Liquid smoke obtained by fast pyrolysis

Abstract: An aqueous solution for flavoring foodstuffs is produced by heating wood or cellulose to between 400-650°C within 1.0 second in a first vessel (1); maintaining the wood or cellulose and the pyrolysis products between 400-650°C for between 0.03-2.0 seconds in the transport reactor (9); reducing the temperature of the pyrolysis products to below 350°C within 0.6 second in a second vessel (2); separating and collecting the liquid products; and diluting the liquid products with water to achieve a partial phase separation and to reduce the benzo[a]­ pyrene concentration to less than 1.0 ppb.

Description: This invention generally relates to the use of liquid smoke manufactured by a fast pyrolysis method for processing, flavoring and coloring meat, fish, poultry and other food products. Background of the Invention Use of liquid smoke solutions as a replacement for smoking by direct contact with smoke produced from wood has become a standard industry practice. When applied to the surface of meats and other proteinaceous foodstuffs, liquid smoke will not only give the item a characteristic smoke flavor, but will react with the proteins to produce the dark color typical of smoked foods. One such aqueous liquid smoke preparation used commercially for surface applications is described in U.S. Patent 3,106,473. This product is produced by partial combustion of hardwood, i.e., sawdust, with limited access to air, followed by subsequent solvation of the desirable smoke constituents into water. A heavy, water insoluble phase which contains tar, polymers, polycyclic aromatic hydrocarbons including benzo[a]pyrene, waxes and other undesirable products unsuitable for use in food applications is discarded. Smoke is a complex and variable mixture of chemicals which are produced from pyrolysis reactions and includes vaporous compounds which are normally liquid at room temperature. Pyrolysis is a general term for the thermal decomposition of any organic material (i.e. wood, plants, fossil fuels etc.) and can occur during a combustion process or in the absence of combustion. In the former, the oxidation or burning of a portion of the organic matter provides the heat required to vaporize and decompose the remainder. In the absence of combustion, heat must be supplied indirectly from some other source (i.e. radiation, a solid or gaseous heat carrier, or conduction through reactor walls, etc.). Pyrolysis produces liquids (i.e. condensable vapors), gasses (non-condensables) and solids (char and ash) in varying proportions depending upon reaction conditions. The liquids can be further sub-divided into water soluble organics and water insoluble tars. It is known that the desirable active ingredients for smoke flavoring are among the water soluble condensable vapors (liquids). Currently liquid smoke is made using conventional pyrolysis which is characterized by relatively slow thermal reactions occurring at moderate temperatures. In the commercial processes, the wood feedstock is dried and ground to sawdust and fed to a reactor system. A typical average reactor temperature is approximately 420°C. Depending on the method of heating, the temperature gradient in the reactor may be from 600°C at the heater to 250°C at the bulk wood surface. Residence times of solids (wood/char) and vapors are approximately 10 minutes and 1 minute respectively. Conventional pyrolysis produces liquid, gas and char yields which are typically 35, 35 and 30% by weight of the wood feedstock, respectively. Since the water insoluble constituents are between 50-65% by weight of the total liquids derived from the wood content, the net yield of raw liquid smoke is relatively low (i.e., 12-20% by weight of the wood feedstock). The pyrolysis products are often passed through a water bath or scrubber. The gaseous products pass through the water bath. The solids and water insoluble tars precipitate out of the water, with the water soluble organics collected in the water as liquid smoke. While there are hundreds of distinct chemical species present in liquid smoke, liquid smoke products have been characterized by three classes of chemicals according to distinct functional groups. The three classes are 1) acids, 2) carbonyls and 3) phenols. This functional definition is useful since phenols are the primary flavoring compounds while carbonyls are responsible mainly for coloration and acids serve as a preservative. Acids and carbonyls also make a secondary contribution to flavor and they enhance the surface characteristics of the meat products. Acids are measured as titratable acidity calculated as acetic acid. Phenols are calculated as 2,6-dimethoxyphenol. The procedure for determining phenols is a modified Gibbs method described in the Journal of the Association of Analytic Chemists , XXV, 779 (1942). Carbonyls are calculated as 2-butanone. The procedure for determining carbonyls is a modified Lappan-Clark method described in Analytical Chemistry , 123, 541-542 (1959). A further measurement that is used to characterize liquid smoke is the browning index. The browning index is used in the smoke flavoring industry to measure the browning performance of a liquid smoke flavor. The browning index uses a spectrophotometric technique that measures, by optical density, the extent to which the carbonyls react with a glycine solution. The browning index is determined from the difference between the adsorption at 400 nanometers of the glycine reacted solution and a control sample. The application of liquid smoke solutions to meat and other food products can be carried out in a number of ways. Where the characteristic smoked color is desired, spraying or dipping can be done on individual items in a batch or continuous mode. Where large batches are to be processed an atomized cloud of liquid smoke can be employed. Alternatively, sausages and hams may be processed in casings into which liquid smoke solutions have been incorporated. In any case, where surface color is the primary effect which is sought, a measure of total carbonyls is used to judge the quantity of smoke required. These compounds react with the available amino groups of proteins at the surface to form the smoked color. The concentration of a specific carbonyl, hydroxyacetaldehyde, is also a good indicator of the color forming potential of liquid smoke. Prior methods of producing liquid smoke suffer from relatively low yields of desirable products and relatively high yields of the undesirable by-products. In addition, the levels of benzo[a]pyrene, a known carcinogen, is relatively high, requiring subsequent dilution of the collected condensable vapors with water to separate out these compounds. The requirement to dilute the collected condensables to limit the level of benzo[a]pyrene below 0.5 ppb prevents the production of liquid smoke having a total acid content above 13% or a browning index above 13.0 without subsequent concentration. Recently new methods have been developed for the rapid thermal processing of carbonaceous feedstocks. These methods have been called fast or flash pyrolysis. Fast or flash pyrolysis of wood or cellulose is a method of imparting a high heating rate to the wood for a very short time and then rapidly quenching the pyrolysis products to a temperature below 350°C. The heating rate for fast pyrolysis is greater than 1000°C per second and vapor residence times are below 2.0 seconds. The WO-A- 88/00935 discloses a method of making an aqueous smoke solution for use in foodstuffs, comprising pyrolysis of lignocellulosic biomass, by using a reactor capable of rapid heat exchange and short gas residence times under the following conditions: gas and vapour residence time is less than ten seconds, solid particle residence time is equal to or greater than the gas and vapour residence time; and the pyrolysis is carried out at 400 - 650°C. The US-A- 4,359,481 contemplates a process for preparing a liquid smoke concentrate for use in foodstuffs by destructive distillation of cellulosis and/or lignin material at 350 - 450°C, which smoke concentrate contains less than 0.2 nanograms of benzpyrene, 0.90 - 1.60 g/l phenolic compounds content to total acid content is respectively 1:(17.0-47.0):(13.0-40.0). While fast pyrolysis methods are known, the research and development in this area has concentrated on producing liquid and gaseous fuels, and on optimizing the production of high energy value fuels. One object of this invention is to provide a method of using the water soluble products from fast pyrolysis to produce liquid smoke in place of conventional liquid smoke to achieve greater yields and higher concentrations of desirable product and lower yields of gaseous and solid by-products, resulting in greater efficiency and a resulting cost savings. Specifically fast or flash pyrolysis results in higher hydroxyacetaldehyde and other carbonyl yields and lower char, benzo[a]pyrene and gas yields. The higher carbonyl yields effects a higher browning index. Further cost efficiencies result from a faster rate of the reaction in fast or flash pyrolysis which permits greater processing efficiencies in that smaller reactor volumes are required to process a given quantity of feedstock. Another object of this invention is to provide a method for preparing a smoke colored and smoke flavored food product by treatment of the food products with the aforementioned liquid smoke solution. Other objects and advantages of the invention will become apparent from the following disclosure and claims. Summary of the Invention The invention comprises a method of making the liquid pyrolysis products from a fast or flash pyrolysis method and using the liquid pyrolysis products in a liquid smoke solution. The liquid smoke solution of the invention is achieved in high yields, i.e. with low char and tar formation. It contains less than 1.0 ppb, and preferably less than 0.5 ppb, of benzo[a]pyrene, a known carcinogen, and has a higher coloring ability than liquid smoke produced by traditional methods. The liquid smoke solution will impart the desired smoked color to meat with milder, less smoky flavor than would be expected from slow pyrolysis liquid smoke solutions. The high ratio of carbonyls (the reactive color forming compounds) to phenols (the flavoring compounds) is indicative of this relatively high coloring ability, low flavor nature of fast pyrolysis liquid smoke solutions. The present invention provides a method of making an aqueous smoke solution for use in foodstuffs comprising heating in the absence of oxygen ground wood or cellulose to between 400-650°C within 1.0 second; maintaining the wood or cellulose together with the pyrolysis products produced from the wood or cellulose between 400-650°C for between 0.03-2.0 seconds; reducing the temperature of the pyrolysis products to below 350°C within 0.6 second to obtain a liquid extract; and isolating the liquid extract. A preferred method of making an aqueous smoke solution for use in foodstuffs comprises heating, in the absence of oxygen, ground wood or cellulose to between 400-650°C within 1.0 second; maintaining the wood or cellulose together with the pyrolysis products produced from the wood or cellulose between 400-650°C for between 0.03-0.60 second; reducing the temperature of the pyrolysis products to below 350°C within 0.6 second to obtain a liquid extract; separating and collecting the liquid extract; diluting the liquid extract with water to achieve a partial phase separation and to obtain an aqueous solution having a benzo[a]pyrene concentration of less than 1.0 ppb, preferably of less than 0.5 ppb, and a browning index to phenols concentration greater than 8.9 to 1 and a ratio of hydroxyacetaldehyde concentration to acetol concentration greater than 5.5 to 1. A further aspect of this invention provides a method of flavoring and coloring an edible food by contacting the food with an aqueous smoke solution produced by fast or flash pyrolysis. Another aspect of the present invention provides a method of making a liquid smoke solution comprising collecting the liquid condensate product obtained by fast or flash pyrolysis of ground wood or cellulose in an oxygen starved atmosphere, without the addition of water; combining one part of the pyrolysis liquid condensate with 0.25-25 parts by weight of water and then separating the resulting non-aqueous phase from the aqueous phase constituting the desired liquid smoke solution. Yet another aspect of the invention provides a method in which sufficient water is added to produce a liquid smoke solution wherein the ratio of the browning index to the phenols concentration is greater than 8.9 to 1. Since fast or flash pyrolysis liquids are produced without the addition of water, unlike conventionally produced liquid smoke solutions, they consist of a single phase. Due to the extremely fast heating rate and short residence time, these solutions are inherently low in benzo[a]pyrene content; however, the levels, while at least of an order of magnitude less than the levels produced by conventional liquid smoke, are still too high for consumption in many countries. Therefore, to reduce the benzo[a]pyrene to less than 0.5 ppb, an addition of water to cause a separation of phases is necessary. Accordingly, the invention comprises the comestible, aqueous soluble fraction of fast pyrolysis products. The use of this particular liquid in the liquid smoke flavoring industry results in a much improved liquid smoke that avoids a number of the shortcomings of the prior art, while at the same time resulting in increased yields and a better quality product. Using fast or flash pyrolysis methods, up to about an 80% by weight yield of liquid products can be realized. Given the right operating parameters, the char yields will be around 6% with the remaining portion of the products being gaseous in nature. The char yields can be reduced to below 1% if desired. Liquid smoke manufactured by fast pyrolysis methods exhibits increased total carbonyls, phenols and acids, and it has a much improved browning index. The total water soluble carbonyls, phenols, acids and browning index of a representative sample of commercial liquid smoke and products according to the invention from two fast pyrolysis methods are set out in Table 1 below. ANALYSIS OF WATER SOLUBLE LIQUIDS Sample Source Yields From Wood Total Carbonyls (% w/w) Total Phenols (% w/w) Total Acids (% w/w) Browning Index Units/100g bone dry wood 1. Fluidized Bed (500° C, 0.5 s) 22.2 1.6 6.9 2877 2. Rapid Thermal Processing (600°C, 0.2 s) 20.7-26.0 1.3-2.0 6.2-7.3 2390-3400 3. Commercial Liquid Smoke 6.0 0.7 5.3 518 % w/w/ - % by weight of product yield from dry wood feedstock as measured in water soluble fraction As can be noted from Table 1, the yield of carbonyls is approximately three times better using liquids manufactured by a fast pyrolysis method over commercial liquid smoke, while the yield of phenols has more than doubled the yield of acids has been improved, and the browning index is about six times better. The level of benzo[a]pyrene, in the fast pyrolysis liquids before dilution and phase separation is at least an order of magnitude lower than liquids produced by known commercial processes. This lower level of benzo[a]pyrene allows a more concentrated product to be produced. The total condensate from conventional pyrolysis contains approximately 750 ppb of benzo[a]pyrene. The level of benzo[a]pyrene in the total condensate from fast pyrolysis is between 5-50 ppb. With fast pyrolysis, after dilution and phase separation, the ratio of carbonyls to phenols is higher, which is indicative of the high browning potential relative to the amount of flavor. In addition, the undesirable by-product yields of gas and solid char are lower and the corresponding disposal costs are lower. Unconcentrated commercial liquid smoke has a browning index between 3.0-13. While methods are available for concentrating liquid smoke to achieve a browning index of up to 25, unconcentrated liquid smoke has a practical upper limit of about 13 as the benzo[a]pyrene levels become excessive if the liquid smoke is permitted to continue to concentrate above this level in the water collection bath. Through the use of fast pyrolysis methods browning indexes of up to 45 can be achieved without using any concentration steps and with levels of benzo[a]pyrenes below 0.5 ppb. The presence of hydroxyacetaldehyde is useful as an index to rate the value of the liquid for smoke coloring applications. The yield of this compound by fast or flash pyrolysis methods increases with a decrease in temperature from 900 to about 500°C and a decrease in residence time. Yields of hydroxyacetaldehyde in excess of 8% by mass can be obtained at reaction temperatures of 550 or 600°C and 100 millisecond vapor residence time. The yield of hydroxyacetaldehyde is much greater from fast pyrolysis methods. A comparison of yields of hydroxyacetaldehyde from two fast pyrolysis methods and commercial liquid smoke is set out in Table 2. As can be noted, yields up to about four times higher are achieved using fast pyrolysis. Hydroxyacetaldehyde is one of the predominant carbonyls in wood pyrolysis liquids and is therefore used as an index to assess a liquid's potential for liquid smoke applications. CHEMICAL ANALYSIS OF THE PYROLYSIS LIQUIDS (Hydroxyacetaldehyde Yields) Sample Source Hydroxyacetaldehyde Yield (% w/w) 1. Fluidized Bed (450 to 550°C, 0.5 s) 7.5 to 8.5 2. Rapid Thermal Processing (550 to 700°C, 0.2 s) 7.0 to 8.0 3. Commercial Liquid Smoke less than 2 Hydroxyacetaldehyde (glycoaldehyde) and acetol (1-hydroxy-2-propanone) are the two predominant carbonyls in pyrolysis liquids. Hydroxyacetaldehyde is much more reactive in terms of browning and its presence is an excellent indication of the browning ability of the liquid. Acetol is a poor browner. The ratio of hydroxyacetaldehyde to acetol can therefore be used as an index of the effectiveness of the carbonyls in the liquids with respect to browning ability. Analyses show that the ratio of hydroxyacetaldehyde to acetol in conventional liquid smoke is typically less than 1.0. However, the average ratio (4 samples) of hydroxyacetaldehyde/acetol in fast pyrolysis liquids is about 6 (5.9) while the maximum measured ratio is 7.2. In effect, not only are more carbonyls produced during fast pyrolysis (i.e. higher yields), but the carbonyls that are produced are more effective browning agents. The parameters that should be optimized in any fast pyrolysis method to produce a suitable liquid product for use as liquid smoke, include: 1) high heating rates of the wood feedstock (greater than 1,000°C per second); 2) a vapor residence time (i.e. the average time that the gas/vapor phase remains in the reactor) greater than 0.15 second and less than 1.0 second and preferably less than 0.6 second; 3) isothermal reaction reactor temperatures between 400-800°C; and 4) quenching of the liquid/vapor product to a temperature of less than 300°C in less than 0.6 second in order to preserve the high liquid yields. When vacuum pyrolysis apparatus is used, the heating rate of the wood or cellulose is much slower than with rapid thermal processing apparatus or with a fluidized bed reactor. Secondary pyrolysis reactions, however, are reduced by quickly removing and cooling the primary pyrolysis vapors. As such, the fast heating rate is not essential as long as the secondary reactions are limited. The major components of the fast pyrolysis process are designed to achieve a very high temperature within a minimum amount of time as well as having a relatively short residence time at that temperature to effect pyrolysis of the wood or cellulose. This short residence time at high temperature has been achieved by a number of systems. One method is a vacuum pyrolysis process that is based on the principle that primary products can be withdrawn from the reactor under vacuum conditions before they have a chance to react further and produce secondary pyrolysis products. This method has been described in Fundamentals of Thermo-Chemical Biomass Conversion , R.P. Overend et al (editors) Elsevier publishers, (1985) in an article entitled "Pyrolysis under Vacuum of Aspen Poplar" by Christian Roy, Bruno de Caumia, Dominique Brouillard and Hughes Menard, the contents of which are incorporated herein by reference. The solid wood feedstock remains in the reactor until completely reacted. Total liquid yields of between 68-74% by weight of the mass of the total wood feedstock have been reported at reaction temperatures of 450°C and a solid heating rate of 10°C/min. and a residence time of up to 2 seconds. At a vapor residence time of about 2.0 seconds the char yields were between 16-20% by weight of the mass of the wood feed material. A second method for obtaining fast pyrolysis is "flash" pyrolysis, using a fluidized bed reactor system operating at temperatures between 400-650°C. Total liquid yields of between 60-70% of the wood feed stock have been obtained with an average vapor residence time of 0.5 second. The char yield was typically between 10-20% of the wood mass. Residence times of up to 3.0 seconds can be achieved. See "Production of Liquids from Biomass by Continuous Fast Pyrolysis" in Bioenergy 84 vol. 3, Biomass Conversion ; D.S. Scott and J. Piskorz, the contents of which are incorporated herein by reference. A third method is a fast pyrolysis process which uses hot particulate solids and/or inert gases to rapidly transfer heat to the carbonaceous feedstocks in a reactor system (Rapid Thermal Processing). This results in very high gas or liquid yields from biomass depending upon the reactor conditions. Char yields are from 0-6% depending upon the feedstock, reactor temperature and residence time. Maximum gas yields are 90% of the feed stock mass at 900°C and maximum liquid yields are 85% of the feed stock mass at 600-650°C. This apparatus can be operated between 350-1000°C with residence times between 0.030-3.0 seconds. A rapid thermal processing apparatus is described in "Characterization Of Solids Mixing In An Ultra-Rapid Fluidized Reactor", by Berg, et al., presented at the Powder and Bulk Solids Conference, Rosemont, Illinois, May 12-15, 1986. Each of these fast pyrolysis methods offer much improved yields and improved quality of the liquid product and gaseous products where applicable, over conventional pyrolysis systems. Brief Description of the Drawings Details of embodiments of the invention are described by reference to the accompanying drawings. Fig. 1 is a schematic representation of one fast pyrolysis flow system known as rapid thermal processing. Fig. 2 is a top plan view of the reactor of the pyrolysis apparatus of Fig. 1. Fig. 3 is a section view on the line III-III of Figure 2. Fig. 4 is a graph of product yields by mass percent as a function of residence time in milliseconds. Fig. 5 is a graph of yields of hydroxyacetaldehyde as a function of reactor temperature. Fig. 6 is a graph of hydroxyacetaldehyde yields as a function of residence time at different temperatures. Detailed Description of Preferred Embodiments In the following description the corresponding elements as shown in each figure of the drawings are given the same reference number. While in the accompanying drawings and description, reference is made to the Rapid Thermal Processing method, similar products can be achieved using the vacuum and flash pyrolysis systems as well as other systems that result in a high temperature with a limited residence time. The major components of the rapid thermal process are illustrated in Figure 1. Rapid mixing and heat transfer are carried out in two vessels. The first vessel (1) or thermal mixer allows heat to be transferred to the wood from hot particulate solids or inert gas which can consist of gaseous nitrogen, suspended particulate solids, or a combination of the two. The second vessel (2), the quencher, allows fast quenching of the products to reduce secondary reactions of the initial pyrolysis products. As shown in Figures 2 and 3 the thermal mixer (1) has opposing converging inlets (3) for the solid heat carrier. This system effectively destroys the radial momentum of the heat carrier causing severe turbulence. Powdered wood feedstocks are then injected from the top of the thermal mixer (1) through a cooled tube (4) into the turbulent region where mixing occurs within 30 milliseconds. After heating and mixing occurs, the wood or cellulose and the primary pyrolysis vapors are maintained at the reaction temperature for between 0.03 and 2.0 seconds depending upon the desired products. The primary pyrolysis vapors are produced as soon as the wood or cellulose is sufficiently heated to start the pyrolysis reactions. The hot gaseous product is rapidly cooled (i.e. less than 30 milliseconds) by the injection of a single tangential stream of cryogenic nitrogen (5). Mechanical table feeders are used to supply wood to the reactor system. The solids pass from sealed hoppers (6) (which have a sufficient inventory of wood or particulate solids) through a double funnel system and are thereby metered onto a rotating table. Two fixed armatures sit near the surface of the rotating table and plough the solids off the outer circumference. From the table, the solids then fall into a conical chamber where they are picked up and carried into the transport line by nitrogen carrier gas. The overall range of the feed rate of biomass or particulate solids is controlled by setting the gap between the lower funnel and the table. Precise control is exercised by the rotation speed of the table. When particulate solids are required to supply the process heat, the feeders (7) send hot particulate solids through a non-mechanical high temperature valve which operates at the reaction temperature. These hot solids are then sent on to the thermal mixer (1). The solid particulate carbonaceous feedstock (or atomized carbonaceous liquids) is then injected axially into the reactor (1) through a water or air cooled tube (4) into the turbulent region where effective mixing and rapid heating to at least 400°C occurs within 0.10 second, and preferably within 0.03 second. The fast pyrolysis of wood is initiated in the thermal mixer (1) and continues in a transport reactor (9). The transport reactor is a length of pipe which is housed in an electrical oven (10). The mixture of hot gases and biomass passes from the thermal mixer (1), through the transport reactor (9), to the quencher (2) and to the solids separator (23). With the manipulation of the reactor volume and by manipulating heat carrier/biomass flow-rates, the residence time can be varied between 0.03-3.0 seconds. Reactor temperatures can be set in the range of 400-1000°C. Preferable reactor temperatures are between 400-800°C and more preferably between 500-600°C. The heating rate that can be achieved with this apparatus is over 10,000°C per second. An efficient cyclonic condensor (25) is used to increase the yield of recovered liquid products. In addition, an electrostatic precipitator (24) can be integrated into a downstream gas line to recover additional liquid products. Even though only the Rapid Thermal Processing apparatus is described herein, the invention defined by the following claims is intended to cover any use of the products of a fast pyrolysis method as liquid smoke flavoring. The wood feedstock can be any suitable wood product, but is preferably red maple. The feedstock should be ground to a fine 100-500 µm powder and then dried prior to use as the pyrolysis feedstock. After collection of the condensates, water is added to cause phase separation to reduce benzo[a]pyrene and tars. The amount of water added beyond that necessary to achieve effective phase separation is a matter of choice. The more water added, the greater the precipitation of higher molecular weight components. Water can be added beyond the phase separation to any desired degree to achieve a desired browning index level. In application to wieners, solutions with browning indexes down to about 3 are useful in producing a desirable smoke flavored and colored product. In some markets where browner, heavily smoked products are preferred, solutions of aqueous smoke flavorings with browning indexes of at least 20 are routinely used. Where atomization is the preferred method of application, it is sometimes difficult to obtain sufficient smoke coloration on meats. In these situations smoke flavoring solutions with browning indexes ranging up to 30 are of use. The amount of water added to the condensates of the instant invention to produce a solution suitable for application to meats or other foods is a function of the effect sought by the processor. Commercially available liquid smoke has browning indexes ranging from a browning index minimum of 3 to a practical upper limit of about 30. This upper limit is a result of the limitations of prior methods of producing liquid smoke. The prior methods generally collect the water soluble condensation in a water bath and it is desired to keep the browning index below 13 to reduce the benzo[a]pyrene concentration. A browning index of above 13 is then achieved by concentration. The result is that it becomes increasingly difficult and expensive to produce a liquid smoke leaving a browning index above 13. The difficulty and expense of concentration sets a practical upper limit of 30 as opposed to a limit beyond which solutions are not useful. On the contrary, if solutions were readily available with browning indexes of 30 or more they would be of particular use in atomization or as a starting material for application to casings as in U.S. Patent 4,504,501. By adding little or no water to condensates of the instant invention, very high browning index solutions can be produced without need or expense of further concentration. EXAMPLE 1 A general summary of the results of fast pyrolysis conducted using rapid thermal process apparatus between 650-800°C using red maple feedstock and nitrogen as the heat carrier using the rapid thermal apparatus is given in Table 3. The apparatus used for these results was rated at 300 g of feedstock per hour. The yields for char and gas represent direct measurements and those for the liquids are by difference. These liquid yield values, however, are very close to the actual liquid yields as verified by the mass balances. All mass percent yields in Table 3 are expressed on a bone dry feedstock basis. It is clear from the results that the char yields are significantly lower and that the liquid yields are significantly higher than the corresponding yields from conventional slow pyrolysis processes. SUMMARY OF THE RED MAPLE PYROLYSIS MASS BALANCE EXPERIMENTS Run number Temp (C) Res Time (ms) Gas Yield (%) Condenser Liquids (%) Remaining Liquids (%) Char (%) Total Recovery (%) RA-21 650 234 24.18 --- 70.52 5.97 100.67 RA-22 650 217 22.87 --- 67.89 5.96 96.72 RA-24 650 392 23.69 22.18 42.00 7.79 95.67 RA-25 650 194 19.83 19.69 45.75 9.69 94.96 RA-26 650 1052 33.47 31.34 27.51 6.61 98.92 RA-1 700 110 29.18 16.91 45.65 3.50 95.24 RA-2 700 152 31.95 17.03 38.74 3.93 91.65 RA-3 700 241 35.64 15.18 43.01 4.18 98.01 RA-5 700 338 40.87 12.87 41.32 2.64 97.71 RA-6 700 339 43.60 18.05 32.2 2.62 96.48 RA-7 700 151 39.56 16.47 40.29 2.29 98.62 RA-8 700 69 25.62 19.89 48.32 4.21 98.04 RA-9 700 226 30.98 16.10 44.39 4.79 96.30 RA-19 700 68 21.79 ---- 72.11 1.42 95.32 RA-27 700 718 43.73 19.73 28.91 3.88 96.24 RA-10 750 351 53.88 13.76 15.48 3.75 86.88 RA-11 750 150 43.25 14.25 39.38 3.00 99.88 RA-12 750 74 39.29 17.85 36.92 2.75 96.81 RA-13 750 71 39.55 13.84 40.20 2.16 95.75 RA-14 750 153 43.14 15.07 33.98 3.11 95.17 RA-15 750 348 54.02 19.0 19.36 4.30 96.68 RA-16 800 329 58.22 9.80 31.59 4.03 103.6 RA-17 800 160 56.06 ---- 37.17 3.72 96.95 RA-18 800 76 41.81 ---- 52.19 1.68 95.69 *Note: - Where condenser liquids are not shown (value not recorded), remaining liquids represents entire liquid sample - These results are on an "as fed" basis. EXAMPLE 2 RAPID THERMAL PROCESS APPARATUS OPERATION AND RESULTS Operating Parameters : Experiments were conducted using poplar wood ground to about 300 · 10⁻⁶ m (300 microns). Wood moisture was about 1% (wet basis). Wood was fed at a rate in the range of 3-5 kg/h. Reaction temperatures were in the range of 400-650°C. Vapor residence times were typically in the range of 600-1200 milliseconds (ms). The heat carrier consisted of silica sand with a mean particle size of about 150 · 10⁻⁶ m (150 microns) and transported by inert nitrogen gas. Equipment and Operating Procedure : Rapid thermal processing apparatus of the type shown in Figures 1, 2 and 3, using hot particulate sand as the heat source, was employed to produce liquid smoke. The apparatus is nominally rated at 5 kilograms of feedstock per hour. Three heat carrier feeders are used to heat up the sand heat carrier and deliver it to the transport lines. Each feeder is about 1.2 meters long and 150 mm outside diameter, and can hold 30 kg of silica sand. The maximum feed rate is about 60 kg per hours (for each feeder) and the maximum temperature of the heat carrier is 1100°C. Feeder control is accomplished via a sparger tube and non-mechanical, high temperature "J" valve. The poplar wood is air dried, milled and classified to a mean particle size of about 300 · 10⁻⁶ m (300 microns). It is then oven dried prior to loading into the biomass feeder. The biomass feeder has an inventory ob about 4 kg. Feed rates can be varied from 0-10 kg per hour, and are independent of the transport gas flow rate and the solid carrier flow rate. The wood feed material is delivered from the "biomass feeder" to the top of the reactor where it is injected into the cloud of turbulent hot solids. Extremely rapid heating of the feed material is achieved as the feedstock and hot sand particles are quickly and thoroughly mixed. After the fast, intimate mixing is complete, the feedstock and solid heat carrier pass through a tubular transport reactor whose length is adjusted to control the processing residence time. The reactor system consists of a rapid thermal mixer and two lengths of transport reactor. Each of these components is housed in its own oven with independent temperature control. Rapid mixing of the feedstocks with the solid heat carrier (i.e. sand) placed in the rapid thermal mixer is effected, and chemical reactions are then allowed to proceed in the transport reactor sections. The first reactor is 1.2 m in length while the second is 0.6 m. The reactor system components are constructed of Sch 40 Inconel 601 (40 mm I.D./1.5" nominal). The products are rapidly cooled in the transfer line after the hot solids (char/sand) are removed in a solids "catch pot" or drop-out vessel. Additional cooling is carried out in the primary (water-cooled) and secondary (dry ice/acetone-cooled) condensers, where condensation of vapors and recovery of liquids also occur. The solids catch pot is an inertial separator constructed of stainless steel which can hold about 100 kg of hot solids. Separation of the gases from the solids is based on the lower momentum of the gas/vapor product (compared to the hot sand) which can change direction more readily than the solids, and escape into the transfer line to be quenched directly with nitrogen gas. The primary condenser is a water-jacketed carbon steel pipe (having both an inner and outer water-jacket) which is lined with a chemical resistant paint. The cooling water enters at about 19°C and cools the product to about 35°C. The secondary condenser is also a lined carbon-steel pipe which is not jacketed but sits directly in an insulated acetone/dry ice bath. It has a tangential gas/vapor inlet which forces the products to the condenser wall where efficient heat transfer can occur. The secondary unit yields a gas exit temperature of about -5°C. Parallel filters are used to collect persistent aerosols, and the clean gas is then directed through an orifice meter to quantify the flow for mass balance closure. A fractional quantity of the product gas is continuously "bled" from the main stream to a gas sample bag for subsequent analyses. The three parallel filters are constructed of stainless steel, have a pore size of 0.5 · 10⁻⁶ m (0.5 micron) and are housed in a single filter vessel. Each of these units are about 50 mm in diameter (outside) and about 0.5 m long. After a run, the condenser, filters and transport lines are washed with acetone, the solution is filtered, and the acetone is evaporated under vacuum to yield the liquid product. Char is determined by ashing several representative samples of the char/sand mixture which is recovered from the solids separator. Gases are analyzed by standard gas chromatography techniques. The results of several typical runs are illustrated in Table 4. SUMMARY OF POPLAR WOOD PYROLYSIS MASS BALANCE EXPERIMENTS RUN NUMBER TEMP. (°C) TIME (ms) PRODUCT YIELDS (% of wood feed) Gas Liquid Char 9 660 800 32.9 60.3 6.8 10 525 835 14.9 78.0 7.0 11 465 1215 7.0 86.0 7.0 12 590 960 20.5 71.8 7.7 EXAMPLE 3 FLUIDIZED BED OPERATION AND RESULTS FLUIDIZED BED OPERATION: Operating Parameters : Experiments were conducted using poplar wood ground to 595 · 10⁻⁶ m (595 microns) (30 mesh). Wood moisture was about 6% (wet basis). Wood was fed at a rate of 1-2.5 kg/h. Reaction temperatures (in the bed) were in the range of 400-650°C. Vapor residence times were typically in the range of 500-700 milliseconds (ms). The fluidized bed consisted of silica sand with a mean particle size of about 720.10⁻⁶m (720 microns). Recycled produce gas (primarily CO, CO₂ and CH₄) was used to fluidize the sand and to transport the wood feedstock into the reactor. Equipment and Operating Procedure : Poplar wood (or other wood species, straw or peat) is air dried, milled and screened to 595 · 10⁻⁶ m (595 micron) particle size. The prepared wood is conveyed from a hopper into a variable speed twin-screw feeder and discharged into a flow of recycled product gas. It is then conveyed directly into the fluidized bed region of the fluidized bed reactor. The reactor bed consists of highly spherical Ottawa silica sand with a mean particle size of about 720 · 10⁻⁶ m (720 micron). The fluidizing gas (primarily CO, CO₂ and CH₄) is preheated in the inlet line by electrical heaters and enters the bed through a porous stainless steel plate at a rate which is equivalent to 1.2-2 times the minimum fluidization velocity. The reactor is wrapped with heating coils for supplemental heating. Pyrolysis products and the recycle gases are swept from the top of the reactor into a cyclone where the dry char is removed from the gas/vapor phase. The gases and vapors are then passed to two condensers and then to a series of filters. The first condenser is normally operated at 20°C while the second is maintained at about 0°C. The filter train consists of an in-line 5 · 10⁻⁶ m (5 micron) mesh screen followed by a filter vessel packed with glass wool. After a run, the condensers are washed with acetone, the solution is filtered, and the acetone is evaporated under vacuum to yield the liquid product. The filters are weighed before and after an experiment and the contents are recovered if the quantity is significant. Char is collected in the char pot (at the cyclone exit) and weighed. Gases are analyzed by standard gas chromatography techniques. The results of several runs over a temperature range of 425-625°C are illustrated in Table 5. FLUIDIZED BED RESULTS: RAPID PYROLYSIS OF POPLAR WOOD TEMP. (°C) RES. TIME (ms) PRODUCT YIELDS (% of wood feed) TOTAL RECOVERY % Gas Liquid Char 425 616 6.0 59.6 (55.9) 30.5 96 450 689 8.6 61.1 (55.8) 25.5 95 465 584 8.6 72.7 (67.2) 18.9 100 500 550 12.5 75.1 (65.8) 12.2 100 500 550 12.1 77.8 (71.2) 11.2 101 500 600 11.9 70.1 (65.8) 13.2 95 541 539 21.2 71.1 (63.7) 9.0 101 541 539 19.1 69.8 (62.1) 9.7 99 550 555 18.6 67.3 (62.0) 10.6 96 625 520 36.7 44.4 (40.3) 7.8 99 The values in parentheses are total organic liquids (i.e. moisture-free). The difference is moisture (water) in the liquid sample. Similar experiments have been conducted with maple and spruce with similar overall yields of char, gas and liquid. As is apparent from the data in Tables 3, 4 and 5, the preferred operating temperature is at the lower ranges with a relatively short residence time of 300-600 milliseconds. However, good yields are achieved throughout the operating range of the rapid thermal processing equipment and over a variety of residence times. As shown in Figure 4, the shorter the residence time that can be achieved, the higher the yields of the preferred liquid product. As noted above, the yield of hydroxyacetaldehyde is a good indication of the browning ability of the liquid smoke. Yields of this compound versus reactor temperature and residence time are set out in Figures 5 and 6. Figure 5 is a graph of hydroxyacetaldehyde yields of the fast pyrolysis of wood against temperature. Figure 5 confirms that the optimum reaction temperatures are between 500-600°C. Figure 6 also confirms that the optimum conditions are between 500-600°C with a short residence time. EXAMPLE 4 A sample of the fluidized bed reactor liquid pyrolysate referred to in Example 3 was diluted with water according to the following proportions. The water soluble fraction was separated and analyzed. DILUTIONS OF FAST PYROLYSIS LIQUIDS Weight % fast pyrolysis liquids in total solution Acids (% w/w) Phenols (% w/w) Carbonyls (% w/w) Browning Index Units Specific Gravity @ 21°C Benzo[a]pyrene ppb 100 10.5 5.50 32.5 49.0 1.245 19.0 85 9.1 3.75 29.2 46.8 1.201 14.0 80 8.7 3.31 26.6 45.6 1.182 3.6 70 7.9 2.42 21.4 35.8 1.148 0.5 65 7.5 2.10 20.2 33.8 1.120 <0.5 60 6.5 1.65 17.5 31.5 1.112 <0.5 40 4.1 0.820 10.3 18.2 1.065 <0.5 20 2.8 0.430 5.4 12.2 1.028 <0.5 10 1.3 0.230 4.9 5.6 1.011 <0.5 These results are indicative of the advantage to adding sufficient water to cause enough phase separation to reduce the benzopyrene content to less than 0.5 ppb. As can be seen from the following Tables 7 and 8, the resulting solutions have substantially higher carbonyl concentration to phenols concentration and browning index to phenols concentration, ratios than commercially available solutions produced by slow pyrolysis processes. RATIO OF CARBONYL AND BROWNING INDEX TO PHENOLS Weight % of fast pyrolysis liquids in total solution Browning index Carbonyls/phenols Browning index/phenols 100 49.0 5.90 8.91 85 46.8 7.79 12.5 80 45.6 8.04 13.8 70 35.8 8.84 14.8 65 33.8 9.62 16.1 60 31.5 10.6 19.1 40 18.2 12.6 22.2 AVERAGE OF TEN REPRESENTATIVE RATIOS FROM SLOW PYROLYSIS LIQUID SMOKE SOLUTIONS Acid Concentration % w/w Browning index Carbonyls/phenols Browning index/phenols 11.5 9.8 6.47 5.76 6.2 5.3 7.78 6.17 As seen in both Tables 7 and 8 the ratios are higher in more dilute solutions. This is because the solubility of carbonyls is the same regardless of concentration while phenols are less soluble in more dilute solutions. Thus, the advantage of water addition to fast pyrolysis serves to reduce phenols thereby reducing flavor while maintaining a high browning potential, and to reduce benzo[a]pyrene solubility to less than 0.5 ppb. As can be seen by comparing the data in Tables 7 and 8, at an equivalent browning index, the ratios of carbonyls to phenols, and browning index to phenols, is significantly greater with fast pyrolysis liquids than with conventional liquid smoke. The higher ratio with fast pyrolysis liquids results in a darker product at a given flavor level. This permits coloring of food with a less smoky flavor or alternatively to achieve a darker product at comparable flavor intensities. The lowest browning index used for smoking meat is about 3.0. This browning index would be used for direct application to foodstuffs. Based on the above results the fast pyrolysis product could be diluted to about a 6.1% w/w solution and still have a browning index above 3.0 EXAMPLE 5 RESULTS OF THE APPLICATION OF FAST PYROLYSIS LIQUIDS TO WIENERS 1. Color/Browning Test Panel About 2.5 lb. strands of skinless wieners obtained from Cher-Make Sausage Co. (Manitowoc, WI) were dipped for 60 seconds in the following: A. Water (control) B. A 10% (W/W) Solution of Fast Pyrolysis Liquids (Fluidized Bed) The wieners were cooked to an internal temperature of 70°C according to the following schedule: 43.3°C for 10 minutes 60.0°C for 45 minutes 71.1°C for 25 minutes 82.2°C until the internal temp. was 70°C After cooking, the wieners were placed in a 4.4°C cooler overnight for subsequent evaluation and testing. The following day the wieners were peeled and a panel of nine observers were asked to indicate which set had the most appealing brown color. All nine indicated that sample B was noticeably browner than the water dipped control (and therefore more appealing). The results are indicative of the ability of the aqueous solutions of fast pyrolysis liquids to react with meat surfaces to give a desirable smoked appearance. 2. Taste Comparison Test Panel About 2.5 lb. strands of skinless wieners obtained from Cher-Make Sausage Co. (Manitowoc, WI) were dipped for 60 seconds in the following: A. A 10% (W/W) solution of Fast Pyrolysis Liquids (Fluidized Bed) B. A solution of slow pyrolysis liquid smoke made according to U.S. Patent 3,106,473, the browning index of which was 3.9. The wieners were cooked to an internal temperature of 70°C according to the following schedule: 43.3° for 10 minutes 60.0°C for 45 minutes 71.1°C for 25 minutes 82.2°C until the internal temp. was 70°C. The following day a panel of nine were asked to taste the wieners which had been peeled and warmed to 49°C. A triangular method (i.e. using three samples, two of the same treatment and one of the other) was used to determine whether the panelists could distinguish between the two treatments. The results indicated that only one of the nine panel members could determine a difference between aqueous solutions of fast pyrolysis liquids and conventional smoke flavorings when applied to the wieners. This is not statistically significant and the usefulness of the former for smoking meats is indicated.

Claims: A method of making an aqueous smoke solution for use in foodstuffs comprising: a) heating in the absence of oxygen ground wood or cellulose to between 400 and 650°C within 1.0 second; b) maintaining the wood or cellulose together with the pyrolysis products produced from the wood or cellulose between 400 and 650°C for between 0.03 and 2.0 seconds; c) reducing the temperature of the pyrolysis products to below 350°C within 0.6 seconds to obtain a liquid extract; and d) isolating the liquid extract. A method of claim 1, wherein the wood or cellulose and the pyrolysis products are maintained between 400 and 650°C for between 0.03 and 0.6 seconds. A method according to any of claims 1 and 2, wherein the liquid extract has a ratio of hydroxyacetaldehyde concentration to acetol concentration greater than 5.5 to 1. A method according to any of the preceding claims, wherein the liquid extract has a ratio of browning index to phenols concentration greater than 8.9 to 1. A method according to claim 2, wherein the liquid extract obtained is separated, collected and diluted with water to achieve a partial phase separation and to obtain an aqueous solution having a benzo[a]pyrene concentration of less than 1.0 ppb, a ratio of browning index to phenols concentration greater than 8.9 to 1 and a ratio of hydroxyacetaldehyde concentration to acetol concentration greater than 5.5 to 1. A fast pyrolysis liquid smoke solution comprising an aqueous solution obtained by a method according to any of the preceding claims having a benzo[a]pyrene concentration of less than 0.5 ppb. A method of flavoring and coloring edible food which comprises: a) heating in the absence of oxygen ground wood or cellulose to at least 400°C within 1.0 second; b) maintaining the wood or cellulose and the pyrolysis products produced from the wood or cellulose at a temperature of at least 400°C for between 0.03 and 2.0 seconds; c) reducing the temperature of the pyrolysis products to at least 300°C within 0.6 seconds to obtain a liquid extract; d) isolating the liquid extract; and e) contacting the food with the liquid extract. A method according to claim 7, wherein the liquid extract has a benzo[a]pyrene concentration of less than 0.5 ppb. An edible food product comprising a proteinaceous food substrate flavored with a liquid extract made by a method according to any of claims 1 to 4. An edible food product of claim 9, wherein the food substrate is selected from meat, poultry or fish.

Inventors: GRAHAM ROBERT GEORGE, UNDERWOOD GARY, GRAHAM, ROBERT GEORGE, UNDERWOOD, GARY
Applicants: ENSYN ENG ASS, ENSYN ENGINEERING ASSOCIATES INC.
Application year: 1989
Main classification: A23L1
IPC codes: A23L1, C07C45, A23B4