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A whippable food product having improved stability characteristics without detectable change in the organoleptic characteristics is provided. The product comprises triglyceride fat, one or more sugars and an emulsifier component comprising destabilizing and stabilizing emulsifiers in amounts sufficient to stabilize the product. This product can be stored at ambient temperatures for extended periods of time and can also be whipped and displayed at ambient temperatures.
1. A whippable oil-in-water emulsion food product comprising triglyceride fat comprising a first fraction of vegetable oil having an iodine value of 5 or less and a second fraction of hardening fat, wherein the first fraction makes up 80-90% of the triglyceride fat; an emulsifier component comprising stabilizing and destabilizing emulsifiers such that the stabilizer to destabilizer HLB ratio is between 1 and 4; and one or more sugars,
wherein the whippable product can be stored and whipped at ambient temperatures and the whipped product prepared from the whippable product can be displayed at ambient temperatures and wherein the triglyceride fat has a profile of solid fat content of about 93 at 10� C., about 79-82 at 20� C., about 68 to 74 at 25� C., 39-50 at 30� C., 20-31 at 35� C., and 15-26 at 40� C.
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This application claims priority to U.S. provisional application No. 60/470,558 filed on May 14, 2003, the disclosure of which is incorporated herein by reference.
The present invention relates generally to the field of whippable food products and more particularly to a whippable food product having improved performance and stability characteristics at ambient temperatures.
Whippable food products are commonly used as toppings, icings, fillings and the like for cakes and other desserts. Different approaches have been used to obtain formulations that possess desirable characteristics including longer shelf life of both unwhipped and whipped products, ease of preparation and use of the whipped product, stability and performance characteristics; the conditions under which whipping can be performed including the whipping temperature; display temperature and display time; and the ease of spreading of the whipped product etc.
Consumer selection of whippable products also depends upon the mouthfeel and taste of the whipped product, and stability indicators such as tendency for hardening, weeping, crazing, bleeding, cracking, sliding or melting off a dessert. Desirable characteristics include a fresh creamy taste with rich smooth appearance, and a lack of off-flavors and odors associated with many vegetable oils and fractions thereof and lack of a lingering or waxy taste.
It has been suggested that selection of emulsifiers, stabilizers, water-soluble solids including sweeteners and inorganic salts, proteins and fats is key to the preparation of such whippable products that possess the desired characteristics and at the same time appeal to the consumer. However, identification of specific combinations of these ingredients has proven to be elusive. Moreover, while stabilizer and destabilizer emulsifiers have been used previously, there has been no identification of the specific ratios of stabilizer to destabilizer emulsifiers so as to optimize their combined function for performance and stability.
In one approach, a triglyceride fat such as "temperate latitude" or "domestic" oil is used. Such oils include soybean oil, canola oil, sunflower oil, corn oil, cottonseed oil, olive oil, peanut oil, rapeseed oil, safflower oil, low linolenic soybean oil, low linolenic canola oil, high oleic sunflower oil, or one or more fractions thereof. Such oils are characterized generally as containing no more than about 5% fatty acids that are of C14 length or less; generally no more than about 15% C16 length fatty acid; and more than about 50% combined of C18 (saturated, mono, di and tri-unsaturated) fatty acid. Such triglyceride fats are recognized to have certain advantageous features including ready availability, appropriate solid fat index, and neutral flavor. However, such oils are recognized to require substantial hydrogenation when used in whipped products. In this regard, it is generally recognized that such domestic oils must be hydrogenated to a resultant iodine value of about 65 to about 75 in order to be useful in the formulation of a stable whip topping, icing or filling.
In general, such oils, if not further refined at substantial cost, are recognized as having (1) off-odors uncharacteristic of a dairy topping and (2) the presence therein following hydrogenation of a sufficient concentration of high molecular weight-saturated fat (stearic acid, C18:0, has a melting point of about 158� F.) that they leave a waxy aftertaste in the mouth that coats, but does not easily clear from the palate following tasting thereof.
An alternate approach to the provision of suitable combinations of triglyceride fat component and emulsifier involves the use of the "high lauric" or tropical oils, as they are known in the art, and that are perceived by consumers to have very desirable cream or butter-like organoleptic properties. Such oils (including hydrogenated forms, fractions or interesterified forms thereof) have, typically, very high degrees of saturation, and yet surprisingly low melting points owing to the high contribution to average molecular weight of the triglyceride therein made by the short length C14, C12, and lower carbon fatty acids.
Representative of such good organoleptic oils are babassu oil, coconut oil, tucum oil, palm kernel oil, and any combinations of the above. Inclusion of such oils (including hydrogenated forms or fractions thereof such as partially hydrogenated palm kernel oil, fully hydrogenated palm kernel oil (meaning to an iodine value of about 1), palm kernel stearine or olein fractions partially hydrogenated coconut oil, fully hydrogenated coconut oil or combinations of any thereof) in the triglyceride fat component of whippable products are recognized to facilitate whippability (including continuous whippability) and to promote stability and presence of desirable organoleptic properties (organoleptic perception) in such products and confections.
Generally, however, such triglyceride fats by themselves do not provide enhanced temperature stability, a desirable feature for contemporary products. When appropriately hydrogenated, they provide improved temperature stability, however; they also contribute to undesirable performance or consumer appeal characteristics, such as, waxy mouth feel, poor getaway, etc.
In addition to the types and blends of fats, emulsifiers have specific roles in topping applications. In the liquid phase stabilizing surfactants are needed to prevent creaming and inversion. When the product is prepared (whipped), destabilizing surfactants are needed to displace the protein from the oil globule and allow a stable foam/topping to be formed from an oil in water emulsion. Accordingly the right proportion is critical to a stable final product.
A variety of emulsifiers have been used in combination with these oils including certain amounts of (and combinations of) Polysorbate 60, hex glycerol distearate, lecithin's, and also sodium or calcium stearoyl lactylate, esterified monoglycerides, diglycerides, sucrose esters, polyethylene glycols (PEGs), polyglycol esters (PGEs) and hydrocolloids with emulsifying properties.
U.S. Pat. No. 6,203,841 to Lynch and assigned to the same assignee as the instant invention provides a whippable food product comprising a triglyceride fat component having a first fraction of a triglyceride fat having an iodine value of less than 5 and a second hardening fat component. The hardening fat component is used at levels of 2-10%.
U.S. Pat. No. 5,962,058 to Ono provides a whippable product wherein the fat component is a blend of diglycerides and triglycerides.
WO 01/41586 to Sikking and U.S. Pat. No. 6,228,417 to Hidaka describes a whippable product comprising transesterified triglycerides. Transesterification is an extensive and complicated process and is known to add significant cost to manufacturing of these products.
U.S. Pat. No. 4,107,343 to Petricca describes a pourable, whippable emulsion having a specific emulsifier combination, which can be used as a food topping and has long-term stability to separation and gelation. Each of these patents/patent applications allude to the difficulty of making a whippable product that can be distributed, stored, prepared and/or displayed at the normal range of ambient temperatures and maintain a desirable organoleptic profile.
Further, U.S. Pat. No. 6,203,841 to Lynch and WO 01/41586 to Sikking both describe that product performance and/or taste were adversely affected in formulations having greater than 10% of hardening fat.
Accordingly, there is an ongoing and unmet need for whippable products having desirable organoleptic characteristics and superior stability at ambient temperatures.
The present invention provides a whippable oil in water emulsion food product which can be prepared from readily available ingredients and which extends the distribution and use temperatures for the unwhipped as well as the whipped products.
The whippable food product of the present invention has good organoleptic and stability characteristics. The product can be stored at −20� C. to 40� C. The time for storage varies with the temperature. For example, at 30� C., the product can be stored for up to 12 months and at 40� C., the product can be stored up to 3 months. The product can be whipped from about 10� C. to about 27� C. and used or displayed at up to 30� C. to obtain confections including icings, toppings, fillings and the like on various food products such as cakes, desserts etc. In its whipped form the product is stable for up to 7 days.
The whippable food product of the present invention comprises an oil in water emulsion of a triglyceride component, water, emulsifier component in an amount sufficient to stabilize the product, and optionally a protein component, one or more sugars, sugar alcohols, hydrocolloids, salts, buffers, anti-oxidants or flavors etc.
The HLB ratio of stabilizing to destabilizing emulsifiers for the present invention is between about 1 to 4. The hydrophilic/lipophilic properties of emulsifiers are affected by the structure of the molecule. These properties are identified by the hydrophilic/lipophilic balance (HLB) value. Low HLB values indicate greater lipophilic tendencies which are used to stabilize water-in-oil emulsions. High HLB values are assigned to hydrophilic emulsifiers, typically used in oil-in-water emulsions.
The triglyceride component comprises fat from more than one fraction. For example, a first fraction comprises fat which has a low iodine value. The iodine value is below 5, preferably lower than 2 and more preferably about 1 or lower. Fats in this group include palm kernel oil, coconut oil, babassu oil, tucum oil or hydrogenated fractions thereof. The first fraction is present in an amount between 80-90% of the total fat. The second fraction of fat comprises a hardening fat. Examples of hardening fat include palm oil, cottonseed oil, lard, tallow, or a stearine fraction thereof. The second fraction (hardening fat fraction) is present in an amount between 10 to 20% of the total fat.
This invention also provides a method for obtaining a whippable food product having improved stability characteristics. The method comprises the steps of blending the dry ingredients and some emulsifiers in an aqueous solution in warm water. A fat phase is prepared by heating the fat and adding remaining emulsifiers to the fat phase. The oil and aqueous phases are mixed and blended. The product is heated to provide a commercially sterile product and then homogenized and further cooled to achieve desired stability.
The present invention also provides a method for obtaining a whipped confection. The product can be whipped by routine methods known in the art to form a whipped confection. The whippable product may be whipped with or without additional ingredients such as various forms of sugars. The product can be whipped to an overrun of up to about 500% at temperatures up to 27� C.
This invention provides a whippable food product having improved stability of the unwhipped product (such as with respect to emulsion breakdown, gelation or inversion) as well as of the whipped confection produced therefrom (such as with respect to cracking, weeping, bulging, sagging or sliding off a cake, or detectable loss of organoleptic characteristics). The food product of the present invention can be easily stored and whipped at ambient temperatures.
This invention provides in particular for certain whipped products and confections having longer stability and desirable organoleptic characteristics. Although not intending to be bound by any particular theory, it is believed that the particular combinations of the ingredients including triglyceride fats, and the ratio of stabilizing and destabilizing emulsifiers contribute to the substantial performance improvements as described herein.
Emulsifiers have specific roles in topping applications. In the liquid phase stabilizing ingredients are needed to prevent creaming and inversion. When the product is prepared (whipped), destabilizing ingredients are needed to displace the protein from the oil globule and allow a stable foam/topping to be formed from an oil in water emulsion. Therefore the right proportion is critical to a stable final product. In the present invention, by understanding and controlling the liquid-crystalline phase of the emulsifiers, we have been able to broaden the temperature range that the invention functions. Maintaining the right mix of emulsion stabilizer and destabilizers keeps the specific liquid-crystalline phase that gives consistent emulsion and foam performance at the temperatures disclosed herein.
Stabilizer (or stabilizing) emulsifiers are agents which inhibit agglomeration, creaming and/or coalescence. Destabilizer (or destabilizing) emulsifiers are agents which promote agglomeration. A characteristic feature of this whippable product is that the stabilizer to destabilizer HLB ratio is between 1 to 4. Non-limiting examples of destabilizer and stabilizer emulsifiers are provided below in Table 1.
The term "stabilizer to destabilizer HLB ratio" as used herein refers to the ratio of the weighted HLB values of stabilizers to the weighted HLB values of destabilizer. Thus, if a formulation has a destabilizer (DS-1) with an HLB of 14.5, present at a concentration of 0.1%, and two stabilizers (S-1 and S-2) with HLB values of 4 and 15 respectively, present at concentrations of 0.1 and 0.3% respectively, the Stabilizer to Destabilizer HLB ratio is calculated as follows. The relative HLB value for DS-1 is the amount of DS-1 times HLB/total amount of emulsifiers (i.e., 0.1�14.5/0.5), which equals 2.9. The relative HLB values for S-1 and S-2 in this example, calculated in a similar manner are 0.8 and 9.0 respectively. Thus, the Stabilizer to Destabilizer HLB ratio is the total relative HLB value for all the stabilizers to the total relative HLB value for the destabilizers. In this example, therefore, this ratio is 3.37.
Representative characteristics and specific improvements (and combinations of improvements) for whipped food products and confections that are achieved according to the practice of the invention include:
a) unwhipped liquid product is easily pourable
b) the product may be whipped with or without additional ingredients such as sugar, powdered sugar, liquid sugar and the like.
c) the unwhipped product can be stored from −20� C. to 40� C. The time for storage varies with the temperature. For example, at 30� C., it can be stored for up to 12 months and at 40� C. it can be stored for at least up to 3 months.
d) the whipped product is a dessert whipped topping, icing or filling with desirable taste and mouth characteristics.
e) the whipped product can be prepared from 10� C. to 27� C.
f) the whipped product can be used/displayed at temperatures up to 30� C. as a topping, icing or filling for cakes, desserts etc. for up to 7 days without any appreciable cracking, weeping, bulging, sagging or sliding off the cake or dessert.
g) it can be whipped to an overrun of up to 500%. Generally the overrun obtained is between 150 to 500%. Overrun (%) is defined as the liquid weight/volume divided by foam weight/volume�100.
h) The water activity is less than or equal to 0.93.
i) the whippable product has a stabilizer to destabilizers HLB ratio of 1 to 4.
The various ingredients of this product are provided below.
The triglyceride fat component contributes to the stability of the product. In one embodiment, the fats useful for the present invention are a blend of two fractions. The first fraction has a low iodine number and includes fats such as palm kernel oil (PKO), coconut oil, babassu oil, tucum oil and hydrogenated fractions thereof. Generally tropical or lauric fats are suitable examples of fats in the first fraction. The iodine value of this fraction is 5 or lower, preferably 2 or lower and more preferably around 1 or lower. It is preferred to have fully hydrogenated fats which would typically have an iodine value of lower than 3. As an example, the iodine value of fully hydrogenated PKO is ≦1.0.
A second fraction comprises a hardening fat. Examples of fats in the second fraction are palm oil, cottonseed oil, lard, tallow or a stearine fraction of any of the above. In one embodiment, the triglyceride fat component is a blend of hydrogenated palm kernel oil and palm oil stearine.
Although not intending to be bound by any particular theory, it is believed that the second fraction contributes to the stability of the whippable product at ambient temperatures without detracting substantially from the organoleptic properties of the first fraction. The first fraction makes up between 80-90% of the total fat with the remaining being made by the second fraction. In different embodiments of the invention, the triglyceride fat component may be made up of first fraction of 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% and 90% with the remaining fat component being made by the second fraction.
The solid fat content (AOCS Official Method cd 16b-93, 1993) and the fatty acid profile (AOCS Official Method Ce 1-62, 1990) of the whippable product from the present invention were determined according to the standard AOCS methods and are presented below in Table 2.
A wide variety of emulsifiers may be employed in amounts on the same order as in the prior art oil-in-water emulsions, for example, about from 0.1% to 3%, preferably about from 0.4% to 1.0% as permissible under FDA guidelines. Suitable emulsifiers include lecithin, hydrolyzed lecithin; mono, di, or polyglycerides of fatty acids, such as stearine and palmitin mono and diglycerides, polyoxyethylene ethers of fatty esters of polyhydric alcohols, such as the polyoxyethylene ethers of sorbitan monostearate (Polysorbate 60) or the polyoxyethylene ethers of sorbitan monooleate (Polysorbate 80); fatty esters of polyhydric alcohols such as sorbitan monostearate or tristearate; polyglycerol esters of mono and diglycerides such as hexaglyceryl distearate; mono- and/or diesters of glycols such as propylene glycol monostearate, and propylene glycol monopahnitate, succinoylated monoglycerides; and the esters of carboxylic acids such as lactic, citric, and tartaric acids with the mono- and diglycerides of fatty acids such as glycerol lacto palrnitate and glycerol lacto stearate, and calcium or sodium stearoyl lactylates and all members of the sucrose ester family thereof, all varieties of diacetyltartaric esters of fatty acids, "DATEMS", and the like, and mixtures thereof.
The emulsifier component of the present invention may also include one or more hydrophilic colloids as stabilizing emulsifiers. These include methylcellulose, carboxy-methylcellulose, hydroxy-propylcellulose, hydroxy-propylmethylcellulose, and microcrystalline cellulose. The HLB values for these hydrophilic colloids are presented in Table 1 under cellulose gums.
As discussed above, the emulsifiers should be selected so that the stabilizer to destabilizer HLB ratio is between 1 and 4.
Thickeners/Gelling Agents
Some gums and starches are useful as thickeners/gelling agents. Those skilled in the art will recognize that these thickeners/gelling may also act as stabilizers and emulsifiers. However, in the present invention, if present in the formulation, these gums have not been included in the calculation of HLB values. These gums could be natural such as plant gums or animal gums. Examples of such gums include gelatins, pectins, alginates, agars, carrageenans, locust beans, guars, acacias, xanthans, karayas, gellans and konjac gums. Starches include corn, potato, wheat, tapioca, rice and any derivatives or modifications thereof. Typically, a gum/starch or combination of gums/starches is employed with a sugar, e.g. dextrose, carrier. The amount of these gums/starches can be varied widely in accordance with the amounts known in prior art compositions, generally about from 0-2%, preferably about 0.1-0.5% as permissible under FDA guidelines.
Optionally proteins can be included in the formulation. Milk proteins such as isolated sodium, potassium or calcium caseinates, protein provided as skim milk, nonfat dry milk, milk protein concentrate, whey protein concentrates, ovalbumin, alpha lactalbumin and beta lactoglobulin can be used. The proteins are generally known to assist in the emulsification and stability of the whipped products. Vegetable proteins including but not limited to soya protein, pea protein, wheat protein, cottonseed protein, peanut protein, and corn protein are also useful. Meat proteins derived as soluble proteins from meat processing may also be used according to the practice of the invention. Egg white may also be used.
The sugars (or sweeteners) useful for the present invention include monosaccharides, disaccharides, polysaccharides, dextrins, maltodextrins and polyols. The sugars may be reducing or non-reducing sugars. The sugar component may comprise one or more sugars, such as sucrose, fructose, dextrose, trehalose, and/or sugar syrups, such as corn syrups, and/or intensive sweeteners, such as acesulfame, thaumatin aspartame, alitame, saccharin, cyclamates, and trichloro sucrose. Other typical sweetener/bulking agents include maltodextrin and polyols such as: polydextrose, maltitol, erythritol, xylitol, mannitol, isomalt, lactitol, glycerin, propylene glycol and sorbitol. For formulation calculations, all of these materials are considered to be included in the sweetener component. For taste purposes and for ease of operation, the sweetener component normally comprises sucrose or sucrose-sorbitol combinations.
The salts useful for the present invention are any edible salts that do not interfere with other ingredients or render an undesirable taste. Salts generally act as buffers and sequestrants. Sequestrants are considered to combine with polyvalent metal ions to form soluble metal complexes that improve the quality and stability of foods and food emulsions. Examples of useful salts are common salt (sodium chloride), and sodium, calcium and potassium: monophosphates, diphosphates, polyphosphates, citrates, chlorides, and the like.
Acidulants can be added to control pH, serve as a preservative and/or to attenuate sweetness, flavor and/or browning. Examples of acidulants suitable for the present invention are phosphoric, tartaric, malic, citric, gluconic, fumaric, and the like. It is preferable to use acidulants so as to maintain a pH range of between 4 to 8.
Other Ingredients
Other ingredients that are useful for the present invention include flavoring agents, colorants, vitamins, minerals milk powder, cream powder etc. Suitable flavoring agents can be employed to impart vanilla, cream, chocolate, coffee, maple, spice, mint, butter, caramel, fruit and other flavors.
The range of total fats in the present product is 12-48%, preferably between 20-30%. The total sugars solids are between 20-60%, preferably between 20-40%. The water is between 25-60% preferably between 35-55%. The proteins are optional and can be added up to 5%, preferably between 0.5 to 2.5%. Various flavors can be added to the product with the range depending upon the required flavor profile.
The following table (Table 3) provides the ranges of various ingredients of the whippable product according to the present invention.
To prepare the product, the dry ingredients (via premix including hydrophilic emulsifiers (HLB ≧6)) are added to the hot water (at about 75� C.). Sugars or sugar solutions are then added to the aqueous phase and the temperature is allowed to equilibrate to about 75� C. allowing the ingredients time to dissolve and mix. The fat phase (˜65� C.) is added along with the lipophilic emulsifiers (HLB<6) and mixed at high speed until a homogenous mixture is formed. The resulting mixture is processed to achieve a desired level of microbial destruction so as to produce a sterile product. In the present invention, the product was processed to achieve a F0 of 10 to 15 (see Canned Foods by Gavin and Weddig National Food Processors Association, 5th Edition, 1995). This can be achieved, for example, by preheating to 75� C.-85� C. followed by heating the product to 140� to 145� C. by either indirect or direct heating methods for a hold time 4 to 10 seconds.
The mixture is then flash cooled to achieve a temperature of 75� C.-85� C., (temperatures <60� C. or >90� C. are known to increase the particle size distribution of the final emulsion), homogenized using a two stage homogenizer to a pressure of 100 to 1000 bar (preferably 200 to 600 bar) and then pre-cooled to 30� C.-60 C, preferably to 40� C. to 50� C. with a final cool to 5� C. to 20� C., preferably to 5� C. 15� C. It was observed that pre-cool temperatures of <30� C. or >60� C. or final cool temperatures >20� C. result in reduced performance quality. The resultant mixture is then filled aseptically. The samples are preferably tempered at 5� C. to 15� C. for 24-96 hours (temperatures >20� C. are known to decrease the stability of the final emulsion) to achieve desired ingredient hydration and fat structure. The tempered product can be used or stored and/or distributed at freezer, refrigeration or ambient temperatures.
The whippable product produced according to the above method can be stored and distributed up to 12 months at from about −20� C. to about 30� C. If stored frozen the product can be thawed by any routine process used in the art.
To obtain a whipped confection, the whippable product of the present invention can be whipped using a paddle, whip, traditional batch mixers (Hobart, Kitchen Aid, Kenwood etc), aeration devices including continuous mixers and the like.
The whippable product can be whipped to an overrun of up to 500%. Typically the overrun is about 150 to 500%. While temperature plays a role in the final overrun, the product can be whipped in about 4-15 minutes at temperatures between refrigeration temperature (about 4� C.) and room temperature (about 27� C.). The whipped product is stable at ambient temperatures for up to 7 days without loss of acceptability.
A variety of whipped confections can be made from the product of this invention. Such confections include fillings, icings, toppings, decorations and the like which can be used for cakes, pies, cookies and the like. The toppings, icings and fillings are used according to routine methods. Further, the whipped product of the present invention may be used with other components to provide for desired toppings, icings or fillings. Recipes for such additional applications can be found in Examples 16-23 of U.S. Pat. No. 6,203,841.
The following non-limiting examples are provided to further illustrate the invention and are not intended to be construed as restrictive in any way.
This embodiment provides one example each of a formulation according to the present invention for an icing and a topping (Table 4).
This embodiment demonstrates that different sugars can be used in the formulations of the present invention. Two formulations comprising either erythritol or sorbitol are presented in Table 5.
In this example, an icing composition (Formulation 3A) according to the present invention was compared with icing composition outside of the present invention (Formulations 3B and 3C). The formulations are shown in Table 6.
The performance characteristics of these formulations were tested up to 4 days as follows. The product was whipped for 6 to 12 minutes and its display characteristics were scored. The display measures assessed were: application to a cake, storage in a bowl and performance using a pastry bag. The results are presented in Tables 7A-7C. NW indicates that the composition did not whip.
In this example, a topping composition according to the present invention (Formulation 4A) was compared to compositions outside of the invention (Formulations 4B and 4C). These formulations are presented below in Table 8.
The performance characteristics of the formulations from Example 2 were tested up to 4 days as described in Example 3. The results are presented below in Tables 9A-9C.
This example further emphasizes the importance of Stabilizing to Destabilizing emulsifier ratios by comparing some stability characteristics of formulations according to the present invention with some formulations outside of the scope of the invention. Various formulations were prepared as presented in Table 10. In addition to the ingredients shown, all the formulations have similar sweeteners, proteins, sodium phosphate, salt, vanilla and sorbate.
Formulations A and B are identical, C, D and E are identical, F and G are identical, H and I are identical and J and K are identical. Formulations A, B, C, D and E were prepared according to the present invention. However, Formulations F, G, H, I, J and K do not fall within the scope of the present invention. Formulations F and G comprise Palm kernel stearine as the second fraction. The Stabilizer to Destabilizer HLB ratio is below 1 for Formulations F, G, J and K, and above 4 for Formulations H and I. Formulations A, C, F, H and J were whipped at 10� C., formulations B, D, G, I and K were whipped at 21� C. and Formulation E was whipped at 25.5� C.
The formulations were tested according to the guidelines of Sensory Evaluation Techniques by Meilgaard et al. (2nd Edition, 1999, CRC Press). The various characteristics tested included Peaking, Penetrometer, Percent Creaming, Pastry Bag time, ease of slicing, air cell coalescence and visual appearance. All attributes were graded on a scale of 1-5. The testers were not aware of the identity of the formulations they were testing.
Whip time refers to the time required to fully aerate and set the texture of topping or icing without inverting or churning the product.
Peaking refers to the texture of the product immediately after whipping. The whipped product is scooped up with a spoon and the spoon is held vertical for 30 seconds. A desirable peaking is a soft peak whose tip is curled down.
Penetrometer refers to the depth of penetration (mm) into a whipped toping or icing by conical probe with a load of 150 grams in 10 seconds.
Pastry Bag time refers to the time a whipped product is useable (with respect to appearance and effort) out of a plastic or cloth bag with a standard rosette pastry tip.
Firmness refers to the mouth feel when the whipped product is compressed in mouth with between tongue and roof of the mouth.
Spreadability refers to the ease of spreading on a cake and evenness of the spread product.
Percent creaming refers to the percentage by volume of aqueous serum to fat layers at a specified storage interval and temperature.
Air cell coalescence refers to the change in appearance of the topping or icing from fine grain texture to coarse pockmarked texture as small air cells combine into larger cells.
The results in Table 10 indicate that the formulations of the present invention (A-E) have superior stability with respect to use and display. The values in bold indicate variance from the optimal value or range.
It will be recognized by those skilled in the art that based on the disclosure provided herein, routine modifications to the various embodiments are possible which are intended to be within the scope of the present invention.
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text: TOP 10 Top 10 Entertainment Agent Provocateur Videos Share Tweet 0 Shares 5. Kylie Minogue This raunchy 90-second ad, which featured Australian pop star Kylie Minogue riding a mechanical bull like her life depended on it, tore through cinemas when it was released in 2001, causing outrage among the more puritanical outlets, who deemed it too racy. In 2009, it was voted the "best cinema ad" of all time, in a poll conducted by Digital Cinema Media, proving once and for all that people really do like watching lingerie-clad pop stars simulate sex. Go figure. Next Page TOP 5 4 3 2 1 Comments Show Comments More Like This Sex and Dating How To Date A Victoria's Secret Model Read More Dating News Trending News: Which Nationality Was Voted As The Sexiest In The World? Read More Trending This Steamy Lingerie Ad Might Be The Best Trailer You'll See Before 'Fifty Shades' Read More Entertainment and Celebrities We May Have Just Found The Hottest Audition Tape For A Bond Girl Ever Read More Entertainment and Celebrities Want To Know Where To Find The Sexiest People On Earth? We'll Let You In On The Secret Read More Entertainment and Celebrities Game Of Thrones Babes: Roxanne McKee Read More Promoted Around the Web Special Features Special Feature From Dating To Fitness, Over 75 Ways Men Are Winning 2015 Read More Special Feature Over 100 Ways To Make This The Most Jaw-Dropping Year Of Your Life Read More Special Feature 100 Ways To Look Better Than You Do Now. Smooth Up, Man. Read More ad


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I'm trying to include a browser specific CSS using the @import style media query as follows:
<style type="text/css">@import url(foo.css) all and (-moz-box-sizing: content-box);</style>
The foo.css then has:
.myStyle { -moz-box-sizing: border-box; }
The idea is that I'll include the foo.css for Firefox (Gecko/Mozilla) browsers. However, it looks like the foo.css is never applied on Firefox. So:
How do I debug in Firefox why the @import media query isn't evaluating to true. I've checked via "InspectQ" to make sure that -moz-box-sizing is indeed context-box in the browser I'm using. But for whatever reason, that media query expression apparently is evaluating to false. What tool(s) can I use to see that evaluation at runtime.
Does anyone see anything wrong with that media query?
Is there a more common way to detect Mozilla browsers using the @import style media query?


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- Horoscopes
- Dear Abby
- Games & Puzzles
- Lifestyle
- Events & Exhibits
- Food & Drink
- Arts & Music
- Movies & TV
Norwich - City building and fire inspectors condemned an apartment building at 94-100 Main St. Wednesday after a 4-inch diameter water line for the sprinkler system burst, flooding the basement and the building's electrical panels, city officials said.
Three of the six units in the building were occupied, and seven people were displaced. Two female tenants are pregnant and one couple has a newborn baby, said Lee Ann Gomes, city Assistant Human Services director. The city paid to house the tenants at the Comfort Suites on Otrobando Avenue Wednesday night.
The tenants also qualify for relocation assistance to new apartments, Gomes said. The city will place a lien on the property to cover those costs. Gomes said one couple has a dog that is being temporarily kenneled at the Norwich dog pound.
The building is owned by 100 Main Street LLC, which lists Steven Eckhouse of South Windsor as the company manager. Norwich businessman Zane Megos is the property manager and has been the main contact person with city officials on the property.
In unrelated cases, Megos faces several criminal charges for taking deposits for apartments and homes that never became available. Megos is due to appear in New London Superior Court Wednesday on those charges.
Fire Marshal Jake Manke said the fire department was alerted to the sprinkler pipe break by a civilian who called police dispatch. Fire crews returning to the station from another call also saw water pouring into the street and responded, Manke said.
The fire department also notified Norwich Public Utilities to shut off the water, and the utility crew called city building inspectors.
Greg Arpin, assistant building official, said the entire building was ordered closed because the electrical system was flooded and the sprinkler system is inoperable. Numerous repairs will be needed before the building can be reopened, Arpin said.
City inspectors also will require certification by a licensed electrician that the electrical system is safe and a complete test of the sprinkler system.
Arpin said inspectors found other building code violations, including an exterior stairway without a handrail and exposed wiring at the building that would have to be addressed before the building is allowed to reopen.
A letter sent Thursday to the owner outlined six conditions for reopening the three-story building.
"A walkthrough inspection shall be conducted by the fire marshal, building official, housing officer and health department," the letter concluded. "Any and all violations cited shall be corrected to the satisfaction of the appropriate department."
30-year-old Mack truck subject of debate in North Stonington
Fire official: Lightning strike likely cause of fire that destroyed home in East Lyme
Senators raise concerns about Yale-New Haven clinic closure plan, citing L+M talks
New London man arrested for failing to safeguard gun discharged at Bennie Dover Jackson Middle School
Community members celebrate SCOTUS decision of same-sex marriage


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Gunmetal Black Ep 01
episode 14.24 / 5.00 3,991 Views
Lucina's First Day
A look at the first day of Lucina in Super Smash4.22 / 5.00 12,498 Views
BATMAN v SUPERMAN final showdown
SPOILERS!!4.16 / 5.00 11,447 Views
Zone tan:im watching you fap
i was part of the site it was borring and didnt contain the stuff that it advertised it did but this cartoon as it is is better that the whol;e site lol id become a member again if theuy pt the stff they advertised when i joined originaly though
cuz... we're better than that! lol
Excellent work, nice to see Zone-Tan finally has a voice.
Video is funny as hell too.
Dat Jello!


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This is obviously common knowledge about Las Vegas but holy shit is the Strip expensive. You're lucky to find a beer under $6 and, when you find one for that price, it's like finding water in the desert. 1,161 more words
Tags » Food And Booze
A Local's Spot
When I travel, I can't stand looking like a tourist. Maybe it's because I live in Aspen and spotting tourists is a pastime for the locals up here. 1,125 more words
Homebrew goo: Make your own energy gel in 10 minutes
A confession: I actually like energy gels. For real.
While it's very in to hate on the taste of gels in favor of quinoa/hummus/kale/lawn clipping balls, I've never turned up my nose at some good, old-fashioned fakery to keep me going on the trail – unless it's coffee-flavored in anyway. 827 more words
Growing Old is Mandatory
Nope, I haven't forgotten this blog. I've been busy…. very busy working, meeting friends, celebrating birthdays, sorting out bills to pay, responding to emails and text messages from relatives around the globe. 106 more words
I <3 Haggis!
On Wednesdays, Betty plays golf and then has dinner at the clubhouse, leaving Doug at home. On Tuesday, she said to us, "what'll you be wanting for your tea* tomorrow?" (*Tea is dinner/supper). 183 more words
Matsu-hip Hip Hooray
Restaurant reviews are tricky. You need to eat a wide variety of items off the menu and to do that at a place like Matsuhisa in Aspen, you need some extra cash and, preferably, an in with someone in the kitchen.* I had an in already and was just waiting for my cash flow to upgrade from its usual leaky faucet status. 1,323 more words
Friday Night BBQ
On Friday night, Doug, Betty, and I had dinner with their friends Trish and Michael. We had a wonderful barbecue and got very, very drunk. It wasn't intentional, it just sort of happened. 269 more words


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New Toyota Minivans Reviews
Autobytel has reviews that will walk you around a car, give you a peek under the hood and get you behind the wheel with an industry expert. Browse by category or get into a specific brand to see how well a car does when put to the test.
Showing 7 of 15 reviews for this vehicle
New 2011 Toyota Sienna Leads Minivan Class in MPG
A new year brings a brand-new, redesigned Toyota Sienna to dealerships. Among the vehicle's many improvements is a boost in fuel efficiency that makes it the current leader in...
10 Things You Should Know About the 2011 Toyota SiennaSportier and more family-friendly than ever
Introduction Nobody really wants to drive a minivan. They're big and boring and they make you look like you've accepted a...
2011 Toyota Sienna Aims for Luxury Niche
The minivan market may not seem like such an important vehicle segment these days, but Chrysler's stranglehold among the people-moving vehicles is so dominant that some competitors...
2009 Toyota Sienna Review
The Sienna has long been a mainstay of Toyota's model lineup and enters the 2009 model year virtually unchanged. The 2009 Toyota Sienna is still available in four trim levels - CE, LE, XLE and XLE...
Kelley Blue Book ® - 2009 Toyota Sienna OverviewVehicle Overview from Kelley Blue Book
Overview: EDITORS' NOTES The 2009 Toyota Sienna is considered one the best minivans on the market today....
Test Drive: 2009 Toyota VenzaWhen a sedan doesn't cut it, and an SUV won't do
Likes: YES! Attractive styling YES! Great cargo room YES! Not an SUV Dislikes: NO! Fuel economy is not a distinct advantage NO! Bigger...
Kelley Blue Book ® - 2004 Toyota Sienna OverviewVehicle Overview from Kelley Blue Book
Body A Minivan No More The new Sienna is a marked improvement over the previous model; it is larger,...


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News Releases
All Releases
|Hoda Kotb to Host Live Call-In Show Exclusively on SiriusXM's TODAY Show Radio Channel
Feb 19, 2015
NEW YORK, Feb. 19, 2015 /PRNewswire/ -- SiriusXM announced today that Hoda Kotb will host a live, one-hour show twice a week on SiriusXM's exclusive channel TODAY Show Radio starting on February 23, 2015. The announcement was made this morning on NBC's TODAY. On her new show, The Hoda Show, Kotb will discuss some of her favorite "water ...
|SiriusXM Announces Broadcast Coverage for DAYTONA 500
Feb 17, 2015
NEW YORK, Feb. 17, 2015 /PRNewswire/ -- SiriusXM, the Official Satellite Radio Partner of NASCAR, will offer listeners comprehensive coverage of the 57th running of the DAYTONA 500, with the live race broadcast, multiple channels carrying in-car audio from some of the sport's top drivers, and daily coverage from Daytona International Speedway on Si...
|SiriusXM and The Players' Tribune Launch New National Radio Show
Feb 17, 2015
NEW YORK, Feb. 17, 2015 /PRNewswire/ -- SiriusXM and The Players' Tribune announced today the creation of a new national radio show that brings the high profile new athlete-inspired media platform founded by Derek Jeter to the airwaves, showcasing the voices of athletes associated with the site and connecting them with listeners around the country....
|SiriusXM Announces Exclusive Valentine's Day Programming
Feb 11, 2015
NEW YORK, Feb. 11, 2015 /PRNewswire/ -- SiriusXM today announced its exclusive Valentine's Day programming, in celebration of the romantic holiday, airing across multiple talk and music channels. SiriusXM's Jenny McCarthy will host "Singled Out ... Again," a special featuring fun, sexy singles meeting up and playing the dating game at ...
|SiriusXM to Broadcast Exclusive ICONOS Event with Latin Urban Pioneer Tego Calderon
Feb 10, 2015
NEW YORK, Feb. 10, 2015 /PRNewswire/ -- SiriusXM announced today that legendary Latin rapper singer-songwriter and actor Tego Calderon will sit down in front of a live studio audience of SiriusXM listeners on Thursday, February 12 for its series "SiriusXM ICONOS," intimate gatherings with iconic Latin musicians, entertainers and ambassadors of Lati...
|SiriusXM Announces Special Programming for NBA All-Star 2015
Feb 9, 2015
NEW YORK, Feb. 9, 2015 /PRNewswire/ -- SiriusXM will offer subscribers extensive coverage of NBA All-Star 2015 - February 12-15 - with more than 30 hours of programming from New York on the SiriusXM NBA Radio channel, plus the live broadcasts of the 64th NBA All-Star Game from Madison Square Garden and other All-Star Weekend events. High...
|SiriusXM to Launch "African Ancestry Radio"
Feb 5, 2015
NEW YORK, Feb. 5, 2015 /PRNewswire/ -- SiriusXM today announced the launch of "African Ancestry Radio," a three-week series of live, call-in shows during which the hosts help listeners and celebrities of African descent in their quest to reconnect with their heritage. Hosted by Gina Paige, co-founder of African Ancestry, and award-winn...
|SiriusXM Reports Fourth Quarter and Full-Year 2014 Results
Feb 5, 2015
NEW YORK, Feb. 5, 2015 /PRNewswire/ -- 2014 Revenue Climbs 10% to $4.18 Billion Net Income Increases 31% to $493 Million in 2014 Record Adjusted EBITDA of $1.47 Billion in 2014, up 26% 2014 Free Cash Flow Reaches Record $1.16 Billion, up 25% $2.5 Billion of Stock Repurchased in 2014 SiriusXM today announced fourth qua...
|SiriusXM and SABR Team Up for New Show on MLB Network Radio
Feb 5, 2015
NEW YORK - February 5, 2015 - SiriusXM will team up with the Society for American Baseball Research (SABR) to launch a new show focused on examining and interpreting the statistical analysis that plays a critical role in baseball today. Behind the Numbers: Baseball SABR Style on SiriusXM will debut on Sunday, February 15 ...
|International DJ and singer Juan Magan to Host Exclusive Show for SiriusXM
Feb 4, 2015
NEW YORK, Feb. 4, 2015 /PRNewswire/ -- SiriusXM today announced the launch of "MixDown with Juan Magan," a new biweekly, bilingual show featuring today's hottest dance tracks, exclusive remixes and the best global club hits. Hosted by Latin Grammy® nominated producer, singer and DJ Juan Magan, the one-hour show will feature many ...
|PGA TOUR and SiriusXM Extend Broadcasting Agreement by 3 Years
Feb 4, 2015
PONTE VEDRA BEACH, Fla. and NEW YORK, Feb. 4, 2015 /PRNewswire/ -- Extensive tournament coverage of the PGA TOUR will continue on SiriusXM PGA TOUR Radio for the next three years following an extension of the TOUR's agreement with SiriusXM. Listeners have access to approximately 24 hours of live golf coverage each week, including hole-by...
|SiriusXM Announces Sports and Entertainment Programming for Super Bowl Week
Jan 27, 2015
NEW YORK, Jan. 27, 2015 /PRNewswire/ -- SiriusXM, the Official Satellite Radio Partner of the NFL, announced today its broadcast plans for Super Bowl Week in Phoenix, Arizona, through February 1. Subscribers will get access to 10 different game broadcasts of Super Bowl XLIX in eight languages plus a wide-ranging mix of sports, entertainment and mu...
|Sirius XM Radio to Announce Full-Year and Fourth Quarter 2014 Results
Jan 26, 2015
NEW YORK, Jan. 26, 2015 /PRNewswire/ -- SiriusXM announced today that it plans to release full-year and fourth quarter 2014 financial and operating results on Thursday, February 5, 2015. SiriusXM will hold a conference call at 8:00 am ET on Thursday, February 5, to discuss these results. Investors and the press can listen to the confere...
|SiriusXM Surpasses 15,000 Dealers Enrolled in the SiriusXM Pre-Owned Program
Jan 23, 2015
SAN FRANCISCO, Jan. 23, 2015 /PRNewswire/ -- SiriusXM today announced at the annual National Automobile Dealers Association Convention and Expo in San Francisco that it has surpassed 15,000 auto dealers enrolled in the SiriusXM Pre-Owned Program. "The SiriusXM Pre-Owned Program launched in the summer of 2011, giving auto dealers the opp...
|Tom Weiskopf Joins SiriusXM PGA TOUR Radio
Jan 22, 2015
NEW YORK, Jan. 22, 2015 /PRNewswire/ -- SiriusXM announced today that 1973 British Open and 1995 U.S. Senior Open Champion Tom Weiskopf has joined the roster of hosts on SiriusXM PGA TOUR Radio (Sirius channel 208, XM channel 93). He will host The Swing on Things with Tom Weiskopf, which will debut Wednesday, January 28 at 1:00 pm ET and...
|PGA of America CEO Pete Bevacqua to Host Monthly Show on SiriusXM PGA TOUR Radio
Jan 20, 2015
NEW YORK, Jan. 20, 2015 /PRNewswire/ -- SiriusXM announced today that Pete Bevacqua, the PGA of America's Chief Executive Officer, will host a new show on SiriusXM PGA TOUR Radio (Sirius channel 208, XM channel 93). State of the Game will make its live debut on Wednesday, January 28, at 8:00 pm ET and air monthly throughout the year. B...
|SiriusXM Announces Special Programming from 2015 PGA Merchandise Show
Jan 15, 2015
NEW YORK, Jan. 15, 2015 /PRNewswire/ -- SiriusXM will feature a special lineup of programming originating from the 62nd PGA Merchandise Show, January 20-23, 2015, in Orlando, Florida, featuring shows hosted by several of the game's top instructors and current and former professionals. SiriusXM's exclusive golf channel - SiriusXM PGA TO...
|SiriusXM Announces Selection Procedures for Leasing a Channel Under Its "Qualified Entity Set-Aside" Program
Jan 15, 2015
NEW YORK, Jan. 15, 2015 /PRNewswire/ -- SiriusXM today announced the selection procedure to lease one Qualified Entity channel to be broadcast via satellite and available online. The lease opportunity is part of SiriusXM's voluntary commitment stemming from the merger of Sirius and XM in 2008. The Federal Communications Commission has m...
|Claude Harmon III to Host New Show on SiriusXM PGA TOUR Radio
Jan 14, 2015
NEW YORK, Jan. 14, 2015 /PRNewswire/ -- SiriusXM announced today that instructor Claude Harmon III will host a new series on SiriusXM PGA TOUR Radio (Sirius channel 208, XM channel 93). Harmon III, one of Golf Digest's 50 Best Teachers, will make his radio debut live from the SiriusXM set at the PGA Merchandise Show in Orlando, FL, on We...
|SiriusXM Exceeds 2014 Subscriber and Financial Targets; Issues 2015 Guidance
Jan 7, 2015
NEW YORK, Jan. 7, 2015 /PRNewswire/ -- SiriusXM today announced that it ended 2014 with 27.3 million subscribers, reporting 1.75 million net subscriber additions in the year, exceeding the company's increased guidance of 1.5 million net additions. Self-pay net additions in 2014 were 1.44 million, exceeding the company's 2014 guidance of 1.25 millio...


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Fun ways to show your American pride on the Fourth
5 ways to get over your ex in a flash
USA wins Women's World Cup!
Exclusive: Teen Beach 2 stars tell all about their thoughts on the movie
Your love horoscope this week is *major*
DIY jewelry storage for the traveling fashionista
Beauty Spy: GL reader Anna I. shares her pretty, natural makeup routine
Super easy & healthy snacks to take to the pool
Have you ever been bullied? Share your story to help other girls!
GL + Disney take a look at the Teen Beach 2 premiere
More Friends = More Fun
GL Tweets !
10 HOURS AGO #BeautySpy: GL reader Anna I. shares her pretty, natural makeup routine: http://t.co/P3yvII6nCn pic.twitter.com/V6ISX6wkEM
11 HOURS AGO The only workout you need this summer: http://t.co/VmVICwjUfc pic.twitter.com/TmQrLcmwB2
12 HOURS AGO This story brings a whole new meaning to lifesaver: http://t.co/j4fDRmuQ66 pic.twitter.com/E8ZchgAuao
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18 Comments | Add Yours
by Pugglegirl1008 on 2/14/2013 6:41:29 AM
aw, thats really sad and sweet
by luette on 2/13/2013 8:20:26 PM
The beginning reminded me of Taylor Swift's "Begin Again." This is so sweet <3
by karenbug88 on 2/13/2013 8:15:13 PM
That's ad :'(
by aki2000 on 2/13/2013 7:45:04 PM
That was so adorable! <3
by purplerainn on 2/13/2013 4:11:44 PM
@islandgirl23..haha same here
Anyway, this is so sweet and well written!! I'll be he remembers a lot of that stuff
by maggie183 on 2/13/2013 3:24:30 PM
by islandgirl23 on 2/13/2013 12:20:47 AM
lol when i saw this i thought of pretty little liars xD
by islandgirl23 on 2/13/2013 12:20:33 AM
Awww! That was so sweet! That's kind of heart breaking that he moved too. And go a girlfriend... ),;
by YouCanCallMeCat on 2/12/2013 11:01:47 PM
That was so sweet.
by emmacd on 2/12/2013 10:16:11 PM
Hey GL chicas! Check out my club, "It's all about Fashion and Beauty!!!" We have advice for any fashion/beauty sitch. Please check it out girlies! <3 Fashion and Beauty Crew
by nazirah817 on 2/12/2013 8:28:16 PM
aww so sweet!!!
by hmeyer on 2/12/2013 7:50:40 PM
Hey girlies! It would be so great if you could check out my club, Style Spy! It's all about fashion, makeup, hair, and style! (Duhh) If you look at my profile, you can find my club and tons of comments about how great Style Spy is! I hope you check it out. Thanks! <3
by ACaseOfMistakenIdentity on 2/12/2013 6:28:20 PM
thats so sweet and if you love fashion and you need advice then join FASHION ADVICE FOR YOU we will answer you questions asap and we really love your comments we give lots of outfit ideas and tips so please join you wont regret it hope to see all at my club
by funnybunny661 on 2/12/2013 6:20:47 PM
Awwh. The ending! T_T //tears
by Chloe<3 on 2/12/2013 6:20:27 PM
<3<3<3 so sweet yet sad...
by 17angie17 on 2/12/2013 6:20:06 PM
Do you like rock and roll music of any era?If so, then join my club "Rock music that rocks"...We will talk about anything, from 70's-modern rock! We have rock trivia, and we share our favorite bands! You can find the club by going to my profile page, and clicking on the club with the awesome electric guitar pic!
by rockchik333 on 2/12/2013 6:09:57 PM
this is so cute! <3
by sammyy99 on 2/12/2013 6:01:02 PM
What your idea of a perfect date?
Win it: Visit all your favorite villains in The Isle of the Lost!
Ever wonder what happened to all of your excellently evil Disney faves? Enter for a chance to check out the new generation of bad guys (and girls) in The Isle of the Lost, a prequel to Disney Channel's Descendants!
CLICK HERE for your chance to win.


text:
Devil May Cry 4: Refrain v1.0 APK
Devil May Cry 4: Refrain v1.0 APK
Devil May Cry 4: Refrain immerses gamers in a gothic supernatural world, where a new protagonist clashes with evil.
Devil May Cry 4: Refrain APK
Download Devil May Cry 4 Refrain Apk. New update with version v.1.0
"Devil May CryR 4 refrain" immerses gamers in a gothic supernatural world, where a new protagonist clashes with evil. As Nero, players will unleash incredible attacks and non-stop combos using a unique new gameplay mechanic, his powerful "Devil Bringer" arm.
Brilliant visuals and intricate details come to life as players explore new and exotic locales. Dynamic action and undeniable style combine with explosive fighting options and a gripping story to produce the incomparable experience that only a Devil May Cry game can deliver.
Game Features:
- Experience the hit console game in the palm of your hand
- Ten epic levels and eight boss fights
- Signature blend of guns and swordplay
- Deep combo system rewards stylish dispatching of enemies
- Customize your play style by collecting and spending red orb
- Unique "Devil Bringer" arm opens up a range of combo options
- Retina display graphics and Game Center achievements
Version: 1.0
Size: 500 kB
Required android: 2.3 and up
- Download
- Install apk
- Download data by yourself
- Play the game
Download : Devil May Cry 4 Refrain Apk
Plz Use AndroZip Root File Manager To Extract The Downloaded Files
Download For Free From File Choco™
Buy It From Google Play
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text:
Original recipe yields 4 servings
Amount per serving ({{servings}} total)
Based on a 2,000 calorie diet
Excellent flavor combination & very easy to whip up! I served it with an Indian meal & with papadaums for dipping! My husband,who is an Indian food lover-just flipped for this!!
This came out really good, but I didn't have tamarind paste. What I had was this chuck of tamarind goo from the asian store. I cut off about a 3/4 cup chuck of it and soaked it in 3/4 cup of w...
This was very easy and tasted just like my favorite Indian restaurants. I did add a bit of salt and would use just a tad less water next time. I also used my tamarind paste since I didn't have...


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You survived Memorial weekend and are making it through the rain. This weekend is party it up with Erick Morillo, celebrate anniversaries at Mokai, and get moving with Pirate Stereo and more.
Mynt presents Amanda Wilson
1921 Collins Ave., Miami Beach
Start the weekend early with a performance by chart topper Amanda Wilson at Mynt. She will be on stage performing hits "Doing It Right", "Runaway" and more. Doors open at midnight. Dress code is strictly enforced and table reservations are strongly suggested.
Mokai 3-Year Anniversary
235 23rd St., Miami Beach
It's been three years since this little gem opened its doors and the parties have been insane from the start. Be there on Friday for the 3-Year Anniversary event that promises to be nothing short of spectacular. DJs Rico and Affect will be on the decks keeping you rocking into the morning hours. For complimentary admission before 12:30 am click here.
Bamboo A-Listers Party
4441 Collins Ave., Miami Beach
Miami's own Erick Morillo returns to take over the turntables at LIV and keep Miami's finest on their toes as they party it up until 5 a.m. Dance to house music hits such as "My Melody" and "Live Your Life." Doors open at 11 p.m.
Also at LIV this week: Thursday get on the floor with Fedde Le Grande and Mednas, Saturday continue the party with special guest Quintino. For tickets click here.
DBerrie at WALL
2201 Collins Ave., Miami Beach
Special guest DBerrie is taking over the posh lounge at the W Hotel to get you moving to the groove alongside Chicco Secci with house beats until 5 a.m. For tables and reservation inquiries firstname.lastname@example.com. Doors open at 11 p.m. and dress code is strictly enforced. For advanced tickets click here.
The Garret Presents His & Hers Saturdays
697 N Miami Ave., Miami
For something more low key, head downtown as Poplife and Off the Radar present His & Hers Saturdays at Grand Central Miami. Special guests Pirate Stereo will be in the house dropping beats alongside Ray Millian and Aramis Lorie. There's no cover and plenty of drink specials to get you dancing. Doors open at 10pm, you must be 21+ to get in.
Club Space presents Strangers and Friends
34 NE 11th Street, Miami
Close out your weekend with Dsan Powell, Patrick M, ALX and more as Club Space presents a night of Strangers and Friends. Let the music bring you together as you dance your cares away. For more information and tickets click here.
LIV Nightclub
[1] http://www.miami.com/nightlife/party-patrol
[2] http://www.myntlounge.com
[3] http://www.mokaimiami.com
[4] http://mokaimiami.com/events.php
[5] http://www.livnightclub.com
[6] http://wantickets.com/Venues/1240/LIV-NIGHTCLUB/
[7] http://www.WALLmiami.com
[8] http://wantickets.com/Events/128037/DBERRIE-at-Wall/
[9] http://www.grandcentralmiami.com
[10] http://www.clubspace.com
[11] http://wantickets.com/Events/128803/STRANGERS-FRIENDS-feat-Patrick-Morana-Terrace-Oliver-Deustchmann-Techno-Loft/
[12] http://www.miami.com/could-be-best-happy-hour-miami-toscana-divino-brickell-article
[13] http://www.miami.com/nightlife/happy-hour
[14] http://www.miami.com/craft-beer-week-keybilly-island-ale-article
[15] http://www.miami.com/restaurants/beer-me-miami
[16] http://www.miami.com/freedom039s-just-another-word-for-an-excuse-booze-plus-dinner-and-drag-show-article
[17] http://www.miami.com/nightlife/velvet-underground
[18] http://www.miami.com/nikki-beach-serves-8-kinds-burgers-independence-day-article
[19] http://www.miami.com/rooftop-1-hotel-south-beach-takes-over-thursday-nights-beach-article
[20] http://www.miami.com/thompson-miami-beach-launches-new-sunday-soir-e-article
[21] http://www.miami.com/regent-cocktail-club-presents-twilight-zone-edition-shameless-burlesque-article
[22] http://www.miami.com/delano-beach-club-debuts-full-moon-night-swim-article
[23] http://www.miami.com/gale-kept-fiesta-going-despite-rain-article
[24] http://www.miami.com/rum-line-offers-chic-and-contemporary-cinco-de-mayo-alternative-article
[25] http://www.miami.com/cinco-de-mayo-parties-miami-and-south-florida-article
[26] http://www.miami.com/whiskey-wednesdays-debuts-prohibition-midtown-miami-article
[27] http://www.miami.com/ball-amp-chain-presents-new-album-series-article


text:
Should I stay or should I go? That's the question some people are asking in the aftermath of Superstorm Sandy.
The storm renewed a debate on whether damaged areas should be restored to the way they were, or whether it's cheaper in the long run to buy out property in flood-prone areas and let nature reclaim the land.
Hard-hit Sea Bright N.J., where three-quarters of the residents remain homeless, vows to rebuild — only higher this time.
But homeowners in the Oakwood Beach section of New York's Staten Island want the government to buy them out.
Several states have tried small-scale buyouts after past floods, but large-scale depopulations are easier said than done. New Orleans considered backing away from some low-lying areas after Hurricane Katrina, but a public outcry halted that plan.
More breaking news
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Archive for Tuesday, November 26, 2013
Legends Outlets to offer all-night shopping, light show
November 26, 2013
Legends Outlets Kansas City will usher shoppers into the holidays with an all-night shopping event Thanksgiving night and a light show every 15 minutes throughout the holiday shopping season.
The Legends lit up its 45-foot holiday tree Saturday at the center of the Civic Courtyard Fountain, when it began its daily light displays, in which festive decorations light up throughout the shopping center, synchronized to music, every 15 minutes. The lighting display shows will continue through Jan. 2.
On Thanksgiving night, The Legends again will have its Moonlight Madness, with 23 consecutive hours of shopping and $5,000 in giveaways.
This year, the first-ever Legends Outlets Cocoa Couture Lounge, presented by Saks Fifth Avenue OFF 5TH, will transform the center courtyard into a comfortable shopping experience. It will open at 9 p.m., one hour before the designer outlets and retailers will open.
Guests are encouraged to wear their most festive pajamas and enter the Cocoa Couture Lounge, featuring $2,000 in gift card giveaways from Saks Fifth Avenue OFF 5TH, complimentary hot cocoa by Mema's Old-Fashioned Bakery, and entertainment. The Lounge will have couches, heaters and tables as a dedicated destination to take a shopping break.
At 10 p.m., the entire Legends Outlets center opens with special sales and promotions. The lounge will serve as a giveaway center until 3 a.m. with $3,000 more in prizes. Winners will be announced via the center-wide speaker system every 15-30 minutes from 10:30 p.m. – 3 a.m. Shoppers must be present to win.
The Legends will have extended holiday hours Dec. 1 through Dec. 23. Stores will be open 9 a.m. to 10 p.m. Monday – Saturday, 10 a.m. to 7 p.m. Sundays. On Christmas Eve, stores will be open 9 a.m. to 5 p.m.
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Kimiko Date-Krumm advances to 2nd round at Wimbledon
Kimiko Date-Krumm advances to 2nd round at Wimbledon
LONDON — Playing an opponent less than half her age, veteran Japanese player Kimiko Date-Krumm needed just 44 minutes to defeat German teenager Carina Witthoeft 6-0, 6-2 in the first round of Wimbledon on Tuesday.
The 42-year-old Date-Krumm is the second oldest player to have won a match at Wimbledon after Martina Navratilova, who was 47 when she reached the second round in 2004.
The 18-year-old Witthoeft was making her Grand Slam debut.
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Food was bland and portion sizes are inconsistent.
One person in our party got one piece of steak that was tough and overdone, the other piece was okay. Meatballs in the spaghetti were burnt.
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Selective hydrogenation of aliphatic dinitriles to aminonitriles is achieved under low pressure with high yield preferably using a Raney nickel or Raney colbalt-containing catalyst.
1. A process of selective partial hydrogenation of aliphatic dinitriles to aminonitriles comprising:
(i) reacting in the presence of hydrogen an aliphatic dinitrile containing 4 to 12 carbons in a reactor at temperatures of from about 25� to 150� C., and at a pressure of from about 50 to 2000 psi in the presence of
(a) a solvent, said solvent being present in at least a 2:1 molar excess and comprising (i) liquid ammonia or (ii) alcohol of from one to four carbon atoms and containing an inorganic base which is soluble in said alcohol and selected from the group consisting of alkali metal hydroxides, alkali metal methoxides, alkali metal carbonates, alkali earth metal hydroxides, alkali earth metal methoxides and alkali earth metal carbonates; and
(b) a raney-type catalyst selected from the group consisting of Raney nickel, Raney cobalt, and Raney nickel promoted with metals or metal oxides selected from Group VIB or promoted with the ferrous metals of Group VIII of the Periodic Table; and
(ii) recovering the corresponding aminonitrile as the major product, selectivity to the aminonitrile increasing to about 95% with decreasing conversion of the starting dinitrile to about 65%.
2. The method of claim 1 wherein the dinitrile is a linear or branched aliphatic diradical containing from 3 to about 12 carbon atoms.
3. The method of claim 2 wherein the dinitrile is a selected from the group consisting of adiponitrile, ethyl succinonitrile, methylglutaronitrile, and dodecanedinitrile.
4. The method of claim 3 wherein the dinitrile is adiponitrile.
5. The method of claim 2 wherein the Raney-type catalyst used is Raney nickel promoted with Cr and Fe in an amount of from about 0.5 to 50.0% by weight of the dinitrile to be hydrogenated.
6. The method of claim 2 wherein the solvent is liquid ammmonia.
7. The method of claim 2 wherein the alcohol is an aliphatic alcohol of one to four carbons.
8. The method of claim 2 wherein the inorganic base is soluble in the alcohol, has a pKb of less than 5.0, and is present in an amount of between 1 and 10% by weight of the dinitrile to be hydrogenated.
9. The method of claim 8 wherein the inorganic base is selected from the group consisting of LiOH, NaOH, and KOH.
10. The method of claim 8 wherein the temperature is from about 50� to 80� C.
11. The method of claim 2 wherein the pressure is from about 250 to 1000 psi.
12. The method of claim 2 wherein the hydrogenation is carried out as a continuous reaction.
13. A process of selective partial hydrogenation of adiponitrile to 6-aminocapronitrile comprising,
reacting a methanolic solution of adiponitrile in the presence of hydrogen, the solution being at least 10:1 molar methanol to adiponitrile, in the presence of Raney nickel in an amount of from 5 to 20% by weight of the adiponitrile used, and further in the presence of an iorganic base from 1 to 10% by weight of the adiponitrile used and introduced as a 50% solution in water;
operating the system at temperatures from about 50� to 80� C., and at pressures from about 250 to 1000 psi; and
recovering 6-aminiocapronitrile as the major product selectivity to 6-aminocapronitrile increasing to about 95% with decreasing conversion of the starting dinitrile to about 65%.
14. The method of claim 13 wherein the hydrogenation is carried out as a continuous reaction.
This invention relates to a low-pressure process for the manufacture of aminonitriles. More particularly, the invention relates to a convenient low-pressure process for the selective partial hydrogenation of dinitriles. The process gives a high yield with high selectivity and high conversion of the starting material through use of a Raney catalyst at moderate temperatures and with either an excess of liquid ammonia or an alcohol solvent containing an inorganic base.
With few exceptions, the hydrogenation of aliphatic dinitriles, NCRCN (I), is usually carried out to completion, i.e., with addition of 4 mol of hydrogen per mol of dinitrile, in order to prepare the corresponding diamines, H2 NCH2 RCH2 NH2 (II). These are used, among other applications, in production of various polyamides. Thus, for example, adiponitrile is hydrogenated to hexamethylenediamine, one of the two monomers required in the production of Nylon 6,6; methylglutaronitrile is hydrogenated to methylpentamethylenediamine and/or 3-methylpiperidine; and dodecanedinitrile is hydrogenated to dodecamethylenediamine.
The preparation of linear aminonitriles by hydrogenation of the corresponding dinitriles is known. U.S. Pat. Nos. 2,208,598 (1940) and 2,257,814 (1941) to Rigby of E.I. du Pont de Nemours and Co. disclose nickel-on alumina and cobalt-containing catalysts in liquid ammonia and teach away from the use of nickel as a catalyst.
A development by Swerdloff (U.S. Pat. No. 2,762,835 (1956)) carries out the essential reaction in a mixed organic solvent, such as methyal (i.e., dimethoxymethane), dioxane, tetrahydrofuran, or methyl cyclohexane, which is inert to hydrogen; the reaction is terminated after at least 40% and before more than 65% of the dinitrile originally present is reacted. A specified method of practicing the invention involves using a hydrogenation catalyst of the ferrous metal group. An organic solvent is used and the reaction is conducted in the presence of anhydrous ammonia. Unreacted dinitrile must be distilled or extracted from the aminonitrile.
The use of Raney nickel and Group VIII metal catalysts in solvents such as benzene and toluene are disclosed in German Pats. 836,938 (1952) and 848,654 (1952), both issued to BASF.
Selectivity to aminonitriles can be achieved using Rh/MgO catalyst, as disclosed in U.S. Pat. Nos. 4,389,348 (1983) and 4,601,859 (1986), both to Allied Corporation, and in a paper "Preparation and Characterization of a Novel Catalyst for the Hydrogenation of Dinitriles to Aminonitriles", F. Mares, J. E. Galle, S. E. Diamond, and F. J. Regina, J. Catl. 112:145-156 (1988). However, the high price of rhodium makes this approach expensive.
The preparation of branched aminonitriles by hydrogenation of the corresponding dinitriles is described in U.S. Pat. No. 3,322,815(1967) and Belg. Pat. No. 681.932 (1966) both issued to National Distillers. These disclose the preparation of 5-amino-2-methylvaleronitrile using a nickel, cobalt, or ruthenium metal catalyst, liquid ammonia or a tertiary alkyl amine and an alkanol solvent. The latter patent describes a two-step process from compounds such as 2-methyleneglutaronitrile.
It is an object of this invention to provide a process of selective partial hydrogenation of aliphatic dinitriles. In one aspect of the invention the process includes (i) hydrogenating a dinitrile over a Raney-type catalyst selected from the group consisting of Raney nickel, nickel promoted with metals or metal oxides selected from Group VIB and ferrous metals of Group VIII of the Periodic Table, and Raney cobalt; (ii) monitoring the reaction of step (i); and isolating the product aminonitrile from the reaction mass before complete conversion of the dinitrile to the diamine. In another aspect of the invention, the dinitrile is hydrogenated in a stirred reactor at temperatures of between about 25 and 150� C., and at hydrogen pressures between about 50 and 2000 psi (0.345 and 13.79 MPa) in the presence of at least a 2:1 excess (ratio of solvent to dinitrile) of a solvent, which can be either liquid ammonia or an alcohol of from one to four carbon atoms and containing an inorganic base. A Raney-type catalyst is used and is selected from the group consisting of Raney nickel, Raney nickel promoted with metals or metal oxides selected from Group VIB and ferrous metals of Group VIII of the Periodic Table, and Raney cobalt. The resulting aminonitrile is recovered as the major product. A further object of this invention is the efficient and useful process for the partial conversion of the dinitrile, adiponitrile, with high selectivity and high yield to 6-aminocapronitrile in an aliphatic alcohol containing an inorganic base or in liquid ammonia and using a promoted Raney nickel catalyst. A still further object is a continuous format for the process.
Various other objects, features, and attendant advantages of the present invention will be more fully appreciated when the present invention is considered in conjunction with the accompanying drawings.
FIG. 1 shows the effect of dilution of adiponitrile (AND) with methyl alcohol (MeOH) on the maximum yield of 6-aminocapronitrile. Experimental conditions used the maximum amount of aminonitrile as a function of the MeOH to ADN molar ratio.
FIG. 2 shows the effect of temperature (t in � C.)on the yield of 6-aminocapronitrile from the adiponitrile. The data show the fraction of aminonitrile as a function of adiponitrile conversion at three different temperatures.
FIG. 3 shows the variation of the concentration of the four main reaction products from the hydrogenation of MGN (1:4.4 in NH3) at 60� C., 500 psi (3.45 MPa) H2 as a function of conversion.
FIG. 4 shows variation in selectivity for the four main products vs. conversion of the starting methylglutaronitrile.
A convenient, low-pressure process resulting in high yield of aminocapronitrile or other aminonitriles at low levels of fully hydrogenated products and byproducts would be of great usefulness for commercial scale production of such compounds.
The present invention relates to a convenient, low pressure method of selective partial hydrogenation of a dinitrile (e.g., adiponitrile) to an aminonitrile (e.g., 6-aminocapronitrile). Half-hydrogenated products NCRCH2 NH2 (III) obtained by Applicant by addition of 2 mol of hydrogen to the starting dinitrile (I), as for example 6-amino-capronitrile derived from adiponitrile, among other applications can be directly polymerized to yield corresponding polyamides, vis. Nylon 6.
The present invention enables the selective practical hydrogenation of aliphatic dinitriles containing from 3 to about 12 carbon atoms to corresponding aminonitriles. Preferably the carbon atoms are arranged in a branched or linear chain. Thus, for example, hydrogenation of adiponitrile to 6-aminocapronitrile, methylglutaronitrile to two isomeric aminonitriles (5-amino-2-methyl-valeronitrile and 5-amino-4-methyl-valeronitrile), and dodecanedinitrile to the corresponding aminonitrile.
An object of the invention is to maximize the formation of 6-aminocapronitrile to simplify the production of Nylon 6. In Applicant's instant process the yield of aminonitrile is much higher than that of the diamine for conversions of the starting dinitrile at least up to 90%. The desired intermediate can be extracted at the point in the reaction when it reaches its highest concentration and further converted to such compounds as Nylon 6 or hexamethylenediamine (HMD). This selectivity is a clear advantage over previous methods. In addition, the present invention demonstrates that selectivities to omega-aminonitriles approaching those claimed for the rhodium catalyst can be achieved by using relatively inexpensive Raney metal catalysts.
This result can be accomplished by carrying out the hydrogenation in an excess of liquid ammonia or in alcohols containing inorganic base in order to control the formation of byproducts, at temperatures from about 25 to 150� C., and at a total pressure from 50 to 2000 psi (0.345 to 13.79 MPa).
The aminonitrile produced in such a way can be directly polymerized to polyamides, or can be added to mixtures and polymerized to other nylon polymers and co-polymers. More particularly, the process enables direct polymerization of 6-aminocapronitrile to Nylon 6.
The starting material may be any aliphatic dinitrile containing from 3 to about 12 carbons, but preferably containing from 6 to 12 carbon atoms such as adiponitrile (ADN), methylglutaronitrile (MGN), or dodecamethylenedinitrile (DDN). Adiponitrile, methylglutaronitrile, and dodecamethylenedinitrile are especially preferred. The process can be run using neat starting materials, but the preferred mode of operation is to carry out the hydrogenation in an appropriate solvent in excess greater than 2:1 (solvent-to-dinitrile).
Convenient and inexpensive hydrogenation catalysts are Raney nickel and Raney cobalt, active, porous materials produced by selectively dissolving a soluble component, such as aluminum or zinc, from an alloy of nickel or cobalt and the soluble component.
The instant reaction can be carried out over commercially available Raney nickel catalysts, including Raney Ni modified by the presence of other metals or metal oxides selected from Group VIB and from ferrous metals of Group VIII of the Periodic Table, and over Raney cobalt. (Group VIB includes Cr, Mo and W. Group VIII includes Fe, Ru, Os, Rh, Ir, Ni, Pd, and Pt.) Especially advantageous for the purpose of obtaining high selectivity to aminonitrile at a reasonable rate are: Raney nickel modified by chromium or by a combination of chromium and iron (e.g., W. R. Grace RNi 2400, or Activated Metals Co. Catalyst 4000), and cobalt-modified Raney nickel (e g , Degussa Co. BN 113 W).
The amount of catalyst added to the reaction medium is experimentally determined by consideration of the type of dinitrile being hydrogenated and the desired rate of the process under the temperature and pressure conditions applied. In general the amount of the Raney-type catalyst is from 0.5 to 50% by weight of the dinitrile to be hydrogenated and preferably from 5 to 20%.
The selectivity to aminonitriles in the title reaction is enhanced by use of a solvent. Liquid ammonia, in amounts greater than 1 mol per mole of the dinitrile (and preferably greater than 2 mol per mole of the dinitrile), can be used as such a solvent (See Example 1). Aliphatic alcohols containing from one to four carbon atoms, used in amounts greater than 1 mol per mole of the dinitrile (and preferably greater than 3 mol per mole of the dinitrile) and in conjunction with either ammonia or an inorganic base, form another group of acceptable solvents. Other solvents were tested (See Example 6 for tetraglyme (2,5,8,11,14-pentaoxapentadecane) and Example 7 for tetrahydrofuran as solvents), but were found less advantageous than the preferred ones. The effect of dilution of a dinitrile with one of the preferred solvents on the maximum observed yield of the aminonitrile is illustrated in FIG. 1 for the case of adiponitrile being hydrogenated in methyl alcohol (with sodium hydroxide as a source of base). As seen in FIG. 1, the maximum yield of 6-aminocapronitrile initially increases with dilution, but seems to reach saturation above 10:1, [MeOH]:[ADN]molar ratio.
Presence of an inorganic base, such as alkali metal hydroxides, methoxides, or carbonates, or alkaline earth metal hydroxides, methoxides, or carbonates, is required when aliphatic alcohols are used as solvents, but not when liquid ammonia is the solvent. Preferred bases are ammonia, lithium hydroxide, sodium hydroxide, and potassium hydroxide. The most preferred base is liquid ammonia. The chosen base should have the pKb value of at most 5 and should be soluble in medium for the hydrogenation reaction. It was found to be beneficial to have between 1 and 10 wt% (relative to the amount of hydrogenated dinitrile) of such base present in the reaction mixture. As seen from Examples 2 and 3, increased concentration of the base accelerates the rate of dinitrile conversion and improves selectivity to the aminonitrile by limiting the amount of undesirable byproducts. In the absence of an inorganic base in the reaction mixture (see Example 8), the hydrogenation process is slow, and increased amounts of undesired products of condensation are found.
The instant reaction can be operated from 25 to 150� C.; the preferred range of temperatures is from 50� to 80� C. At lower temperatures, the rate of hydrogenation reaction is too slow, and temperature control of the exothermic process becomes too involved to be practical. At higher temperatures, rates of hydrogenation of both the dinitrile and the aminonitrile are greatly accelerated. This makes it difficult to determine precisely the holdup time required for maximum aminonitrile concentration to be reached. The higher temperature also lowers selectivity to aminonitrile. In addition, increased formation of condensation products is observed at higher temperatures, resulting in lower selectivity to aminonitriles. The dependence of the yield of aminonitrile on conversion of the starting dinitrile at various temperatures is shown in FIG. 2.
The low pressure aspect of this invention offers advantages in lower engineering costs compared to the high pressure industrial operation required by currently practiced methods. Additionally, the low pressure does not accelarate the reaction rate, which is useful in determining the optimum point of selectivity of the desired products.
The instant hydrogenation method can operate under pressures of hydrogen ranging from that pressure sufficent to maintain an acceptable forward movement in the production line to pressures of less than about 2000 psi (13.79 MPa). However, the preferable range of operational pressure is from about 250 to 1000 psi (1.72 to 6.89 MPa).
The desired product of the title reaction, aminonitrile, is an intermediate in the process of hydrogenation of dinitriles to diamines. Its concentration in the reacting mixture passes through a maximum as the reaction progresses. The main objective of this invention is to maximize the concentration of the aminonitrile in the reacting mixture, at the highest possible conversion of the starting dinitrile. The yield of the aminonitrile, and the position of the maximum with respect to dinitrile conversion, depend on operating conditions such as temperature, hydrogen pressure, amount and kind of catalyst, dilution of starting dinitrile, amount of inorganic base added, as well as on the kind of solvent. These variables influence the optimum contact time for the reaction in ways that are understood by those skilled in the art. Additionally, FIGS. 1-4 provide useful guidance in choosing the parameters of several of these variables.
The process of the invention can be operated batch-wise or continuously in an appropriate reactor. Stirring or agitation of the reaction mixture can be accomplished in a variety of ways known to those skilled in the art. It is essentially the partial hydrogenation of the starting dinitrile to the corresponding aminonitrile over a promoted Raney catalyst, and with high selectivity achieved at high conversion of the dinitrile in a solvent selected, that makes this process efficient and useful.
The present invention is further defined in the following Examples, in which all parts and percentages are by weight and degrees are Celsius, unless otherwise stated. It should be understood that these Examples, while indicating preferred embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characterisitcs of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. All such modifcations are intended to fall within the scope of the appended claims.
A 300 cc autoclave, equipped with a stirrer and a dip tube to allow sampling of its content, was charged with 60 g (0.55 mol) of adiponitrile, 0.4 g cyclododecane (internal standard for GC analysis), and 7 g Raney Ni 2400 (W. R. Grace Co) catalyst. The autoclave was flushed with nitrogen, and 100 cc (3.6 mol) of liquid ammonia was introduced; the autoclave was then heated to 80� C. The autoclave was connected to a source of hydrogen kept at 1000 psi (6.89 MPa); the rate of agitation was increased to 2000 rpm, and the first sample was taken. Subsequent samples were withdrawn every 30 min and analyzed by GC in order to construct concentration profiles of the main reaction components. Complete conversion of the starting dinitrile was obtained within 2 h on stream. At 70% adiponitrile conversion, Applicant found ca. 60.5% 6-aminocapronitrile, and 9% hexamethylenediamine; selectivity (defined as in F. Mares, et al., J. Catal., 112, 145-156, 1988 ) to aminocapronitrile was 86%. At that conversion of the starting dinitrile, byproduct concentration was low: 0.5% of dimers (including bis-hexamethylenetriamine), and trace amounts of other byproducts like hexamethyleneimine and tetrahydroazepine. Selectivity to aminocapronitrile decreased with increasing conversion of the starting dinitrile, for example to 77.5% at 80% conversion.
The same autoclave as in Example 1 was charged with 20 g of adiponitrile, 200 cc of methanol, 2 g of NaOH solution (50% by wt), 5 g of the Raney Ni 2400 (W. R. Grace Co.) catalyst, and 0.4 g of cyclododecane. Reaction was carried out at 80� C. and 500 psi (3.45 MPa) hydrogen pressure. Total conversion of the starting dinitrile was achieved in 2 h. At 70% adiponitrile conversion Applicant found ca. 58% aminocapronitrile, 11% hexamethylenediamine, and ca. 1.5% total of other byproducts, for selectivity to aminocapronitrile of 83%.
The reaction was conducted as in Example 2, but twice as much sodium hydroxide was used (i.e., 4 g of the 50% NaOH solution); reaction conditions were 70� C. and 500 psi (3.45 MPa) hydrogen pressure. Selectivity to aminocapronitrile was 89.5% at 70% adiponitrile conversion and was still high at higher levels of adiponitrile conversion, i.e., 82.5% at 80% conversion and 75.5% at 90% conversion.
The autoclave described in Example 1 was charged with 75 g (0.39 mol) of dodecanedinitrile, 9 g of Raney Ni, Co modified (Degussa BN 113 W), and 0.5 g of cyclododecane. After flushing with nitrogen, 20 cc (0.82 mol) of liquid ammonia was added. The molar ratio of the dinitrile to ammonia was 1:2.1. Hydrogenation was carried out at 80� C and 500 psi (3.45 MPa) total pressure. Selectivity to the aminonitrile was 71% at 50% conversion of the starting dinitrile and decreased as the reaction progressed further, for example, to 63% at 60% conversion of the dinitrile, due to increasing contribution of dodecamethylenediamine, the main byproduct of the hydrogenation reaction.
The autoclave described in Example 1 was charged with 70 g methylglutaronitrile, 10 g Raney Ni modified with Cr and Fe (W. R. Grace Co, catalyst 2400), 0.5 g cyclododecane standard, and 70 cc of liquid ammonia. The molar ratio of the dinitrile to ammonia was 1:4.45. The hydrogenation reaction was carried out at 60� C. and at 500 psi (3.45 MPa) total pressure. Total conversion of the starting dinitrile was achieved in ca. 3 h, but process was continued for total of 5 h.
Variation of the concentration of main reaction products with conversion of the starting methylglutaronitrile is shown in FIG. 3. In this Figure "AN 1" represents 5-amino-2-methylvaleronitrile, AN 2 represents 5-amino-4-methylvaleronitrile, "ANs" is the sum of both isomeric forms of aminonitrile, and "MPMD" is methylpentamethylenediamine, the final product of hydrogenation.
Selectivity of methylglutaronitrile conversion to the main products is shown in FIG. 4. The selectivity to AN 1 is higher than to AN 2. The overall selectivity to aminonitriles (ANs) is 88% at 75% methylglutaronitrile conversion, decreasing with further conversion of the starting dinitrile, but is still 84% at 90% conversion. Selectivities to 3-methylpiperidine and to the diamine are also shown for comparison.
The autoclave was charged with 20 g adiponitrile, 200 cc tetraglyme (2,5,8,11,14-pentaoxapentadecane), 5 g of the Raney Ni 2400 catalyst, 2.5 g NaOH solution (50%), and 0.5 g cyclododecane, and operated as in Example 2. Reaction was slow, and only 55% conversion of the adiponitrile was reached after 3 h on stream. At that point Applicant found 37.5% aminocapronitrile and 17.5% hexamethylenediamine for selectivity to 6-aminocapronitrile of 68%.
The same experiment as in Example 6 was repeated using tetrahydrofuran instead of tetraglyme as the solvent. Reaction was slower than observed in Examples 1 and 2, and ca. 92% of the starting dinitrile was converted during 3 h on stream. At 70% adiponitrile conversion Applicant found 43% 6-aminocapronitrile and 27% hexamethylenediamine, for selectivity to 6-aminocapronitrile of 61%.
The autoclave was charged with 20 g adiponitrile, 200 cc of methanol, and 5 g of Raney Ni 2400 catalyst. No base was added in this test. At 70� C. and 500 psi (3.45 MPa) of hydrogen, only 42% of the starting dinitrile was converted in 3 h of operation. At that point Applicant found 32% of the 6-aminocapronitrile and 2.4% of the hexamethylenediamine, the balance being hexamethyleneimine and products of condensation of the above compounds (formed via elimination of ammonia).
The process described in Example 8 is not suitable for commercial production of 6-aminocapronitrile.
Methanolic solutions of adiponitrile (at least ten-fold molar excess of the alcohol) are hydrogenated in a well-stirred autoclave at 62� C. (�b 3) and at hydrogen pressure 1000 psi (i.e., 68 atm, 6.89 MPa), in the presence of a (Cr+Fe) promoted Raney Ni catalyst, representing 12% by weight of the adiponitrile, and in the presence of an inorganic base, such as NaOH, representing 5% by weight of the adiponitrile, and introduced as a 50% solution in water. Agitation of the solution was accomplished using an air-drawn stirrer operated at >1500 rpm. After 2.5 hours of operation, 90% of the starting adiponitrile is converted, with the selectivity to aminonitrile (6-aminocapronitrile) being 82%. Higher selectivities to aminonitrile can be achieved at lower conversions of the adiponitrile.
The process described in Example 9 is suitable for high selectivity of 6-aminocapronitrile.
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