JPH06504946A - adsorbent material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] adsorbent material The present invention provides an adsorbent material containing acid-treated clay minerals, a method for producing the same, and a method for producing the same. Concerning the refining of oil using this.

Oils of animal or vegetable origin are produced in large quantities and used in the food industry.

These oils, such as sunflower seed oil, soybean oil, which are triglyceride oils of vegetable origin , rapeseed oil, coconut oil, palm oil, peanut oil, etc., are oily when extracted. Contains various ingredients that affect color, stability, flavor, or odor, making the oil a qualified product. These ingredients must be removed before they can be sold.

One of the major types of triglyceride oil contaminants is phosphorus compounds of various compositions. It is. Some of these compounds are mixtures of phosphoric acid, glycerides and nitrogen bases. It's ester. The composition of these esters consists of a wide variety of natural fatty acids. Species of constituent glycerides, which may be either g- or tri-glycerides based on and, for example, choline, ethanolamine or inositol, etc. It may vary depending on the type of constituent bases. Such compounds often contain phosphorus It is called olivid (phosphol 1 pids). Sometimes phosphatides Other phosphorus compounds called (phosphotides) contain nitrogen bases. Alternatively, it may be of some similar composition.

Additionally, contaminant phosphorus compounds include simple glycerophosphate, inorganic phosphates, and Includes hydrolysis products of sphatides or phospholibids.

Other contaminants in as-extracted or partially processed oils are trace metals, soaps and such as carotenoids and chlorophyll, which naturally manifest the characteristic levels of certain oils. Contains pigment.

Adsorption of phosphorus compounds from oil onto microporous solid materials such as amorphous silica There are a number of patented proposals for the refining of oils by adsorption or The term sorbent simply refers to some or all of the phosphorus compounds or other contaminants. It merely indicates the ability to remove one compound or contaminant from the oil. It does not attempt to indicate the presence of a specific site on or inside an adsorbed solid. Not suitable for amorphous silica, e.g. instability of aqueous silicate solutions by acid neutralization It is amorphous silica produced by chemical reaction. An illustration of such a proposal is the diameter The pore volume of pores larger than 60 angstroms is at least 50%. Crystalline silica is described in EP 247,411 with a p of about 3.5 or less. EP 295 No. 418 discloses that the surface area of pores with a diameter of at least 2 nm is at least 400 m 2/g of precipitated amorphous silica can be found in EP 361,622. can.

Additionally, by adsorbing phosphorus compounds onto metal oxide silica adsorbents precipitated from oil, Proposals have also been made for refining the oil. One such example is the surface area Precipitated metal oxide silica adsorption where at least 40% are pores with a radius of at least 2 nm Agents can be found in EP 269173. Silica oxide The adsorbent is a coprecipitate of metal ions and silicate ions, e.g. aluminate ions. or stage settling followed by extended aging, washing, drying and baking. Prepared by composition. Furthermore, a similar proposal is for at least 150m” 7g table sedimentation with a pore volume of at least 0.6 ml/g for pores with a diameter of 4 to 20 nm; An adsorbent that is alumina-silica can be found in EP 376,406. can.

It has been practiced for many years to treat oil with various clay mineral products called bleaching earths. There is. Such products may, for example, be treated with strong acids to reduce surface area and porosity. For example, increased to 50-500m27g or more, and by washing , residual acids and clay minerals aluminum and/or natural clay minerals The acid salt formed by the reaction of another metal component with the acid is removed and Up to about 70% silicon, calculated as Al2O3, in substantial amounts, e.g. containing more than about 10% aluminum and at least some degree of crystallinity; A product is formed. Such acid-treated clays include phosphoribits, etc. was found to have a clear and substantial ability to remove phosphorus compounds from oil. It is.

The present invention is derived from acid-treated clay and is useful in the removal of phosphorus compounds from oil. It can exhibit greatly enhanced activity as well as efficacy in removing other impurities. The present invention provides a new class of adsorbent materials that can be obtained. These new adsorbents have Contains clay that has been acid treated under certain harsh but controlled conditions.

Therefore, the present invention involves treating a layered clay mineral with a strong acid to increase its surface area by at least 25 0 m’/g and wash the acid-treated clay mineral product to remove residual acid and Suitable for use in oil refining, including treatment to remove acid salts formed by A method for producing an adsorbent material, the acid-treated clay mineral product being washed after said acid treatment. The silicon content calculated as Stow in the dry weight is 80-99%, and Ah Bound aluminum, i.e. aluminum that does not leach into water, calculated as Os The content is controlled to be 0.1% or more and less than 360% by dry weight. Provides a method for identifying

The invention also relates to the treatment of oils, particularly for removing phosphorus compounds formed therein from oils. silicon having a surface area of at least 250 m2/g, calculated as 5ift. The content is 80-99% by dry weight, and Al 20. The bond al calculated as Acid-treated layered clay with a mineral content of 0.1% or more and less than 3.0% by dry weight A method of using a sorbent material containing ray minerals is provided.

Furthermore, the present invention has a surface area of at least 250 m2/g and has a surface area of at least 250 m2/g. The silicon content calculated as 80-99% by dry weight and Al2 (calculated as h) Acid treatment with a combined aluminum content of 0.1% or more and less than 3.0% by dry weight An adsorbent material containing a processed layered clay mineral is provided as a composition.

The acid-treated layered clay mineral product of the present invention is not found in, for example, precipitated silica adsorbents. It is usually considered beneficial if the product has a maximum surface area. However, the best performance is not at the largest surface area, but at a medium size. It is demonstrated. Similarly, its best performance is at maximum silica:aluminum ratio. and the highest performance that can be achieved by the product of the invention in the refining of oils. Although its surface area and silica content are both lower than conventional commercial products, can outperform the best performance achieved by commercially available precipitated silica adsorbents. It should be noted that The mechanistic reasons for these differences are unknown, but the This may be related to the structural characteristics obtained as a result of harsh acid treatment of clay minerals. .

The layered clay minerals used according to the invention are bilayer minerals, e.g. halloysite-ene. It has a layered structure such as kaolin such as plaite minerals, attapulgite or sepiolite. or preferably smectite clay, etc. It can be a three-layer sheet textured clay mineral. Natural clay minerals are the primary Although contemplated, similar synthetic materials are not excluded.

Smectite clay mineral has the following general formula: % formula % (0) (2-octahedral type) (M"+++, y+zmnf!20) (R"5-yLi"y) (Si<- *^1. )o,, (on>(3-octahedral formula) %formula%( (3-octahedral type) [In the formula, Mlo is the valence m necessary to fill the negatively charged space lattice. represents an exchangeable cation such as Ca++, Mg'' with R'' is magnesium or iron, and R3° represents aluminum or iron, 2:1 layer type with C can be defined as a group of phyllosilicates. The smectite mineral group is beidellite, nontronite, sabonite, and hectite, which are submineral groups of ronite. Minerals used in accordance with the present invention include lite and sauconite. Montmorillonite (2-octahedral type) or sabonite or hectorite (3 - minerals belonging to the octahedral) group are particularly preferred; The earth is composed of monate containing mainly exchangeable cations of Ca″″ and Mg″. It is morillonite and can provide a raw material suitable for the present invention.

Acid treatment involves partial removal of calcium or magnesium cations by hydrogen cations. or be responsible for complete replacement and have a fundamental effect on the texture of layered clay minerals . Smectite minerals, for example, form 10-bonds with adjacent tetrahedral silica sheets. Made of octahedral alumina sheets bonded together to form clay plate slits. It has a layered structure in which the repeating distance of crystal axes or basal voids are similar to dry clay minerals. It is on the order of 10 angstroms in minerals, but in hydrated clay minerals. 0 strong acids, i.e. acids with pKa values lower than 3.0, e.g. acid, mineral acids such as nitric acid or hydrochloric acid, and organic acids such as oxalic acid to form layered clay minerals. When processed, the alumina layer at the periphery of the plate slit is attacked and the aluminum or other tissue components exudate and remove 15 angstroms in a plate lift. This results in pores having diameters exceeding 20 to 50 angstroms in diameter.

As the acid treatment becomes more severe, the clay mineral structure gradually becomes more intense and becomes more integrated. in which each sheet of silica tetrahedron is formed in the structure according to the invention. They are bonded together by a large amount of residual aluminum held in a bonded form. this may be responsible for the altered adsorption properties observed in clay minerals. , and has a very different texture from either precipitated silica or precipitated alumina-silica. A highly open and distinctive high silica content aluminosilicon with a narrow pore size distribution It is expected to give an acid salt structure.

When calculating the silicon content of natural clay minerals such as smectite as 5i02, dry The effect of the acid treatment according to the present invention is within the range of about 50 to 60% by dry weight. increasing the leaching rate of magnesium and another component, e.g. magnesium, and washing The total silicon content in acid-treated products is reduced by removing them in the form of soluble salts. Silicon content in clay minerals in normal acid treatment is to increase the silicon content When calculated as SiO□, the dry weight increases from about 60% to about 70%. Ru. Some such products contain aluminum that binds to the clay structure and is not removed by washing with water. Substantial amount of aluminum, usually 10% of the dry weight of the clay, calculated as Al2O3 , but much more is retained in the original clay tissue. Many Another clay component, iron in an amount of, for example, about 5% when calculated as FezO*, is also present. can exist. Acidic salts formed during acid treatment are removed by washing with water as usual. be done. In contrast, the acid treatment of layered clay minerals according to the present invention has a dry weight of 8 Achieves a higher SiO2 content than before, which is more than 5% or even more than 90%. At the same time, aluminochemistry due to the remainder of the bonded aluminum was confirmed by MASNMR. Controlled to avoid complete destruction of icate. This acid treatment is a strong acid aqueous solution. This is done by fermenting clay minerals in a rally. For example, the time, temperature, pressure or concentration of acid used for acid treatment, etc. The harshness of the acid treatment is made more severe by increasing the amount of acid. Suitable acids are strong mineral acids, preferably sulfuric acids. An acid, for example, at an initial concentration of 77 to 100% by weight in a water-repellent slurry. It can be used at a concentration of about 10 to 40% by weight, preferably 15 to 30% by weight. . Acid: So that the weight ratio of clay is 0.25 to 2.0, calculated as 100% acid. Fermentation is preferably carried out for 5 to 25 hours when atmospheric pressure fermentation is used. Preferably, it is carried out for 10 to 16 hours, and when pressure crushing is used, it is carried out for 1 to 8 hours.

Pressure disintegration is carried out to about 200 psig (about 13.5 bar), preferably about 150 psig. It can be suitably carried out under pressures up to psig (approximately 10 bar) and is also preferred. Preferably, it is carried out at a temperature suitable for generating the necessary pressure. Atmospheric pressure fermentation is about 70~ 100'C1 Preferably, it can be carried out at a temperature of about 80°C or more and less than 100°C. Fermentation is , can be terminated at a desired point by quenching with cold water. After finishing, The acid-treated clay mineral slurry is pumped to a suitable filter press. 10 to 40 microns, where it is washed with water to the desired residual acidity, and or the desired residual water to create a powder preferably in the 15-25 micron range. In an advantageous embodiment of the invention, the oil is dried to a 8 to 30% by weight, preferably, although not essential, for maximum efficiency The product is dried so that the free water content is within the range of 17% or more and less than 25%. It will be done.

The adsorbent produced by the present invention is calculated as Al2O or FezO3. , at least 0.2% to 1.5% of bonded aluminum that does not leach into water; less than 0.5%, usually at least 0.0% iron and/or non-leaching to water It may contain 5% or more, for example, at least 0.1% or more and 0.3% or less. Preferably, each of these comprises another, non-water leaching component that may be present in the clay structure. The adsorbent of the present invention has a wide pore size distribution with a small amount of The diameter often ranges from 20 to 200 Angstroms.

According to a preferred embodiment of the invention, washing of soluble acid salts formed during the acid treatment control the amount of salt remaining in the acid-treated clay mineral product and/or The water wash leaves a residual amount of the acid used in the treatment, preferably between 0.1 and 5 in the cleaning product. % Hedley acidity.

Hetley acidity of clay can be defined as % free acidity, following steps It can be measured by Accurately weigh 5.1g from 4.9g of clay mineral sample, Add 100ml of distilled water to the weighed sample, boil for 2 minutes, filter it, and boil Wash 3 times using 50cm3 of distilled water, and then mix the R solution and washing solution. Titrate with 0.1 M sodium hydroxide using a phenolphthalein indicator. measurement Results were expressed as % weight of <1 acid based on the weight of the clay sample. This controlled As a result of the cleaning, the product of the invention preferably has the aforementioned bonded aluminum and In addition to iron and/or iron, aluminum leached into water is calculated as ALO3 and is ゜05-3% amount and/or iron leached into water calculated as Fezes Another small amount leached into the water in an amount of 0.05-1%, corresponding to other components of clay minerals It can be contained together with salt. Products that have undergone such controlled cleaning is particularly effective in removing phosphorus compounds from oil.

The adsorbent produced according to the present invention can be prepared from oil by methods known in the art. The adsorbent of the present invention can be used alone or in combination with is one or more other adsorbents, such as but not limited to Bleaching soil for decolorization, oniu for removal of pigments or polycyclic aromatic carbohydrates clay that has been replaced or pillared clay, Silica can be used in combination with amorphous silica or sequentially added to oil. Ru. As a suitable treatment, the absorbent of the invention may be added per 100 parts of oil, each expressed in parts by weight. Using about 0.1 to 3.0 parts of adhesive, about 15% of This can then be treated for ~40 minutes to remove the adsorbent from the oil. can be done. Higher or lower amounts of adsorbent, shorter or longer treatments Other conditions, such as processing time or temperature rise, will of course be used depending on the particular oil being processed. The above conditions are for illustrative purposes only.

Treatment using the adsorbent of the present invention can be carried out either before or after alkaline refining or degumming. At the point, extracted raw vegetable oil, liquid animal fat, fish oil or mineral oil or synthetic oil It can be implemented against aimed at reducing phospholipid residue levels Processing according to the invention eliminates the need for alkaline refining or degumming of vegetable oils; The product of the present invention is suitable for the adsorption of phospholipids. On the other hand, it also has the function of removing trace metals, soaps, and pigments from oil. .

The present invention will be explained by the following examples, but these examples do not limit the scope of the invention in any way. Examples 2-6 and 1, which are not intended to define but merely illustrate the invention. Examples 10 to 16 are examples of the present invention, and Examples 1 and 7 to 9 are comparative examples thereof.

Mixed calci obtained from Los Traneos, Spain ummagnesium montmorillonite clay mineral, clay:acid (100%) ratio 1 : 1.25 with sulfuric acid under atmospheric pressure in an aqueous medium with stirring for 16 hours at 95 heated to ℃.

The slurry is rapidly cooled, passed through a V-V to separate the clay from the acid, and washed to remove any residual acid. The dryness was adjusted to the desired value and then dried to the desired moisture content. processing clay Some samples were taken and these were washed again to further reduce acidity. moisture content After drying to about 20%, the product or a part thereof is analysis, acidity measurements and certain physical measurements, and a known amount of phosphoribic acid. was used to treat a sample of water-gummed soybean oil that contained oil phosphoryl The decrease in pit content was measured by X-ray fluorescence spectrometry and : Expressed in ppm of phosphorus removed per 1 g of adsorbent in the oil part ratio range. , which is shown as the "K" value in the table below. The higher this "K" value, the High ability to remove phosphorus.

The sample so produced had the composition and properties shown below.

Clothes-1 Before acid treatment 1 61.8225.71 3.94 0.27 5.60 1.05 1.4 5 0.16 72 - After acid treatment and cleaning 2 94.44 3.12 0.75 0.14 0.66 0.51 0.2 0 0.10 371 2.53 96.85 0.34 0.23 0.11 0.11 2.06 0.15 0.11 321 L, S4 97.31 0.80 0.20 0.07 0.26 1.24 0.12 - 327 2.05 95.63 0.78 0.21 0.11 0.2B 2. F2 0.14 0.11 316 3.96 94.00 3.18 0.59 0 ．． 16 0.78 1.04 0.50 0.11 365 3.0 Degumming with water The "K" values of the samples after being used to treat soybean oil were as shown below.

Substitute Test number processing K 90m1in 175mIin 5 a 64 72 6 a 53 - 7 b 49 56 8 c 39 48 a: Washed according to the invention and dried to a moisture content of about 20%.

After treatment with baa, it was washed and dried again under the same conditions.

C: Commercially available amorphous silica adsorbent, trade name: Trisyl )It was used.

In the following tests, expressed as a ratio of SiOx:AlxO2, and acid:clay The S10□ content, which was changed by changing the ratio of minerals, was It was shown that there is a relationship with the "K" value in standard processing of oil. W1 processing The surface area of clay minerals is related to phosphorus removal, and the use of clays with less surface area Although the removal rate is relatively low, the surface area is smaller than the 5IOx:Al2O5 ratio and It was found that the removal of phosphorus peaked before reaching its maximum and then decreased.

Once the ceremony Examiner 5 100° Rei's second visit (to) Vba Koni-mutual 19□LNL h 9 0.25 214 13 5.4 10 0.35 310 16 6.411 0.50 374 28 7.6 12 0.60 455 25 10.813 0.75 473 24 16 ．． 614 0.90 443 36 44.615 1.00 399 32 65.616 1.25 373 40 139.0 Very high S iOx:A lto3 ratio, e.g. greater than about 300:1 or greater than about 275:1. Even if it is only slightly increased, the “K” value tends to decrease.

□　N+　PCT/GB　92/View241 Front page continuation (72) Inventor: Davies, Mary Elizabeth United Kingdom, Double I2.0 E.D. Cheshire, Warrington, Saint Pridget's Crows 41 (72) Inventor Turner, Philip James United Kingdom, Double A 8/7 PNC, Widnes, Cradleley

Claims (1)

[Claims] 1. The layered clay mineral is treated with a suitable strong acid to reduce its surface area to at least 250 m2. /g, and the acid-treated clay mineral product is washed to remove residual acid and thereby Adsorption suitable for use in oil refining, including treatment to remove acid salts formed A method for producing a clay mineral product, wherein SiO2 is added to an acid-treated clay mineral product after cleaning. Contains 80-99% silicon by dry weight, calculated as A12O3. Contain 0.1% or more and less than 3.0% of combined aluminum by dry weight. A method for producing an adsorbent material, characterized in that the acid treatment is controlled. 2. The layered clay mineral may be kaolinite, attapulgite, sepiolite or sumeite. 2. The method according to claim 1, wherein the method is ctite. 3. 3. The strong acid according to claim 1 or 2, wherein the strong acid has a pKa value of less than 3.0. How to put it on. 4. Containing the strong acid at a concentration of 10 to 40% by weight, and calculated as 100% acid. An aqueous slurry having a weight ratio of acid:clay mineral of 0.25 to 2.0 is formed. 4. A method according to claim 3, wherein the layered mineral is processed. 5. The content of bound aluminum calculated as Al2O is at least 0.2%. The method according to any one of claims 1 to 4, wherein the acid treatment is performed so that the acid treatment becomes so. 6. The acid-treated clay mineral has a Hedley acidity of 0.1 in the product after washing. 6. The method according to any one of claims 1 to 5, wherein the washing is carried out to a concentration of -5%. 7. The acid-treated clay mineral reduces Hedley acidity in the product after cleaning. 7. The method of claim 6, wherein the washing is performed to at least 1%. 8. Adsorption suitable for use in oil refining, containing acid-treated layered clay minerals agent material having the following properties: a surface area of at least 250 m2/g, silicon content calculated as SiO2 is 80-99% by dry weight, and Combined aluminum content calculated as Al2O3 is 0.1% or more by dry weight3 ．． Adsorbent material, characterized in that it is less than 0%. 9. The combined aluminum content calculated as Al2O3 is at least 9. Adsorbent material according to claim 8, which is 0.2%. 10. additionally characterized by a Hedley acidity of 0.1-5.0%. The adsorbent material according to claim 8 or 9. 11. 10. The adsorbent material has a Hedley acidity of at least 1%. Adsorbent materials described in . 12. Aluminum or Fe2O3 leached into water calculated as Al2O3 Claimed to contain at least 0.05% additional water-leaching iron calculated as follows: The adsorbent material according to any one of items 8 to 11. 13. By contacting the adsorbent material according to claim 8 with oil, phosphorus compounds or or other contaminants from oil. 14. Contacting the adsorbent material produced by the method of claim 1 with oil. A method for removing phosphorus compounds or other contaminants from oil. 15. The adsorbent material may contain one or more bleaching earths, onium exchanged clays, Claim 1: Used in combination with clay, Hillard clay or amorphous silica. 3 or 14. 16. The oil is comprised of about 0.1 to 3 parts by weight of the adsorbent material per 100 parts by weight of oil. 16. A method according to any one of claims 13 to 15, wherein the method is treated by: