WO1991014379A1 - Procede de fabrication d'hydroxyacetaldehyde - Google Patents

Procede de fabrication d'hydroxyacetaldehyde Download PDF

Info

Publication number
WO1991014379A1
WO1991014379A1 PCT/US1991/002024 US9102024W WO9114379A1 WO 1991014379 A1 WO1991014379 A1 WO 1991014379A1 US 9102024 W US9102024 W US 9102024W WO 9114379 A1 WO9114379 A1 WO 9114379A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxyacetaldehyde
condensate
haa
foodstuff
solution
Prior art date
Application number
PCT/US1991/002024
Other languages
English (en)
Inventor
John A. Stradal
Gary. L. Underwood
Original Assignee
Red Arrow Products Company Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Red Arrow Products Company Inc. filed Critical Red Arrow Products Company Inc.
Publication of WO1991014379A1 publication Critical patent/WO1991014379A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78Separation; Purification; Stabilisation; Use of additives
    • C07C45/81Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/04Preparations for care of the skin for chemically tanning the skin
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78Separation; Purification; Stabilisation; Use of additives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78Separation; Purification; Stabilisation; Use of additives
    • C07C45/80Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78Separation; Purification; Stabilisation; Use of additives
    • C07C45/81Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Definitions

  • This invention relates generally to a process to produce hydroxyacetaldehyde from a pyrolyzed carbohydrate-containing feedstock and, more specifically, to a process to produce hydroxyacetalde- hyde from the water soluble fraction of pyrolysis products obtained from a pyrolyzed carbohydrate- containing feedstock such as wood, cellulose, sugars or starches.
  • Aqueous solutions of hydroxyacetaldehyde are useful to color or brown proteinaceous materials and to produce natural flavors when combined with ammonia or amines.
  • Hydroxyacetaldehyde, HO-CH 2 -CHO, (HAA) is the simplest aldehyde-alcohol or sugar.
  • HAA Hydroxyacetaldehyde
  • An early compila ⁇ tion of some physical characteristics and a synthesis of HAA by thermally degrading an aqueous solution of dihydroxymaleic acid is reported by Fenton and Jackson, J. Chem. Soc, 79:774 (1902). In this report, the authors heated an aqueous solution of dihydroxymaleic acid and then distilled the heated solution under reduced pressure. The viscous fraction that distilled at near 100 °C was collected and found to crystallize after cooling.
  • HAA may actually exist in solution in at least three different monome_ric or dimeric forms and as a mixture of stereoisomers. See, for example, Michelsen and Klaboe, J. of Molecular Structure, 4:293-302 (1969), Collins and George, J.
  • HAA is sold as a crystalline dimer having a melting point of between 80-90 °C depending on the stereoisomeric composition of the crystalline material.
  • HAA has also been identified in complex and variable mixtures of chemicals provided by the pyrolysis of carbohydrate-containing feedstocks.
  • a typical carbohydrate pyrolysis products mixture includes condensible liquids, non-condensible gases, and solids. The relative proportions of these materials are dependent on both the type of feed stock and the actual conditions of the pyrolysis. Many of the different chemicals actually identified in typical pyrolysis mixtures are present found in only trace or very small amounts. Other chemicals, however, are present in sufficient quantities to provide the possibility of isolating a particular chemical, such as hydroxyacetaldehyde, if economical separation schemes are available.
  • a primary pyrolysis liquid is condensed from wood pyrolysis vapors containing a mixture of water soluble and water insoluble organic compounds.
  • a sufficient amount of water is added to the condensed liquid product to allow the separation of the water insoluble compounds from the water soluble compounds by extraction.
  • the extractable water soluble compounds include a number carbonyl compounds such as sugars, ketones, aldehydes and acids.
  • Identifiable compounds include oligosaccharides, cellobiosan, glucose, fructose, glyoxal, methylglyoxal, levoglucosan, 1,6- anhydroglucofuranose, HAA, formic acid, formaldehyde, acetic acid, ethylene glycol, acetol, acetaldehyde, and methanol.
  • HAA formic acid, formaldehyde, acetic acid, ethylene glycol, acetol, acetaldehyde, and methanol.
  • the bulk of the water soluble compounds probably originate from cellulose and hemicellulose present in wood. In total, over 300 compounds have been identified in wood pyrolysis mixtures which makes isolating a specific compound a daunting challenge.
  • HAA is believed to be very reactive, and if heated, especially in basic solutions, rapidly undergoes condensation reactions.
  • the present invention provides a process to produce HAA from a multicomponent aqueous mixture which is obtained by pyrolyzing a carbohydrate-containing feedstock and collecting the condensible vaprous products produced by pyrolysis to give a first aqueous condensate.
  • the first condensate is distilled under reduced pressure to give a second condensate having a reduced water content and the second condensate is combined with a sufficient amount of an organic solvent to give a homogenous solution containing at least 2% by weight HAA.
  • the HAA present in the solution is precipitated and then separated from the HAA depleted liquid.
  • a preferred first condensate is prepared by the fast pyrolysis of corn syrup to give a condensate containing about 16% HAA.
  • carbohydrate-containing feedstocks may be used including wood, cellulose, sugars or starches.
  • any mono-, di-, tri- or polysaccharide which contains glucose or glucose monomers may be used to practice the present invention.
  • Suitable saccharides include glucose, dextrose, invert sugar, lactose, malt syrup, molasses, starch hydrolysates and fractions therefore, sucrose, cellobiose, hemi-cellulose and cellulose.
  • Wood also serves as a suitable feedstock although the presence of components in wood, in addition to cellulose, may provide an unduly complex pyrolysis mixture.
  • Other suitable feedstock sources include plant derived material such as seed, leaf and fruit fibers as well as plant derived syrups and extracts.
  • preferred feedstocks have a low nitrogen content which is typically associated with proteins or amines. If the nitrogen content is too high, the yield of HAA is reduced because the HAA generated during pyrolysis reacts with proteins and amines under typical pyrolysis conditions.
  • the nitrogen content of wood is generally less than about 0.5% and pyrolysis yields of 1% or more HAA, but the pyrolysis of mesquite, a wood having an extremely high nitrogen content, produces no measurable or a negligible amount of HAA in a pyrolysis condensate.
  • Condensates useful to practice this invention may be obtained from carbohydrate-containing feedstocks using pyrolysis and extraction methods which are well known in the liquid smoke art.
  • fast pyrolysis liquids, water soluble fractions of fast pyrolysis liquids, or concentrated conventional liquid smoke solutions having about 1-35% by weight HAA are all useful in practicing the invention.
  • a preferred condensate is the concentrated water soluble extracts of a pyrolysis product produced by the fast pyrolysis of hardwood particles and a particularly preferred condensate is the concentrated water soluble extracts of produced by the fast pyrolysis of corn syrup.
  • Aqueous solutions containing HAA produced by the present invention are useful for browning a foodstuff by contacting the external surface of the foodstuff with a solution of HAA.
  • browning likely occurs as a result of HAA reacting with the foodstuff proteins.
  • the browning process may also occur when the foodstuff is cooked in a microwave.
  • Foodstuffs which may benefit by the presence of HAA to impart desired browning include cheeses, meats, sausages and encased food products, poultry and fish.
  • HAA solutions may be used to form natural flavors by reacting with ammonia, amines or amino acids or to inhibit warmed over flavors in meat products.
  • compositions of HAA may also be used to make a topical skin coloring or tanning product comprising a suitable topical vehicle and an amount of HAA suitable to impart a brown color to skin.
  • Fig. 1 schematically represents a fast pyrolysis apparatus including an upflow reactor.
  • the present invention provides a process of producing HAA from an aqueous condensible vaporous pyrolysis products of carbohydrate-containing feedstocks such as wood, cellulose, sugars or starches.
  • the aqueous condensates resulting from the pyrolysis of suitable feedstocks are made up of a complex and variable mixture of chemicals produced during pyrolysis.
  • Pyrolysis is a general term for the thermal decomposition of any organic material including wood, plants, and fossil fuels. Thermal decomposition may occur either with the combustion of the feedstock or without the combustion of the feedstock.
  • Pyrolysis with combustion normally uses the oxidation or burning of a portion of the organic material to provide the heat necessary to vaporize and decompose the bulk of the material. Pyrolysis without combustion uses heat supplied from an independent source in order to vaporize and decompose the organic material. Suitable heat sources include radiation, solid or gaseous heat carriers, or heated reactors and reactor walls.
  • Suitable methods include both conventional and fast pyrolysis processes.
  • a suitable conventional process is described in U.S. Patent 3,106,473 to Hollenbeck. This process produces an aqueous condensate by extracting desirable smoke constituents generated by a partial combustion of hardwood sawdust into water. Preferably, the partial combustion occurs with limited access to air.
  • Aqueous condensates produced by conventional processes typically have less than about 2% by weight HAA. If desired, the aqueous condensates may be concentrated by well known evaporation procedures before being used in the process of this invention.
  • Fast pyrolysis techniques also provide a product which may be used to practice this invention.
  • Suitable fast pyrolysis procedures are described in U.S. Patent 4,876,108 to Underwood et al.
  • Fast pyrolysis rapidly heats a suitable feedstock to temperatures in excess of 400 °C in less than 2.0 seconds and then collects condensible vaprous constituents produced by the rapid heating.
  • the rapid heating occurs in the absence of air in order to prevent oxidation of reactive constituents before they are collected.
  • a suitable fast pyrolysis process generates products having between 1-35% by weight HAA.
  • an aqueous extract of a wood fast pyrolysis condensate containing about 50% organic solids is a suitable condensate.
  • an aqueous extract of a cellulose pyrolysis condensate is suitable.
  • Still another condensate is obtained by pyrolyzing glucose or a glucose solution.
  • a particular preferred condensate may be obtained by pyrolyzing a corn syrup solution.
  • a preferred condensate may be about 25-30°
  • the solids content of an aqueous condensate may be increased to a desired concentration using well known evaporative methods.
  • a preferred concentrated condensate may be about 50-60° Brix.
  • Evaporative methods which do not subject the aqueous condensate to elevated temperatures for extended periods of time are preferred because HAA degradation is minimized by such methods.
  • the distillation of the condensate is preferably performed under reduced pressure in order to keep the distillation temperature as low as possible which minimizes thermal losses of HAA due to degradation, subsequent reaction or decomposition.
  • the vacuum provided by an aspirator is generally sufficient for performing the distillation, pressures of about -29 inches of mercury are sufficient.
  • the amount of water in the HAA enriched condensate is preferably below about 5% by weight in order for a homogenous solution to form when it is combined with methylene chloride. If the HAA enriched condensate contains more than about 5% water, two phases form when is combined with methylene chloride and HAA does note precipitated.
  • two batch distillations instead of one, the above three criteria may be successfully met. In the first distillation all the components of the starting feed up to and including the HAA rich fraction are distilled over in one fraction as quickly as possible to minimize the time the stillpot is at an elevated temperature. The high water content of this fraction (about 30-40%) prevents precipation.
  • a second distillation in which the water is distilled off and the water reduced still bottoms from this second distil ⁇ lation is the material that is HAA enriched.
  • typical second condensates include constituents which are normally liquid or water soluble at ambient temperatures.
  • the principle organic constituent which is present in the second condensate at distillation temperatures between 20-45 °C at about -29 inches of mercury is acetol although trace amounts of HAA are present in the second condensate at temperatures of about 25 °C and acetic acid, another major constituent, is present in the second condensate in significant percentages at temperatures between 30-60 ⁇ C.
  • the second condensate is found to contain the greatest concentration of HAA and the fraction collected between 45-85 °C, and preferably between 60-70 °C, is used to precipitate HAA from the condensate using procedures described below.
  • concentration of HAA is enriched by vacuum distillation, fractions containing the greatest percentages of HAA are still contaminated with substantial quantities of other organic constituents depending on the type of feedstock and the method used to pyrolyze the feedstock.
  • the enriched HAA second condensate is added to an organic solvent in a sufficient amount to give an homogeneous solution without causing a phase separation between the aqueous and organic portions of the solution.
  • sufficient methylene chloride is added to the second condensate to effect precipitation of HAA without forming two phases.
  • the addition of an amount of methylene chloride which is sufficient to give a homogenous solution provides for HAA to slowly precipitate provided that the overall concentration of HAA in the homogenous solution is greater than about 2% by weight.
  • the temperature of the homogeneous solution may be lower to aid precipitation. Temperatures of -4°C have been found to be useful for the precipitation process.
  • the undesired organic constituents present in the second condensate remain solubilized in the methylene chloride/water solution and HAA may be recovered by simple filtration to separate the precipitated product and the undesired liquids. Any residual traces of undesired constituents may be removed by washing the precipitated HAA with fresh cold methylene chloride.
  • solvents or mixtures of solvents besides methylene chloride may be used to precipitate HAA from the HAA enriched second condensate.
  • a suitable solvent must be chosen to include a proper range of hydrogen bonding parameters and an appropriate polarity index in order to allow the HAA to precipitate but still solubilize the undesired organic constituents present in the second condensate.
  • a suitable solvent must also be easy to separate from the precipitated HAA.
  • One suitable alternative solvent is chloroform.
  • HAA may also precipitate directly from the second condensate enriched distillate when the HAA concentration is greater than about 14% by weight and the water content is less than about one percent by weight.
  • the solid HAA which precipitates directly without mixing with another solvent may be readily filtered from the unwanted liquid and washed with methylene chloride to remove any undesired organic constituents present with the precipitated HAA.
  • Precipitated HAA produced by this invention may be used in a wide variety of applications in both the food and cosmetic industries.
  • meat sources such as beef, pork, lamb, poultry, and fish
  • aqueous solutions of HAA to impart varying degrees of coloring or browning to the meat.
  • any desired degree of browning may be developed without imparting strong or overpowering smoke flavors which are present in traditional liquid smoke products.
  • Any well known application method including but not limited to atomizing, dipping, spraying, brushing, or soaking may be used to contact a foodstuff with an aqueous HAA solution.
  • well known additives such as gums, thickeners, preservatives, or flavorings may be incorporated in the aqueous HAA solutions to produce browning and flavoring solutions most suitable for application to a particular type of foodstuff.
  • Aqueous HAA solutions of at least about 0.5- 10% by weight of HAA may be prepared and applied to foodstuffs. Upon heating to typical foodstuff preparation temperatures, as obtained in a microwave oven for example, a desirable golden brown color is produced on the foodstuff.
  • the three principal stages of the reaction between sugars and proteins include: 1) formation of an aldosylamine between the sugar and protein amino acids and rearrangement to l-amino-l-deoxy-2-ketose (amadori compound); 2) loss of the amino functionality from the amadori compound to form carbonyl intermediates through several pathways; and 3) halogen degradation of additional amino acids by reacting with the carbonyl intermediate produced in the above pathways to form aldehydes, ammonia, and carbon dioxide.
  • the first step in the production of Maillard reaction products in foodstuffs containing glucose is the formation of a two carbon atom amino compound, particularly a 1,2- enaminol.
  • the enaminol includes a two carbon atom fragment derived from glucose
  • HAA is formed by glucose decomposition before reaction with an amino acid because temperatures of about 225 °C. are required to initiate thermal glucose decomposition while the presence of 1,2-enaminols can be detected when glucose and protein amino acids are reacted at much lower temperatures. This suggests that HAA is not an isolatable intermediate of the Maillard reaction.
  • N,N- disubstituted pyrazine cation radicals were formed by reacting glucose and n-butylamine. These pyrazine radicals were believed to be the product of the reaction of a two carbon fragment derived from glucose that is formed by the degradation a glycosylamine initially formed by reacting glucose and protein amines. The two carbon enaminol fragment subsequently condenses with a second enaminol to give the reported pyrazine.
  • HAA-amine derivatives were postulated by Namiki, et al., however, they did not indicate that HAA was produced directly from the fragmentation of glucose as is the case in the pyrolytic decomposition of glucose.
  • glucose has been used as a browning agent, the high temperatures required to obtain significant browning with glucose limits the usefulness of glucose as a browning agent. This is particularly important for microwave foodstuffs because actual preparation temperatures are not as high as traditional cooking and heating procedures. Therefore, to obtain suitable browning on foodstuffs prepared by microwave, it is preferable to preform HAA by pyrolysis of a carbohydrate-containing foodstuff and then apply the HAA to a foodstuff.
  • aqueous HAA solution for coloring or browning protein may be demonstrated by a simple qualitative test. Briefly, a filter paper (Whatman #1, 7.5 cm) is soaked in an aqueous glycine solution (22 g glycine dissolved in 100 ml of 5.5 pH phthalate buffer) and then dried. A drop of a dilute solution of HAA in water is applied to the dried filter paper, the paper is again dried and is then heated in an oven at 150°F to allow the HAA to react with the glycine. The intensity of color increases approximately proportionally to the increase in HAA concentration. This test has shown aqueous HAA solutions as dilute as 0.1% by weight react with glycine to produce a visible brown color on the filter paper.
  • a preferred process food browning foodstuffs or inhibiting warmed over flavor is to obtain HAA from a carbohydrate-containing feedstock and apply sufficient quantities of the HAA to the foodstuff to produce the desired result.
  • the amount required and method of application will vary widely depending of the effect desired, the specific type of foodstuff and the particular conditions of preparing the foodstuff.
  • To impart browning to a microwavable meat product the application of about a 1-5% by weight aqueous HAA solution produces a desirable golden brown color to the meat.
  • concentrations of HAA in an aqueous solution suitable to impart a rich golden brown color to meat when the meat is cooked in a microwave oven are listed in Table 2.
  • aqueous HAA solution may be applied to the surface of Swift Premium Brown and Serve Sausages by a 2 to 3 second dip.
  • the dipped sausages are then microwaved for one minute along with untreated sausages which serve as controls. After microwaving, the sausages are evaluated for visual color appeal. Solutions having a HAA concentration as low as 0.05% impart a noticeable golden brown color to microwaved sausages. Table 2 Surface Coating Total Product
  • HAA hydroxyacetaldehyde
  • an aqueous HAA solution may also be applied to foodstuffs indirectly by applying the liquids to foodstuffs indirectly by applying the HAA solution to sausage and foodstuff casings.
  • the indirect application to casings allows a processor to impart a brown color to a particular food stuff.
  • Any well known method may be used to contact the sausage or foodstuff casing with an aqueous HAA solution. See, for example, the methods disclosed in U.S. Patents 3,330,669 and 4,504,500. Suitable methods for contacting foodstuff casing with an HAA solution are also described in U.S. patent application Serial No. 07/416,963 filed October 4, 1989, the relevant portions of which are incorporated herein by reference.
  • Food casings suitable for use with the present invention include tubular casings, and preferably tubular cellulosic casings, that are prepared by any of the methods well known in the art.
  • Such casings are generally non-fibrous, flexible, thin-walled seamless casings formed of regenerated cellulose or cellulose ethers, such as hydroxyethyl cellulose, and having a variety of diameters.
  • Tubular cellulosic casings having a fibrous reinforcing web embedded in the wall of the casings, commonly called fibrous food casings, are also suitable.
  • a HAA solution may be applied to the outer surface of the food casing by passing the casing through a bath of the HAA solution.
  • the solution is generally allowed to soak into the casing for an amount of time sufficient for the casing to incorporate the desired amount of material into the casing, before doctoring off any excess solution by passing the casing through squeeze rolls or wipers.
  • the solution may also be externally applied to the casing by methods other than dipping, such as spraying, brushing or roll-coating.
  • Another method of treating the casing with solution involves passing a flattened, tubular, cellulose sausage casing over guide rolls through a dip tank which contains the solution. The casing passes over additional guide rolls after exiting the dip tank, and then passes between squeeze rolls which minimize any excess carryover of the solution.
  • the casing is then sent on to conventional further processing, including conventional humidification, as may be required, and conventional shirring.
  • a HAA solution may be applied to the internal surface of the casing by any of several well known procedures. These include slugging or bubble coating, spraying, and coating while shirring.
  • the slugging method for coating the inside of a casing involves filling a portion of the casing with the solution, so that a "slug” generally resides at the bottom of a "U” shape formed by the casing, and then moving the continuous indefinite length of casing so that the "slug” remains confined within the casing, while the casing moves past the slug and is coated on its inside wall by the solution.
  • the casing may then be shirred by conventional methods or, before shirring, it may be dried or humidified to a desired water content suitable for shirring or further processing.
  • the need for conventional drying or humidification after external treatment depends on the water content of the casing after treatment and the type of casing. If the casing is a non-fibrous casing, a water content within the range of about 8-18 wt. % water immediately before shirring is typical, and for fibrous casing a water content within the range of about 11-35 wt. % water immediately before shirring is typical, where weight percent is based on the total weight of casing including water.
  • An aqueous HAA solution is also a particularly preferred when used with collagen casings because HAA is difunctional and thus is an effective cross-linking agent.
  • the physical properties of the collagen casings may be improved by the cross-linking provided by hydroxyacetaldehyde.
  • HAA may also be used in the cosmetic industry as an active ingredient in artificial skin tanning products including liquids, lotions, creams and gels.
  • Conventional artificial skin tanning preparations use dihydroxyacetone as the active ingredient to impart a colored or brown color to skin.
  • Dihydroxyacetone may impart a yellow-orange tone to the skin and has been associated with mutagenic properties in lab tests.
  • HAA may be used alone or as a supplemental browning agent in artificial skin tanning preparations.
  • FIG. 1 illustrates an apparatus which may be used for the fast pyrolysis of carbohydrate-containing feedstock by a rapid thermal process.
  • Bin (40) stores a supply of the feedstock in granular or powder form.
  • the feedstock is removed from the bin (40) by an auger (42) and fed to the lower interior portion of the reactor (44) above a windbox (101) and a grid plate (43).
  • the auger (42) may be water cooled at the inlet to the reactor to prevent premature pyrolysis, which can produce tarry materials.
  • a solution or syrup of a carbohydrate-containing liquid feedstock may be injected into the reactor using a suitable well known injector apparatus.
  • Heated storage tank (110) stores a supply of a liquid feedstock.
  • the liquid feedstock is pumped from the storage tank (110) by a pump 112 through a steam jacketed conduit (114).
  • the liquid feedstock enters the reactor (44) through an injector nozzle (116).
  • the injector nozzle (116) may be cooled at the inlet to the reactor by a water-cooled jacket (118) to prevent premature pyrolysis of the liquid feedstock in the injector nozzle.
  • a stream of recirculation gas transport fluid is fed by a conduit (100) into the windbox (101), through the grid plate (43) and into the lower portion of the reactor (44) containing a heat transfer medium such as sand (45). Rapid mixing and conductive heat transfer from the sand (45) to the sugar or starch feedstock occurs in the reactor (44).
  • Pyrolytic conversion of the feedstock to a raw product vapor is initiated and continues through the reactor with upward flow into the primary cyclone separator (48).
  • the pyrolysis stream comprising sand (45) and pyrolysis vapor is removed from the reactor (44) by conduit (46) and fed to primary cyclone separator (48).
  • the hot sand (45) is removed from the product vapor stream in the separator (48) and recycled by means of a conduit (50) to the reactor (44).
  • the recycled sand (45) is reintroduced into the lower portion of the reactor (44) at a point above the grid plate (43).
  • Product vapor containing char is withdrawn from the primary cyclone separator (48) by a conduit (52) and fed to a secondary cyclone separator (54) which can be a high efficiency reverse flow cyclone separator. Char and solid sand fines are removed in the secondary cyclone and fed therefrom to a char catchpot (56) for disposal or further handling as desired.
  • the hot product stream is withdrawn from the top of the secondary separator (54) through a conduit (58) which feeds the vapor comprising condensible and noncondensible constituents and some fine residual char and ash to the lower interior space of a baffled condenser (60) where the vapor is immediately quenched.
  • the condenser (60) uses the product liquid as the quench medium.
  • the condensed liquid product is withdrawn from the bottom of the condenser (60) through a conduit (62) and is fed to a pump (64) which pumps it to a heat exchanger (66) indirectly cooled by water.
  • the cooled product liquid is removed from the heat exchanger (66) and returned by conduit (68) to the top of the condenser (60) as a spray.
  • a conventional transparent vertical sight indicator (61) is mounted on the lower part of the first condenser (60). The sight indicator has high and low liquid level marks.
  • Non-condensed product vapor is withdrawn from the top of the condenser (60) by conduit (70) and is fed to a packed second condenser column (72) where it is further cooled.
  • Liquid is withdrawn by a conduit (74) from the bottom of the packed second condenser and fed to a pump (76) which pumps it through a water cooled heat exchanger (78). Cooled liquid product is removed from the heat exchanger (78) by conduit (80) and is fed to the top of the packed second condenser column (72).
  • a conventional transparent vertical sight indicator (73) is mounted on the lower part of the second condenser (72).
  • the sight indicator has high and low liquid level marks. When the high level mark is reached raw pyrolysis liquid is withdrawn through conduit (75) until the liquid level reaches the low mark.
  • a vapor stream is removed from the top of the packed second condenser column (72) by a conduit (82) and fed through a water cooled heat exchanger (84) from which it is fed to a conduit (86) which feeds it to a mist eliminator (88).
  • the vapor is fed from the mist eliminator (88) to a conduit (90) which delivers the vapor to a filter (92).
  • Liquid is removed from the bottom of the filter (92) by means of a conduit (102) and recirculated to the bottom portion of the second condenser column (72) above the level of liquid in the column.
  • a portion of the resulting clean by-product gas stream is ducted from the filter (92) by a conduit (94) and fed to conduit (96) which feeds it to a gas recirculation blower (98).
  • the recirculated gas is fed from the blower (98) to a conduit (100) which feeds it into the bottom of the reactor (44).
  • Example 1 describes the distillation of pyrolysis condensates.
  • Example 2 describes precipitating HAA,
  • Example 3 describes coloring or browning a foodstuff,
  • Example 4 describes wing HAA in a skin tanning product.
  • Example 5 describes using HAA to inhibit warmed over flavor in a foodstuff.
  • the concentration values for the organic components in the described liquids are given as °Brix values.
  • the °Brix values were obtained using standard refractory techniques which are well known in the sugar industry.
  • the percent weight per volume (% wt./vol.) values for HAA were obtained using gas chromatography and comparing the peak integrations of a sample of a liquid (diluted if necessary) with peak integrations of a standard curve generated from a 1-5% serial dilution of hydroxyacetaldehyde in water.
  • Example 1 This example provides the distillation profiles of different pyrolysis condensates.
  • the three pyrolysis products are a raw fast pyrolysis condensate, a 50 brix aqueous extract of a fast pyrolysis condensate, and a 55 Brix liquid smoke solution, Charsol Supreme ® sold by Red Arrow Products Co. Inc. (Manitowoc, I).
  • This example illustrates specific conditions which may be used to precipitate HAA.
  • the data in Table 7 indicate a distillate fraction condensate (DFC) of greater than about 6% by weight HAA and less than about 3% water is needed for HAA to precipitate from the distillate fraction condensate (DFC) upon addition of methylene chloride (10 ml added to 1 g DFC).
  • DFC distillate fraction condensate
  • methylene chloride 10 ml added to 1 g DFC
  • HAA precipitates from the distillate fraction condensate at ambient temperatures without the addition of methylene chloride.
  • a fast pyrolysis extract produced by the rapid pyrolysis of hardwood sawdust was distilled under a vacuum of -29 inches of mercury.
  • the DFC cut obtained at 60-70°C. was found to contain 28% hydroxyacetaldehyde by gas chromatography and 5% water by benzene azeotropic distillation.
  • Various additional amounts of water were then added to 10 portions of this DFC and then one gram of each of the mixtures was added to methylene chloride (10 ml) and allowed to stir at -4°C overnight. The next day the methylene chloride mixtures were examined for precipitated HAA.
  • Table 9 The results obtained are listed in Table 9.
  • a 70° Brix aqueous extract of raw fast pyrolysis liquid obtained from pyrolyzing corn syrup was distilled under a vacuum of -29 inches of mercury.
  • a condensate was collected at temperatures from 50 -70 °C was found to be enriched in HAA. This condensate was added to a ten-fold excess of methylene chloride and gave two phases: a top aqueous phase that contained the bulk of the HAA and a lower methylene chloride phase which seemed to extract most of the other organic constituents from the condensate.
  • the two phase solution was cooled and stirred, the HAA remained in the aqueous phase and did not precipitate.
  • Example 3 This example shows the capability of an aqueous HAA solution to brown proteinaceous foodstuffs. Precipitated HAA was dissolved in an amount of water sufficient to give an 2.0 wt./vol. % solution. This aqueous HAA solution was coated on pieces of white string cheese and on raw ground beef. The coated string cheese and ground beef were then microwaved for three minutes. Both the coated string cheese and ground beef turned a dark brown smoked color. Uncoated string cheese and ground beef were used as controls and did not change color when microwaved.
  • Two extruded, raw, uncooked and untreated hot dogs (Chermak Sausage Company, Manitowoc, Wisconsin) were wrapped in a cellulose casing material.
  • One hot dog was dipped in an aqueous solution of 5% acetic acid, 1% xanthan gum, and 1% HAA.
  • the other hot dog was dipped in an aqueous solution of 5% acetic acid and 1% xanthan gum and served as a control.
  • Both hot dogs were placed in the respective solutions for 45 seconds and then both hot dogs were heated in an oven which cooked the hot dogs according to the following program: 110 °F for 10 minutes, 140 °F for 45 minutes, 160 °F for 15 minutes, and 180 °F for 10 minutes.
  • both hot dogs were rinsed thoroughly in cold water and then the outer casing was removed.
  • the hot dog treated with the solution containing 1% HAA had developed a brown smoked color compared to the untreated hot dog that had a light red cured color. Both hot dogs were essentially equivalent in flavor.
  • HAA HAA with other carbonyl compounds
  • Mixtures of HAA with other carbonyl compounds may also be used to import brown color to a foodstuff.
  • the microwave browning capability of HAA, 1,3-dihydroxyacetone, and glucose in aqueous solutions Five percent solutions of mixtures listed below were applied to the surface of the sausages of example 9 by dipping the sausages for about 2 seconds into each solution. The sausages were then heated in a microwave for about one minute along with non-treated sausages as controls. The following results were obtained.
  • Example 4 This example shows the capability of precipitated HAA to artificially tan skin.
  • An amount of moisturizing hand cream, Jergens EVERSOFT ® (The Jergens Skin Care Laboratories) and a sufficient amount of HAA were combined to provide a 8.0 wt./vol. % mixture.
  • a portion of the mixture was applied to the skin of human test subjects along with a portion of the moisturizing hand cream without added HAA.
  • the mixture containing the HAA turned the subject's skin a dark tan color compared to the control which had no color change.
  • the skin tanning ability of HAA isolated by the method was compare to 1,3-dihydroxyacetone (a commonly used active ingredient in artificial skin tanning lotions).
  • HAA and 1,3-dihydroxyacetone were each combined with a skincare lotion, Jergens EVERSOFT ® (The Jergens Skin Care Laboratories) to provide two 5.0 wt./vol. % mixtures.
  • a portion of each mixture was applied to the skin of human test subjects.
  • the mixture containing HAA turned the skin a golden tan color as where the 1,3-dihydroxyacetone mixture turned the skin an orange-red color.
  • Additional mixtures were also made to provide 2.5 wt./vol. % of each compound in the skin lotion described above.
  • the color produced by the mixture on the skin of human test subjects was observed to be superior to either compound alone in both the intensity and the goldeness of the color imparted to the skin.
  • Example 5 This example shows the ability of an aqueous HAA solution to inhibit warmed over flavor in meat.
  • Lean turkey thigh meat was ground two times through a 1/8 inch plate on in commercial meat grinder.
  • Two samples (100 g) were treated with 1500 ppm and 15,000 ppm HAA, respectively, which had been isolated from a fat pyrolysis wood condensate. Both samples were placed in 500 ml Erlenmeyer flasks and then heated in a boiling water bath until an internal temperature of 70°C was reached. The flasks were then covered and placed in a 4°C cooler for 48 hours. After storage, both samples were evaluated for warmed over flavor by-a taste panel.
  • the organoleptic evaluation was done by comparing a freshly cooked sample which had not been subjected to storage to the treated samples.
  • the fresh control was cooked by bringing the internal temperature to 70°C in a boiling water bath.
  • the treated samples were also brought to 70°C.
  • Eight panelists were asked to taste the samples and assign each with a numerical value between 1 and 5 with 5 having the least amount of warmed over flavor, panelists were instructed that the fresh control had a value of 5.
  • the average values obtained are illustrated in Table 11.
  • the data show significant inhibition of warmed over flavor by an HAA solution.
  • the taste panel values indicate a positive dose response correlation between the flavor of meat sample and the amount of HAA added to the meat sample.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Emergency Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé de fabrication d'hydroxyacétadéhyde cristallin précipité à partir d'un mélange complexe de produits fournis par la pyrolyse (44) d'un substrat contenant de l'hydrate de carbone (40, 110). Cette méthode consiste à distiller un premier condensat de pyrolyse (63, 75) sous une pression réduite pour produire un second condensat enrichi en hydroxyacétaldéhyde, à combiner le second condensat avec un solvant pour produire une solution homogène, à précipiter de l'hydroxyacétaldéhyde à partir de cette solution, et à séparer l'hydroxyacétaldéhyde précipité de la solution. Des solutions aqueuses d'hydroxyacétaldéhyde précipité sont utiles pour dorer des aliments et pour produire des saveurs en mettant l'hydroxyacétaldéhyde en contact avec de l'ammoniaque ou des amines. D'autre part, l'hydroxyacétaldéhyde précipité peut être utilisé pour fabriquer un produit de bronzage artificiel contenant un véhicule topique qui convient et une quantité d'hydroxacétaldyde suffisante pour brunir la peau.
PCT/US1991/002024 1990-03-26 1991-03-26 Procede de fabrication d'hydroxyacetaldehyde WO1991014379A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US48984990A 1990-03-26 1990-03-26
US498,849 1990-03-26
US53573590A 1990-06-08 1990-06-08
US535,735 1990-06-08

Publications (1)

Publication Number Publication Date
WO1991014379A1 true WO1991014379A1 (fr) 1991-10-03

Family

ID=27049849

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/002024 WO1991014379A1 (fr) 1990-03-26 1991-03-26 Procede de fabrication d'hydroxyacetaldehyde

Country Status (1)

Country Link
WO (1) WO1991014379A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0656753A4 (fr) * 1991-08-12 1995-02-08 Red Arrow Prod Co Enveloppe alimentaire impregnee et procede de preparation.
EP0878132A2 (fr) * 1997-04-21 1998-11-18 Red Arrow Products Company LLC Composition de brunissement et procédé de dorer des produits à base de pâte
WO1999057999A1 (fr) * 1998-05-11 1999-11-18 Swift-Eckrich, Inc. Procede d'obtention d'une surface croustillante sur un produit carne precuit entierement fait de muscle
WO2005006889A1 (fr) * 2003-07-11 2005-01-27 Red Arrow Products Company Llc Procede permettant de former des marques de gril sur un aliment
WO2007059831A1 (fr) * 2005-11-24 2007-05-31 Unilever N.V. Procede de prevention de la croissance microbienne

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3106473A (en) * 1961-12-27 1963-10-08 Red Arrow Products Corp Aqueous smoke solution for use in foodstuffs and method of producing same
US3615503A (en) * 1969-02-27 1971-10-26 Eastman Kodak Co Color-developing composition containing an antioxidant
US3806609A (en) * 1970-05-11 1974-04-23 V Goblik Method of producing liquid smoke
US3957745A (en) * 1974-07-25 1976-05-18 Universal Oil Products Company Flavoring and fragrance compositions
US4359481A (en) * 1978-01-03 1982-11-16 Internationale Octrooi Maatschappij "Octropa" B.V. Liquid smoke concentrate
US4876108A (en) * 1987-11-12 1989-10-24 Ensyn Engineering Associates Inc. Method of using fast pyrolysis liquids as liquid smoke
US4938868A (en) * 1988-05-02 1990-07-03 Nelson Thomas R Method of distilling under partial vacuum
US4994297A (en) * 1987-11-12 1991-02-19 Ensyn Engineering Associates, Inc. Method of using fast pyrolysis liquids as liquid smoke

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3106473A (en) * 1961-12-27 1963-10-08 Red Arrow Products Corp Aqueous smoke solution for use in foodstuffs and method of producing same
US3615503A (en) * 1969-02-27 1971-10-26 Eastman Kodak Co Color-developing composition containing an antioxidant
US3806609A (en) * 1970-05-11 1974-04-23 V Goblik Method of producing liquid smoke
US3957745A (en) * 1974-07-25 1976-05-18 Universal Oil Products Company Flavoring and fragrance compositions
US4359481A (en) * 1978-01-03 1982-11-16 Internationale Octrooi Maatschappij "Octropa" B.V. Liquid smoke concentrate
US4876108A (en) * 1987-11-12 1989-10-24 Ensyn Engineering Associates Inc. Method of using fast pyrolysis liquids as liquid smoke
US4994297A (en) * 1987-11-12 1991-02-19 Ensyn Engineering Associates, Inc. Method of using fast pyrolysis liquids as liquid smoke
US4938868A (en) * 1988-05-02 1990-07-03 Nelson Thomas R Method of distilling under partial vacuum

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
(SCOTT et al.), "Chemicals and Fuels from Biomass Flash Pyrolysis", RENEWALDE ENERGY BRANCH, ENERGY MINES AND RESOURSES CANADA, (OTTAWA, CANADA), published 1988, See Pages 12 and 28-33. *
PROG. FOOD NUTRI. SCI., Volume 5, published 1981, by PERGAMON PRESS LTD., (GREAT BRITAIN), (M. NIMIKI et al.), "Formation of Novel Free Radical Products in an Early Stage of Maillard Reaction". *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0656753A4 (fr) * 1991-08-12 1995-02-08 Red Arrow Prod Co Enveloppe alimentaire impregnee et procede de preparation.
EP0656753A1 (fr) * 1991-08-12 1995-06-14 Red Arrow Products Co. Inc Enveloppe alimentaire impregnee et procede de preparation
EP0878132A2 (fr) * 1997-04-21 1998-11-18 Red Arrow Products Company LLC Composition de brunissement et procédé de dorer des produits à base de pâte
EP0878132A3 (fr) * 1997-04-21 1999-05-26 Red Arrow Products Company LLC Composition de brunissement et procédé de dorer des produits à base de pâte
WO1999057999A1 (fr) * 1998-05-11 1999-11-18 Swift-Eckrich, Inc. Procede d'obtention d'une surface croustillante sur un produit carne precuit entierement fait de muscle
WO2005006889A1 (fr) * 2003-07-11 2005-01-27 Red Arrow Products Company Llc Procede permettant de former des marques de gril sur un aliment
WO2007059831A1 (fr) * 2005-11-24 2007-05-31 Unilever N.V. Procede de prevention de la croissance microbienne

Similar Documents

Publication Publication Date Title
US5393542A (en) Process for producing hydroxyacetaldehyde
CA2105658C (fr) Preparations aromatisantes et colorantes obtenues par pyrolyse de sucres et amidons
US5397582A (en) Flavoring and browning materials by pyrolysis of sugars and starches
US5135770A (en) High browning liquid smoke composition and method of making a high browning liquid smoke composition
CA1131067A (fr) Concentre de fumee liquide
US4876108A (en) Method of using fast pyrolysis liquids as liquid smoke
US4994297A (en) Method of using fast pyrolysis liquids as liquid smoke
US20040022912A1 (en) Production of glycolaldehyde by hydrous thermolysis of sugars
US5270067A (en) Impregnated casing and method of making the same
EP0462230B1 (fr) Compositions liquides de fumage traitees avec des resines
KR101210571B1 (ko) 표고버섯이 함유된 천연조미료의 제조방법
US5039537A (en) High browning liquid smoke composition and method of making a high browning liquid smoke composition
WO1991014379A1 (fr) Procede de fabrication d'hydroxyacetaldehyde
Nunomura et al. Isolation of 4-hydroxy-5-methyl-3 (2H)-furanone, a flavor component in shoyu (soy sauce)
US5952029A (en) Process to produce grilled flavor composition
US4522838A (en) 2-Acetyl-1-pyrroline and its use for flavoring foods
KUBOTA et al. Identification of the characteristic volatile flavor compounds formed by cooking squid (Todarodes pacificus Steenstrup)
Ikins et al. N-Nitrosamine formation in fried bacon processed with liquid smoke preparations
EP0859555A1 (fr) Procede d'elimination des hydrocarbures presents dans des compositions de fumaison et d'aromatisation liquides
Swain Volatile flavor constituents of pork cured with and without nitrite
EP1069117A1 (fr) 4-Alkanoyl-3-thiazolines et leur utilisation comme parfums et arômes
Park et al. A study of “sweet” flavor in lamb produced by feeding protected sunflower seed
JP3064922B2 (ja) フレーバーエキスの製造法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA FI JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase
122 Ep: pct application non-entry in european phase