WO2010037636A1

WO2010037636A1 - An alkalinity controlling composition and method of making the same and uses thereof

Info

Publication number: WO2010037636A1
Application number: PCT/EP2009/062014
Authority: WO
Inventors: Jens Eskil Trudsoe; Helle Bech Olsen
Original assignee: Cp Kelco Aps
Priority date: 2008-10-02
Filing date: 2009-09-16
Publication date: 2010-04-08
Also published as: AR075088A1; TW201016721A

Abstract

An alkalinity controlling composition having a pectin-containing material. The pectin-containing material may be from a fruit material, a vegetable material, or combination thereof. The pectin-containing material may be treated with an alkali treatment composition. The alkalinity controlling composition may be used in products that control the alkalinity of human skin or on animal skin, such as lotions, creams, or animal litters.

Description

Title: An alkalinity controlling composition and method of making same And Uses Thereof

Background

1. Field of the Art

The exemplary embodiments relate to a skin-protecting alkalinity-controlling composition comprising at least one carboxylic acid polysaccharide, as well as the use of such a composition for skin protection and/or alkalinity control.

2. Description of Related Art

When poultry, chicken or other animals with foot pads walk around in their own excrements, the liberated ammonia may cause burns and ulcers on the animals' feet. This may be very painful for the animal, and may lead to the animal becoming inactive, further accelerating the burning process and leaving the animal vulnerable to other ani- mals. In addition, the burns may increase the risk of inflammation. It is estimated that in the UK alone, 100,000 chickens die prematurely every day due in part to these issues.

Some publications disclose compositions useful for use in personal care products for human skin and for use on animal skin. For example, EP 1812120 (incorporated herein by reference in its entirety) discloses a skin-protecting alkalinity controlling composition comprising one or more carboxylic acid polysaccharides wherein at least one of said carboxylic acid polysaccharide(s) is a high DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%. EP 1812120 also teaches a skin- protecting alkalinity controlling composition comprising a mixture of at least one high DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 70% to about 100%, more preferably from about 80% to about 100%, and at least one low DE carboxylic acid polysaccharide having a degree of esterification (DE) in the range from about 5 to about 70 %, more preferably from about 5% to about 40%, and most preferably from about 10% to about 35%. The compositions disclosed in EP 1812120 comprise polysaccharides, which have gone through a purification process such as filtering and an isolation process such as alcohol precipitation to yield refined polysaccharides. However, such polysaccharides may be relatively expensive, particularly if used to reduce or eliminate hock burns. In US Patent No. 1 ,365,000 (incorporated herein by reference in its entirety), McDiII discloses a pectin containing product based on citrus fruit. The process in McDiII separates the oil, the juice and the seeds and then grounds the remaining pulp. After drying, the crude pectin preparation may be boiled in the juice to form jellies by adding sugar.

In US Patent No. 1 ,838,949 (incorporated herein by reference in its entirety), Leo discloses performing a low pH extraction at boiling after which he increases the pH with a buffer salt to protect the pectin. Instead of filtering, he sieves the extract to remove seeds and undigested fibers, and after homogenizing the mass to colloidal size, he precipitates it in alcohol. Leo does make some separation and he precipitates the crude pectin in alcohol.

In US Patent No. 2,132,065 (incorporated herein by reference in its entirety), Wilson discloses treating washed and finely ground peel with soda ash at pH 8.5 and 35 ⁰C for 12 hours. After washing, pressing and drying, Wilson discloses dissolving the material in boiling water with trisodium phosphate and sodium hydroxide, and the resulting product may be used as such for quenching steel, or it may be precipitated in alcohol and dried.

The description herein of certain advantages and disadvantages of known compositions, processes, and methods, is not intended to limit the scope of the embodiments. Indeed, the embodiments may include some or all of the processes, methods, and treatment compositions described above without suffering from the same disadvantages.

Summary

In view of the foregoing, the present embodiments provide alkalinity controlling compositions that are relatively inexpensive. More particularly, the embodiments described herein relate to alkalinity controlling compositions, which surprisingly provide buffering effects and pH reductions over time that are comparable to refined pectin, although the compositions are made from pectin-containing starting materials without significant purification. The skin care compositions of the present embodiments may be used on humans or animals, such as to reduce or eliminate hock burns. It is therefore a feature of an embodiment to provide an alkalinity controlling composition that includes a pectin-containing material.

In accordance with another embodiment, a product for skin protection or alkalinity con- trol for human skin or animal skin, includes an alkalinity controlling composition with a pectin-containing material.

In accordance with another embodiment, a litter material for animals includes an alkalinity controlling composition with a pectin-containing material.

In accordance with yet another embodiment, a method for making an alkali controlling composition with a pectin-containing material includes the steps of: (a) providing a pectin-containing material; (b) treating the pectin-containing material in an aqueous alkali at a pH of from about 8 to about 10, for a period of time ranging from about 1 hour to about 4 hours at a temperature ranging from about 50 ⁰C to about 75°C; and (c) washing the treated pectin-containing material with a solution comprising about 60% alcohol to remove excess alkali.

Brief description of drawing figures

Purposes and advantages of the exemplary embodiments will be apparent to those of ordinary skill in the art from the following detailed description in conjunction with the appended drawings in which:

FIG. 1 illustrates the DE of pectin from untreated dry peel and alkali treatment directly on dry peel, in accordance with an exemplary embodiment.

FIG. 2 illustrates the M_w of pectin from untreated dry peel and alkali treatment directly on dry peel in accordance with an exemplary embodiment.

FIG. 3 shows the titration curves of pectin-containing material from untreated and directly alkali treated peel in accordance with an exemplary embodiment.

FIG. 4 shows the DE of pectin from dry peel with direct alkali treatment followed by precipitation in accordance with an exemplary embodiment. FIG. 5 shows the M_w of pectin from dry peel with direct alkali treatment followed by precipitation in accordance with an exemplary embodiment.

FIG. 6 shows titration curves of pectin-containing material from dry peel with direct al- kali treatment followed by precipitation in accordance with an exemplary embodiment.

FIG. 7 shows the DE of pectin from dry ground peel with direct alkali treatment followed by precipitation in accordance with an exemplary embodiment.

FIG. 8 shows the M_w of pectin from dry ground peel with direct alkali treatment followed by precipitation in accordance with an exemplary embodiment.

FIG. 9 shows titration curves of pectin-containing material from dry ground peel with direct treatment followed by precipitation in accordance with an exemplary embodiment.

FIG. 10 shows the DE of conventional acid extracted pectin, alkali treated pectin extract, and alkali treated dry pectin, in accordance with an exemplary embodiment.

FIG. 11 shows the M_w of conventional acid extracted pectin, alkali treated pectin extract, and alkali treated dry pectin, in accordance with an exemplary embodiment.

FIG. 12 shows titration curves of conventional acid extracted pectin, alkali treated pectin extract and alkali treated dry pectin, in accordance with an exemplary embodiment.

FIG. 13 shows titration curves of untreated peel before and after acid wash in accordance with an exemplary embodiment.

FIG. 14 shows buffer capacity of various peel derived products in accordance with an exemplary embodiment.

FIG. 15 shows titration curves of pectin-containing materials from commercial pectin production in accordance with an exemplary embodiment.

FIG. 16 shows buffer capacity of pectin-containing materials obtained from commercial raw materials and from the commercial pectin production in accordance with an exemplary embodiment. FIG. 17 shows titration curves of alkali treated wet peel in accordance with an exemplary embodiment.

FIG. 18 shows total alkali consumption of selected pectin-containing materials in accordance with an exemplary embodiment.

FIG. 19 shows pH reduction in litter for samples with varied concentrations of untreated peel in accordance with an exemplary embodiment.

FIG. 20 shows litter pH reduction over time for samples with non-treated peel and alkali treated peel in accordance with an exemplary embodiment.

FIG. 21 shows the effect over time on litter pH for samples with non-treated peel in ac- cordance with an exemplary embodiment.

Detailed description of exemplary embodiments

The following description is intended to convey a thorough understanding of the em- bodiments by providing a number of specific embodiments and details involving an alkalinity-controlling composition for skin protection or alkalinity control. It is understood, however, that the invention is not limited to these specific embodiments and details, which are exemplary only. It is further understood that one possessing ordinary skill in the art, in light of known compositions and methods, would appreciate the use of the invention for its intended purposes and benefits in any number of alternative embodiments.

The exemplary embodiments described herein relate to an alkalinity controlling composition having a pectin or pectin-containing material, that may provide alkalinity control on human skin and on animal skin. Surprisingly, the inventors have found that pectin- containing materials may be treated to provide buffer capacity, and that pectin- containing materials themselves offer a surprisingly high consumption of alkali. Exemplary pectin and pectin-containing materials may bind ammonia-up to about 6 times the amount of sodium hydroxide. Without intending to be bound by a particular theory, it is believed that the compositions of the exemplary embodiments may control the liberation of ammonia from animal excrements, thereby providing a means of reducing or eliminating the impact of ammonia on hock burns, reducing or eliminating the unwanted fertilization from air born ammonia emitted from animal farms, and reducing or eliminating the discomfort and health hazard of air born ammonia emitted from animal farms.

In exemplary embodiments, the alkalinity controlling composition may include pectin derived from pectin-containing materials including, but not limited to, fruits and vegetables. Examples of pectin-containing materials include but are not limited to citrus fruits such as whole fruit and peel from orange, lemon, lime, grapefruit, mandarin, Clementine; apple and apple residue from apple juice manufacture; berries and berry residue from juicing; and beet and beet residue from for instance sugar extraction. For a list of other examples of pectin-containing materials see Kertesz, Z. I.: The pectic substances, lnterscience Publishers, Inc., New York (1951). In exemplary embodiments, the composition may contain pectin derived from citrus peel and sugar beet residues from sugar extraction, more preferably from citrus peel, and even more pref- erably from orange peel.

In exemplary embodiments, the pectin-containing materials may be provided fresh, washed with water, washed with aqueous acid and used as such, or dried before shipment and/or use. In exemplary embodiments, the pectin-containing materials include fresh and dried citrus peel and dry sugar beet from sugar extraction; more preferably the pectin-containing materials include dried citrus peel; and even more preferably dried orange peel.

In an exemplary embodiment, an alkalinity controlling composition may include pectin- containing material derived from treated dried citrus peel. Exemplary dried peel may be un-ground or ground to a particle size of about 2 - 4 mm. The dried peel may be treated in water or in alkali water having a pH ranging from about 8 to about 10, preferably at pH from about 9 to about 10, and even more preferably at pH of about 10. The dry peel may be treated in water or alkali water for a period of time ranging from about 1 hour to about 4 hours, at a temperature ranging from about 50 ⁰C to about 75 ⁰C. The dried peel also may be treated in an alkaline aqueous alcohol of 60%. Exemplary alcohols include methanol, ethanol and isopropyl alcohol. The mixture of alkaline water and peel may be precipitated in 2 - 3 volumes of alcohol after treatment. In exemplary embodiments, the treated material may be washed in a mixture of a mineral acid or organic acid and alcohol to remove excess alkali. An exemplary acid is hydrochloric acid. The acid washing may be followed by washing in 60% alcohol to remove excess acid. Exemplary pectin-containing material from treated dried peel may be used as-is, or it may be dried. For example, the treated dried peel may be dried at a temperature of about 68 ⁰C to about 105 ⁰C, for a time ranging from about 2 to about 16 hours. Exemplary pectin in the pectin-containing material derived from treated dried peel may have a degree of esterification (DE) in the range from about 3% to about 77%. The pectin in the pectin-containing material may have a molecular weight (M_w) ranging from about 29,000 Dalton to about 120,000 Dalton. The pectin-containing material may show buffer capacity in the range from about 2.5 ml 0.1 M NaOH per pH unit to about 20 ml 0.1 M NaOH per pH unit. Exemplary pectin-containing material from treated dried peel may show a total alkali consumption ranging from about 5 mmol NaOH per g pectin-containing material, to about 12 mmol NaOH per g pectin- containing material; the corresponding consumption of ammonia may be about 6 times higher.

In another exemplary embodiment, an alkalinity controlling composition may include pectin-containing material derived from treated pectin in its dry form, in its precipitated form, or as a solution or extract. These exemplary pectin-containing materials may be treated in aqueous alkali or in alkaline 60% alcohol at pH about 10 for a period of time ranging from about 0 hours to about 3 hours, at a temperature of about 50 ⁰C. In em- bodiments in which the pectin is an extract, the treated extract may be precipitated in 2 - 4 volumes 80% alcohol. The precipitate or dry pectin may then be washed with 60% alcohol, washed with acid in alcohol, and washed free of excess acid with 60% alcohol to produce the pectin-containing material. This material may be used as such or dried, such as at a temperature of about 68 ⁰C to about 105 ⁰C for about 2 to about 16 hours. Exemplary pectin in the pectin-containing material resulting from this exemplary method may have a DE in the range of about 27% to about 62% when the starting material is orange peel and may be higher, such as up to about 78%, when using another citrus peel product. The pectin in the pectin-containing materials resulting from this exemplary method may have a molecular weight ranging from about 77,000 Dalton to about 154,000 Dalton. The pectin-containing material may show buffer capacities in the range from about 14 ml 0.1 M NaOH per pH unit to about 26 ml 0.1 M NaOH per pH unit.

In yet another exemplary embodiment, an alkalinity controlling composition may include pectin-containing material derived from the various waste streams of commercial pectin production. It will be understood that pectin is bound to various extents in pectin- containing plant materials. In commercial pectin production, several extraction steps may be used to maximize pectin yield, whereby the residue (waste stream) from one extraction step is utilized in the following extraction step. The final waste product from the last extraction step is commonly used as cattle feed. In exemplary embodiments, the alkalinity controlling composition may include pectin-containing material from any of these waste streams. Exemplary pectin-containing material from the first extraction step and from the cattle feed may show buffer capacities in the range from about 2 ml 0.1 M NaOH per pH to about 5.2 ml 0.1 M NaOH per pH. Exemplary pectin-containing material from the waste streams may have a total alkali consumption of from about 5 mmol NaOH per g pectin-containing material to about 8.2 mmol NaOH per g pectin- containing material.

In yet another exemplary embodiment, an alkalinity controlling composition may include pectin-containing material derived from sugar beet from sugar extraction. Exemplary pectin-containing material derived from sugar beet show a buffer capacity in the range of from about 0.8 ml 0.1 M NaOH per pH unit to about 3.2 ml 0.1 M NaOH per pH unit. Exemplary pectin-containing material derived from sugar beet may have a total alkali consumption range of from about 5 mmol NaOH per g pectin-containing material to about 8 mmol NaOH per g pectin-containing material.

In yet another exemplary embodiment, an alkalinity controlling composition may include pectin-containing material from fresh and wet orange peel. Exemplary pectin- containing material from fresh and wet orange peel may have buffer capacity ranges from about 20 ml 0.1 M NaOH per pH unit to about 32 ml 0.1 M NaOH per pH unit. Exemplary pectin-containing material from fresh and wet orange peel may have total alkali consumption of about 2 mmol NaOH per g pectin-containing material.

In various exemplary embodiments, the alkalinity controlling composition may include any combination of the foregoing exemplary pectins or pectin-containing materials, or any known or later-developed pectins or pectin-containing materials. It will be understood which pectins and pectin-containing materials are suitable for use in the alkalinity controlling composition, based upon the disclosure herein.

In various exemplary embodiments, the alkalinity controlling composition having the pectin-containing material may be contained in products to provide skin protection or alkalinity control for human skin or animal skin. For example, the alkalinity controlling composition may be included in products such as skin creams, skin lotions, deodorant products, fragrance products, hair care products, shaving products, soap products, bath salts, and other such products. The alkalinity controlling composition may be included in absorbent articles such as feminine hygiene products, diapers, and other such products. Other products which may benefit from the inclusion of the alkalinity controlling composition include, for example, ostomy products, wound care products, lotionized tissues, fabric treating products, laundry rinse products, and the like. Individuals having ordinary skill in the art will understand the products that may include the alkalinity controlling composition and other applications for the alkalinity controlling composition, in accordance with the description herein. For example, suitable products and applications include those described in relation to a similar composition in EP 1812120 and PCT/DK2005/000285, the disclosures of which are incorporated herein by reference, in their entirety.

In exemplary embodiments, products containing the alkalinity controlling composition, may contain an effective amount of the alkalinity controlling composition, and of the pectin-containing material, so that the product may effectively reduce or eliminate ammonia. For example, in some exemplary embodiments, a product may contain a sufficient amount of alkalinity controlling composition to provide about 3% to about 10% pectin-containing material in the product. One having ordinary skill in the art will understand how to determine an effective amount for a particular product, and how to incorporate the alkalinity controlling composition into those products, in accordance with the description herein.

In various exemplary embodiments, the alkalinity controlling composition including the pectin and pectin-containing materials may be used to reduce the pH of poultry litter, such as chicken litter. In some embodiments the litter may contain an alkalinity controlling composition with pectin-containing material from non-treated peel. In some embodiments the litter may contain an alkalinity controlling composition with pectin- containing material from a mixture of non-treated peel and alkali treated peel. In exemplary embodiments, the total concentration of pectin-containing material in the litter is in the range from about 3% to about 10%.

In order that various embodiments of the present invention may be more fully under- stood, the invention will be illustrated, but not limited, by the following examples. No specific details contained therein should be understood as a limitation to the present invention.

Examples and Test Methods Equipment:

• Water baths at 25 ⁰C and 50 ⁰C

• Beakers

• Cover film

• Magnetic stirrer • Bϋchner funnel

• Filtering cloth

• Titration burette

• Potato peeler

• Auto pipette

Materials

• Orange peel - P-9718

• Fresh oranges purchased at the local supermarket

• Sugar beet pellets from the factory • High ester pectin residue from first extraction in processing plant

• Low ester pectin residue from first extraction in processing plant

• Cattle feed from processing plant

• Chicken litter from Danish poultry breeder

• Demineralized water • 0.5 M NaOH

• 0.1 M NaOH

• 2.5% NH₃

• 100% IPA

• 60% IPA • Concentrated HNO₃

• Concentrated HCI

• Ion exchange resin - Lewatit S-1468 Titration method

1. A solution was prepared as follows: 2 g. pectin-containing material was dissolved in 200 g. demineralised water at 20⁰C. (Wet peel pectin, which had not been dried, was used in a concentration of 20 g per 200 g demineralised water.) 2. The solution was placed in a thermostatically controlled water bath at 25 ⁰C and continuously stirred. 3. 0.1 M NaOH was added to the solution and pH recorded as a function of added

0.1 M NaOH. 4. Long term alkali consumption method

1. A solution was prepared as follows: 2 g. pectin-containing material was dissolved in 200 g. demineralised water at 20⁰C. (Wet peel pectin, which had not been dried, was used in a concentration of 20 g per 200 g demineralised water.)

2. The solution was placed in a thermostatically controlled water bath at 25 ⁰C and continuously stirred.

3. 0.1 M NaOH was added to the solution and pH recorded as a function of added 0.1 M NaOH.

4. The addition of 0.1 M NaOH was continued until there was no longer a change in pH.

Example 1 : Features of untreated and directly alkali treated dry orange peel.

Test sample 0 was an untreated dry orange peel. Test samples 1 and 2 were prepared according to the following methods.

Test Sample 1 : Treatment of dry peel in demineralized water

40 g dry peel was added to 800 ml demineralized water and placed in water bath at 50 °C. 0.5 M NaOH was added to pH = 8.0 and pH was maintained at 8.0 for 3 hours while stirring. After treatment, the preparation was filtered on Bϋchner funnel, washed with a mixture of 600 ml 100% IPA, 400 ml demineralized water and 50 ml concentrated HCI, and finally washed with a 60% IPA solution until the wash liquid became chloride-free. The material was then dried over night at 68 ⁰C.

Test Sample 2: Treatment of dry peel in IPA 40 g dry peel was added to 800 ml 60% IPA and placed in water bath at 50 ⁰C. 0.5 M NaOH was added to pH =8.0 and pH was maintained at 8.0 for 3 hours while stirring. After treatment, the preparation was filtered on Bϋchner funnel, washed with a mixture of 600 ml 100% IPA, 400 ml demineralized water and 50 ml concentrated HCI, and fi- nally washed with a 60% IPA solution until the wash liquid became chloride-free. The material was then dried over night at 68 ⁰C.

Table 1 shows DE and M_w of the pectin component of the various treated pectin- containing materials as they are used in or during commercial pectin production. In or- der to determine DE and M_w, the treated peel products were extracted in demineralized water at 70 ⁰C for one hour, filtered, precipitated in IPA, dried and milled.

Table 1 : DE and Mw of pectin in untreated and in directly treated dry orange peel

It was noted that the Test 1 sample resulted in some loss of pectin.

FIG. 1 shows the DE of the test samples, and FIG. 2 shows the M_w of the test samples. FIGS. 1 and 2 show that compared to untreated dry peel, alkali treatment in 60% IPA reduces DE to some extent but appears to leave the molecular weight intact. However, FIGS. 1 and 2 show that alkali treatment in demineralized water leads to a substantial reduction in both DE and M_w.

Table 2 and FIG. 3 show the titration data for test samples 0, 1 , and 2. Table 2: Titration of pectin in untreated and in untreated and in directly treated dry orange peel

The slopes of the titrations curves in FIG. 3 show that the buffer capacity increases with lower DE. The data also shows that an acid wash of the treated peel provides for a buffering effect within a larger pH range.

Thus, these data indicate that in order to avoid loss of pectin during alkali treatment, one may perform the alkali treatment under conditions where the pectin is insoluble. The data also indicates that by performing the alkali treatment in alcohol, a major reduction in DE will require longer alkali treatment times or higher alkali treatment tem- peratures.

Example 2: Features of directly alkali treated dry orange peel followed by alcohol precipitation.

Test samples 3 - 5 were prepared according to the following method.

Test Samples 3, 4, and 5: Treatment of dry peel in demineralized water followed by precipitation in IPA

40 g dry peel was added to 800 ml demineralized water and placed in water bath at 50 0C. 0.5 M NaOH was added to obtain pH = 8.0, 9.0 and 10.0, respectively, and the pH was maintained for 3 hours while stirring. The treated preparations were poured into 2000 ml 100% IPA and drained on Bϋchner funnel. The drained material was washed with a mixture of 600 ml 100% IPA, 400 ml demineralized water and 50 ml concen- trated HCI, and finally washed with a 60% IPA solution until the wash liquid became chloride-free. The material was then dried over night at 68 ⁰C.

Table 3 and FIGS. 4 and 5 show DE and M_w of the pectin component of the various treated pectin-containing materials. Table 3: Directly alkali treated dry orange peel - Precipitated

FIG. 4 and FIG. 5 show that as the pH during treatment increases, the DE drops substantially, as does the molecular weight. This drop is particularly noticeable at pH above 9.

Compared to peel treated in alcohol, the alkali treated peel followed by precipitation shows a larger drop in DE and in M_w.

Table 4 and FIG. 6 show the titration data for test samples 3, 4, and 5.

Table 4: Titration of alkali treated peel

FIG. 6 shows that as the pH during alkali treatment is increased, the buffer effect of the pectin increases. A dramatic increase results from an alkali treatment at pH 10.

Example 3: Features of directly alkali treated dry and ground orange peel followed by alcohol precipitation

Test samples 6, 7, 8, and 9 were prepared according to the following method.

Test Samples 6, 7, 8 and 9: Treatment of dry and ground peel in demineralized water followed by precipitation in IPA

40 g ground dry peel was added to 800 ml demineralized water and placed in water bath at 50 ⁰C. 0.5 M NaOH was added to obtain a pH of 9.0 or 10.0 (see table) and pH was maintained for 3 hours while stirring. The treated preparation was poured into 2000 ml 100% IPA and drained on Bϋchner funnel. The drained material was washed with a mixture of 600 ml 100% IPA, 400 ml demineralized water and 50 ml concentrated HCI, and finally washed with a 60% IPA solution until the wash liquid became chloride-free. The material was then dried over night at 68 ⁰C.

For test sample 8, the pH was 10 during treatment, and the treatment time was increased to 4 hours.

For test sample 9, the pH was 10 during treatment, and the treatment temperature was raised to 75 ⁰C.

Table 5 and FIGS. 7 and 8 show DE and M_w of the pectin component of the various treated pectin-containing materials. Table 5: Directly alkali treated dry and ground orange peel

FIGS. 7 and 8 show that as the pH is increased during the alkali treatment in deminer- alized water, the DE drops substantially. Increasing time or temperature during the treatment does not appear to have much impact. Grinding of the peel before alkali treatment leads to a substantially larger reduction in DE compared to using un-ground peel.

With respect to molecular weight, grinding of the peel before alkali treatment does have some impact. However, the molecular weight is more impacted by alkali treatment time and not by alkali treatment temperature.

Table 6 and FIG. 9 show the titration data for test samples 6-9. Table 6: Titration of alkali treated peel being precipitated

FIG. 9 shows that as the pH during treatment increases, so does the buffering effect of the pectin. The buffering effect appears to follow the DE, i.e. as the DE is reduced, the buffering effect increases. pH appears to provide the biggest impact on the buffering effect. Since grinding of the peel leads to lower DE, grinding also leads to a bigger buffering effect.

Example 4: Features of untreated and alkali treated pectin and alkali treated pectin extract.

Test samples 10, 11 , 12, and 23 were prepared according to the following method.

Test Sample 10: Extraction of pectin from dry orange peel

65 g dry orange peel was added to 2200 ml demineralized water, heated to 70 ⁰C and pH was adjusted within the range 1.7 - 1.8 with HNO₃. While stirring, the extraction was performed during 5 hours and then filtered through acid washed filter aid (Celite). The filtered extract was ion exchanged with 50 ml ion exchange resin on sodium form and filtered. The ion exchanged extract was then precipitated in 3000 ml 80% IPA and washed once in 60% IPA. The washed precipitate was dried over night at 68 ⁰C.

Test Sample 11 : Extraction of pectin from dry orange peel followed by alkali treatment of the extract

65 g dry orange peel was added to 2200 ml demineralized water, heated to 70 ⁰C and pH was adjusted within the range 1.7 - 1.8 with HNO₃. While stirring, the extraction was performed during 5 hours and then filtered through acid washed filter aid (Celite). The filtered extract was ion exchanged with 50 ml ion exchange resin on sodium form and filtered. At 50 ⁰C, the ion exchanged extract was then added 0.5 M NaOH to pH = 10.0 and maintained at pH = 10.0 for 15 minutes. The treated extract was precipitated in 3000 ml 80% IPA and washed with a mixture of 600 ml 100% IPA, 400 ml demineral- ized water and 50 ml concentrated HCI, and finally washed with a 60% IPA solution until the wash liquid became chloride-free. The material was then dried over night at 68°C.

Test Sample 12: Extraction of pectin from dry orange peel followed by alkali treatment of the dry precipitate

65 g dry orange peel was added to 2200 ml demineralized water, heated to 70 ⁰C and pH was adjusted within the range 1.7 - 1.8 with HNO₃. While stirring, the extraction was performed during 5 hours and then filtered through acid washed filter aid (Celite). The filtered extract was ion exchanged with 50 ml ion exchange resin on sodium form and filtered. The ion exchanged extract was then precipitated in 3000 ml 80% IPA and washed once in 60% IPA. The washed precipitate was dried over night at 68 ⁰C. The dry precipitate was ground and suspended in 500 ml 60% IPA. pH was adjusted 10.0 with 0.5 M NaOH and the treatment was carried out for 3 hours at 50 ⁰C after which, the treated material was washed with a mixture of 600 ml 100% IPA, 400 ml demineralized water and 50 ml concentrated HCI, and finally washed with a 60% IPA solution un- til the wash liquid became chloride-free. The material was then dried over night at 68 ⁰C.

Test sample 23 was prepared similar to test sample 11 , except that it was additionally acid washed.

Table 7 and FIGS. 10 and 11 show DE and M_w of the pectin component of the various treated pectin-containing materials.

FIGS. 10 and 11 show that a standard extraction of pectin yields pectin with DE of about 61% and molecular weight of about 154000. When the liquid extract is treated with alkali at pH 10 at 50 ⁰C for 15 minutes, the DE drops to about 28%. However, when the dry pectin is treated with alkali at pH 10 for 3 hours at 50 ⁰C, the DE drops marginally, only. The same pattern is observed for the molecular weight, although the molecular weight of treated dry pectin drops relatively more than the DE does.

Table 8 and FIG. 12 show the titration data for test samples 10-12 and 23. Table 8: Titration of untreated and alkali treated pectin and alkali treated pectin extract with and without acid wash

The slopes of the titration curves in FIG. 12 show that standard pectin extract has the lowest buffer effect (14.06 ml 0.1 M NaOH per pH-unit). Close to is the buffer effect of alkali treated dry pectin (17.28 ml 0,1 M NaOH per pH-unit), and the highest buffer effect is achieved with pectin made through alkali treatment of the liquid extract (25.97 ml 0.1 M NaOH per pH-unit) and subsequent acid wash. Thus, the buffer capacity follows the DE.

Test sample 17 was prepared as follows. Test Sample 17: Acid wash of neutral, dry and ground peel

6 g dry and ground orange peel was washed 10 minutes in a mixture of 300 ml 60% IPA and 15 ml concentrated HCI at room temperature. The peel was drained off and washed in 60% until the liquid gave no chloride reaction. The resulting acid washed peel was dried at 105 ⁰C for 2.5 hours.

Table 9 and FIG. 13 show the titration data for test samples 0 (untreated peel) and 17 (untreated peel after acid wash).

Table 9: Titration of untreated peel as is and untreated peel after acid wash

As shown in FIG. 13, washing of non-alkali treated peel with acid to reduce pH of the inherent pectin product, substantially increases the buffering effect.

In summary, with respect to peel treatment, ranking of the buffer capacity from highest to lowest is shown in Table 10, and in FIG. 14. Table 10: Ranking of buffer effect

As shown in FIG. 14 the highest buffer capacity is obtained through an alkali treatment of the extract from the peel at a pH of 10 followed by acid wash or unwashed with acid. However, alkali treated ground peel and alkali treated un-ground peel at pH above 9 provide for substantial buffer capacity. Also alkali treatment of dry pectin at pH of 10 provides for high buffer capacity as does regular acid extracted pectin. As the treatment pH is reduced to 8 or 9, the buffer capacity becomes smaller, and the lowest buffer effect is obtained by ground and untreated peel.

Example 5: Buffer capacity of pectin-containing materials from commercial pectin production.

Test samples 18-22, summarized in Table 11 below, were made according to the following methods. Table 11 : Materials from commercial pectin production

Test Sample 18: High ester pectin residue from first extraction

High ester pectin residue after first extraction was collected from the filters. The wet residue was washed with 60% IPA on Bϋchner funnel until all nitrate was washed out. The washed residue was dried at 68 ⁰C over night and ground.

Test Sample 19: Low ester pectin residue from first extraction

Low ester pectin residue after first extraction was collected from the filters. The wet residue was washed with 60% IPA on Bϋcher funnel until all nitrate was washed out. The washed residue was dried at 68 ⁰C over night and ground.

Test Sample 20: Sugar beet residue from sugar extraction

Dry sugar beet pellets obtained after sugar extraction was ground.

Test Sample 21 : Acid wash of sugar beet residue from sugar extraction

6 g dry and ground dry sugar beet pellets obtained after sugar extraction was washed 10 minutes in a mixture of 300 ml 60% IPA and 15 ml concentrated HCI at room temperature. The peel was drained off and washed in 60% until the liquid gave no chloride reaction. The resulting acid washed peel was dried at 105 ⁰C for 2.5 hours.

Test Sample 22: High ester pectin residue from the end of the pectin extraction (cattle- feed) The residue going to cattle-feed was collected, dried and ground.

Table 12 and FIG. 15 show the titration data for test samples 18-22.

Table 12: Titration of materials from commercial pectin production

From the above data, the following ranking in buffer capacity are calculated in table 13.

Table 13: Ranking of buffer capacity of pectin-containing materials from pectin produc- tion

Both residues from the production of low ester parting and high ester pectin provide for high buffer capacities with residue from low ester production being highest in buffer capacity. Acid washed sugar beet shows buffer capacity comparable to that of high ester pectin residue, and interestingly, the cattle feed, which is the final waste product from the pectin production shows quite some buffer capacity. The lowest buffer capacity is obtained by untreated sugar beet.

All the buffer capacity data from examples 1 - 5 are compiled in FIG. 16. All these pec- tin materials show buffer effect. The most effective are the alkali treated extract, the alkali treated ground peel, the alkali treated dry pectin and the extracted pectin. It is surprising that the alkali treated ground peel products are among the most effective. Of the less effective materials, it is noticeable that the residues from both the LM production and the HM production are more effective than sugar beet and that the cattle feed is more effective than straight sugar beet.

Based on this data, if one desired a buffer effect alone the optimal material may be pectin having the lowest possible degree of esterification or an alkali treated peel, where the alkali treatment had taken place at high pH.

Example 6: Buffer capacity of orange peel from oranges bought in the local supermarket.

Test samples 13-16 were prepared according to the following methods.

Test Samples 13 and 14: Alkali treatment of fresh and wet peel at pH 10 and pH 11

20 oranges purchased at the local supermarket were peeled to remove the outer flavedo. Afterwards, the peeled peel was pressed to remove the juice and the remain- ing material was blended to a particle size of about 2 - 4 mm. 400 g of this material was added to 2000 ml demineralized water, heated in water bath to 50 ⁰C and pH adjusted to 10 and 11 with 0.5 M NaOH. The pH was maintained at pH = 10 for 3 hours. The treated material was subsequently poured into 5000 ml 100% IPA, drained on cloth, lightly hand pressed and washed in 3000 ml 60% IPA mixed with 150 ml concentrated HCI for 10 minutes. Afterwards, the material was washed in 60% IPA until the wash liquid became chloride-free. The washed material was dried at 68 ⁰C over night.

Test 15: Wet peel without alkali treatment, dried and ground

Wet orange peel having the outer flavedo removed was dried at 68 ⁰C overnight and ground

Test 16: Wet peel as is

Wet orange peel having the outer flavedo removed was blended to a particle size of about 2 - 4 mm. Buffering effect and alkali consumption over time was measured using 2O g wet peel per 200 ml demineralized water.

Table 14 shows DE and M_w of the pectin component of the various treated pectin- containing materials.

Table 14: Features of orange peel from locally purchased oranges

Table 15 and FIG. 17 show the titration data for test samples 13-16.

Table 15: Titration of orange peel from locally purchased oranges

FIG. 17 shows that wet peel treated with alkali at pH 10 for 3 hours provides for a buffering effect of about 30.61 ml 0.1 M NaOH per pH. The same peel treated at higher pH but for a shorter time provides for a buffering effect of about 20.83 ml 0.1 M NaOH per pH.

Although one cannot directly compare these buffer capacities with the ones in examples 1 - 5, it is nonetheless surprising that peel from oranges bought in the local supermarket, for which no special measures have been taken to preserve the pectin in the peel, are so effective in relation to buffer capacity.

The above data indicates that any peel is suitable for use in the alkalinity controlling compositions of the exemplary embodiments.

Example 7: Total alkali consumption of selected pectin-containing materials

While the foregoing examples focused on buffer capacity, the following focus on total consumption over time of alkali, which also is an important property.

Table 16 shows the alkali consumption of selected pectin-containing materials. In 200 ml demineralized water, 2 g dry products were used, whereas 20 g of the wet material was used. The alkali consumption went on from about 10 days to about 25 days, during which period, 0.1 M NaOH was added up to a pH of about 9. As the pH dropped, pH was adjusted back to pH about 9. In one experiment, a 2.5% (1.5 M) solution of NH₃ was used, too. Table 16: Alkali consumption over time of pectin-containing materials

It should be noted, that in the experiment using ammonia, no ammonia odor was noted until about 40 ml ammonia solution was added. It is equally noteworthy that pectin- containing material consumes considerably more ammonia than the same material consumes sodium hydroxide.

FIG. 18 shows the ranking of the alkali consumption. Untreated dry orange peel is by far the material, which consumes the largest amount of alkali over time. Next to untreated orange peel is the residue from the first extraction of low ester pectin, ground untreated sugar beet and mildly alkali treated orange peel. As treatment increases, the alkali consumption appears to decrease with a lemon pectin extract providing the lowest alkali consumption over time. It should be noted that cattle feed is comparable to the more treated materials and more alkali consuming that a lemon pectin.

At least a partial explanation for untreated peel being most effective with respect to total alkali consumption is that the treatments in themselves involve consumption of alkali.

Example 8: Effect of pectin-containing material on chicken litter

Test samples A, B, and C were prepared and tested according to the following method. Titration of chicken litter

Chicken litter was obtained from a chicken farmer the day after the chicken had been removed from the stable.

• Test A

1. 3O g litter was suspended in 300 ml demineralized water and pH measured

2. 0.5 g ground dry orange peel (P-9718) was added and pH measured. 3. Further 0.5 g peel was added until a total of 4 g peel had been added.

4. After the last addition of peel, the pH was measured at intervals up to 26 hours.

• Test B 1. 3O g litter was suspended in 300 ml demineralized water and pH measured

2. 1 g alkali treated peel according to Test No. 7 was added and pH measured after 1 hour and after 2 hours

3. Further 0.5 g peel was added and pH measured after 2 hours after 4 hours and after 4,5 hours

4. Another 0.5 g peel was added and pH measured. pH was measured again after 3 hours and after 26 hours.

• Test C 1. 6 g orange peel (P-9718) was suspended in 300 ml demineralized water and pH measured

2. 60 g litter was added and pH measured at intervals up to 22 hours and 35 minutes.

(Note: In order not to induce discomfort to the rest of the staff, these experiments were carried out during a week-end, which means that there are no data relating to longer time consumptions.)

Table 17 shows the titration results from Test A with litter. Table 17: Effect of non-treated orange peel on litter pH

Table 18 shows the titration results from Test B with litter. Table 18: Effect of alkali treated orange peel on litter pH

Table 19 shows titration results from Test C. Table 19: Effect of litter on non-treated orange peel pH

FIG. 19 shows the results in Table 17 dealing with the pH drop in chicken litter as a result of adding different amounts of non-treated peel. The data indicates that as the amount of added non-treated peel is increased, the pH of the litter drops.

As shown in FIG. 20, the pH-drop continues over time, with the drop with 2 g non- treated peel being about one pH unit over 24 hours. With alkali treated peel, the initial pH-drop is higher, but within the first couple of hours, the pH actually increases. This indicates, that a mix of non-treated and alkali treated peel might provide the maximum effect.

FIG. 21 shows the effect over time on litter pH using non-treated peel. In this test, the litter was added to a suspension of non-treated peel. Initially, the pH increases and then gradually the pH drops and reaches a pH of about 5.5 during the first 24 hours.

In summary, this data indicates that pH reduction in litter is possible with either untreated peel or treated peel. In addition, the data indicates that a mix of non-treated and alkali treated peel might be the most effective means of reducing the initial pH and maintaining a low pH over time. Preferably, the peel concentration in the initial litter should be from about 3% to about 10%.

In the preceding specification, the invention has been described with reference to various exemplary embodiments. It will, however, be evident that various modifications and changes may be made thereto, and additional exemplary embodiments may be implemented, without departing from the broader scope of the invention as set forth in the claims that follow. The specification and drawings are accordingly to be regarded in an illustrative rather than restrictive sense.

Claims

What is claimed is:

I . An alkalinity controlling composition comprising pectin-containing material. 2. The alkalinity controlling composition according to claim 1 wherein the pectin- containing material comprises fruit material, vegetable material, or any combination or mixture thereof.

3. The alkalinity controlling composition according to claim 2 wherein the pectin- containing material comprises ground pectin-containing material. 4. The alkalinity controlling composition according to claim 2 wherein the pectin- containing material comprises fresh citrus peel, fresh apple pomace, fresh sugar beet residue from sugar extraction, dried citrus peel, dried apple pomace, dried sugar beet residue from sugar extraction, or any combination or mixture thereof.

5. The alkalinity controlling composition according to claim 4 wherein the pectin- containing material comprises dried orange peel, dried lemon peel, dried lime peel, dried grape fruit peel, or any combination or mixture thereof.

6. The alkalinity controlling composition according to claim 2 wherein the pectin- containing material comprises a residue from commercial pectin production.

7. The alkalinity controlling composition according to claim 6 wherein the residue comprises pectin residue from a first extraction of pectin in commercial pectin production, cattle feed resulting from commercial pectin production, or any combination or mixture thereof.

8. The alkalinity controlling composition according to claim 2 wherein the pectin- containing material comprises an alkali-treated pectin-containing material. 9. The alkalinity controlling composition according to claim 3 wherein the pectin- containing material comprises alkali treated fresh citrus peel, alkali treated dried citrus peel, fresh apple pomace, dried apple pomace, fresh sugar beet residue from sugar extraction, dried sugar beet residue from sugar extraction, or any combination or mixture thereof. 10. The alkalinity controlling composition according to claim 9 wherein the pectin- containing material comprises alkali treated dried orange peel, alkali treated dried lemon peel, alkali treated dried lime peel, alkali treated dried grape fruit peel, or combinations or mixtures thereof.

I I . The alkali controlling composition according to claim 1 wherein the pH of the pectin-containing material is from about 2 - 4.

12. The alkalinity controlling composition according to claim 1 , wherein the pectin- containing material comprises a pectin with a DE in the range from about 3% to about 77%.

13. The alkalinity controlling composition according to claim 1 , wherein the pectin- containing material comprises a pectin with a molecular weight of from about

29,000 Dalton to about 154,000 Dalton.

14. The alkalinity controlling composition according to claim 1 , having a buffer capacity of from about 0.8 ml 0.1 M NaOH per pH unit to about 32 ml 0.1 M NaOH per pH unit. 15. The alkalinity controlling composition according to claim 1 , having a total alkali consumption of from about 2 mmol NaOH per g pectin-containing material to about 12 mmol NaOH per g pectin-containing material.

16. The alkali controlling composition according to claim 1 , having a total consumption of ammonia of from about 12 mmol NH₃ per g pectin-containing material to about 72 mmol NH₃ per g pectin-containing material.

17. A method for making an alkali controlling composition having a pectin- containing material comprising the following steps: a. providing a pectin-containing material; b. treating the pectin-containing material in an aqueous alkali at a pH of from about 8 to about 10, for a period of time ranging from about 1 hour to about

4 hours and at a temperature ranging from about 50 ⁰C to about 75 ⁰C; and c. washing the treated pectin-containing material with a solution comprising about 60% alcohol to remove excess alkali.

18. The method according to claim 17 wherein the pectin-containing material com- prises un-ground or ground, fresh or dry pectin.

19. The method according to claim 17 wherein the pectin-containing material comprises precipitated pectin.

20. The method according to claim 17 wherein the pectin-containing material comprises a pectin solution or extract. 21. The method according to claim 17 wherein the pectin-containing material comprises a waste product from a commercial pectin production.

22. The method according to claim 17 wherein the aqueous alkali comprises up to about 60% alcohol.

23. The method according to claim 17 further comprising the step of precipitating the treated pectin-containing material in 2 - 3 volumes of alcohol.

24. The method according to claim 17 further comprising the step of washing the treated pectin-containing material with mineral acid or organic acid dissolved in 60% alcohol.

25. The method according to claim 17 further comprising the step of drying the treated pectin-containing material at a temperature ranging from about 68 ⁰C to about 105

⁰C.

26. A product for skin protection or alkalinity control for human skin or animal skin, comprising the alkalinity controlling composition of claim 1.

27. The product of claim 26 comprising a skin cream, a skin lotion, a deodorant prod- uct, a fragrance product, a hair care product, a shaving product, a soap product, a bath salt product, a feminine hygiene product, a diaper, an ostomy product, a wound care product, a lotionized tissue product, fabric treating product, or laundry rinse product, or any combination thereof.

28. The product according to claim 26, wherein said alkalinity controlling composition is present in an amount effective to reduce or eliminate ammonia.

29. The product of claim 26 wherein the concentration of pectin-containing material in the product is from about 3% to about 10%.

30. A litter material for animals comprising the alkalinity controlling composition of claim 1. 31. The litter material of claim 30, wherein the alkalinity controlling composition is mixed with litter material for poultry.

32. The litter material of claim 30, wherein said alkalinity controlling composition is in an amount effective to reduce or eliminate ammonia.

33. The litter material of claim 30, wherein the concentration of pectin-containing mate- rial in the litter material is from about 3% to about 10%.