CA2350746C - Method for the purification and recovery of waste gelatin - Google Patents
Method for the purification and recovery of waste gelatin Download PDFInfo
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- CA2350746C CA2350746C CA002350746A CA2350746A CA2350746C CA 2350746 C CA2350746 C CA 2350746C CA 002350746 A CA002350746 A CA 002350746A CA 2350746 A CA2350746 A CA 2350746A CA 2350746 C CA2350746 C CA 2350746C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J1/00—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites
- A23J1/001—Obtaining protein compositions for foodstuffs; Bulk opening of eggs and separation of yolks from whites from waste materials, e.g. kitchen waste
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
- A23J3/00—Working-up of proteins for foodstuffs
- A23J3/04—Animal proteins
- A23J3/06—Gelatine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
- B01D61/146—Ultrafiltration comprising multiple ultrafiltration steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09H—PREPARATION OF GLUE OR GELATINE
- C09H3/00—Isolation of glue or gelatine from raw materials, e.g. by extracting, by heating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
Abstract
Method and apparatus for treating a waste material containing gelatin in which the waste material stream (5) is combined with a solvent stream (2) which is capable of dissolving the gelatin and any softening agent contained therein and then treating the resulting product to obtain a recoverable and usable gelatin containing stream exiting receiver (34) and any components contained in the original waste stream.
Description
METHOD FOR THE PURIFICATION AND
RECOVERY OF WASTE GELATIN
Field of the Invention This invention is generally directed to a process for recovery, purifying and recycling gelatin waste made from gelatin and derivatives thereof and in particular, to a process for recovery, purifying and recycling gelatin waste, its derivatives, and components contained within gelatin waste resulting from industrial encapsulation processes.
Eackground of the Invention Gelatin and gelatin derivatives are used to encapsulate the products of several industries. Examples are described in U.S. Pat. No. 5,074,102, issued to Simpson et al, and include the encapsulation of medicinal compounds such as drugs and vitamins;
employment of gelatin encapsulation in food packaging, such as for powdered instant coffee or spices; in candy manufacturing; in fertilization of ornamental plants and/or indoor plants; in packaging of sensitive seeds in combination with protective agents and/or fertilizers; and in the packing of single dyestuffs or mixtures of various drugs.
In each of the above-recited manufacturing and production processes, a certain amount of the encapsulating material and the encapsulated material (e.g.
vitamins) is lost as waste. Frequently, the amount lost as waste of the encapsulating material approaches 50% or more of the total starting material, depending on the arrangement of production employed. When considering that the cost of the encapsulating material in the United States averages approximately $3.10 per pound ($6.82 per kilo) as of _ September, 1997, it is clear that the economic consequences of such waste can be significant. As a result, manufacturers have attempted to off set poor production efficiency by recycling the waste material for reuse. Such attempts, however, have not been met with a great deal of success.
Prior art methods of gelatin recovery and purification suffer from a variety of shortcomings to be discussed in further detail below. Before these shortcomings can be fully appreciated, however, the composition of the encapsulation waste material itself should be further understood. In general, waste material of encapsulation processes is comprised of a variable number of components added to a gelatin base. Among them are solvents (usually water); softening agents and oil coatings (when desired);
and, contaminants in the form of residual active ingredients, i.e. the substance being encapsulated. In addition, colorings and preservatives may also be added.
Thus, it can be observed that successful recycling involves not only the recovery of gelatin from surrounding oils, but also the removal of the remaining components of the waste in order to achieve a relatively pure, reusable product.
RECOVERY OF WASTE GELATIN
Field of the Invention This invention is generally directed to a process for recovery, purifying and recycling gelatin waste made from gelatin and derivatives thereof and in particular, to a process for recovery, purifying and recycling gelatin waste, its derivatives, and components contained within gelatin waste resulting from industrial encapsulation processes.
Eackground of the Invention Gelatin and gelatin derivatives are used to encapsulate the products of several industries. Examples are described in U.S. Pat. No. 5,074,102, issued to Simpson et al, and include the encapsulation of medicinal compounds such as drugs and vitamins;
employment of gelatin encapsulation in food packaging, such as for powdered instant coffee or spices; in candy manufacturing; in fertilization of ornamental plants and/or indoor plants; in packaging of sensitive seeds in combination with protective agents and/or fertilizers; and in the packing of single dyestuffs or mixtures of various drugs.
In each of the above-recited manufacturing and production processes, a certain amount of the encapsulating material and the encapsulated material (e.g.
vitamins) is lost as waste. Frequently, the amount lost as waste of the encapsulating material approaches 50% or more of the total starting material, depending on the arrangement of production employed. When considering that the cost of the encapsulating material in the United States averages approximately $3.10 per pound ($6.82 per kilo) as of _ September, 1997, it is clear that the economic consequences of such waste can be significant. As a result, manufacturers have attempted to off set poor production efficiency by recycling the waste material for reuse. Such attempts, however, have not been met with a great deal of success.
Prior art methods of gelatin recovery and purification suffer from a variety of shortcomings to be discussed in further detail below. Before these shortcomings can be fully appreciated, however, the composition of the encapsulation waste material itself should be further understood. In general, waste material of encapsulation processes is comprised of a variable number of components added to a gelatin base. Among them are solvents (usually water); softening agents and oil coatings (when desired);
and, contaminants in the form of residual active ingredients, i.e. the substance being encapsulated. In addition, colorings and preservatives may also be added.
Thus, it can be observed that successful recycling involves not only the recovery of gelatin from surrounding oils, but also the removal of the remaining components of the waste in order to achieve a relatively pure, reusable product.
Extraction has been the principle method for accomplishing removal of oils, actives and the like in the pharmaceutical industry. While several solvents have been used in the prior art in an effort to accomplish separation, each suffer from a variety of shortcomings not the least of which is the necessity of ultimately removing yet another component, i.e. the solvent itself, from the recycled materials. To date, the most popular and widely used solvents used to separate gelatin from oils and actives are chlorinated solvents such as, for example, 1,1,1,-trichloroethane with naphtha. The use of chlorinated solvents, however, is accompanied by high costs, disposal problems, and most importantly, environmental concerns. Attempts have been made to use other solvents including isopropyl alcohol, methyl isobutyl ketone, toluene, hexane, heptane, acetone, and acetone/water mixtures, but the resulting yields are insufficient and/or the separation is poor. Furthermore, some of these chemicals are relatively expensive and present similar environmental, disposal, and safety concerns as the chlorinated solvents. None of them have been found to separate oils and actives with a high degree of efficiency.
U.S. Patent No. 5,288,408, issued to Schmidt et al, discloses a method of recycling gelatin-based encapsulation waste material, and more specifically, to a process for the recovery and purification of gelatin and softening agents therefrom. In the preferred embodiment, deionized water is added to the waste material thereby forming an aqueous solution of gelatin and glycerin dispersed within the remaining oil and residual active-ingredient components of the waste material. Extraction methods WO 00/29097 PC'f/US99/27095 are employed under specific conditions to effect separation of the tower aqueous phase from the upper oil phase. The lower phase is hot filtered to remove any remaining traces of oil or other contaminants and the filtrate is then charged to a concentration vessel adapted for vacuum distillation. The water solvent is thus removed under specific thermal and atmospheric conditions until the desired concentration of gelatin and glycerin is achieved. A pure, concentrated aqueous gelatin-glycerin solution results which may be stored or further prepared for immediate reuse. Although this process lends itself to the removal of dyes and active ingredients with additional chemical reactions and processing, such dyes, active ingredients, and glycerin are not removed in situ.
Clear gelatin contains no dye, colorants or the like. It is used to make clear gelatin capsules in the pharmaceutical, neutraceutical, and nutrient industries and other industries as well. Because dyes are not present, there is a need to provide a cost efficient and effective manner for recycling the gelatin and glycerin for reuse. Gelatin may have suspended particles such as titanium dioxide which impart a color to the gelatin. Such particles can be more easily removed from the waste gelatin than dyes and colorants which are water soluble.
It would, therefore, be desirable to provide a method for recycling gelatin-based encapsulation waste material that recycles gelatin and glycerin in situ without the need for any additional processing. It would be a further advance in the art of recycling waste gelatin if an in situ process could be developed that is especially effective in recycling gelatin and gelatin containing suspended particles without thermal degradation in a cost efficient and effective manner. It would be a still further advance in the art to provide a cost efficient and effective method of recycling gelatin whether clear or coloured and whether or not the gelatin contains suspended particles (e.g. a colorant).
It would be a still further advance in the art to provide a method of recovering valuable components from a waste gelatin recovery process.
Summary of the Invention The present invention is generally directed to the recovery of waste gelatin alone or in combination with other components of a waste gelatin product through the separation and treatment of a waste gelatin stream into an aqueous and non-aqueous substream.
In a broad aspect, the present invention relates to a method of treating a waste material containing gelatin comprising: (a) combining the waste material and a solvent for the gelatin under conditions sufficient to form a first liquid containing gelatin, said waste material containing at least one first component which can not effectively be separated from the first liquid into a non-solvent based layer; (b) separating the first liquid into a solvent based layer containing the gelatin and said at least one first component and a non-solvent based layer; and (c) treating the solvent based layer with a process selected from the group including liquid: liquid centrifugation, submicro/microfiltration, coalescers, and combinations thereof which removes the first component from the solvent based layer to form a second liquid containing gelatin having a higher purity than the first liquid being at least substantially devoid of the first liquid.
If desired, the second liquid may be concentrated by removing at least some of the solvent, solvent soluble active ingredients, softening agent, dyes and other solvent soluble impurities to provided at least a substantially purified second liquid.
Brief Description of the Drawings The following drawings in which like reference characters indicate like parts are illustrative of embodiments of the invention and are not intended to limit the invention as encompassed by the claims forming part of the Application.
Figure 1 is a schematic view of an embodiment of the method of gelatin recovery and purification in accordance with the present invention; and Figure 2 is a schematic view of a further embodiment of the invention similar to Figure 1 in which a separate, external degassing operation is provided to remove dissolved gases (e.g. air) from the recovered gelatin.
Detailed Description Of The Preferred Embodiments Gelatin is a protein derivative of collagen obtained, in general, by the boiling of skin, white connective tissues, and bones of animals, and by the partial hydrolysis of collagen, in particular. As a colloid it has unique physical properties. Of particular significance to the present invention is its tendency to stay in solution and its ability to form dispersions in oils. Gelatin remains a solid at standard atmospheric pressure and temperature absent the presence of a sufficient quantity of solvent.
Softening agents are sometimes added to plasticize the gelatin when soft, gelatin shells are desired. Agents such as glycerin, sorbitol, or other similar polyols are commonly employed as softening agents: Glycerin is a preferred softening agent.
The soft elastic capsule-forming material may be used to enclose active components in the form of powders, liquids, or combinations thereof. Oils, such as vitamin A, vitamin C, and beta-carotene, for example, are frequently encapsulated by such soft gel materials in the pharmaceutical, cosmetic, and nutritional industries.
Additionally, other oils like mineral oil or medium chain triglycerides (MCT's) may be used to coat the outer surface of the gel-capsule during processing. Thus, it can be seen that the waste product of the encapsulation process may have, in addition to gelatin and a softening agent such as glycerin, many components (e.g. oily components) which must be removed before the gelatin waste is available for reuse as _7_ a relatively pure product. !n some instances, coloring agents and preservatives may also be incorporated into the gelatin mass. Commonly used preservatives include methylparaben, propylparaben, and sorbic acid. w Present methods of encapsulating active components employ a ribbon or sheet of gelatin which is then die punched to form capsules. As much as 50% or more of the gelatin starting material (i.e. gelatin ribbon) is either discarded as a waste by-product or recycled. The latter option requires the removal of ail of the above-mentioned components. The present invention provides a novel and effcient method of purifying and recycling the waste material without experiencing the shortcomings of the prior art.
It will be understood that other proteins with ; hysical and chemical properties similar to gelatin exist and may also be recycled by the present process. Similarly, glycerin is only one example of a softening agent which may be recovered; thus, neither gelatin nor glycerin are intended to be limiting.
Reference is now made to Figure 1 wherein an embodiment of the present invention for the purification and recovery of gelatin and/or glycerin is illustrated. A
suitable solvent such as deionized (D.1.) water is added through a conduit 2 in an amount sufficient to dissolve the waste gelatin material, typically in an amount of up to about five volumes, based on the quantity of waste gelatin, preferably from about 0.5 to 5.0 volumes is added to a dissolution/separation vessel 4 which may be provided with a heating jacket known in the art. The solvent is preheated to a temperature of _g_ from about 30 to 70°C to make the waste gelatin in a convenient flowable condition. The waste gelatin material is then charged either batchwise or continuously to the dissolution/separation vessel 4 via a conduit 5 which may be made of stainless steel or glass-lined construction and sized according to a desired batch size. The dissolutionlseparation vessel 4 may also be provided with a conventional agitation device such as a stirrer (not shown). The waste material to be recovered is diluted with the solvent (e.g. deionized water) typically at atmospheric pressure under heating at a temperature from about 30 to 70°C to a preferred concentration of from about 8% to 45% gelatin by weight. Agitation is simultaneously performed to effect dissolution of the gelatin and the softening agent (e.g. glycerin).
A solution of gelatin and glycerin (i.e. solvent based layer (e.g. aqueous layer)]
is thus formed within the remaining oily component and residual active-ingredient components [i.e. non-solvent based Payer (e.g. non-aqueous layer)]. As used herein the term "solvent based layer" shall mean a layer or phase in which the components contained therein are dissolved in the solvent. The term "non-solvent based layer" shall mean a layer or phase in which the components therein do not dissolve in the solvent and therefore may be separated from the solvent based layer. Since water is the preferred solvent, reference will be made hereinafter to the aqueous layer and non-aqueous layer.
_g_ The above recited concentration level of gelatin (from about 8% to 45%) is a preferred concentration for achieving rapid and thorough separation of the upper non-solvent based layer (e.g. non-aqueous layer) from a lower solvent based layer (e.g.
aqueous layer). The upper non-aqueous layer is either discarded or sent via a conduit _.
6 to a recycling system 8 which is known in the art. If recycled, the non-aqueous layer may be separated into oily components including, but not limited to, vitamins (for vitamin containing products (e.g. vitamin E}), mineral oil, garlic oil, fish oil, beta carotene, and vitamin E, which emerge through conduit 10.
Once the gelatin is completely dissolved within the vessel 4, agitation is terminated and the mass is allowed to either 1 ) stand to effect separation of the solvent based layer (e.g. aqueous layer) from the non-aqueous layer then further processed to remove residual oils and/or particulates or, 2) alternatively, the entire mass may be sent directly to an appropriate apparatus for separation of the aqueous and non-aqueous layers.
If the mass is allowed to stand to effect separation of the oils, it has been observed that for a batch size of about 150 Kg, for example, approximately 1 to 3 hours were required for separation. Separation of the lower aqueous layer from the upper non-aqueous layer within the vessel 4 can be facilitated by a sight glass incorporated into the recycling system 8. Accordingly, differences between the two layers are visually determined to effect accurate separation. Alternatively, an oil skimmer may be employed to remove the non-aqueous layer, as previously indicated, which is discarded or further processed in the recycle system, while the lower aqueous layer is further processed as discussed below.
The separation and recovery of the individual oily components within the non-aqueous layer of the recycling system can be accomplished by a variety of processes including, but not limited to, fractional distillation, short path distillation, and reverse osmosis.
in general, distillation is a process in which a liquid is vaporized, recondensed, and collected in a receiver. The liquid which has vaporized is collected in a receiver.
The resultant liquid (i.e. condensed vapor) is referred to as the condensate or distillate.
Distillation is a process for purifying liquids by separating the liquid into its components. It is based on the difference in the volatility of the liquids.
Volatility is a general term used to describe the relative ease with which molecules (liquid or solid) may escape from the surface to form a vapor. The vapor pressure of a liquid is related to the ease with which the liquid volatilizes (i.e. a relatively volatile substance exerts a relatively high vapor pressure at room temperature). The more volatile a substance, the higher its vapor pressure and the lower its boiling point.
Fractional distillation is the separation and purification, by distillation, of finro or more liquids into various fractions. It is a systematic redistillation of progressively purer distillates or fractions. A fractionating column is used to essentially perform a large number of successive distillations without the necessity of actually collecting and ..
redistilling the various fractions. A fractionating column may be packed with glass beads, glass helices, metal screens or ceramic saddles to effect fractionation.
A series of distillations involving partial vaporization and condensation concentrates the more volatile component in the first fraction of distillate and the less volatile component in the last fraction or in the residual liquid. The vapor leaves the surface of the liquid and passes up the packing of the column. The vapor condenses on the cooler surfaces and redistills, typically many times before entering the condenser. By means of long and efficient distillation columns, two liquids may be completely separated.
Short path distillation is especially suitable for substances that cannot be distilled by any of the ordinary distillation methods because (1 ) the substance is viscous, and any condensed vapors tend to plug the distilling column or condenser; and/or (2) the vapors of the substance are extremely susceptible to condensation.
Short path distillation differs from other distillations because (1 ) a condensed vapor flows to the distillate receiver or collector; (2) very low pressure (high vacuum) _12_ WO 00/29097 PCTlUS99/27095 in the system favors vaporized molecules reaching the condensing surface without collision with other molecules to condense prematurely; (3) there is a very short distance between the surface of the evaporating liquid and the condenser surface; and (4) the substance has a residence time in the presence of heat which is very short so that thermal degradation is prevented.
A short path distillation apparatus typically includes a rotating still.
Materials are fed into the rotating still and distributed evenly and thinly over a heated evaporating surface. The substance distills in a short time and the vapors condense and run into a collector. The degree of vacuum is controlled to collect the distillate effectively at the condenser. The pressure can be as low as 1 arm Hg.
Short path distillation as described herein is also known as molecular, wiped ftlm, thin film, failing film, and rising film distillation. Short path distillation systems are commercially available from companies such as Pope Scientific in Saukville, WI
and Artisan industries in Waltham, MA.
Reverse osmosis is a process whereby dissolved solids or a miscible liquid are removed from water by applying a pressure differential across a semi-permeable membrane. The semipermeable membrane allows water to flow therethrough, but does not allow other components from passing through the membrane. Reverse osmosis equipment is commercially available from companies such as Pall Filtron in Northborough, MA and Millipore Corporation in Bedford, MA.
As described above, the dissolved gelatin is separated into a solvent based layer (e.g. aqueous layer) and a non-solvent based Payer (e.g. non-aqueous layer).
The non-aqueous layer is then treated by any of the above described methods to recover the oils contained in the non-aqueous stream.
If the separated aqueous layer contains particulates and/or oily type materials, the aqueous layer may then be treated, to remove residual oils and/or particulates preferably by means of hot filtration processes as more fully described below.
The aqueous layer is sent through a heated transfer conduit 14, to a hot filtration assembly 18. The hot filtration assembly 18 is particularly desirable if the aqueous layer contains particulate matter or residual oil matter.
The method of hot filtration employed for the removal of oils and/or particulates may include, but is not limited to, techniques such as liquid:liquid centrifugation, sub-micro/micro-filtration, liquid:liquid coalescers, absorbents and filter aids such as, but not limited to, diamataceous earth, activated carbon, clay or activated clay, colloidal silica, porous acrylic resins and the use of oil soluble salts to break any emulsion that may exist.
Liquid:liquid centrifugation is based on the principal that the rate of separation of two immiscible liquids is increased significantly by the application of centrifugal force which can be thousands of times that of gravity. The force exerted on the liquids is directly proportional to the speed of rotation, the radius of rotation, and the mass of the liquids.
The force exerted on rotating immiscible liquids, i.e, aqueous and non-aqueous liquids, is described in terms of relative centrifugal force or number of g's which is expressed as multiples of the force of gravity. Centrifuges are rated by their relative centrifugal force which can typically range from 10 to hundreds of thousands.
Relative centrifugal force can be controlled by varying the speed or the centrifuge head or rotor.
As a method of hot fltration in the subject invention, the aqueous layer to be hot filtered is maintained at a temperature sufficient to allow flow into the centrifuge; higher temperatures and/or higher dilutions may also enhance an efficient separation by reducing the viscosity of the liquids to be separated. A temperature of from about 30°C
to 70°C and a dilution volume of up to 5 volumes, preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is preferred.
The efficiency of separation may be enhanced by employing a relatively higher centrifugal force in the range of from about 5,000 to 25,000. The resulting, clarified aqueous layer containing gelatin and glycerin is collected for reuse and the residual oils and/or particulates are either discarded or collected for potential recovery as discussed hereinafter.
Liquid:liquidaolid centrifugation can also be utilized to achieve separation of the gelatin and softening agent (e.g. glycerin) from the particulates and/or residual oils.
This procedure is preferred when the waste gelatin stream contains particufates which are at least a part of the coloring system (e.g. titanium dioxide).
Commercial liquid:liquid and/or liquid:liquidaolid centrifugation equipment is available from companies such as Westfalia Separator U.S. in Northvale, NJ and Alfa Laval in Warminster, PA.
Micro or sub-micro filtration refers to a method of removing small particles from a liquid. Particulates as used herein include, but are not limited to, solid particulates which do not have sufficient mass to settle out of solution and/or emulsions and micro-emulsions which do not readily separate from a liquid. Micro or sub-micro filtration can be achieved through the use of micron or sub-micron pore sized filters including, but not limited to cartridge type filters, also known as "depth" or "dead end" filters and tangential flow type fitters. Tangential flow type filters are the preferred filters for this purpose. The pore size of the preferred filters is typically in the range of from about 0.1 and 2.0 microns.
Temperature and dilution are important considerations in improving the efficiency of the filtration process by varying the viscosity of the liquid. A
temperature of from about 30°C to 70°C and a dilution volume of up to 5 volumes preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is preferred.
Micro or sub-micro filtration equipment is commercially available from suppliers such as Millipore Corporation in Bedford, MA.
A liquidaiquid coalescer, may be used to remove residual oils from the aqueous layer. The coalescer enhances the collection of the oil droplets (the dispersed phase liquid) into larger droplets which will separate more easily from the aqueous layer (the continuous phase liquid).
Generally, for the subject application, a multiple stage system may be employed.
Such systems remove the designated materials in stages such as by first removing particulates. Once the particulates are removed the remaining liquid may then be treated with a coaiescer to remove residual oil from the aqueous gelatin and glycerin.
A temperature of from about 30°C to 70°C and a dilution volume of typically up to 5 volumes, preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is desirable. Commercial coalescers are readily available such as those supplied by Millipore Corporation in Bedford, MA.
Filter aids containing diatomaceous earth can be employed for removal of particulates and/or residual oils. Diatomaceous earth, more commonly known as Celite or Filter Aid, is a very pure and inert material which forms a porous film or cake on a filter medium such as, but not limited to, filters made from paper, nylon and _, polypropylene as are typically used in filtration systems using filtration apparatus such as, but not limited to Nutsch filters, Rosenmund fitters and/or centrifuges.
Diatomaceous earth can be employed: 1 ) by forming a slurry with an appropriate solvent, such as water, then filtering the slurry through an appropriate apparatus, such as a Nutsch or Rosenmund type filter, or a platelcoated plate filter such as a sparkler filter, to form a thin film or cake or 2} by adding the diatamaceous earth directly to the product to be filtered to form a slurry which is then filtered forming a porous thin cake or film. A temperature of from about 30°C to 70°C and a dilution volume of up to 5 volumes, preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is desirable. Other filter aids besides diatamaceous earth include, but are not limited to silica, acrylic resins, clay and activated carbon.
Absorbents which may be used to treat the solvent based layers include zeolitic materials.
In particular, the lower aqueous phase may be heated, preferably hot filtered in the filtration assembly 18 if particulates and/or residual oils are present at a temperature of approximately the same as above (i.e. from about 30'C to 70°C) preferably through liquid:liquid centrifugation or micro/sub-micro filtration as described above to remove any remaining traces of oily components or other contaminants through a conduit 20 and optionally forwarded to the recycling system 8 . Other types of filtration equipment which may be employed include plate filters, or coated plate filters like, for example, a sparkler filter. The preferred material of construction for these type of fitters is stainless steel. Alternatively, nutche filters of the Rosenmund type or cartridge filters may be used for the purpose.
The employment of the hot filtration systems mentioned above separates particulates and/or oils from the aqueous layer containing gelatin and the softening agent (e.g. glycerin).
Depending on the concentration of the gelatin and glycerin in the resulting filtrate, the filtrate may be returned directly to gelatin mass manufacturing or the Citrate may be transported via heated conduit 22 to a concentration assembly 16 which may be in the form of a diafiltration assembly and concentrated by removing some of the solvent (e.g. water). For solutions having a gelatin concentration greater than about 10% gelatin wtlwt (e.g. 10% wt/wt to 45% wtlwt), the aqueous solution may be charged to a concentration apparatus adapted for vacuum distillation such as disclosed in Schmidt et al., U.S. Patent No. 5,288,408, or to a diafiltration system such as disclosed in Schmidt U.S. Patent No. 5,945,007. Alternatively, the filtrate may be subjected to short path distillation as previously described.
.19_ Short path distillation for this aspect of the present invention is carried out under controlled conditions to facilitate the removal of water at a lower temperature to prevent thermal. degradation of the recoverable gelatin. Evaporator temperatures typically from about 50'C to 120'C, and typically pressures 20 to 30 in. Hg, preferably 22-28 in. Hg _.
are employed to remove water. Such temperatures and short contact time do not cause decomposition of the protein-based gelatin which affects its bloom strength. The water distillate is passed through a condenser to waste or recycle. The residue contains the gelatinlglycerin mixture for reuse.
As an example, waste gelatin material is diluted with solvent (e.g. water) at a ratio of 3:1, water:waste gelatin material, the following illustrates the distitlate:residue ratios which may be via the chosen distillation process, to achieve a desired level of recycled gelatin and glycerin.
To achieve a 25% recycle level for gelatin and glycerin from the above described 3:1 dilution, the distillation should preferably result in a distillate:
residue ratio of 50:50.
To achieve a 40% recycle level for gelatin and glycerin from the above described 3:1 dilution, the distillation should preferably result in a distillate: residue ratio of 62.5:37.5.
In both examples the residue contains the gelatin and glycerin for recycle.
_20_ Diafiitration may be employed at the concentration assembly 16 to remove residual water soluble active ingredients, glycerine, water, and other water-soluble components such as preservatives and dyes and to provide gelatin in a form that is of sufficient purity and quality to permit reuse.
Diafiltration is a technique using ultrafiltration membranes to remove or fractionate different size molecules in macromolecular solutions. An ultra~ltration membrane retains macromolecules that are larger than the nominal molecular weight limit (NMWL) of the membrane and freely passes molecular species which are significantly smaller than the NMWL of the membrane. Macromolecules retained by the membrane are concentrated, while the low molecular weight species are removed.
Typically, the macromolecules must be "washed" using multiple wash volumes to remove residual smaller molecules, hence the name diafiltration (i.e.
filtration using ultrafiltration membranes and washing).
For continuous diafiltration, a supply of macromolecules (e.g. gelatin) is added via the conduit 22 to the diafiltration assembly 16 at the same rate as the frltrate is being removed. This is also referred to as constant volume diafiltration. The concentration of the macromolecules does not change during the diafiltration process.
Discontinuous diafiltration involves first concentrating the macromolecule (e.g.
gelatin) batch to a predetermined volume, and then reconstituting the sample to its original volume with replacement solvent. This is repeated until the smaller molecules are removed.
Referring to Figure 1 diafiltration may be accomplished by first heating the system from about 50°C to 65°C by recirculating heated, deionized water typically for about 15 minutes through the conduit 24. The hot, aqueous feed stream is then pumped through fhe assembly 16 via a conduit 22 and concentrated to the desired gelatin/water concentration as discussed hereinafter. When the desired water/gelatin concentration is achieved, fresh, hot (e.g. from about 50 to 65°C), deionized water is fed into the system at exactly the same rate as the effluent exiting the system; the effluent being water and all water soluble components. Once the water soluble components have been removed, the remaining gelatin/water solution is recycled for gelatin encapsulation.
The filters that can be employed in the concentration/diafrtration step are known and available in the art. Such frlters include screen filters including open channel filters and the like. The selection of a suitable filter for the purification of gelatin must be capable of separating gelatin (typically having a molecular weight of from about 30,000 to 50,000) from smaller molecules.
The recovered aqueous gelatin solution is concentrated to a final solids (gelatin) concentration of at least between about 20% by weight, preferably from about 30% and WO 00/29097 PC'T/US99/27095 50%. The remaining concentrated gelatin is then purified using between about 1 and 20 diafiltration volumes of water, preferably between about 3 and 10 diafiltration volumes to provide recovered gelatin that is sufficiently pure to permit reuse and which leaves the diafiitration assembly 16 via a conduit 26 to a receiver 34. A
portion of the purified recycled gelatin may be sent back to the gelatin dissolving step via a conduit 28 to remove additional impurities from the gelatin to thereby obtain an even purer product.
Impurities such as dyes, actives, water, preservatives and glycerine can be removed from the diafiltration assembly via conduit 30.
Recovery of the above-mentioned impurities obtained from the diafiltration assembly 16 via the conduit can be performed in a recycling system 32. This system can be based on distillation systems including fractional distillation, short path distillation and reverse osmosis as previously described in connection with the recycle system 8.
Fractional distillation and reverse osmosis are preferred for recovery of the stream 30 with reverse osmosis being the most preferred method.
The process stream 30 in addition to containing the above mentioned impurities may contain from about 1 % to 70% by volume of glycerol in water, typically from about 3% to 7% by volume. The process stream 30 is treated at temperature of from about 0°C to 30°C, more typically from about 5°C to 20°C. Typically recovery of glycerol is at WO 00/2909'7 PCT/US99/27095 least 65% by volume, more typically from about 65% to 95%, most preferably from about 80% to 95% by volume.
In some instances, dyes and pigments that are used to color gelatin capsules have an affinity for the gelatin in the waste stream. Recovery of the gelatin alone may, therefore, require that steps be taken to eliminate this affinity so that the dyes can be removed. In general, it is necessary to take these steps following the hot filtration process and prior to the concentration/diafiltration process.
Suitable methods for eliminating the affinity between dyes and/or pigments and the gelatin include use of, for example, activated clay, carbon cartridge filtration; carbon slurry fom~ation followed by filtration to remove the carbon; pH adjustment to eliminate adhesion of the dye to the gelatin, followed by direct diafiltration to remove the dyes, and then adjustment of the pH back to the normal processing pH (e.g. from about 5 to 7); or, a combination of these methods.
If an affinity exists between the dyes and/or pigments, once the affinity has been eliminated, diafiltration can be performed to obtain recovered gelatin.
Alternatively, diafiltration itself will remove these dyes and/or pigments with sufficient diafiltration volumes. It is understood that the recycling system described can be incorporated into a conventional encapsulation apparatus to provide repeated or continual recycling of waste encapsulation materials.
Entrapped air may be a consideration during the process of manufacturing gelatin mass for encapsulation into soft gelatin capsules. General practice in the soft gelatin capsule manufacturing industry is to manufacture the gelatin mass under vacuum, for the express purpose of removing air, on a mezzanine or second floor then feed the molten gelatin mass, by gravity, to the encapsulation machines on the first floor.
In the absence of a building configuration conducive to gravity feed to the encapsulation machines, gelatin mass can be transferred by air pressure or pumps.
The choice of pump must be such that as little air as possible is introduced into the gelatin mass. Examples of appropriate pumps may be, but are not limited to, peristaltic, moyno, and sine type pumps.
The ultrafiltration process of the present invention can generate flow rates in excess of 200 liters per minute. Although proper engineering and design of the diafiltration system will minimize or eliminate introduction of air from external sources, the flow rates generated may nonetheless, introduce some air into the gelatin.
The air can be entrapped or dissolved in the viscous gelatin mass. Under these circumstances, it is desirable to degas or remove at least most of the air from the gelatin.
Typical practices in analytical chemistry for degassing dissolved air in water and/or organic solvents used as a mobile phase for High Performance Liquid Chromatography (HPLC) are: 1 ) pass the water and/or organic solvents through a 0.45 micron membrane filter and/or 2) sparge the water andlor organic solvent with an inert gas such as nitrogen and/or 3) allow the water and/or organic solvent to be exposed to ' molecular sieves until completely degassed.
It is also known in the art that microfllters are available commercially in the micron range similar to that used to degas mobile phase for HPLC analysis.
Such filters may be obtained for example from AIG Technology of Needham, IVlassachusetts.
Any of the above-mentioned methods of degassing may be employed in the present invention. If, for example, a membrane filter (e.g. 0.45 micron) were employed to degas the gelatin, the filter could be incorporated into the diafiltration system 16 shown in Figure 1. For example, the aqueous layer passing through the conduit 14 to the diafiltration system 16 is first treated as described above to remove impurities via the conduit 30. The recovered gelatin may then be filtered with a membrane filter to remove air within the diafiltration system 16.
In another embodiment of the present invention, the degassing operation may be established externally of the diafiltration system. Referring to Figure 2, the recovered gelatin is sent via the conduit 26 to a conduit 27 which leads to a degassing system 29 (e.g. a membrane filter). Once the gas (e.g. air) is removed from the gelatin, the degassed gelatin is sent via the conduit 31 to be recycled or recovered.
It is understood that the above described recycling system may be incorporated into a conventional encapsulation apparatus to provide repeated or continual recycling of waste encapsulation materials.
Although the present invention has been described with reference to the particular embodiments herein set forth, it is understood that the present disclosure has been made only by way of example and that numerous changes in details of construction may be resorted to without departing from the spirit and scope of the invention. Thus, the scope of the invention should not be limited by the foregoing specifications.
U.S. Patent No. 5,288,408, issued to Schmidt et al, discloses a method of recycling gelatin-based encapsulation waste material, and more specifically, to a process for the recovery and purification of gelatin and softening agents therefrom. In the preferred embodiment, deionized water is added to the waste material thereby forming an aqueous solution of gelatin and glycerin dispersed within the remaining oil and residual active-ingredient components of the waste material. Extraction methods WO 00/29097 PC'f/US99/27095 are employed under specific conditions to effect separation of the tower aqueous phase from the upper oil phase. The lower phase is hot filtered to remove any remaining traces of oil or other contaminants and the filtrate is then charged to a concentration vessel adapted for vacuum distillation. The water solvent is thus removed under specific thermal and atmospheric conditions until the desired concentration of gelatin and glycerin is achieved. A pure, concentrated aqueous gelatin-glycerin solution results which may be stored or further prepared for immediate reuse. Although this process lends itself to the removal of dyes and active ingredients with additional chemical reactions and processing, such dyes, active ingredients, and glycerin are not removed in situ.
Clear gelatin contains no dye, colorants or the like. It is used to make clear gelatin capsules in the pharmaceutical, neutraceutical, and nutrient industries and other industries as well. Because dyes are not present, there is a need to provide a cost efficient and effective manner for recycling the gelatin and glycerin for reuse. Gelatin may have suspended particles such as titanium dioxide which impart a color to the gelatin. Such particles can be more easily removed from the waste gelatin than dyes and colorants which are water soluble.
It would, therefore, be desirable to provide a method for recycling gelatin-based encapsulation waste material that recycles gelatin and glycerin in situ without the need for any additional processing. It would be a further advance in the art of recycling waste gelatin if an in situ process could be developed that is especially effective in recycling gelatin and gelatin containing suspended particles without thermal degradation in a cost efficient and effective manner. It would be a still further advance in the art to provide a cost efficient and effective method of recycling gelatin whether clear or coloured and whether or not the gelatin contains suspended particles (e.g. a colorant).
It would be a still further advance in the art to provide a method of recovering valuable components from a waste gelatin recovery process.
Summary of the Invention The present invention is generally directed to the recovery of waste gelatin alone or in combination with other components of a waste gelatin product through the separation and treatment of a waste gelatin stream into an aqueous and non-aqueous substream.
In a broad aspect, the present invention relates to a method of treating a waste material containing gelatin comprising: (a) combining the waste material and a solvent for the gelatin under conditions sufficient to form a first liquid containing gelatin, said waste material containing at least one first component which can not effectively be separated from the first liquid into a non-solvent based layer; (b) separating the first liquid into a solvent based layer containing the gelatin and said at least one first component and a non-solvent based layer; and (c) treating the solvent based layer with a process selected from the group including liquid: liquid centrifugation, submicro/microfiltration, coalescers, and combinations thereof which removes the first component from the solvent based layer to form a second liquid containing gelatin having a higher purity than the first liquid being at least substantially devoid of the first liquid.
If desired, the second liquid may be concentrated by removing at least some of the solvent, solvent soluble active ingredients, softening agent, dyes and other solvent soluble impurities to provided at least a substantially purified second liquid.
Brief Description of the Drawings The following drawings in which like reference characters indicate like parts are illustrative of embodiments of the invention and are not intended to limit the invention as encompassed by the claims forming part of the Application.
Figure 1 is a schematic view of an embodiment of the method of gelatin recovery and purification in accordance with the present invention; and Figure 2 is a schematic view of a further embodiment of the invention similar to Figure 1 in which a separate, external degassing operation is provided to remove dissolved gases (e.g. air) from the recovered gelatin.
Detailed Description Of The Preferred Embodiments Gelatin is a protein derivative of collagen obtained, in general, by the boiling of skin, white connective tissues, and bones of animals, and by the partial hydrolysis of collagen, in particular. As a colloid it has unique physical properties. Of particular significance to the present invention is its tendency to stay in solution and its ability to form dispersions in oils. Gelatin remains a solid at standard atmospheric pressure and temperature absent the presence of a sufficient quantity of solvent.
Softening agents are sometimes added to plasticize the gelatin when soft, gelatin shells are desired. Agents such as glycerin, sorbitol, or other similar polyols are commonly employed as softening agents: Glycerin is a preferred softening agent.
The soft elastic capsule-forming material may be used to enclose active components in the form of powders, liquids, or combinations thereof. Oils, such as vitamin A, vitamin C, and beta-carotene, for example, are frequently encapsulated by such soft gel materials in the pharmaceutical, cosmetic, and nutritional industries.
Additionally, other oils like mineral oil or medium chain triglycerides (MCT's) may be used to coat the outer surface of the gel-capsule during processing. Thus, it can be seen that the waste product of the encapsulation process may have, in addition to gelatin and a softening agent such as glycerin, many components (e.g. oily components) which must be removed before the gelatin waste is available for reuse as _7_ a relatively pure product. !n some instances, coloring agents and preservatives may also be incorporated into the gelatin mass. Commonly used preservatives include methylparaben, propylparaben, and sorbic acid. w Present methods of encapsulating active components employ a ribbon or sheet of gelatin which is then die punched to form capsules. As much as 50% or more of the gelatin starting material (i.e. gelatin ribbon) is either discarded as a waste by-product or recycled. The latter option requires the removal of ail of the above-mentioned components. The present invention provides a novel and effcient method of purifying and recycling the waste material without experiencing the shortcomings of the prior art.
It will be understood that other proteins with ; hysical and chemical properties similar to gelatin exist and may also be recycled by the present process. Similarly, glycerin is only one example of a softening agent which may be recovered; thus, neither gelatin nor glycerin are intended to be limiting.
Reference is now made to Figure 1 wherein an embodiment of the present invention for the purification and recovery of gelatin and/or glycerin is illustrated. A
suitable solvent such as deionized (D.1.) water is added through a conduit 2 in an amount sufficient to dissolve the waste gelatin material, typically in an amount of up to about five volumes, based on the quantity of waste gelatin, preferably from about 0.5 to 5.0 volumes is added to a dissolution/separation vessel 4 which may be provided with a heating jacket known in the art. The solvent is preheated to a temperature of _g_ from about 30 to 70°C to make the waste gelatin in a convenient flowable condition. The waste gelatin material is then charged either batchwise or continuously to the dissolution/separation vessel 4 via a conduit 5 which may be made of stainless steel or glass-lined construction and sized according to a desired batch size. The dissolutionlseparation vessel 4 may also be provided with a conventional agitation device such as a stirrer (not shown). The waste material to be recovered is diluted with the solvent (e.g. deionized water) typically at atmospheric pressure under heating at a temperature from about 30 to 70°C to a preferred concentration of from about 8% to 45% gelatin by weight. Agitation is simultaneously performed to effect dissolution of the gelatin and the softening agent (e.g. glycerin).
A solution of gelatin and glycerin (i.e. solvent based layer (e.g. aqueous layer)]
is thus formed within the remaining oily component and residual active-ingredient components [i.e. non-solvent based Payer (e.g. non-aqueous layer)]. As used herein the term "solvent based layer" shall mean a layer or phase in which the components contained therein are dissolved in the solvent. The term "non-solvent based layer" shall mean a layer or phase in which the components therein do not dissolve in the solvent and therefore may be separated from the solvent based layer. Since water is the preferred solvent, reference will be made hereinafter to the aqueous layer and non-aqueous layer.
_g_ The above recited concentration level of gelatin (from about 8% to 45%) is a preferred concentration for achieving rapid and thorough separation of the upper non-solvent based layer (e.g. non-aqueous layer) from a lower solvent based layer (e.g.
aqueous layer). The upper non-aqueous layer is either discarded or sent via a conduit _.
6 to a recycling system 8 which is known in the art. If recycled, the non-aqueous layer may be separated into oily components including, but not limited to, vitamins (for vitamin containing products (e.g. vitamin E}), mineral oil, garlic oil, fish oil, beta carotene, and vitamin E, which emerge through conduit 10.
Once the gelatin is completely dissolved within the vessel 4, agitation is terminated and the mass is allowed to either 1 ) stand to effect separation of the solvent based layer (e.g. aqueous layer) from the non-aqueous layer then further processed to remove residual oils and/or particulates or, 2) alternatively, the entire mass may be sent directly to an appropriate apparatus for separation of the aqueous and non-aqueous layers.
If the mass is allowed to stand to effect separation of the oils, it has been observed that for a batch size of about 150 Kg, for example, approximately 1 to 3 hours were required for separation. Separation of the lower aqueous layer from the upper non-aqueous layer within the vessel 4 can be facilitated by a sight glass incorporated into the recycling system 8. Accordingly, differences between the two layers are visually determined to effect accurate separation. Alternatively, an oil skimmer may be employed to remove the non-aqueous layer, as previously indicated, which is discarded or further processed in the recycle system, while the lower aqueous layer is further processed as discussed below.
The separation and recovery of the individual oily components within the non-aqueous layer of the recycling system can be accomplished by a variety of processes including, but not limited to, fractional distillation, short path distillation, and reverse osmosis.
in general, distillation is a process in which a liquid is vaporized, recondensed, and collected in a receiver. The liquid which has vaporized is collected in a receiver.
The resultant liquid (i.e. condensed vapor) is referred to as the condensate or distillate.
Distillation is a process for purifying liquids by separating the liquid into its components. It is based on the difference in the volatility of the liquids.
Volatility is a general term used to describe the relative ease with which molecules (liquid or solid) may escape from the surface to form a vapor. The vapor pressure of a liquid is related to the ease with which the liquid volatilizes (i.e. a relatively volatile substance exerts a relatively high vapor pressure at room temperature). The more volatile a substance, the higher its vapor pressure and the lower its boiling point.
Fractional distillation is the separation and purification, by distillation, of finro or more liquids into various fractions. It is a systematic redistillation of progressively purer distillates or fractions. A fractionating column is used to essentially perform a large number of successive distillations without the necessity of actually collecting and ..
redistilling the various fractions. A fractionating column may be packed with glass beads, glass helices, metal screens or ceramic saddles to effect fractionation.
A series of distillations involving partial vaporization and condensation concentrates the more volatile component in the first fraction of distillate and the less volatile component in the last fraction or in the residual liquid. The vapor leaves the surface of the liquid and passes up the packing of the column. The vapor condenses on the cooler surfaces and redistills, typically many times before entering the condenser. By means of long and efficient distillation columns, two liquids may be completely separated.
Short path distillation is especially suitable for substances that cannot be distilled by any of the ordinary distillation methods because (1 ) the substance is viscous, and any condensed vapors tend to plug the distilling column or condenser; and/or (2) the vapors of the substance are extremely susceptible to condensation.
Short path distillation differs from other distillations because (1 ) a condensed vapor flows to the distillate receiver or collector; (2) very low pressure (high vacuum) _12_ WO 00/29097 PCTlUS99/27095 in the system favors vaporized molecules reaching the condensing surface without collision with other molecules to condense prematurely; (3) there is a very short distance between the surface of the evaporating liquid and the condenser surface; and (4) the substance has a residence time in the presence of heat which is very short so that thermal degradation is prevented.
A short path distillation apparatus typically includes a rotating still.
Materials are fed into the rotating still and distributed evenly and thinly over a heated evaporating surface. The substance distills in a short time and the vapors condense and run into a collector. The degree of vacuum is controlled to collect the distillate effectively at the condenser. The pressure can be as low as 1 arm Hg.
Short path distillation as described herein is also known as molecular, wiped ftlm, thin film, failing film, and rising film distillation. Short path distillation systems are commercially available from companies such as Pope Scientific in Saukville, WI
and Artisan industries in Waltham, MA.
Reverse osmosis is a process whereby dissolved solids or a miscible liquid are removed from water by applying a pressure differential across a semi-permeable membrane. The semipermeable membrane allows water to flow therethrough, but does not allow other components from passing through the membrane. Reverse osmosis equipment is commercially available from companies such as Pall Filtron in Northborough, MA and Millipore Corporation in Bedford, MA.
As described above, the dissolved gelatin is separated into a solvent based layer (e.g. aqueous layer) and a non-solvent based Payer (e.g. non-aqueous layer).
The non-aqueous layer is then treated by any of the above described methods to recover the oils contained in the non-aqueous stream.
If the separated aqueous layer contains particulates and/or oily type materials, the aqueous layer may then be treated, to remove residual oils and/or particulates preferably by means of hot filtration processes as more fully described below.
The aqueous layer is sent through a heated transfer conduit 14, to a hot filtration assembly 18. The hot filtration assembly 18 is particularly desirable if the aqueous layer contains particulate matter or residual oil matter.
The method of hot filtration employed for the removal of oils and/or particulates may include, but is not limited to, techniques such as liquid:liquid centrifugation, sub-micro/micro-filtration, liquid:liquid coalescers, absorbents and filter aids such as, but not limited to, diamataceous earth, activated carbon, clay or activated clay, colloidal silica, porous acrylic resins and the use of oil soluble salts to break any emulsion that may exist.
Liquid:liquid centrifugation is based on the principal that the rate of separation of two immiscible liquids is increased significantly by the application of centrifugal force which can be thousands of times that of gravity. The force exerted on the liquids is directly proportional to the speed of rotation, the radius of rotation, and the mass of the liquids.
The force exerted on rotating immiscible liquids, i.e, aqueous and non-aqueous liquids, is described in terms of relative centrifugal force or number of g's which is expressed as multiples of the force of gravity. Centrifuges are rated by their relative centrifugal force which can typically range from 10 to hundreds of thousands.
Relative centrifugal force can be controlled by varying the speed or the centrifuge head or rotor.
As a method of hot fltration in the subject invention, the aqueous layer to be hot filtered is maintained at a temperature sufficient to allow flow into the centrifuge; higher temperatures and/or higher dilutions may also enhance an efficient separation by reducing the viscosity of the liquids to be separated. A temperature of from about 30°C
to 70°C and a dilution volume of up to 5 volumes, preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is preferred.
The efficiency of separation may be enhanced by employing a relatively higher centrifugal force in the range of from about 5,000 to 25,000. The resulting, clarified aqueous layer containing gelatin and glycerin is collected for reuse and the residual oils and/or particulates are either discarded or collected for potential recovery as discussed hereinafter.
Liquid:liquidaolid centrifugation can also be utilized to achieve separation of the gelatin and softening agent (e.g. glycerin) from the particulates and/or residual oils.
This procedure is preferred when the waste gelatin stream contains particufates which are at least a part of the coloring system (e.g. titanium dioxide).
Commercial liquid:liquid and/or liquid:liquidaolid centrifugation equipment is available from companies such as Westfalia Separator U.S. in Northvale, NJ and Alfa Laval in Warminster, PA.
Micro or sub-micro filtration refers to a method of removing small particles from a liquid. Particulates as used herein include, but are not limited to, solid particulates which do not have sufficient mass to settle out of solution and/or emulsions and micro-emulsions which do not readily separate from a liquid. Micro or sub-micro filtration can be achieved through the use of micron or sub-micron pore sized filters including, but not limited to cartridge type filters, also known as "depth" or "dead end" filters and tangential flow type fitters. Tangential flow type filters are the preferred filters for this purpose. The pore size of the preferred filters is typically in the range of from about 0.1 and 2.0 microns.
Temperature and dilution are important considerations in improving the efficiency of the filtration process by varying the viscosity of the liquid. A
temperature of from about 30°C to 70°C and a dilution volume of up to 5 volumes preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is preferred.
Micro or sub-micro filtration equipment is commercially available from suppliers such as Millipore Corporation in Bedford, MA.
A liquidaiquid coalescer, may be used to remove residual oils from the aqueous layer. The coalescer enhances the collection of the oil droplets (the dispersed phase liquid) into larger droplets which will separate more easily from the aqueous layer (the continuous phase liquid).
Generally, for the subject application, a multiple stage system may be employed.
Such systems remove the designated materials in stages such as by first removing particulates. Once the particulates are removed the remaining liquid may then be treated with a coaiescer to remove residual oil from the aqueous gelatin and glycerin.
A temperature of from about 30°C to 70°C and a dilution volume of typically up to 5 volumes, preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is desirable. Commercial coalescers are readily available such as those supplied by Millipore Corporation in Bedford, MA.
Filter aids containing diatomaceous earth can be employed for removal of particulates and/or residual oils. Diatomaceous earth, more commonly known as Celite or Filter Aid, is a very pure and inert material which forms a porous film or cake on a filter medium such as, but not limited to, filters made from paper, nylon and _, polypropylene as are typically used in filtration systems using filtration apparatus such as, but not limited to Nutsch filters, Rosenmund fitters and/or centrifuges.
Diatomaceous earth can be employed: 1 ) by forming a slurry with an appropriate solvent, such as water, then filtering the slurry through an appropriate apparatus, such as a Nutsch or Rosenmund type filter, or a platelcoated plate filter such as a sparkler filter, to form a thin film or cake or 2} by adding the diatamaceous earth directly to the product to be filtered to form a slurry which is then filtered forming a porous thin cake or film. A temperature of from about 30°C to 70°C and a dilution volume of up to 5 volumes, preferably from about 0.5 to 5 volumes of a suitable solvent, such as water, is desirable. Other filter aids besides diatamaceous earth include, but are not limited to silica, acrylic resins, clay and activated carbon.
Absorbents which may be used to treat the solvent based layers include zeolitic materials.
In particular, the lower aqueous phase may be heated, preferably hot filtered in the filtration assembly 18 if particulates and/or residual oils are present at a temperature of approximately the same as above (i.e. from about 30'C to 70°C) preferably through liquid:liquid centrifugation or micro/sub-micro filtration as described above to remove any remaining traces of oily components or other contaminants through a conduit 20 and optionally forwarded to the recycling system 8 . Other types of filtration equipment which may be employed include plate filters, or coated plate filters like, for example, a sparkler filter. The preferred material of construction for these type of fitters is stainless steel. Alternatively, nutche filters of the Rosenmund type or cartridge filters may be used for the purpose.
The employment of the hot filtration systems mentioned above separates particulates and/or oils from the aqueous layer containing gelatin and the softening agent (e.g. glycerin).
Depending on the concentration of the gelatin and glycerin in the resulting filtrate, the filtrate may be returned directly to gelatin mass manufacturing or the Citrate may be transported via heated conduit 22 to a concentration assembly 16 which may be in the form of a diafiltration assembly and concentrated by removing some of the solvent (e.g. water). For solutions having a gelatin concentration greater than about 10% gelatin wtlwt (e.g. 10% wt/wt to 45% wtlwt), the aqueous solution may be charged to a concentration apparatus adapted for vacuum distillation such as disclosed in Schmidt et al., U.S. Patent No. 5,288,408, or to a diafiltration system such as disclosed in Schmidt U.S. Patent No. 5,945,007. Alternatively, the filtrate may be subjected to short path distillation as previously described.
.19_ Short path distillation for this aspect of the present invention is carried out under controlled conditions to facilitate the removal of water at a lower temperature to prevent thermal. degradation of the recoverable gelatin. Evaporator temperatures typically from about 50'C to 120'C, and typically pressures 20 to 30 in. Hg, preferably 22-28 in. Hg _.
are employed to remove water. Such temperatures and short contact time do not cause decomposition of the protein-based gelatin which affects its bloom strength. The water distillate is passed through a condenser to waste or recycle. The residue contains the gelatinlglycerin mixture for reuse.
As an example, waste gelatin material is diluted with solvent (e.g. water) at a ratio of 3:1, water:waste gelatin material, the following illustrates the distitlate:residue ratios which may be via the chosen distillation process, to achieve a desired level of recycled gelatin and glycerin.
To achieve a 25% recycle level for gelatin and glycerin from the above described 3:1 dilution, the distillation should preferably result in a distillate:
residue ratio of 50:50.
To achieve a 40% recycle level for gelatin and glycerin from the above described 3:1 dilution, the distillation should preferably result in a distillate: residue ratio of 62.5:37.5.
In both examples the residue contains the gelatin and glycerin for recycle.
_20_ Diafiitration may be employed at the concentration assembly 16 to remove residual water soluble active ingredients, glycerine, water, and other water-soluble components such as preservatives and dyes and to provide gelatin in a form that is of sufficient purity and quality to permit reuse.
Diafiltration is a technique using ultrafiltration membranes to remove or fractionate different size molecules in macromolecular solutions. An ultra~ltration membrane retains macromolecules that are larger than the nominal molecular weight limit (NMWL) of the membrane and freely passes molecular species which are significantly smaller than the NMWL of the membrane. Macromolecules retained by the membrane are concentrated, while the low molecular weight species are removed.
Typically, the macromolecules must be "washed" using multiple wash volumes to remove residual smaller molecules, hence the name diafiltration (i.e.
filtration using ultrafiltration membranes and washing).
For continuous diafiltration, a supply of macromolecules (e.g. gelatin) is added via the conduit 22 to the diafiltration assembly 16 at the same rate as the frltrate is being removed. This is also referred to as constant volume diafiltration. The concentration of the macromolecules does not change during the diafiltration process.
Discontinuous diafiltration involves first concentrating the macromolecule (e.g.
gelatin) batch to a predetermined volume, and then reconstituting the sample to its original volume with replacement solvent. This is repeated until the smaller molecules are removed.
Referring to Figure 1 diafiltration may be accomplished by first heating the system from about 50°C to 65°C by recirculating heated, deionized water typically for about 15 minutes through the conduit 24. The hot, aqueous feed stream is then pumped through fhe assembly 16 via a conduit 22 and concentrated to the desired gelatin/water concentration as discussed hereinafter. When the desired water/gelatin concentration is achieved, fresh, hot (e.g. from about 50 to 65°C), deionized water is fed into the system at exactly the same rate as the effluent exiting the system; the effluent being water and all water soluble components. Once the water soluble components have been removed, the remaining gelatin/water solution is recycled for gelatin encapsulation.
The filters that can be employed in the concentration/diafrtration step are known and available in the art. Such frlters include screen filters including open channel filters and the like. The selection of a suitable filter for the purification of gelatin must be capable of separating gelatin (typically having a molecular weight of from about 30,000 to 50,000) from smaller molecules.
The recovered aqueous gelatin solution is concentrated to a final solids (gelatin) concentration of at least between about 20% by weight, preferably from about 30% and WO 00/29097 PC'T/US99/27095 50%. The remaining concentrated gelatin is then purified using between about 1 and 20 diafiltration volumes of water, preferably between about 3 and 10 diafiltration volumes to provide recovered gelatin that is sufficiently pure to permit reuse and which leaves the diafiitration assembly 16 via a conduit 26 to a receiver 34. A
portion of the purified recycled gelatin may be sent back to the gelatin dissolving step via a conduit 28 to remove additional impurities from the gelatin to thereby obtain an even purer product.
Impurities such as dyes, actives, water, preservatives and glycerine can be removed from the diafiltration assembly via conduit 30.
Recovery of the above-mentioned impurities obtained from the diafiltration assembly 16 via the conduit can be performed in a recycling system 32. This system can be based on distillation systems including fractional distillation, short path distillation and reverse osmosis as previously described in connection with the recycle system 8.
Fractional distillation and reverse osmosis are preferred for recovery of the stream 30 with reverse osmosis being the most preferred method.
The process stream 30 in addition to containing the above mentioned impurities may contain from about 1 % to 70% by volume of glycerol in water, typically from about 3% to 7% by volume. The process stream 30 is treated at temperature of from about 0°C to 30°C, more typically from about 5°C to 20°C. Typically recovery of glycerol is at WO 00/2909'7 PCT/US99/27095 least 65% by volume, more typically from about 65% to 95%, most preferably from about 80% to 95% by volume.
In some instances, dyes and pigments that are used to color gelatin capsules have an affinity for the gelatin in the waste stream. Recovery of the gelatin alone may, therefore, require that steps be taken to eliminate this affinity so that the dyes can be removed. In general, it is necessary to take these steps following the hot filtration process and prior to the concentration/diafiltration process.
Suitable methods for eliminating the affinity between dyes and/or pigments and the gelatin include use of, for example, activated clay, carbon cartridge filtration; carbon slurry fom~ation followed by filtration to remove the carbon; pH adjustment to eliminate adhesion of the dye to the gelatin, followed by direct diafiltration to remove the dyes, and then adjustment of the pH back to the normal processing pH (e.g. from about 5 to 7); or, a combination of these methods.
If an affinity exists between the dyes and/or pigments, once the affinity has been eliminated, diafiltration can be performed to obtain recovered gelatin.
Alternatively, diafiltration itself will remove these dyes and/or pigments with sufficient diafiltration volumes. It is understood that the recycling system described can be incorporated into a conventional encapsulation apparatus to provide repeated or continual recycling of waste encapsulation materials.
Entrapped air may be a consideration during the process of manufacturing gelatin mass for encapsulation into soft gelatin capsules. General practice in the soft gelatin capsule manufacturing industry is to manufacture the gelatin mass under vacuum, for the express purpose of removing air, on a mezzanine or second floor then feed the molten gelatin mass, by gravity, to the encapsulation machines on the first floor.
In the absence of a building configuration conducive to gravity feed to the encapsulation machines, gelatin mass can be transferred by air pressure or pumps.
The choice of pump must be such that as little air as possible is introduced into the gelatin mass. Examples of appropriate pumps may be, but are not limited to, peristaltic, moyno, and sine type pumps.
The ultrafiltration process of the present invention can generate flow rates in excess of 200 liters per minute. Although proper engineering and design of the diafiltration system will minimize or eliminate introduction of air from external sources, the flow rates generated may nonetheless, introduce some air into the gelatin.
The air can be entrapped or dissolved in the viscous gelatin mass. Under these circumstances, it is desirable to degas or remove at least most of the air from the gelatin.
Typical practices in analytical chemistry for degassing dissolved air in water and/or organic solvents used as a mobile phase for High Performance Liquid Chromatography (HPLC) are: 1 ) pass the water and/or organic solvents through a 0.45 micron membrane filter and/or 2) sparge the water andlor organic solvent with an inert gas such as nitrogen and/or 3) allow the water and/or organic solvent to be exposed to ' molecular sieves until completely degassed.
It is also known in the art that microfllters are available commercially in the micron range similar to that used to degas mobile phase for HPLC analysis.
Such filters may be obtained for example from AIG Technology of Needham, IVlassachusetts.
Any of the above-mentioned methods of degassing may be employed in the present invention. If, for example, a membrane filter (e.g. 0.45 micron) were employed to degas the gelatin, the filter could be incorporated into the diafiltration system 16 shown in Figure 1. For example, the aqueous layer passing through the conduit 14 to the diafiltration system 16 is first treated as described above to remove impurities via the conduit 30. The recovered gelatin may then be filtered with a membrane filter to remove air within the diafiltration system 16.
In another embodiment of the present invention, the degassing operation may be established externally of the diafiltration system. Referring to Figure 2, the recovered gelatin is sent via the conduit 26 to a conduit 27 which leads to a degassing system 29 (e.g. a membrane filter). Once the gas (e.g. air) is removed from the gelatin, the degassed gelatin is sent via the conduit 31 to be recycled or recovered.
It is understood that the above described recycling system may be incorporated into a conventional encapsulation apparatus to provide repeated or continual recycling of waste encapsulation materials.
Although the present invention has been described with reference to the particular embodiments herein set forth, it is understood that the present disclosure has been made only by way of example and that numerous changes in details of construction may be resorted to without departing from the spirit and scope of the invention. Thus, the scope of the invention should not be limited by the foregoing specifications.
Claims (12)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of treating a waste material containing gelatin comprising:
(a) combining the waste material and a solvent for the gelatin under conditions sufficient to form a first liquid containing gelatin, said waste material containing at least one first component which can not effectively be separated from the first liquid into a non-solvent based layer;
(b) separating the first liquid into a solvent based layer containing the gelatin and said at least one first component and a non-solvent based layer; and (c) treating the solvent based layer with a process selected from the group including liquid: liquid centrifugation, submicro/microfiltration, coalescers, and combinations thereof which removes the first component from the solvent based layer to form a second liquid containing gelatin having a higher purity than the first liquid being at least substantially devoid of the first liquid.
(a) combining the waste material and a solvent for the gelatin under conditions sufficient to form a first liquid containing gelatin, said waste material containing at least one first component which can not effectively be separated from the first liquid into a non-solvent based layer;
(b) separating the first liquid into a solvent based layer containing the gelatin and said at least one first component and a non-solvent based layer; and (c) treating the solvent based layer with a process selected from the group including liquid: liquid centrifugation, submicro/microfiltration, coalescers, and combinations thereof which removes the first component from the solvent based layer to form a second liquid containing gelatin having a higher purity than the first liquid being at least substantially devoid of the first liquid.
2. The method of claim 1 wherein the first component is selected from oily type materials, particulates and combinations thereof having an affinity for the solvent.
3. The method of claim 1 wherein step (c) comprises treating the solvent based layer with a tangential flow filter.
4. The method of claim 1 wherein step (c) is carried out at a temperature of from about 30 to 70°C.
5. The method of claim 4 wherein the solvent based layer is diluted at a dilution volume of up to 5 volumes of said solvent.
6. The method of claim 1 wherein the waste material contains oily type materials and particulates, step (c) comprising removing the oily type materials and particulates from the solvent based layer to form a filtrate and recycling the filtrate.
7. The method of claim 1 wherein the waste material contains oily type materials and particulates, step (c) comprising removing the oily type materials and particulates from the solvent based layer to form a filtrate and treating the filtrate to remove at least some of the solvent.
8. The method of claim 7 wherein the step of treating the filtrate comprises subjecting the filtrate to a process selected from the group consisting of vacuum distillation, diafiltration and short path distillation.
9. The method of claim 1 wherein the waste material contains a softening agent, said softening agent being separated into the second liquid.
10. The method of claim 9 wherein the softening agent is glycerin.
11. The method of claim 9 further comprising subjecting the second liquid to ultrafiltration to remove the softening agent therefrom.
12. The method of claim 1 wherein the solvent is water.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10858498P | 1998-11-16 | 1998-11-16 | |
| US60/108,584 | 1998-11-16 | ||
| US12811599P | 1999-04-07 | 1999-04-07 | |
| US60/128,115 | 1999-04-07 | ||
| US14133299P | 1999-06-28 | 1999-06-28 | |
| US60/141,332 | 1999-06-28 | ||
| US38370399A | 1999-08-26 | 1999-08-26 | |
| US09/383,703 | 1999-08-26 | ||
| US09/385,405 | 1999-08-30 | ||
| US09/385,405 US20020070165A1 (en) | 1998-11-16 | 1999-08-30 | Method for the purification and recovery of waste gelatin |
| PCT/US1999/027095 WO2000029097A1 (en) | 1998-11-16 | 1999-11-15 | Method for the purification and recovery of waste gelatin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2350746A1 CA2350746A1 (en) | 2000-05-25 |
| CA2350746C true CA2350746C (en) | 2006-10-03 |
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|---|---|---|---|
| CA002350746A Expired - Fee Related CA2350746C (en) | 1998-11-16 | 1999-11-15 | Method for the purification and recovery of waste gelatin |
Country Status (6)
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| EP (1) | EP1137481A4 (en) |
| JP (1) | JP2002529589A (en) |
| KR (1) | KR100674488B1 (en) |
| AU (1) | AU760327B2 (en) |
| CA (1) | CA2350746C (en) |
| WO (1) | WO2000029097A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1202742A4 (en) * | 1999-07-15 | 2003-08-27 | Technologies L L C Ab | Method and apparatus for the recovery of non-solvent type fills from gelatin capsules |
| ES2354292T3 (en) * | 2003-09-19 | 2011-03-11 | Research In Motion Limited | ELECTRONIC HAND AND ASSOCIATED METHOD DEVICE THAT PROVIDES TIME DATA IN A MESSENGER ENVIRONMENT. |
| CN103788171A (en) * | 2014-01-30 | 2014-05-14 | 方琴 | Decoloration method of dyed gelatin soft capsule shell waste |
| CN103819711A (en) * | 2014-01-30 | 2014-05-28 | 方琴 | Decoloring method of dye gelatin hard capsule shell waste |
| KR101463768B1 (en) * | 2014-07-17 | 2014-11-21 | 창성소프트젤 주식회사 | Method and device for the recovery of gelatin |
| CN104130718A (en) * | 2014-07-30 | 2014-11-05 | 安徽黄山胶囊股份有限公司 | Recovery usage method for waste gelatin solutions, waste gelatin heads and enteric gelatin heads |
| WO2017083254A1 (en) | 2015-11-09 | 2017-05-18 | R.P. Scherer Technologies, Llc | Process for recovery of waste gel-mass from softgel manufacturing process |
| CN111135982A (en) * | 2020-01-17 | 2020-05-12 | 武汉嘉宏和设备有限公司 | Sealant recycling system and method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB415088A (en) * | 1933-01-17 | 1934-08-17 | British Drug Houses Ltd | Improvements in or relating to the distillation of liquids containing vitamins |
| GB1098716A (en) * | 1965-10-21 | 1968-01-10 | Aminodan As | A process for the recovery of oil and protein from waste water |
| US5074102A (en) * | 1989-10-26 | 1991-12-24 | American Cyanamid Company | Flat track modified soft shell capsule filling machine |
| DE4041433A1 (en) * | 1990-12-21 | 1992-06-25 | Siemens Ag | Multiphase sample mixt. prepn. appts. - includes back-flushable cross-flow filter |
| US5242597A (en) * | 1992-07-24 | 1993-09-07 | Eastman Kodak Company | Fixed cycle time ultrafiltration process |
| US5288408A (en) * | 1992-10-26 | 1994-02-22 | Chemical Industry Consultants, Inc. | Method of gelatin recovery and purification from encapsulation processes |
| JP2640330B2 (en) * | 1993-11-08 | 1997-08-13 | 富士カプセル株式会社 | Method for recovering gelatin from soft capsule products |
| US5945001A (en) * | 1998-03-03 | 1999-08-31 | A.B. Technologies, L.L.C. | Method for the purification and recovery of waste gelatin using diafilters |
| ATE296156T1 (en) * | 1998-03-03 | 2005-06-15 | Technologies L L C Ab | METHOD FOR CLEANING AND REUSING WASTE GELANTINE |
-
1999
- 1999-11-15 JP JP2000582138A patent/JP2002529589A/en active Pending
- 1999-11-15 WO PCT/US1999/027095 patent/WO2000029097A1/en not_active Application Discontinuation
- 1999-11-15 KR KR1020017006172A patent/KR100674488B1/en not_active IP Right Cessation
- 1999-11-15 CA CA002350746A patent/CA2350746C/en not_active Expired - Fee Related
- 1999-11-15 AU AU16257/00A patent/AU760327B2/en not_active Ceased
- 1999-11-15 EP EP99958995A patent/EP1137481A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000029097A1 (en) | 2000-05-25 |
| CA2350746A1 (en) | 2000-05-25 |
| EP1137481A4 (en) | 2003-01-15 |
| AU760327B2 (en) | 2003-05-15 |
| KR20010093082A (en) | 2001-10-27 |
| AU1625700A (en) | 2000-06-05 |
| KR100674488B1 (en) | 2007-01-25 |
| JP2002529589A (en) | 2002-09-10 |
| EP1137481A1 (en) | 2001-10-04 |
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