FI88453C - Procedure for selectively removing basic substances - Google Patents

Abstract

A process is provided for the selective removal of basic materials from plant products, in particular, for removing nicotine from tobacco without materially affecting the content of the other components of the tobacco. Tobacco is traversed with a solvent in the supercritical state or in the liquid state wherein nicotine and the other components dissolve in the solvent. The solvent is then passed through an acid-containing trap where the solvent is essentially freed of nicotine. The solvent, depleted of nicotine and enriched in the other components, is then recycled to the tobacco to reextract nicotine. In addition, the tobacco may be pretreated with a chemical base which does not substantially react withe the tobacco components under ambient conditions but rather is activated under the conditions of the extraction process. Pretreatment of the tobacco with a chemical base neutralizes nicotine salts and permits the extraction process to be carried out under milder conditions.

Description

! 88453

Method for the selective removal of alkaline substances For the selective removal of basic substances

The invention relates to extraction methods, and more particularly to a method for the selective removal of basic substances from plant products. The invention can be used for the selective extraction of specific substances from a wide variety of plant products. However, it is particularly well suited for the extraction of nicotine from tobacco, in connection with which it is thus described.

Numerous methods for removing nicotine from tobacco have been proposed in the art. However, most of these methods are not sufficiently selective for nicotine, and these methods also remove other ingredients from tobacco. The removal of these other ingredients adversely affects the desired flavor aroma properties of the tobacco. Other methods have generally been found to be limited in scope and effectiveness, and are often complex and expensive to implement.

Nicotine is extracted from tobacco using organic solvents, and the nicotine salt with or without neutralization.

Examples of such processes are those described in U.S. Patent Nos. 678,362 (Froehling), 1,196,184 (Villiers-Stuart), 2,048,624 (Roselius), 2,128,043 (Garner), 2,227,863 (Rhodes) and 3,096,773 (Prilly et al.). Nicotine has also been extracted from tobacco with aqueous solutions with or without neutralization of the nicotine salt. As examples. such processes include those described in U.S. Patent Nos. 2,822,306 (Beuel et al.), 2,582,075 · * (Severi), and 3,874,392 (De Brunn et al.). Nicotine is:: separated from tobacco extract solutions, and nicotine-free ·; ··; the solvent made is returned to the tobacco. As examples of these .1. processes include those described in U.S. Patent Nos. 283,622 (Liebreich et al.), 802,437 (Wimmer), 2,805 · 667 (von Bethmann), 3,046,997 (Hind) and 3,139,435 (Staley et al. ). Nicotine is also separated from the solution of the tobacco extracts, and the nicotine-free solvent saturated with the other components is recycled back to the extraction tank. Examples of these processes are those described in U.S. Patent Nos. 1,294,310 (Sayre et al.), 1,577,768 (Smith), 1,813,333 (Andrews), 3,396,735 (von Bethmann) and 3,612,066 (Jones). ).

Nicotine is transferred from the tobacco to the substrate without the use of a solvent by bringing the tobacco into close contact with the acid-treated substrate, as disclosed in U.S. Patent 4,215,706 (Larson). This process can be carried out with or without heating.

U.S. Patent No. 4,153,063 (Roselius) describes a method for removing nicotine from tobacco by contacting the tobacco with an extractive solvent in a supercritical state. In a one-step extraction process, moist tobacco is extracted as a supercritical solvent. The solvent is then evaporated. Since in this case also the aroma components are removed from the tobacco in addition to the nicotine, a multi-stage process has been proposed. In a multi-step process, the dry tobacco is extracted in an extraction vessel as a solvent in a supercritical state to remove aroma components. As the solvent expands in the second vessel, it cools to a subcritical state and the aroma components separate. The solvent is then returned to the supercritical state and returned to the extraction vessel, and the above steps are repeated until the flavor components are removed from the tobacco. The gas in the supercritical state is then passed through an aqueous solution of sulfuric acid to humidify the gas and absorb the nicotine. A moist gas in a supercritical state is introduced into an extraction vessel to increase its moisture content to about 20-25% and to extract nicotine from the tobacco. The tobacco and the moist gas in the supercritical state are then dried by lowering the temperature of the gas while continuing to circulate it through the extraction vessel and sulfuric acid solution to transfer water from the gas to this solution. The aroma components separated in the previous step are collected in a gas thus dried in a supercritical state of 3,885,453 to obtain an extract containing aroma components, from which the aroma components are returned to the tobacco by expanding and cooling the extract in a tobacco-containing extraction vessel.

This multi-step extraction process is expensive and time consuming. In addition, prolonged treatment of flavor components may adversely affect their properties.

The present invention provides a method, the characteristic features of which are defined in the appended claims. With the method according to the invention, nicotine can be removed from the tobacco without at the same time removing the desired aroma-generating components. The tobacco is extracted with a solvent that is in either a supercritical state or a liquid state. The nicotine is then selectively removed from the enriched solvent by passing the solvent through a separator containing a non-volatile acid which is insoluble in the extraction solvent. The separator may be combined with a carrier medium. The nicotine-depleted solvent, enriched in other components, is then recycled. to tobacco again to extract nicotine.

Alternatively, the tobacco can be pretreated chemically with a basic (alkaline) compound that does not react significantly with the tobacco components at ambient conditions, but that effectively increases the amount of nicotine extracted under the conditions prevailing in the extraction process. Pretreatment of the tobacco with a basic compound neutralizes the nicotine salts and allows the extraction process to be carried out under milder conditions.

It is an object of the invention to provide a method for selectively lowering nicotine levels in tobacco using a single step extraction process and with or without separate retention tanks.

4 88453

Another object of the invention is to provide a method for transferring nicotine from one tobacco substrate (leaf material or restored leaves) to another tobacco substrate (leaf material, restored leaf material or tobacco stems) or a non-tobacco substrate.

Another object of the invention is to provide a method for transferring flavor and aroma components (with or without nicotine) from one tobacco substrate (leaf material or reconstituted leaves) to another tobacco substrate (leaf material, reconstituted leaf material or tobacco stems) or a non-tobacco substrate.

Another object of the invention is to provide a method for attenuating or removing flavors or aromas.

It is a further object of the invention to provide a process using adsorption media (full aromatic tobacco filler, reconstituted leaf materials, tobacco stems, cotton mold, cellulose, carbon, cocoa shells, other plant by-products, porous ceramic material, porous metal selector, etc.), nicotine removal In order to facilitate.

It is a further object of the invention to provide a method using aqueous adsorption media (water, aqueous acid solution, aqueous salt solution, etc.) which facilitates the selective removal of nicotine.

It is also an object of the invention to provide a method for extracting nicotine from tobacco under relatively mild conditions.

These and other objects and advantages of the invention will be apparent from the following description.

Figure 1 shows an apparatus for removing alkaline materials.

5 88453

Figure 1 shows a preferred apparatus for removing nicotine from tobacco and tobacco blends. The extraction tank 1 is filled with a tobacco sample and the retention tanks 2 and 3 are filled with an acid-saturated carrier medium or water, which preferably contains some acid. The extracting solvent is fed to a tank 1 connected to a pump 4 and to a mass flow meter 5. The pressure in the tank is regulated by a filling pump (not shown) and the temperature is regulated by a heat exchanger 6. The extraction solvent is passed to the top of the extraction tank, passes down through the sample and exits the bottom of the tank. As it passes through the sample, the extracting solvent is enriched with the components of the sample. The solvent is then recycled through one or both of the two separators 2 or 3, re-introduced into the tank from its top, running downwards and leaving the bottom of the tank. The retention time can be divided between separators 2 and 3. As it passes through the separator or separators, the nicotine contained in the solvent reacts with and is retained by the acid, while the other aroma components contained in the solvent pass freely through the separator or separators. The solvent, which has been made nicotine-free and enriched in other components, is then recycled by recycling it back to the extraction tank.

The extraction tank is preferably designed for radial flow or axial flow of solvent. Both retention tanks are preferably designed for radial flow or axial flow, but are not required. . mirror that they are designed in the same way as the extraction tank. The radial flow of solvent results in the least possible condensation of the solid material in the tank and may allow the pressure to drop less ····; in each tank. It will be apparent to those skilled in the art that multi-directional flow is effective, for example - ·· flow from bottom to top, from top to bottom or radially inwards or outwards in each tank. It will also be apparent to those skilled in the art that the pump can be located on any of the many lines in the system.

A particularly advantageous operation makes it possible for the same extraction tank to contain both a tobacco sample and a relatively small volume-retaining material. The material to be retained in this operation is placed in the bottom part of the extraction tank, a porous plate is placed on top of this separator and the tobacco is placed in the extraction tank on said porous plate, the plate carrying the tobacco. Retention tanks 2 and 3 are removed from the flow system by means of valves. The extraction of the tobacco sample is then carried out as before by passing the solvent to the top of the extraction tank and passing it down through the sample until it leaves the bottom of the tank.

One advantage of this method is that it does not require an additional tank for a relatively large amount of adsorption material to separate nicotine. The possibility of extraction in a single tank leads to a more economical method for the reasons mentioned above, and also because the ratio of solvent to tobacco can be significantly reduced. The possibility to use less solvent also leads to less degradation and loss of flavor-producing components, and thus to a better tobacco product.

In another embodiment of the invention, the tobacco may be chemically pretreated with a basic compound that does not react significantly with the tobacco components under ambient conditions, but is activated under the conditions prevailing in the extraction process. Nicotine is thus released from its salts and immediately transferred to the extraction solvent before other base-induced chemical events are triggered in the tobacco. Since the solubility of the free nicotine base is generally greater than the solubility of the nicotine salts in selected extraction solvents, the extraction process can be carried out under milder conditions. The pretreatment may be, for example, spraying or wetting the tobacco with an alkaline component or a suitable solution thereof.

It will be apparent to those skilled in the art that said chemically basic compounds are, for example, those which are not necessarily affected by the process conditions, but which nevertheless effectively increase the amount of nicotine extractable by the process of the invention.

Numerous extraction solvents capable of dissolving nicotine in both the liquid and gas phases can be used to reduce the nicotine content in tobacco. In this invention, the most preferred solvent is carbon dioxide in its supercritical state. Other useful solvents include, for example, halogenated hydrocarbons having up to about 4 carbon atoms, such as CF <, CHFsCCIFs, CBrFs, CFa = CHa, CF3-CF aCF a, CHClFa, CClaFa, CHClaF, CClFs, CBrFs, CFCl = CFa , CH 5 -CFa, octafluorocyclohutane, and hydrocarbons having up to about 5 carbon atoms, such as propane, butane, pantane; other useful solvents include NaO, SF 3 and argon. Mixtures of solvents or additives or co-solvents can be used in the process to obtain better solubilizing properties. In addition, water, ammonia or aqueous ammonia solution can be mixed with the extraction solvent to obtain better dissolving properties. Carbon dioxide is the most preferred solvent because it is a naturally occurring compound and because it leaves no non-tobacco residues in the extracted tobacco.

The solvent in the supercritical state is such a gas phase solvent at a sufficiently high temperature that it cannot be liquefied by increasing the pressure. The solvent in the subcritical state is a solvent that can be liquefied by adding pressure.

· '; Supercritical carbon dioxide is carbon dioxide that has a temperature greater than its critical temperature, i.e., greater than 88453 8 31.3 ° C, and that has a pressure greater than its critical pressure, i.e., greater than about 70 atmospheres. The extraction with carbon dioxide in the supercritical state is carried out at a pressure of about 70 to 1500 atmospheres and at a temperature just above the critical temperature to about 120 ° C. The temperature and weight ranges for the supercritical state of other useful solvents are generally of the same order of magnitude.

The preferred acids used in this invention are non-volatile and insoluble in the extraction solvent under the extraction conditions. Useful acids include sulfuric, phosphoric and nitric acids. Other useful acids include, for example, polycarboxylic acids such as tartaric acid, citric acid, malic acid, malonic acid, succinic acid and glutamic acid. Monovalent salts of the above acids, such as alkali metal salts, are generally preferred because these salts are less volatile and less soluble in the solvent. Monopotassium citric acid is the preferred salt of the acid. The monoammonium and diammonium salts of the above acids can also be used in the process. Polyhydric salts of the above acids are also useful, but are less effective in terms of nicotine separation.

The acid contained in the separator is preferably, but not necessarily, in contact with a support medium which does not impede the flow of solvent. The acid may be impregnated into, applied to, or otherwise in contact with the support medium. Useful support media include carbon, tobacco filler, restored leaf materials, tobacco stems, cotton fabric, cellulose, cocoa shells, other plant by-products, porous ceramic material, porous metal, and the like. Tobacco stems can be long stalks, cut and coiled, torn, swollen, processed or untreated. Particularly preferred carrier media are torn tobacco stems and cocoa shells.

The acid-carrying medium may even be water, as in the case of bubbling the solvent through an aqueous acid solution. The preferred separating material is an aqueous solution of citric acid. A particularly preferred separating material is an aqueous solution of monopotassium citrate.

The ratio of acid to nicotine may range from about 10: 1 to 1: 1, preferably from about 4.5: 1 to 1.5: 1.

The concentration of acid in the carrier medium is not critical. The concentration should be such that the volume of carrier medium required in the container is kept to a minimum, but still so small as not to interfere with the flow of solvent through the carrier medium. The concentration of acid in the carrier medium may vary, but in the case of tobacco stems the content is generally about 5 to 40% by weight, preferably about 15% by weight. Higher concentrations of acid, i.e. saturated or crystalline forms, are not excluded from the invention.

The chemical bases used in the present invention to pretreat tobacco are bases that do not react significantly with the tobacco components at ambient conditions. Chemical bases that react significantly with tobacco components at ambient conditions can initiate base-catalyzed chemical events in tobacco by blackening it or otherwise adversely affecting its burning properties. Rather, the preferred base is a compound that effectively increases the amount of nicotine extracted without unduly increasing the extraction of flavor components.

- ·· Such a base can react with the components of the tobacco under the conditions prevailing during the extraction process. In this way, the nicotine is released from its salts and immediately transferred to the extraction solvent before other chemical events induced by 10,885,43 bases are initiated in the tobacco. Since the solubility of the free nicotine base in the extraction solvent is higher than that of the nicotine salts, the extraction process can be carried out under milder conditions. In this way, the quality of the subjective combustion properties is maintained. Chemical bases which do not react significantly under ambient conditions but which are activated under the conditions prevailing during the extraction process include ammonium bicarbonate, sodium or potassium carbonate or bicarbonate, glycosylamines, N-glycosides of aldoses, N-glycosides of ketoses and other glycosides.

Other chemical bases may also be used in the practice of this invention, such as ammonia, aqueous ammonia, trimethylamine and triethylamine, which are capable of effectively increasing the amount of nicotine extractable under extraction conditions, although some of these compounds may adversely affect the subjective properties of tobacco. In general, bases which release nicotine from its acid salts are effective in carrying out the present invention, and in particular bases having a pK i greater than about 7.2 and less than about 10. Combinations of suitable bases may also be used within the scope of the present invention.

The glycosylamine useful in the present invention can be represented by the following formula:

B

-c-NH,

HO-C-H

0 ao — c_h

| I

HO-C-H

1 -C-H

R

wherein R is hydrogen, a methyl or methylol substituent.

11 d 8 4 5 3

An example of a glycosylamine compound according to the invention is 1-amino-1-deoxyglucose (R = CHaOH). Other glycosylamine compounds which may be mentioned are 1-amino-1-deoxymannose (mannosylamine), 1-amino-1-deoxyribose (ribosylamine), 1-amino-1-deoxygalactose (galactosylamine), 1-amino-1 -deoxyiramnose (rhamnosylamine), 1-amino-1-deoxyfucose (fucosylamine), 1-amino-1-deoxyxylose (xylosylamine), 1-amino-1-deoxyarabinose (arabinosylamine), 1-amino-deoxyloxose (lyxosylamine) ) and the like.

The glycosylamine compounds within the scope of the invention in their pure form are stable and odorless compounds at ambient temperature. In addition, these glycosylamine compounds decompose at a relatively low pyrolysis temperature (e.g., 200-300 ° C), releasing ammonia, pyrazine, and the like.

Ammonia-derived glycosylamines having an unsubstituted amino group (-NH2) are more stable than glycosylamines in which this amino group is substituted (-NHR or NRa). If the amino group has an amino acid structure, then self-catalyzed Amadori rearrangement, i.e. the conversion of the N-glycoside of the aldose sugar to the amine derivative of the corresponding ketose, takes place, in addition to other side reactions at room temperature.

Another preferred embodiment of the invention comprises pretreating the tobacco by spraying it with an aqueous solution of ammonium bicarbonate. Ammonium bicarbonate is useful if it is used in about 1% of the dry weight of the tobacco (w / w) and can be used up to 3% of the dry weight of the tobacco. The resulting tobacco is generally softer than untreated tobacco after extraction.

Neutralization of nicotine salts can also be accomplished by simultaneously adding a source of base during supercritical extraction 12 38453 so that neutralization and extraction of nicotine occur simultaneously and no significant base-induced chemical events are initiated in the tobacco.

In a typical example of the process of the invention, the acid-containing retainer is prepared by impregnating an aqueous solution of an acid, such as mono-potassium citric acid, on a carrier, such as expanded tobacco stems. This retaining material is then placed in an extraction tank, a porous plate is placed on top of the acid-containing retention material, and the tobacco to be extracted is placed on top of this plate. The solvent is introduced into the tank, the pressure is raised to 260 atmospheres and the temperature is raised to 70 ° C.

The extractable tobacco is modified to have an oven volatile content of about 25%. The percentage of volatiles in the oven (% OV) in tobacco is a measure of moisture content and a small proportion of other components and is determined as follows: weight loss of the sample after 3 hours% OV = 100 * C_sample weight The supercritical extractant is then passed through the tobacco. a solvent such as carbon dioxide, and nicotine and other components are soluble in the extraction solvent. The enriched supercritical solvent is then passed through an acid-containing arrester, releasing the solvent from the nicotine. The supercritical solvent, which has been made nicotine-free and enriched in other components, is then recycled back into the tobacco. Flavor-developing components are extracted from the tobacco only during the early stages of the cycle, because the solvent is rapidly saturated with these components. Because nicotine is continuously removed from the solvent, the solvent is able to extract additional amounts of nicotine from the tobacco when it is recycled.

13 38 453

The process is continued until the nicotine level in the tobacco is reduced as desired. Usually 30 to 60 minutes is enough. The advantage of this process is that essentially nicotine is removed from the supercritical solvent while retaining substantially the aroma-generating components therein.

Valves and other instrumentation may be installed so that the equipment allows (a) bypassing the COa flow to each tank, (b) COa flow from the extraction tank to any retaining tank, (c) COa flow both up and down in any tank , (d) shorter maintenance time, (e) use of both large and small COa filling pumps, and (f) pressure drop instrumentation to measure up and down flow pressure differences in containment tanks. In the case of upstream, COa flows in the opposite direction to gravity and in the case of downstream, in the same direction as it.

In order to better preserve the subjective combustion properties of the tobacco, the extraction tank can be bypassed during the CO2 filling and heating cycle, whereby the COa stream is directed only through the retention tanks. After the extraction-to-process conditions have been reached, the CO 2 stream is passed through the extraction tank or tanks. The conditions of the extraction process are reached quickly (in 4-8 minutes). In the experiment using this method, the start of each extraction run was recorded when the process conditions were reached (temperature, pressure) and the end of each run was recorded when the required weight of CO 2 solvent (m / m, mass of extracting solvent / mass of tobacco) had passed through the tobacco. through.

Table 1 illustrates the results obtained in the extraction runs performed using the adsorbent carrier. 'coal.

Full flavor American Blend tobacco with an oven volatile content of 14 38453 (OV) of 25% was extracted for a period of 30 minutes using activated carbon as adsorbent (run-16, Table 1). The nicotine content of the tobacco was reduced by 97.2%. . The aroma of the tobacco was better based on subjective experiments compared to tobacco that had been extracted for longer periods of time.

When potassium citrate-saturated activated carbon was used as the adsorbent carrier, the ratio of carbon to tobacco was significantly reduced from 2: 1 carbon alone to 0.25: 1. The amount of nicotine extracted was slightly lower due to the passage of nicotine through the retention columns. The characteristics of the tobacco (aroma, taste and other burning properties) were very poor (runs -17, -18, Table 1).

In an effort to extract only the characteristic tobacco characteristics, tobacco that had not been pre-wetted was extracted with supercritical carbon dioxide under COA reference conditions (260 atmospheres, 70 ° C, 12% OV, 30 minutes, 150 m / m). In contrast to the published patent literature (U.S. Patent 4,153,063, Roselius), 94.4% of the nicotine was removed from tobacco (Run-21, Table 1).

Table 2 shows the results of extraction runs performed using potassium citrate-treated stems as the adsorbent carrier.

In the experiments shown in Table 2, the best overall results in terms of characteristics were obtained when torn stems were used as the adsorbent carrier, with a weight ratio of stems to tobacco of about 1: 1 and a molar ratio of potassium citrate to nicotine of 8: 1 (run-41, Table 2). The retaining material was divided equally between the two retaining columns. The subjective quality was almost the same as in the unextracted comparison and 93.7% of the nicotine had been removed from the tobacco. An extraction period of one hour was used in the case of a lower CO 2 flow rate to minimize the compression of the stems.

15 38452

Table 2 also shows the following results:

The use of two retention columns results in the elimination of higher amounts of nicotine than the use of a single retention column containing the same amount of retention material.

The retention time divided into 15 and 45 minutes or 20 and 40 minutes in the holding tanks 2 and 3, respectively, is more advantageous than the retention time divided into two 30-minute periods (based on nicotine permeation profiles).

A high ratio of stems to tobacco, for example greater than about 2: 1, results in the "stem-like" property of extracted tobacco.

Drying the stems in advance to obtain the highest possible potassium citrate charge results in a toasted nuance. The use of pre-dried stems produces a more acceptable product.

Removal of as much nicotine as possible from full flavored tobacco requires (1) a high potassium citrate content in the stems, (2) a carrier that adsorbs low background nicotine, and (3) the use of two retention combinations.

Torn stems are the most preferred stem type for the adsorbent carrier. The use of cut and coiled stems is likely to lead to a pressure drop problem and the use of long stems leads to poor nicotine extraction.

Table 3 shows the results of extraction runs using potassium citrate-treated full-flavor, American blended tobacco as the adsorbent carrier.

The characteristic features were judged to be good, but the nicotine removal was poor, about 83-88% (Table 3) due to the large amount of nicotine already present in the adsorbent carrier. Elimination of higher amounts of nicotine is likely to require a significantly higher potassium citrate loading.

Large amounts of components characteristic of full-flavor tobacco were present in the CO 2 at the end of the extraction, as evidenced by the waxy layer on the metal surfaces in the extraction and retention tanks.

Table 4 shows the results of extraction times using non-tobacco adsorbent carriers.

When pure 100% cotton fabric treated with potassium citrate was used to remove nicotine from tobacco, the characteristic features, thin and weak mouthpiece, were not rated as good as in the case of stems treated with potassium citrate (run-27, Table 4).

The use of pure alpha-cellulose treated with potassium citrate resulted in poor removal of nicotine from tobacco, probably due to the uneven distribution of potassium citrate in the cellulose carrier. Characteristic features were assessed as unsatisfactory, bitter green, dry, and hard (run-32, Table 4).

The use of cocoa shells as an adsorbent carrier resulted in a 96.9% removal of nicotine using a single retaining column. Characteristic features were judged to be acceptable, tobacco-like, slightly burnt, and sweet without mouth-watering (run-30, Table 4).

The use of cocoa shells as an adsorbent carrier also makes it possible to transfer the desired flavors from one natural substrate (cocoa shells) to another substrate (tobacco). The desired flavors can also be transferred from the Burley tobacco to the carrier formed by the expanded stems.

17 38453

Table 5 shows the results of extraction runs performed using unwashed, coarsely torn stems, unwashed, finely torn stems, and washed, finely torn stems as the adsorbent carrier.

The combinations of stem type and torn stem particle size were used to test the extraction efficiency and product quality. The best extraction efficiency was achieved with washed, finely torn Bright stems.

Table 6 shows the results of numerous extraction runs performed using washed, finely torn Bright stems.

More than 96% extraction of nicotine was achieved, but the subjective burning properties of the product were judged to be moderate.

Table 7 shows the results of extraction runs performed using pretreatment of tobacco filler with 2% ammonium bicarbonate.

The following variables were tested:

The solvent to tobacco ratio was reduced from 150 m / m to 113 m / m, the extraction time was shortened from 60 minutes to 45 minutes, and the temperature of the extraction process was lowered from 70 ° C to 55 ° C. The characteristic features were rated as very good and the nicotine extraction was high, over 96%.

When tobacco pretreated with 2% ammonium bicarbonate was taken at 70 ° C for 30 minutes using a ratio of 75 m / m, 95.2% of the nicotine was removed (run 51, Table 5). However, the characteristics were not rated as good as with the product obtained at lower extraction temperatures of 18,885,453.

A further reduction in the extraction time (30 minutes) and a further reduction in the solvent to tobacco ratio (75 m / m) at 55 ° C resulted in a decrease in extraction efficiency with 94% removal of nicotine (run 57, Table 5).

Table 8 shows the results of the extraction runs carried out using a single tank apparatus with upstream and downstream flow.

In the case of upstream, the carbon dioxide flows in the opposite direction with respect to gravity, and in the case of downstream, the carbon dioxide flows in the direction of gravity. The fluidization velocity is initially about 1.1 cm / s and the pressure drop only becomes significant at a velocity of about 1.6 cm / s. The tobacco extraction results obtained at an upstream flow rate of 0.9 cm / s were advantageous compared to the control run with a downward flow (run 4IB compared to run 49B, Table 8).

Table 8 also shows the relationship between the ratio m / m and the extraction time.

The importance of the solvent-tobacco ratio was determined in two experiments by varying the extraction time (from 30 minutes to 75 minutes) with the ratio m / m remaining the same. The results show that a minimum ratio of solvent to tobacco (about 113 m / m) is required for nicotine extraction of more than 96%. The extraction time is not considered important in the tested area (run 45 ... 30 minutes; run 66 ... 45 minutes; run 67 ... 75 minutes).

Tobacco materials dissolved in carbon dioxide COa, without nicotine, were collected in two runs from a fully aromatic, American-blended filler (runs 42, 43, Table 8). Tobacco was pretreated with potassium citrate to convert nicotine 19 88 453 to salt. Tobacco solubles were extracted with supercritical carbon dioxide CO 2 at 260 atmospheric pressure and 55 ° C.

The disclosed process was also used to store carbon dioxide-dissolved tobacco materials in a tobacco filler (Run 45, Table 8) obtained from an expanded tobacco process based on carbonated ice as described in U.S. Patent Nos. Re 32,013 and 32,014.

Numerous samples were taken of the carbon dioxide during the extraction runs, showing that the nicotine concentration in the carbon dioxide follows the first-order extraction rate.

Tables - general remarks

All runs were performed at a pressure of about 260 atmospheres and a temperature of 70 ° C, with an oven volatile concentration of 25%.

The evaluation of the characteristics is based on the "zero" value of the non-extractable, full-flavored, American-blended tobacco. A positive value means improved properties.

All runs were performed without extraction during the heating phase by bypassing the retention tanks during the filling and heating phase.

The oven volatility of the tobacco filler in the extraction tank decreased when the stem volatility of the stems was 25% and 35%, respectively. When the volatile concentrations in the stems of the stoves were 45% and 55%, no management decisions could be drawn from the results.

The stems were not pre-dried before treatment with potassium citrate at the following times (10, 25, 26, 28, 29, 31, 35-39, 41-47).

38453 20

Explanations of the tables AB 2% ammonium bicarbonate ALPHA alpha-cellulose CARBON activated carbon COCOA cocoa shells from which fine particles have been removed by sieving COT cotton CRS cut and wound stalks ETOH ethyl alcohol FF full aroma = American mixed tobacco mitrate m. on the surface of the carrier) LS long stalks LTAR low tar alloy pack M / M carbon dioxide mass / tobacco mass PG propylene glycol SS torn stems STP stemless tobacco mixture UCSS unwashed, coarsely torn stems UFSS unwashed, finely torn stems WFSS. jSw 2 m nl O 3 Ή? j tn> c “h ° ° * * <*> 6 ft '' '' g ιβ T3 4->

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The following examples illustrate the invention.

Example 1

In each of the holding tanks 2 and 3 shown in Fig. 1, 2.2 kg of a cotton cloth impregnated with 2 liters of an aqueous solution containing 920.8 g of monopotassium citrate was placed. 12 kg of full-blown cigarette aroma, American blended tobacco filler (25% OV) was placed in the extraction tank 1.

The valves leading to the retention tanks were closed and the temperature of the supercritical carbon dioxide COa was raised to 70 ° C and the pressure to 260 bar. The valve to the first detent was then opened and a stream of supercritical carbon dioxide was circulated through the extractor and the first detent for 15 minutes. At the end of this time, the valve to the second detent was opened and the valve to the first detent was closed. The stream of supercritical carbon dioxide was recycled to the second arrester again for 15 minutes. After this total extraction time of 30 minutes, the recycle was stopped and the CO 2 was removed from the system. The tobacco blend and retention materials were removed from the system and analyzed for nicotine. The nicotine content of the tobacco blend was reduced by 77.4%. The tobacco blend retained a strong, characteristic aroma that did not differ from the aroma of the non-extractable blend.

When burned, a similar tobacco effect was achieved as with unextracted tobacco.

Example 2 4.4 kg of expanded clear tobacco stems were impregnated with 1.78 liters of an aqueous solution of monopotassium citrate to give a carrier consisting of moistened stems containing 409.8 g of monopotassium citrate. This retaining carrier was placed in the bottom of the extraction tank 1. A porous plate was placed on top of the retaining material, and 3.52 kg of Burley tobacco (25% OV) was placed in the tank of the extractor. The retaining tanks 2 and 3 shown in Figure 1 were removed from the flow system by setting the valves in a suitable manner. A supercritical stream of CO 2 was circulated through the extractor, the temperature and pressure of which were set at 70 ° C and 260 atmospheres, respectively. After an extraction time of 30 minutes, recycling was stopped and CO 2 was removed from the system. The tobacco product (Burley) and retaining material (swollen stems) were removed and analyzed for nicotine. The nicotine content had decreased by 92.4% in the Burley tobacco produced. Analysis of the retaining material formed from the expanded arms showed a corresponding increase in the nicotine content. The resulting Burley tobacco retained a strong characteristic aroma that was not subjectively different from the aroma of non-extractable Burley tobacco.

When the extracted Burley tobacco was smoked, a similar tobacco effect was obtained as that obtained from the unextracted tobacco.

Claims (15)

37 88453 A method for selectively removing basic components from a solvent in an extraction process, wherein said basic components, together with other substances, are extracted from the material as a high pressure solvent, either a liquid at about 50 to 300 atmospheres or a supercritical fluid at a critical temperature of the solvent. from a temperature of about 120 ° C and a pressure of about 70 to 1500 atmospheres, and the solvent is contacted with a non-volatile acidic substance, characterized in that said basic components are removed from the extracting solvent while retaining said other substances in the solvent by reacting said pressurized liquid or supercritical fluid. extracting solvent directly after extraction of the material into contact with a non-volatile acid or a salt of an acid which is insoluble in said extracting solvent and which removes said basic components from the solvent without simultaneously removing the other substances mentioned in the same solvent. A method according to claim 1, characterized in that said acid or acid salt is a polycarboxylic acid or a monovalent salt thereof. Process according to Claim 1 or 2, characterized in that said extraction solvent is carbon dioxide, argon, SFe or N 0, a lower halogenated hydrocarbon or a lower hydrocarbon. Process according to Claim 1, 2 or 3, characterized in that the non-volatile acid or salt of the acid is. t dissolved or suspended in water, acid, aqueous acid solution "" · or aqueous salt solution. 38 8 8 4 53 Method according to any one of the preceding claims, characterized in that said acid or acid salt is incorporated in a carrier medium. Method according to Claim 5, characterized in that the carrier medium is made of cotton fabric, tobacco stems, carbon, cellulose or tobacco filler. Process according to one of the preceding claims, characterized in that the solvent is recycled from contact with the acid or acid salt back to the extraction step. Process according to any one of the preceding claims, characterized in that said basic component is nicotine. Process according to Claim 8, characterized in that the nicotine is obtained from the tobacco under normal conditions by extraction with a gaseous solvent in the presence of at least 10% by weight of moisture, based on the weight of the tobacco, and that the nicotine is selectively removed from the solvent with a non-volatile acid. Process according to Claim 9, characterized in that the tobacco has a moisture content of at most 30% by weight. Process according to one of the preceding claims, characterized in that the non-volatile acid salt is monopotassium itate a. Process according to any one of the preceding claims, characterized in that said basic components are obtained from a plant product containing a plurality of substances, including acid salt forms of said basic components, and in that process said plant product is first contacted with a chemical base which does not reacts substantially with the acid salt forms of said basic components and not with other components of the plant under ambient conditions, but is capable of reacting with said acid salts under the conditions prevailing in the extraction process, after which the plant product is contacted with said extracting solvent in either with the acidic forms of the basic components present, prior to contacting said extracting solvent with said evaporating solvent. with a non-acid or an acid salt. Process according to Claim 12, characterized in that the chemical base has a pK i of greater than 7.2 and less than 10. Process according to Claim 12 or 13, characterized in that the chemical base is ammonium bicarbonate, glycosylamine, aldose N-glycoside or ketose N-glycoside. Process according to Claim 12 or 13, characterized in that the chemical base is sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonia, aqueous ammonia, triethylamine or trimethylamine. 40 88 453