WO2004064997A1 - Nouvelles microcapsules pouvant etre utilisees comme agent d'extraction, en particulier pour l'extraction de contaminants contenus dans l'eau ou dans le sol - Google Patents

Nouvelles microcapsules pouvant etre utilisees comme agent d'extraction, en particulier pour l'extraction de contaminants contenus dans l'eau ou dans le sol Download PDF

Info

Publication number
WO2004064997A1
WO2004064997A1 PCT/CH2004/000030 CH2004000030W WO2004064997A1 WO 2004064997 A1 WO2004064997 A1 WO 2004064997A1 CH 2004000030 W CH2004000030 W CH 2004000030W WO 2004064997 A1 WO2004064997 A1 WO 2004064997A1
Authority
WO
WIPO (PCT)
Prior art keywords
acrylamide
capsules
membrane
water
extraction
Prior art date
Application number
PCT/CH2004/000030
Other languages
English (en)
Inventor
Anne Peters
Nadège CORDENTE
Ian Marison
Original Assignee
Inotech Ag
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 Inotech Ag filed Critical Inotech Ag
Publication of WO2004064997A1 publication Critical patent/WO2004064997A1/fr

Links

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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/306—Pesticides

Definitions

  • the invention refers to extraction techniques, more specifically to a novel extraction system suitable for contaminants like pesticides and herbicides removal.
  • Nanofiltration is another way to remove pesticides simultaneously with nitrates from water(Wittmann, Cote et al. 1998; Van der Bruggen, Everaert et al. 2001). Pesticides such as ethyl parathion or atrazine can also be reduced rapidly in the presence of iron powder(Ghauch, Rima et al. 1999).
  • Organothiophosphorus pesticides can be removed from contaminated water using a water-immiscible organic solvent immobilized on a supported liquid membrane.
  • the phosphorus-based substance is extracted into the solvent by contacting the contaminated water on one side of the membrane, whereas on the other side there is solution containing a hydroxy-affording strong base that will react with the phosphorus-based substance to form a non toxic product (Vandergrift and Steindler 1989).
  • Another alternative for removal of organothiophosphorus pesticides is the use of supercritical CO 2 for their extraction, combined with their degradation by Fenton's reagent(Yu 2002).
  • Silver complexed chitosan microparticles were aslo shown to be adsorbents for pesticide removal such as methyl parathion (Yoshizuka, Lou et al. 2000).
  • the invention proposes a new and original extraction system composes of microcapsules which proved quite efficient for the removal of water or soil contaminants like herbicides or pesticides.
  • These microcapsules contain an oil core surrounded by a hydrogel polymer membrane and have a diameter which can vary within a wide range, for example between about 0.800 and about 1.500 mm
  • a first object of the invention is to provide microcapsules consisting of a lipophilic liquid core surrounded by a hydrogel polymer membrane, wherein:
  • the lipophilic liquid core component is an oil of natural or chemical origin or a water immiscible organic solvent or a mixture of same;
  • the hydrogel membrane is made of suitable polycations or polyanions associated with unsaturated monomers like acrylamide or its derivatives by electrolytic interactions or chemical cross-linking, preferably a cross-linked polymer membrane made by copolymerization of alginate with monomers selected from acrylamide and acrylamide derivatives.
  • a process for the preparation of said microcapsules which comprises a) selecting an oil of natural or chemical origin or a water immiscible organic solvent or a mixture of same as lipophilic liquid core constituent; b) selecting unsaturated monomers like e.g. acrylamide and/or acrylamide derivatives and suitable polycations or polyanions as constituents of the mixture subject to interaction ; c) initiating and then performing interaction of the selected constituents up to the desired polymerization level of the hydrogel membrane ; and d) subjecting then the core and the membrane components to a suitable microcapsulation technology, e.g. the laminar jet break-up co-extrusion technique. Interaction of the selected polycations or polyanions with suitable monomers can imply electrolytic interaction and chemical cross-linking as well.
  • Preferred hydroge membrane components comprise alginate which is then cross linked to monomers selected from acrylamide or acrylamide derivatives.
  • Still a further object of the invention is a method for extracting lipophilic soil or water contaminants, which comprises adding the above mentioned microcapsules to contaminated waste water or the like in an amount sufficient to extract the said contaminants, keeping them in contact under stirring with the said contaminants for a time sufficient to achieve the desired extraction rate and eventually recovering the loaded microcapsules from the aqueous medium.
  • the process which is proposed within the frame of the invention is based on liquid- core microcapsules which combine long term stability with high extraction rates. Direct contact of the extracting medium and water is avoided, a high interfacial area is provided, very little agitation is required and the capsules may be simply removed by sedimentation or flotation. Due to the high stability it should be feasible to back extract the pesticide/ herbicide or carry out a chemical oxidation or other decomposition reaction directly, and recycle the capsules. Alternatively the capsules could be disposed of by incineration. Due to the high partition coefficient, the herbicide/pesticide can be accumulated to high concentrations within the capsules which further facilitates the determination of the quantity of herbicide/pesticide present in waste water.
  • the adequate solvent for the extraction of atrazine, methylparathion, ethylparathion and 2,4- dichloro-phenoxyacetic acid is encapsulated in a porous hydrogel membrane, which is composed of alginate and polyacrylamide. They offer the advantage of having a very large interfacial contact area thanks to their small radius, Rajing a fast extraction. On the other side the presence of the membrane physically separates the organic phase from the water to be treated, leading to the use of less solvent compared to liquid-liquid extraction.
  • Atrazine, 2,4-D, methylparathion and ethylparathion are chosen as examples.
  • Dibutylsebacate (dibutyl decanedioate or DBS, CAS 109-43-3) and oleic acid (cis-9- octadecenoic acid or OA, CAS 112-80-1) were of analytical grade and obtained from Fluka (Buchs, Switzerland).
  • MIGLYOL ® 812 glycerol tricaprylate/caprate
  • glycero! trioctanoate/decanoate or M was of analytical grade and obtained from Dynamit Nobel (Pl ⁇ ss Staufer AG, Basel, Switzerland).
  • LogP oct is a criterion which describes the hydrophobicity of compounds with respect to an octanol/ water mixture (Verm ⁇ e and Tramper 1995). Values given in this study were obtained by calculation via the website of Syracuse Research Corporation (http://esc.syrres.com/interkow/kowdemo.htm) or determined experimentally. Experimentally determined values were measured by liquid- liquid extraction experiments in which each of the four herbicides/pesticides were added to 10 mL de- ionized water to the desired concentration.
  • a quantity of each of the three organic phases (0.35 mL dibutyl sebacate, migyol or oleic acid) were added to the aqueous solutions followed by shaking for 5 min, on an orbital shaker set to 400 rpm. The emulsions were subsequently allowed to stand at room temperature for 18 hours to reach equilibrium, before measuring the concentration of pesticide/ herbicide in the aqueous phase.
  • a stock solution of acrylamide (AA) /methylene-bis-acrylamide (MBA) (23.5% AA, 2.5% MBA) was prepared and filtered (Steritop 0.2 ⁇ m, Millipore, corporation 80Ashby Road Bedford MA 01730-2271).
  • the stock solutions of alginate and AA/MBA were then combined, with agitation, in a ratio of 1 :1 in order to prepare a solution with the desired final concentrations.
  • Liquid- core capsules of different sizes were prepared using the co-extrusion jet- break- up technique.
  • the encapsulator (Inotech Encapsulator IEM) was fitted with a concentric nozzle with an internal diameter of 200 ⁇ m and an external diameter of 300 ⁇ m or an internal diameter of 400 ⁇ m and an external diameter of 500 ⁇ m.
  • Two syringe pumps (200 series, kd Scientific, Boston, USA) were connected to the encapsulator to supply the organic phase through the central nozzle and polymer solution through the external nozzle.
  • Spherical capsules were obtained by the application of a vibrational frequency with defined amplitude to the co- extruded jet and collected in a gelling bath placed 18 cm below the nozzle and agitated by a magnetic stirrer (length 4cm). Polymer flow rate, oil flow rate and vibration frequency were empirically determined for the different solutions and for the different nozzles used. Further details of the technique for the production of liquid- core capsules using the prilling technique have been described elsewhere (Peters et al., 2002).
  • the capsules can be described as having an external radius (r ext ) and an internal radius (organic phase radius, ⁇ nt )- Three different size capsules were produced with the following characteristics: (1) small capsules, r ext 0.398 mm, ⁇ ⁇ t 0.264 mm; (2) medium capsules, r ex t 0.496 mm, n n t 0.305 mm; (3) large capsules, r ex t 0.76 mm, nnt 0.407 mm.
  • the capsules were used immediately or incubated for 4 hours in 10 mL of tri-sodium citrate solution (20 g/L) to complex calcium ions and thereby release alginate into the solution (Peters et al. 2002). Measurement of capsule size distribution
  • the size and size distribution of capsules was determined using a microscope (Zeiss Axiolab, Switzerland) fitted with a video camera (CCD-IRIS, Sony, Japan) interfaced to a PC operating with the Cyberview (Cervus International, Courtaboeuf, France) image analysis software. A sample of 60-200 capsules was examined and the mean standard deviation determined.
  • the estimated volume of each size capsule used in the extraction experiments are: (1) 1.7 mL small capsules (r ex t 0.398 mm, nnt 0.264 mm); (2) 2.0 mL medium capsules (r ex t, 0.496 mm, nnt, 0.305 mm); (3) 3.0 mL (r ext , 0.76 mm; n n t, 0.407 mm).
  • the volume of capsules required was determined using a graduated tube. The capsules were filtered through a porous mesh and placed in a conical flask followed by the addition of 10 mL of the aqueous solution containing pesticide/ herbicide and agitated in a rotary shaker.
  • the main resistance to mass transfer of the herbicide/pesticide into the capsules was determined using a model described by (Stark 2001).
  • the capsule is considered to be a bead composed of an imaginary phase of alginate/polyacrylamide and organic phase.
  • the concentration of the herbicide inside the bead is obtained through a mass balance (eq. 2):
  • V aq is the aqueous phase volume
  • V b is the capsule volume
  • the UV absorption spectra ( Figure 1) for methylparathion (MP) show a maximum at a wavelength of 278 nm.
  • the partition coefficient K defined as the ratio of the MP concentration in the organic phase to that in the aqueous phase after 18 h incubation, were estimated to have values of 116, 98 and 29 for DBS, MIGLYOL and oleic acid respectively. Similar results were observed for atrazine, EP and 2,4-D with the three different oils tested (results not shown). As a result DBS showed the highest level of extraction of MP (Figure 1).
  • capsules (R ex t, 0.496; R
  • the EP, MP and atrazine concentrations in the aqueous phase rapidly declined to reach an equilibrium at which approximately 75% of the initial concentration remained after 10, 45 and 100min respectively ( Figure 2).
  • the higher rate of EP extraction compared to the other two compounds reflects the considerably higher hydrophobicity (logP oct , 3.73) of this compound. In the case of 2,4-D, an equilibrium was attained after only 15 min at 76% of the initial concentration ( Figure 2) and probably reflects that this compound is the least hydrophobic of those tested.
  • the capsule membranes are essentially composed of alginate together with crossed linked polyacrylamide of which the former is complexed with calcium ions to form a hydrogel while the latter is considerably more hydrophobic in nature.
  • the presence of calcium alginate in the membrane may create a resistance to mass transfer of the pesticides/ herbicides into the organic phase core
  • capsules were prepared and incubated in the presence of sodium citrate which complexes calcium ions and results in the liquifaction of the alginate, which may then diffuse out of the capsular membrane.
  • the efficiency of the system is dictated by the partition coefficient of the solvent with respect to the products to be recovered.
  • a high partition coefficient of the herbicides/ pesticides between the organic and the aqueous phase enables a rapid transfer of the compounds to the organic phase, accumulation of high concentrations within the organic solvent as well as allowing the use of small volumes of the solvent.
  • a solvent is usually chosen which has a lower density than water, in order to allow good separation of the two phases, and should not form stable emulsions.
  • the solvent should also be poorly soluble in water (high logP), have a melting point below room temperature as well as a low viscosity in order to facilitate the handling of the solvent.
  • capsules composed of a dibutyl sebacate core surrounded by a cross-linked polyacrylamide/alginate membrane, may be altered following treatment with chelating agents such as tri-sodium citrate. After such treatments, the capsules become more elastic, although the mechanical resistance (burst force) is unaffected over the pH range 4 to 9, and the membrane thickness increases. In addition the rate of extraction of pesticides/herbicides increases by a factor of 3 to 5- fold compared with similar capsules, which have not been treated with citrate ( Figures 7 and 8; Table 1). Since the membrane thickness of capsules treated with citrate is larger than that for non- treated capsules, it might be expected that the mass transfer resistance within the membrane is higher and that the rate of extraction would decrease.
  • chelating agents such as tri-sodium citrate
  • the capsule membrane In the absence of citrate the capsule membrane is probably composed of a dense mixture of polyacrylamide and calcium alginate. When capsules are treated with citrate, calcium ions are removed from the calcium alginate complex resulting in a more loose membrane structure composed essentially of polyacrylamide interpenetrated by sodium alginate. As a result the membrane becomes more hydrophobic and less dense, thereby facilitating diffusion of the hydrophobic herbicides and pesticides.
  • k ⁇ _ values for methylparathion (Table 1) clearly show that the main resistance to mass transfer is located in the membrane.
  • relatively hydrophilic low molecular weight proteins and compounds such as glucose
  • it has been shown that they can diffuse freely through hydrogel membranes composed of alginate (Tanaka, Matsumura et al. 1984).
  • This situation is comparable to the membranes composed of cross- linked alginate/ polyacrylamide which show a kL of 1.3 x 10 "6 m/s for methylparathion (Table 1).
  • kL values are approximately three- fold higher (3.6 x 10 "6 m/s) after treatment with citrate.
  • phase toxicity is reduced by the presence of a membrane that physically separates the oil phase from the aqueous phase.
  • Molecular toxicity is also reduced since the solvents used have very high partition coefficients, resulting in low concentrations of solvent in the aqueous phase at equilibrium.
  • FIG. 1 UV spectra of aqueous phase concentrations of methylparathion (MP) during liquid-liquid extraction using dibutyl sebacate (DBS), MIGLYOL and oleic acid over a period of 18 h. Symbols: Initial concentration (solid line) and concentration of MP in aqueous phase after 18 h (dashed line) in presence of DBS; Initial concentration (solid line with squares) and concentration of MP in aqueous phase after 18 h (dashed line with squares) in presence of Migloyl; Initial concentration (solid line with crosses) and concentration of MP in aqueous phase after 18 h (dashed line with crosses) in presence of oleic acid
  • Figure 2 Extraction kinetics for Atrazine, Methylparathion, Ethylparathion and 2,4-D using liquid- core capsules containing DBS with an external radius (R ext ) of 0.496mm at an agitation rate of 400rpm. Symbols: c(t)/c0 ratio of concentration at time t to initial concentration; Ethylparathion (diamonds), methylparathion (squares), atrazine (triangles) and 2,4-D (crosses).
  • Figure 3 Effect of agitation on the extractions kinetics for Ethylparathion using liquid- core capsules containing DBS with an external radius (R ex t) of 0.398mm. Symbols: No agitation (diamonds), 200 rpm (squares) and 400rpm (triangles).
  • Figure 4 Effect of agitation on the extractions kinetics for Methylparathion using liquid- core capsules containing DBS with an external radius (R ext ) of 0.398mm. Symbols: No agitation (diamonds), 200 rpm (squares) and 400 rpm (triangles). c(t)/c0 ratio of concentration at time t to initial concentration.
  • Figure 5 Effect of agitation on the extractions kinetics for Methylparathion using liquid- core capsules containing DBS with an external radius (R ext ) of 0.496 mm. Symbols: No agitation (diamonds), 200 rpm (squares), 300 rpm (light triangles) and 400 rpm (dark triangles). c(t)/c0 ratio of concentration at time t to initial concentration.
  • Figure 6 Effect of agitation on the extractions kinetics for Methylparathion using liquid- core capsules containing DBS with an external radius (R ext ) of 0.760 mm. Symbols: No agitation (diamonds), 200 rpm (squares), and 400 rpm (dark triangles). c(t)/c0 ratio of concentration at time t to initial concentration.
  • Figure 7 Extraction kinetics for Methylparathion using liquid- core capsules containing DBS with an external radius (R ext ) of 0.398 mm at an agitation rate of 400rpm. Symbols: c(t)/c0 ratio of concentration at time t to initial concentration; Capsules not treated with citrate (diamonds), capsules treated with citrate (squares).
  • Figure 8 Extraction kinetics for Methylparathion using liquid- core capsules containing DBS with an external radius (R ex t) of 0.496 mm at an agitation rate of 400rpm. Symbols: c(t)/c0 ratio of concentration at time t to initial concentration; Capsules not treated with citrate (diamonds), capsules treated with citrate (squares).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Soil Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des microcapsules constituées d'un noyau liquide lipophile entouré d'une membrane polymère d'hydrogel. Le noyau liquide lipophile est constitué d'une huile d'origine naturelle ou chimique ou d'un solvant organique non miscible dans l'eau ou d'un mélange de ceux-ci. La membrane d'hydrogène est constituée de polycations ou polyanions adéquats associés à des monomères insaturés tels que le lacrylamide ou ses dérivés, et elle est obtenue par des interactions électrolytiques ou une réticulation chimique, cette membrane étant de préférence une membrane de polymère réticulée produite par copolymérisation d'alginate avec des monomères sélectionnés parmi le lacrylamide et ses dérivés. Les microcapsules présentées peuvent être utilisées en tant qu'agent d'extraction de contaminants lipophiles contenus dans le sol ou dans l'eau, notamment à partir d'eaux usées ou de substances analogues.
PCT/CH2004/000030 2003-01-23 2004-01-20 Nouvelles microcapsules pouvant etre utilisees comme agent d'extraction, en particulier pour l'extraction de contaminants contenus dans l'eau ou dans le sol WO2004064997A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CHPCT/CH03/00051 2003-01-23
CH0300051 2003-01-23

Publications (1)

Publication Number Publication Date
WO2004064997A1 true WO2004064997A1 (fr) 2004-08-05

Family

ID=32739294

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH2004/000030 WO2004064997A1 (fr) 2003-01-23 2004-01-20 Nouvelles microcapsules pouvant etre utilisees comme agent d'extraction, en particulier pour l'extraction de contaminants contenus dans l'eau ou dans le sol

Country Status (1)

Country Link
WO (1) WO2004064997A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008132707A1 (fr) * 2007-04-26 2008-11-06 Sigmoid Pharma Limited Fabrication de minicapsules multiples
WO2009020594A1 (fr) * 2007-08-07 2009-02-12 Auburn University Stabilisation de l'eau au moyen de microparticules
EP2266405A2 (fr) 2004-03-12 2010-12-29 Danisco A/S Enzymes fongiques lipolytiques
FR2964017A1 (fr) * 2010-09-01 2012-03-02 Capsum Procede de fabrication d'une serie de capsules de taille submillimetrique
WO2013177267A1 (fr) * 2012-05-22 2013-11-28 Cidra Corporate Services Inc. Billes/bulles polymères modifiées, chargées, fonctionnalisées par des molécules pour attirer et fixer des particules minérales d'intérêt pour une séparation par flottation
US8911777B2 (en) 2007-04-04 2014-12-16 Sigmoid Pharma Limited Pharmaceutical composition of tacrolimus
US9220681B2 (en) 2012-07-05 2015-12-29 Sigmoid Pharma Limited Formulations
US9278070B2 (en) 2009-05-18 2016-03-08 Sigmoid Pharma Limited Composition comprising oil drops
US9302270B2 (en) 2011-05-25 2016-04-05 Cidra Corporate Services Inc. Mineral separation using functionalized filters and membranes
US9731221B2 (en) 2011-05-25 2017-08-15 Cidra Corporate Services, Inc. Apparatus having polymer surfaces having a siloxane functional group
US9821024B2 (en) 2010-11-25 2017-11-21 Sigmoid Pharma Limited Immunomodulatory compositions
US9878036B2 (en) 2009-08-12 2018-01-30 Sigmoid Pharma Limited Immunomodulatory compositions comprising a polymer matrix and an oil phase
US10434138B2 (en) 2013-11-08 2019-10-08 Sublimity Therapeutics Limited Formulations
US10603676B2 (en) 2011-09-13 2020-03-31 Cidra Minerals Processing Inc. Mineral processing
US10993987B2 (en) 2014-11-07 2021-05-04 Sublimity Therapeutics Limited Compositions comprising Cyclosporin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0780282A (ja) * 1993-06-24 1995-03-28 Ebara Res Co Ltd 高分子ヒドロゲル粒状物、その製造方法およびそれを利用する微生物固定化方法
US20010002656A1 (en) * 1999-12-03 2001-06-07 Ulrich Schnegg Process for preparing monodisperse adsorber resins and their use
US20020050659A1 (en) * 2000-02-09 2002-05-02 William Toreki Hydrocapsules and method of preparation thereof
US20020136770A1 (en) * 1999-10-22 2002-09-26 Douglas Quong Method of delivering active material within hydrogel microbeads

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0780282A (ja) * 1993-06-24 1995-03-28 Ebara Res Co Ltd 高分子ヒドロゲル粒状物、その製造方法およびそれを利用する微生物固定化方法
US20020136770A1 (en) * 1999-10-22 2002-09-26 Douglas Quong Method of delivering active material within hydrogel microbeads
US20010002656A1 (en) * 1999-12-03 2001-06-07 Ulrich Schnegg Process for preparing monodisperse adsorber resins and their use
US20020050659A1 (en) * 2000-02-09 2002-05-02 William Toreki Hydrocapsules and method of preparation thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199521, Derwent World Patents Index; Class A97, AN 1995-158037, XP002279692 *

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2266405A2 (fr) 2004-03-12 2010-12-29 Danisco A/S Enzymes fongiques lipolytiques
US9844513B2 (en) 2007-04-04 2017-12-19 Sigmoid Pharma Limited Oral pharmaceutical composition
US10434140B2 (en) 2007-04-04 2019-10-08 Sublimity Therapeutics Limited Pharmaceutical cyclosporin compositions
US10434139B2 (en) 2007-04-04 2019-10-08 Sublimity Therapeutics Limited Oral pharmaceutical composition
US8911777B2 (en) 2007-04-04 2014-12-16 Sigmoid Pharma Limited Pharmaceutical composition of tacrolimus
US9114071B2 (en) 2007-04-04 2015-08-25 Sigmoid Pharma Limited Oral pharmaceutical composition
US9387179B2 (en) 2007-04-04 2016-07-12 Sigmoid Pharma Limited Pharmaceutical cyclosporin compositions
US9675558B2 (en) 2007-04-04 2017-06-13 Sigmoid Pharma Limited Pharmaceutical cyclosporin compositions
US9585844B2 (en) 2007-04-04 2017-03-07 Sigmoid Pharma Limited Oral pharmaceutical composition
US8951570B2 (en) 2007-04-26 2015-02-10 Sigmoid Pharma Limited Manufacture of multiple minicapsules
WO2008132707A1 (fr) * 2007-04-26 2008-11-06 Sigmoid Pharma Limited Fabrication de minicapsules multiples
US9402788B2 (en) 2007-04-26 2016-08-02 Sigmoid Pharma Limited Manufacture of multiple minicapsules
WO2009020594A1 (fr) * 2007-08-07 2009-02-12 Auburn University Stabilisation de l'eau au moyen de microparticules
US9999651B2 (en) 2009-05-18 2018-06-19 Sigmoid Pharma Limited Composition comprising oil drops
US9278070B2 (en) 2009-05-18 2016-03-08 Sigmoid Pharma Limited Composition comprising oil drops
US9878036B2 (en) 2009-08-12 2018-01-30 Sigmoid Pharma Limited Immunomodulatory compositions comprising a polymer matrix and an oil phase
FR2964017A1 (fr) * 2010-09-01 2012-03-02 Capsum Procede de fabrication d'une serie de capsules de taille submillimetrique
US9821024B2 (en) 2010-11-25 2017-11-21 Sigmoid Pharma Limited Immunomodulatory compositions
US9731221B2 (en) 2011-05-25 2017-08-15 Cidra Corporate Services, Inc. Apparatus having polymer surfaces having a siloxane functional group
US9827574B2 (en) 2011-05-25 2017-11-28 Cidra Corporate Services, Inc. Mineral separation using sized-, weight- or magnetic-based polymer bubbles or beads
US11731143B2 (en) 2011-05-25 2023-08-22 Cidra Corporate Services Inc. Mineral separation using functionalized membranes
US9302270B2 (en) 2011-05-25 2016-04-05 Cidra Corporate Services Inc. Mineral separation using functionalized filters and membranes
US9327294B2 (en) 2011-05-25 2016-05-03 Cidra Corporate Services Inc. Synthetic bubbles or beads having hydrophobic surface
US9943860B2 (en) 2011-05-25 2018-04-17 Cidra Corporate Services Inc. Mineral recovery in tailings using functionalized polymers
US11135597B2 (en) 2011-05-25 2021-10-05 Cidra Corporate Services Llc Method and system for releasing mineral from synthetic bubbles and beads
US9981272B2 (en) 2011-05-25 2018-05-29 Cidra Corporate Services, Inc. Techniques for transporting synthetic beads or bubbles in a flotation cell or column
US9981271B2 (en) 2011-05-25 2018-05-29 Cidra Corporate Services Llc Method and system for releasing mineral from synthetic bubbles and beads
US11117141B2 (en) 2011-05-25 2021-09-14 Cidra Corporate Services Inc. Mineral separation using sized-, weight- or magnetic-based polymer bubbles or beads
US10357782B2 (en) 2011-05-25 2019-07-23 Cidra Corporate Services Llc Flotation separation using lightweight synthetic beads or bubbles
US9352335B2 (en) 2011-05-25 2016-05-31 Cidra Corporate Services Inc. Synthetic beads/bubbles functionalized with molecules for attracting and attaching to mineral particles of interest
US10603676B2 (en) 2011-09-13 2020-03-31 Cidra Minerals Processing Inc. Mineral processing
US11654443B2 (en) 2011-09-13 2023-05-23 Cidra Minerals Processing Inc. Mineral processing
WO2013177267A1 (fr) * 2012-05-22 2013-11-28 Cidra Corporate Services Inc. Billes/bulles polymères modifiées, chargées, fonctionnalisées par des molécules pour attirer et fixer des particules minérales d'intérêt pour une séparation par flottation
US9839919B2 (en) 2012-05-22 2017-12-12 Cidra Corporate Services Inc. Charged engineered polymer beads/bubbles functionalized with molecules for attracting and attaching to mineral particles of interest for flotation separation
US9220681B2 (en) 2012-07-05 2015-12-29 Sigmoid Pharma Limited Formulations
US9950051B2 (en) 2012-07-05 2018-04-24 Sigmoid Pharma Limited Formulations
US10434138B2 (en) 2013-11-08 2019-10-08 Sublimity Therapeutics Limited Formulations
US10993987B2 (en) 2014-11-07 2021-05-04 Sublimity Therapeutics Limited Compositions comprising Cyclosporin

Similar Documents

Publication Publication Date Title
WO2004064997A1 (fr) Nouvelles microcapsules pouvant etre utilisees comme agent d'extraction, en particulier pour l'extraction de contaminants contenus dans l'eau ou dans le sol
Imdad et al. A critical review on heavy metals removal using ionic liquid membranes from the industrial wastewater
Ognier et al. Influence of macromolecule adsorption during filtration of a membrane bioreactor mixed liquor suspension
Hande et al. Highly selective monitoring of metals by using ion-imprinted polymers
Kyzas et al. Treatment of real effluents from dyeing reactor: Experimental and modeling approach by adsorption onto chitosan
Rahchamani et al. Adsorption of methyl violet from aqueous solution by polyacrylamide as an adsorbent: Isotherm and kinetic studies
Aloulou et al. Modified cellulose fibres for adsorption of organic compound in aqueous solution
Whelehan et al. Removal of pharmaceuticals from water: Using liquid-core microcapsules as a novel approach
Jawor et al. Removing cadmium ions from water via nanoparticle-enhanced ultrafiltration
Wyss et al. A novel approach for the extraction of herbicides and pesticides from water using liquid‐core microcapsules
US9120687B2 (en) Polymer inclusion membranes for use in processes for treating thiocyanate containing aqueous solutions
Williams et al. Removal of ibuprofen and 4-isobutylacetophenone by non-dispersive solvent extraction using a hollow fibre membrane contactor
Sadeghi et al. Membranes with thin hydrogel selective layers containing viral-templated palladium nanoparticles for the catalytic reduction of Cr (VI) to Cr (III)
Niedergall et al. Removal of micropollutants from water by nanocomposite membrane adsorbers
Leepipatpiboon et al. Separation of Co (II) and Ni (II) from thiocyanate media by hollow fiber supported liquid membrane containing Alamine300 as carrier—investigation on polarity of diluent and membrane stability
Muthuraman et al. Use of vegetable oil in supported liquid membrane for the transport of Rhodamine B
Boukarma et al. Kinetic and equilibrium isotherm studies for the removal of acid blue 113 dye by dried corallina officinalis alga as a novel eco-friendly adsorbent
Ghoshal et al. Liquid–membrane filters
Cui et al. Reactive extraction of p-nitrophenol using tributylphosphate in solvent naphtha or n-octanol
González et al. Current trends in sample preparation for the determination of primary aromatic amines in environmental samples
Gourdon et al. A comparative study of cadmium uptake by free and immobilized cells from activated sludge
Gumí et al. Vanillin release from macrocapsules
Zulfikar et al. Removal of humic acid from aqueous solution using dual PMMA/PVDF composite nanofiber: kinetics study
Liu et al. A biomimetic absorbent for removal of trace level persistent organic pollutants from water
Fávere et al. Use of chitosan microspheres as remedial material for acidity and iron (III) contents of coal mining wastewaters

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase