will be suitable for use in this process.
  • the required porosity may be achieved by the creation of an artificial pore network of interparticle voids in the 6 to 500 nm (60 to 5000 A) range.
  • non-porous silicas i.e., fumed silica
  • Silicas, with or without the required porosity may be used under conditions which create this artificial pore network.
  • the criterion for selecting suitable amorphous silicas for use in this process is the presence of an "effective average pore diameter" greater than 6 nm (60 A). This term includes both measured intraparticle APD and interparticle APD, designating the pores created by aggregation or packing of silica particles.
  • the APD value (in Angstroms) can be measured by several methods or can be approximated by the following equation, which assumes model pores of cylindrical geometry: where PV is pore volume (measured in cubic centimeters per gram) and SA is surface area (measured in square meters per gram).
  • Both nitrogen and mercury porosimetry may be used to measure pore volume in xerogels, precipitated silicas and dialytic silicas. Pore volume may be measured by the nitrogen Brunauer-Emmett-Teller ("B-E-T") method described in Brunauer et al., J. Am. Chem. Soc., Vol. 60, p. 309 (1938). This method depends on the condensation of nitrogen into the pores of activated silica and is useful for measuring pores with diameters up to about 60 nm (600 A). If the sample contains pores with diameters greater than about 60 nm (600 A), the pore size distribution, at least of the larger pores, is determined by mercury porosimetry as described in Ritter et al., Ind. Eng. Chem.
  • pore volume of hydrogels For determining pore volume of hydrogels, a different procedure, which assumes a direct relationship between pore volume and water content, is used. A sample of the hydrogen is weighed into a container and all water is removed from the sample by vacuum at low temperatures (i.e., about room temperature). The sample is then heated to about 232 to 371°C (450 to 700°F) to activate. After activation, the sample is reweighed to determine the weight of the silica on a dry basis, and the pore volume is calculated by the equation: where TV is total volatiles, determined by the wet and dry weight differential. An alternative method of calculating TV is to measure weight loss on ignition at 954°C (1750°F), (see Equation (9) in Example II). The PV value calculated in this manner is then used in Equation (1).
  • the surface area measurement in the APD equation is measured by the nitrogen B-E-T surface area method, described in the Brunauer et al., article, supra.
  • the surface area of all types of appropriately activated amorphous silicas can be measured by this method.
  • the measured SA is used in Equation (1) with the measured PV to calculate the APD of the silica.
  • amorphous silica used in this invention is not believed to be critical in terms of the adsorption of soaps and phospholipids. However, where the finished products are intended to be food grade oils care should be taken to ensure that the silica used does not contain leachable impurities which could compromise the desired purity of the product(s). It is preferred, therefore, to use a substantially pure amorphous silica, although minor amounts, i.e., less than about 10%, of other inorganic constituents may be present.
  • suitable silicas may comprise iron as Fe 2 0 3 , aluminum as A1 2 0 3 , titanium as Ti0 2 , calcium as CaO, sodium as Na 2 0, zirconium as Zr0 2 , and/or trace elements.
  • Oil Samples used in the following examples were prepared by combining Oil A (see Table III), a caustic refined soybean oil sampled after caustic treatment and primary centrifuge but before water wash, with either Oil Sample E or Oil Sample E' degummed soybean oils prepared as described below and not subjected to caustic treatment.
  • Sample E' was prepared in the same manner as Oil Sample E Table III, for which analytical results are shown; insufficient quantities of Oil Sample E' precluded separate analysis, but it is assumed that the identically degummed oils were substantially identical.
  • Oil Sample A contained large quantities of soaps (362 ppm) determined by measuring alkalinity expressed as sodium oleate (ppm) by A.O.C.S. Recommended Practice Cc 17-79.
  • the acid degummed oils having not been contacted with caustic, contained no soap, but contained significant levels of phosphorus, as indicated by the values for Oil Sample E, which contained 22.0 ppm phosphorus, measured by inductively coupled plasma ("ICP") emission spectroscopy.
  • ICP inductively coupled plasma
  • Oil Sample A was mixed in varying proportions (as indicated in Table III) with Oil Sample E or E' to prepare Oil Samples B, C and D, which are relatively constant for phosphorus and associated metal ions but which contain significantly different levels of soap.
  • Oil Sample B contained 75% Oil Sample A and 25% Oil Sample E.
  • Oil Sample C contained 50% Oil Sample A and 50% Oil Sample E'.
  • Oil Sample D contained 25% Oil Sample A and 75% Oil Sample E'.
  • Each Oil Sample was analyzed as described above for trace contaminants (P, Ca, Mg, Fe and Cu) and for soaps. The results are shown in Table III.
  • the acid degummed oils (Oil Samples E and E') were prepared by heating 500.0 gm oil, covered with foil and blanketed with nitrogen, in a 40°C water bath. Next, 500 ppm 85% phosphoric acid (0.25 gm) was added to the oil and stirred for twenty minutes while maintaining the nitrogen blanket. Ten milliliters of deionized water was added and mixed for one hour. The sample was centrifuged at 2300 rpm for thirty minutes. The top layer was the degummed oil used in the experiment (the bottom layer, comprising the gums, was (discarded).
  • Example I The Oil Samples prepared in Example I were treated with the amorphous silica described in Example I.
  • a 100.0 gm quantity of the Oil Sample (A, B, C, D, or E) was heated at 100°C, and the silica was added in the amount indicated in Table IV. The mixture was maintained at 100°C, while being stirred vigorously, for 0.5 hours. The silica was separated from the oil by filtration.
  • the treated, filtered Oil Samples were analyzed for soap and trace contaminant levels by the methods described in Example I. The results, shown in Table IV, indicate that:
  • Example II The data obtained from Example II demonstrate that the capacity of amorphous silica for phospholipid and soap removal actually increases with increasing soap content of the starting oil until a maximum adsorbent capacity is approached.
  • the data in Table V were calculated from Table IV in order to obtain values for the adsorption capacity of the amorphous silica. Calculations were made as follows.
  • the capacity of the amorphous silica for combined soaps and phospholipids (C S - PL ), expressed as a percent, can be defined as: where the change in concentrations of soaps and phospholipids in the oil (from before to after contact with the silica adsorbent) are defined as: where "Silica (db, gm)" is the weight in grams of the silica after ignition at 1750°F.
  • C PL amorphous silica

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EP87106683A 1986-05-14 1987-05-08 Method for treating caustic refined glyceride oils for removal of soaps and phospholipids Expired - Lifetime EP0247411B1 (en)

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Application Number Priority Date Filing Date Title
AT87106683T ATE59060T1 (de) 1986-05-14 1987-05-08 Verfahren zur behandlung von kaustisch raffinierten glyceridoelen zur entfernung von seifen und phospholipiden.

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US86320886A 1986-05-14 1986-05-14
US863208 1986-05-14

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EP (1) EP0247411B1 (ja)
JP (1) JPS6327600A (ja)
CN (1) CN1029318C (ja)
AR (1) AR242428A1 (ja)
AT (1) ATE59060T1 (ja)
AU (1) AU600485B2 (ja)
CA (1) CA1298853C (ja)
DE (1) DE3766651D1 (ja)
ES (1) ES2019324B3 (ja)
GR (1) GR3001427T3 (ja)
IN (1) IN171401B (ja)
MX (1) MX170388B (ja)
PH (1) PH26631A (ja)
PT (2) PT84208B (ja)
ZA (1) ZA873334B (ja)

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GB8823006D0 (en) * 1988-09-30 1988-11-09 Unilever Plc Process for refining glyceride oil
GB8906443D0 (en) * 1989-03-21 1989-05-04 Unilever Plc Process for refining glyceride oil using silica hydrogel
CA2052046A1 (en) * 1990-09-25 1992-03-26 Luis Otto Faber Schmutzler Process for refining glyceride oil
CA2040677A1 (en) * 1991-04-03 1992-10-04 Gabriella J. Toeneboehn Fatty chemicals and wax esters
US5449797A (en) * 1992-04-13 1995-09-12 W. R. Grace & Co.-Conn. Process for the removal of soap from glyceride oils and/or wax esters using an amorphous adsorbent
DE4223945A1 (de) * 1992-07-21 1994-01-27 Rhenus Wilhelm Reiners Gmbh & Verfahren zur mikrobiologischen Reinigung von Kühlschmierstoff enthaltenden Abwässern der metallverarbeitenden Industrie mit Hilfe eines speziellen Phospholipids
AU3027900A (en) * 2000-01-05 2001-07-16 Caboto Seafoods Process for refining animal and vegetable oil
JP2002080885A (ja) * 2000-09-07 2002-03-22 Nisshin Oil Mills Ltd:The 食用油製造プラント及び食用油製造方法
EP2491128A1 (en) * 2009-10-21 2012-08-29 Novozymes A/S Method for treatment of oil
FR2953854B1 (fr) * 2009-12-16 2012-12-28 Inst Francais Du Petrole Procede de conversion de charges issues de sources renouvelables avec pretraitement des charges par dephosphatation a chaud
CN106987312B (zh) * 2017-04-12 2021-04-13 西北大学 一种油脂同时脱磷脱酸的方法
BR112020022313A2 (pt) * 2018-05-02 2021-05-18 Reg Synthetic Fuels, Llc método para aprimorar gorduras, óleos e graxas residuais e de baixo valor

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GB599595A (en) * 1945-03-27 1948-03-16 Anderson Clayton & Co Improved method of refining glyceride oils
GB1476307A (en) * 1973-08-24 1977-06-10 Unilever Ltd Chemical process
JPS5614715A (en) * 1979-07-17 1981-02-13 Mitsubishi Electric Corp Control circuit of television receiver
JPS57174400A (en) * 1981-04-16 1982-10-27 Bitaminzu Inc Manufacture of wheat embryo lipid products
AU578968B2 (en) * 1984-09-13 1988-11-10 Allegheny Ludlum Steel Corp. Method and apparatus for direct casting of crystalline strip by radiantly cooling
US4629588A (en) * 1984-12-07 1986-12-16 W. R. Grace & Co. Method for refining glyceride oils using amorphous silica
US4734226A (en) * 1986-01-28 1988-03-29 W. R. Grace & Co. Method for refining glyceride oils using acid-treated amorphous silica
DE3775008D1 (de) * 1986-11-24 1992-01-16 Unilever Nv Metall-oxid-siliziumdioxid enthaltendes sorbentmittel und dessen verwendung zur oelraffinierung.
JP3067894B2 (ja) * 1992-07-16 2000-07-24 新日本製鐵株式会社 無方向性電磁鋼板用薄鋳片の製造方法

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PT84865B (pt) 1990-02-08
AR242428A1 (es) 1993-03-31
MX170388B (es) 1993-08-19
PT84208B (pt) 1989-03-30
CN1029318C (zh) 1995-07-12
PT84208A (en) 1987-02-01
ZA873334B (en) 1987-11-02
AU600485B2 (en) 1990-08-16
ATE59060T1 (de) 1990-12-15
CN87101626A (zh) 1988-01-20
JPS6327600A (ja) 1988-02-05
CA1298853C (en) 1992-04-14
ES2019324B3 (es) 1991-06-16
AU7294687A (en) 1987-11-19
GR3001427T3 (en) 1992-09-25
PT84865A (en) 1987-06-01
DE3766651D1 (de) 1991-01-24
IN171401B (ja) 1992-10-03
EP0247411A1 (en) 1987-12-02
PH26631A (en) 1992-08-19

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