WO1999002256A1 - Argile decolorante et son procede de fabrication - Google Patents

Argile decolorante et son procede de fabrication Download PDF

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Publication number
WO1999002256A1
WO1999002256A1 PCT/US1998/013701 US9813701W WO9902256A1 WO 1999002256 A1 WO1999002256 A1 WO 1999002256A1 US 9813701 W US9813701 W US 9813701W WO 9902256 A1 WO9902256 A1 WO 9902256A1
Authority
WO
WIPO (PCT)
Prior art keywords
clay
weight
acid
acid solution
bleaching
Prior art date
Application number
PCT/US1998/013701
Other languages
English (en)
Inventor
David D. Brooks
Dov Shaked
Domingo Chavez
Shirley Brophy
Original Assignee
Oil-Dri Corporation Of America
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oil-Dri Corporation Of America filed Critical Oil-Dri Corporation Of America
Priority to BR9810572-8A priority Critical patent/BR9810572A/pt
Priority to AU82806/98A priority patent/AU8280698A/en
Publication of WO1999002256A1 publication Critical patent/WO1999002256A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates

Definitions

  • This invention relates to a bleaching clay which is effective in the removal of colored impurities found in mineral, vegetable, and animal oils and to a method of making such a product.
  • a historical method of removing colored impurities from oils entails intimately contacting the oil with a bleaching clay, such as Fuller's earth (bentonite) or an acid-activated clay [A.D. Rich, "Bleaching Clay, " Industrial
  • a commercial process for the production of acid-activated bleaching clay entails mixing an aqueous clay slurry with a high dose of concentrated acid at elevated temperatures (100°C to 121 °C), followed by washing and drying of the acidulated product.
  • this prior art method results in high levels of residual acid effluent and salts thereof whose removal and disposal costs are expensive (U.S. Pat. No. 3,617,215 to Massaire et. al.).
  • the present invention is an improvement over prior art methods of making bleaching clay because a wider variety of raw clay sources can be utilized in an environmentally-friendly, non-slurry process. Thus, production expenses are diminished and recycling costs are eliminated. Also, the lower moisture content bleaching clay is very stable during storage unlike higher moisture content bleaching clay. Summary of the Invention
  • a bleaching clay product and an environmentally-friendly, non- slurry method for the manufacture of the bleaching clay product is described.
  • a clay with a moisture content in the range of no more than about 45 % by weight is combined with a relatively small amount of an aqueous acid solution, ground to a mean particle size in the range of about 25 to about 45 microns in a grinder, and dried to a moisture content of no more than about 13% by weight.
  • the foregoing operations can occur sequentially or concurrently as long as the acidified product has a moisture content of no more than about 13 % by weight.
  • the acid content in the dried clay product is in the range of about 1 to about 5 % by weight, based on the dry weight (zero moisture) of the clay product.
  • the obtained clay product may be utilized for bleaching purposes in numerous applications.
  • a bleaching clay useful in the removal of colored impurities in oils is produced by a non-slurry process whereby a relatively small amount of acid is misted onto ground clay.
  • the clay starting material (raw clay) preferably is of the palygorskite-smectite variety having a slurry pH value of about 7.2 to about 8.4 units. The moisture content of this clay starting material is no more than about 45% by weight. If necessary for the type of grinder used, the raw clay may be pre-dried to reduce its moisture content prior to comminution.
  • the clay is acidified and ground to a mean particle size of about 25 to about 45 microns in a grinder, such as an impact mill, e.g. a Williams mill, or a roller mill, such as a Raymond mill.
  • the ground clay is dried to a moisture content of no more than about 13% by weight prior to the addition of acid; however, the acid can be added first to the raw clay which is then dried and ground, either sequentially or concurrently.
  • the desired relatively low moisture content can be attained concurrently with grinding.
  • the ground clay can be dried, e.g. , in a cyclone-type drier, after grinding but prior to acidification.
  • a clay product moisture content in excess of about 13% by weight adversely affects the stability of the acidified clay during storage.
  • the ground clay is dried to a moisture content of about 8 to about 10% by weight and combined with a relatively small amount of an aqueous acid solution to provide an acid content of the clay in the range of about 1 to about 5 % by weight, based on the dry weight (zero moisture) of the product.
  • the acid content of the clay is in the range of about 2.5 to about 5% by weight, based on the dry weight of the product.
  • the aqueous acid solution preferably contains an acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, and citric acid. Acid mixtures can be used as well.
  • a concentrated aqueous sulfuric acid solution is utilized.
  • the sulfuric acid solution preferably contains sulfuric acid at a level in the range of about 93 to about 98% by weight in water.
  • Concentrated hydrochloric acid usually contains about 36% by weight hydrochloric acid
  • concentrated phosphoric acid usually contains about 85 % by weight phosphoric acid
  • concentrated citric acid solution usually contains about 50% by weight citric acid.
  • the technique used to combine the dried clay and the acid can be any technique that is convenient, although misting or spraying the acid onto the dried clay is preferred.
  • the acidulated clay may be used for bleaching purposes without further work-up.
  • EXAMPLE 1 Manufacture and Evaluation of Bleaching Clay
  • Raw palygorskite-smectite clay with a moisture content of about 45 % by weight was acidified with sulfuric acid (95 % by weight) by misting with an atomizer, then ground and concurrently substantially dried in an impact mill (Williams Mill) to a mean particle size of about 30 to about 34 microns and to a relatively low moisture content.
  • the moisture content of the ground, dried clay was about 10% by weight.
  • Enough acid was misted onto the ground clay to provide an acid content of either about 1 % by weight (Sample A) or about 3.5% by weight (Sample B), based on the dry weight of the clay (zero moisture), as determined by measurement with a LECO sulfur analyzer, corrected for moisture.
  • the pH of an aqueous solution of the clay was measured using a pH meter.
  • Control samples, Sample A' and Sample B' were also made using the Williams Mill according to the same acid specifications but with a relatively higher moisture content than Samples A and B.
  • To determine the activity of the bleaching clay about 100 g of canola oil was heated to about 60 °C (140°F) and contacted with an acidified clay sample in a distillation flask which was heated to a temperature of about 110°C (230°F) with agitation and held at that temperature for 30 minutes under 660 mm Hg (26 inches Hg) vacuum.
  • Sample A (0.9% acid by weight)
  • about 1.5 % by weight of the bleaching clay based on the weight of the oil was added.
  • Tables 1 and 2 demonstrate the performance stability of the present product over an extended time period at an elevated temperature.
  • Table 2 In the accelerated stability study (Table 2), about 20 g of each clay was placed into five glass bottles and the lids sealed with tape. The samples were placed into an oven at a temperature of about 110°F and one of each clay sample was removed at a given time interval for testing. The samples were compared to the standards defined above, stored at ambient temperature.
  • Sample A A' B B' pH (5% slurry) 5.0 5.1 2.9 2.9 moisture (wt.%) 10.2 15.8 9.0 14.0 acid (wt.%) 0.9 1.0 3.7 3.5 mean particle size 33.48 35.19 35.43 38.32 ( ⁇ m) median particle 29.00 31.30 30.92 33.78 size ( ⁇ m) filtration time 125 136 62 68 (s/50 ml)
  • Raw palygorskite-smectite clay (pH 7.37) having a moisture content of about 45 % by weight was fed to an impact mill (Williams Mill) and was ground to a mean particle size of about 38.8 microns while being dried to a free moisture content of about 9 to about 10% by weight. Thereafter, the obtained clay product was sprayed with aqueous concentrated sulfuric acid to provide a sulfuric acid content in the bleaching clay product of either about 2.8 to about 3.5% by weight, based on the dry weight of the product.
  • Chl chlorophyll
  • ppb 2 RT room temperature
  • Raw palygorskite-smectite clay (pH 7.37) having a moisture content of about 45 % by weight was fed to an impact mill (Williams Mill) and was ground to a mean particle size of about 38.8 microns while being dried to a free moisture content of about 9 to about 10% by weight. Thereafter the obtained clay product was sprayed with concentrated sulfuric acid (95 % by weight), aqueous phosphoric acid (85% by weight), and mixtures thereof at levels indicated in Table 5, below. The obtained products were then tested for bleaching activity using canola oil in the same manner as described in Example 2, above. The observed results are compiled in Table 5, below.
  • Chl chlorophyll
  • Raw palygorskite-smectite clay (pH 7.3) having a moisture content of about 45 % by weight was ground and dried in an impact mill (Williams Mill) to a mean particle size of about 31.6 microns and a free moisture content of about 3 to about 5 % by weight. Thereafter, the obtained dried clay product was sprayed with an aqueous hydrochloric acid solution (36% by weight). The obtained acidified products were then tested for bleaching activity using canola oil in the same manner as described in Example 2, above, except that 660 mm Hg was the applied vacuum. The observed results are compiled in Table 6, below.
  • the preceding data shows effective bleaching activity with HCl activated clay at a relatively low free moisture content.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne une argile décolorante acidifiée, permettant d'éliminer des impuretés colorées d'huiles alimentaires. On fabrique cette argile selon un procédé écologique n'utilisant aucune suspension d'argile, ce procédé consistant à broyer, à acidifier, et à sécher l'argile jusqu'à une teneur en humidité à l'état libre ne dépassant pas 13 pour cent en poids. La teneur en acide du produit argileux ainsi obtenu varie entre 1 et 5 pour cent en poids environ, et de préférence entre 2,5 et 5 pour cent en poids environ, sur la base du poids sec de ladite argile.
PCT/US1998/013701 1997-07-07 1998-06-30 Argile decolorante et son procede de fabrication WO1999002256A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR9810572-8A BR9810572A (pt) 1997-07-07 1998-06-30 Argila de branqueamento e método de fabricação.
AU82806/98A AU8280698A (en) 1997-07-07 1998-06-30 Bleaching clay and method of manufacture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88912297A 1997-07-07 1997-07-07
US08/889,122 1997-07-07

Publications (1)

Publication Number Publication Date
WO1999002256A1 true WO1999002256A1 (fr) 1999-01-21

Family

ID=25394541

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/013701 WO1999002256A1 (fr) 1997-07-07 1998-06-30 Argile decolorante et son procede de fabrication

Country Status (4)

Country Link
CN (1) CN1264320A (fr)
AU (1) AU8280698A (fr)
BR (1) BR9810572A (fr)
WO (1) WO1999002256A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001085336A1 (fr) * 2000-05-05 2001-11-15 Oil-Dri Corporation Of America Procede de production d'argile decolorante
WO2005087366A1 (fr) 2004-03-12 2005-09-22 Süd-Chemie AG Procede pour reduire la teneur en dioxine d'une terre decolorante
WO2007065461A1 (fr) * 2005-12-09 2007-06-14 Süd-Chemie AG Procede de sorption d'au moins une molecule d'acide nucleique a l'aide de phyllosilicates d'activation acide
US7897051B2 (en) 2005-12-16 2011-03-01 Sud-Chemie Ag Method for separating proteins from liquid media
US20110166011A1 (en) * 2008-09-18 2011-07-07 Mizusawa Industrial Chemicals, Ltd. Novel active clay and decolorizing agent for animal and plant fats and oils or for mineral oils
US8394975B2 (en) 2006-11-07 2013-03-12 Sud-Chemie Ag Amorphous adsorbent, method of obtaining the same and its use in the bleaching of fats and/or oils
WO2015128273A1 (fr) * 2014-02-28 2015-09-03 Clariant International Ltd Argile blanchissante sèche, modifiée et activée par un acide, procédé de fabrication et utilisation associés

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10324561A1 (de) * 2003-05-30 2004-12-16 Süd-Chemie AG Semi-synthetische Bleicherde
CN101016157A (zh) * 2006-02-09 2007-08-15 浙江海力生制药有限公司 提纯蒙脱石的方法和提纯蒙脱石及其组合物
CN114288985A (zh) * 2021-12-29 2022-04-08 浙江工业大学 一种黑滑石吸附材料及其制备方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671058A (en) * 1951-07-21 1954-03-02 Filtrol Corp Process for preparation of acid activated clay
US3617215A (en) * 1966-12-10 1971-11-02 Mizusawa Industrial Chem Dry acid treatment process of alumina-silica-type clay
US4717699A (en) * 1986-01-02 1988-01-05 American Colloid Company Process for acid treating clay for improved filtration
US4919818A (en) * 1987-01-28 1990-04-24 American Colloid Company Process for extruding and treating clay for improved filtration
US5008226A (en) * 1989-05-16 1991-04-16 Engelhard Corporation Process for making acid activated bleaching earth using high susceptibility source clay and novel bleaching earth product
US5783511A (en) * 1995-11-30 1998-07-21 Oil-Dri Corporation Of America Process for selecting raw material and making a bleaching clay

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671058A (en) * 1951-07-21 1954-03-02 Filtrol Corp Process for preparation of acid activated clay
US3617215A (en) * 1966-12-10 1971-11-02 Mizusawa Industrial Chem Dry acid treatment process of alumina-silica-type clay
US4717699A (en) * 1986-01-02 1988-01-05 American Colloid Company Process for acid treating clay for improved filtration
US4919818A (en) * 1987-01-28 1990-04-24 American Colloid Company Process for extruding and treating clay for improved filtration
US5008226A (en) * 1989-05-16 1991-04-16 Engelhard Corporation Process for making acid activated bleaching earth using high susceptibility source clay and novel bleaching earth product
US5783511A (en) * 1995-11-30 1998-07-21 Oil-Dri Corporation Of America Process for selecting raw material and making a bleaching clay

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001085336A1 (fr) * 2000-05-05 2001-11-15 Oil-Dri Corporation Of America Procede de production d'argile decolorante
US6365536B1 (en) * 2000-05-05 2002-04-02 Oil-Dri Corporation Of America Method of making bleaching clay
WO2005087366A1 (fr) 2004-03-12 2005-09-22 Süd-Chemie AG Procede pour reduire la teneur en dioxine d'une terre decolorante
WO2007065461A1 (fr) * 2005-12-09 2007-06-14 Süd-Chemie AG Procede de sorption d'au moins une molecule d'acide nucleique a l'aide de phyllosilicates d'activation acide
US7897051B2 (en) 2005-12-16 2011-03-01 Sud-Chemie Ag Method for separating proteins from liquid media
US8394975B2 (en) 2006-11-07 2013-03-12 Sud-Chemie Ag Amorphous adsorbent, method of obtaining the same and its use in the bleaching of fats and/or oils
US20110166011A1 (en) * 2008-09-18 2011-07-07 Mizusawa Industrial Chemicals, Ltd. Novel active clay and decolorizing agent for animal and plant fats and oils or for mineral oils
WO2015128273A1 (fr) * 2014-02-28 2015-09-03 Clariant International Ltd Argile blanchissante sèche, modifiée et activée par un acide, procédé de fabrication et utilisation associés
EA030274B1 (ru) * 2014-02-28 2018-07-31 Клариант Интернэшнл Лтд Модифицированная сушкой, активированная кислотой отбеливающая земля, способ ее получения и применение

Also Published As

Publication number Publication date
CN1264320A (zh) 2000-08-23
AU8280698A (en) 1999-02-08
BR9810572A (pt) 2000-09-19

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