LU81611A1 - METHOD FOR OBTAINING A NITRATE-FREE SOLUTION FROM A NITRATE-CONTAINING PRODUCT SOLUTION - Google Patents

Description

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_ η - A 28 222 Aug 15, 1979.

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'METHOD FOR OBTAINING A NITRATE-FREE SOLUTION FROM A NITRATE-CONTAINING PRODUCT SOLUTION

The invention relates to a method for obtaining a target solution essentially free of nitrates, nitrites and ammonium compounds from an aqueous product solution 5 obtained by washing out tobacco plant parts as a tobacco extract by eliminating the nitrates, nitrites and ammonium compounds. metabolic, aerobic assimilation caused by microorganisms with largely gentle transfer of the remaining solution components of the product solution into the target solution.

1o

In some cases, nitrates contained in tobacco, when converted, lead to substances that are undesirable for human consumption, for example nitrogen oxides in tobacco smoke. This can be avoided by withdrawing the nitrates before they can have the desired effect. For this purpose, the undesired compounds are washed out and eliminated in the aqueous product solution. The water-soluble substances which pass into the aqueous solution when washed out can then be added to the washed-out starting substances after the nitrates are no longer present in the aqueous solution. The nitrates should be removed as completely as possible.

What applies to nitrates also largely applies to nitrites and ammonium compounds, and it is therefore desirable that, in addition to the nitrates, the nitrites and ammonium compounds are also removed. In contrast, others are said to be in the watery. Substances contained in the product solution should not be broken down or J modified.

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The object of the invention is to design a method of the type mentioned at the outset in such a way that it can be operated economically under these conditions - in particular with the lowest possible consumption of additives and energy.

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The invention is characterized in that a predetermined working mixture portion of a working mixture obtained from product solution and additives and admixed with the microorganisms is broken down into a nitrate, nitrite and ammonium compounds-1o the assimilation state is maintained-by maintaining this working mixture portion with one of a nitrate concentration of 3 up to 7.5 g · l "" 1 (grams of nitrate per liter of additional solution), a phosphate concentration of 1.0 to 10 g. 1 (gram of phosphate per liter of additional solution) and a carbon source 15 in a concentration of 16.5-10 assimilable carbon atoms per nitrate molecule adjusted additional solution obtained from the product solution and additives continuously under -1-1

Compliance with a dilution rate of 0.1 to 0.35 1 · 1. h (liters of additional solution per liter of working mixture portion per 20 hours) and in the aeration range of 0.8 to 2.5 l. 1 . min. (Liters of air per liter of working mixture portion per minute), in the pH range from 3.5 to 6 and in the temperature range from 25 ° C (degrees Celsius) to 37 ° C, each is kept on a triplet of values, which with regard to a large Ver-25 ratio of mined nitrate to carbon used is favorable, and by continuously treating the mixture from the working mixture portion is removed at such a decrease rate that the volume of the working mixture portion remains constant; and that the target solution is obtained by withdrawing the biomass from 30% of the removed, treated mixture.

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Il 'Μ I - 3 - A 28 222) 1 ** j If two sizes are optimized for the triplet of values, experience has shown that the third size is very variable. For example, with ventilation at 1.5 1. l "* 1. min." 1 and a pH value of 5.5 select the temperature between 26 ° C and 37 ° C 5 and you can, for example, with a ventilation of 1.5 1.1. min. and a temperature of 30 c select the pH between 3.9 and 5.5 and you can as another example at a pH of 5.5 and a temperature of 30 ° C the ventilation in the range 0.5 to 1.0 1. Select I * "1. Min.-1 and is still in the range of very favorable operating conditions.

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The invention achieves a continuous process and only this makes it possible (apart from the one-off start-up phase, whose products can be discarded if necessary) to maintain and, if necessary, readjust the operating conditions recognized as optimal within certain tolerance limits. In contrast, in a discontinuous, batch-wise, so-called batch process, a wide variety of treatment stages are run through and the entire batch must be discarded if an error occurs. In the batch process, the assimilation conditions have to be re-established for each batch and this takes hours. As a result, the throughput is limited and a higher outlay in terms of investment and personnel is required than in the method according to the invention.

The prescribed nitrate concentration, if it is not present in the product solution from the outset, is adjusted by concentration or dilution. Carbon and phosphate are added in the required amount. If there is a higher concentration of phosphate and / or carbon in the product solution from the start, this can be tolerated. The concentrations are matched to one another in such a way that the carbon and the phosphate are used by the microorganisms when assimilating the nitrate, so that as little as possible the best of these additives get into the target solution.

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The pH is preferably adjusted with orthophosphoric acid or potassium hydroxide.

Since the product solutions to be treated are solutions obtained from natural 5 products, the other components of which differ from pall to case, the optimal operating conditions are not always the same under all circumstances, but are within the specified ranges .

1o The invention is preferably applicable to tobacco, but it is not limited to this application. Foodstuffs and other luxury foods are also known which contain nitrates, nitrites and / or ammonium compounds which, when converted, lead to substances which are undesirable for human consumption, for example nitrosamines. One can counteract this, as with tobacco, by eliminating the undesirable compounds. If these are present in an aqueous solution from the outset, this aqueous solution is used as the product solution, otherwise, as with tobacco, washing out results in a product solution in which the undesired compounds are eliminated and which can then be added to the starting product again .

In the case of tobacco, the operating conditions 25 can be based on the nitrate concentration of the product solution, because. the percentage of nitrites and ammonium compounds accompanying the nitrates in the main types of tobacco is approximately the same within the scope of the accuracy required here. This is by no means the pall for food and other luxury foods.

3o Therefore, instead of a nitrate concentration, the starting point is the concentration of the total compounds to be eliminated, i.e. the concentration of the total of nitrates, nitrites and ammonium compounds, which should be 3 to 7.5 g · 1 in the additional solution. All other parameters can be the same as for tobacco treatment treatment. 1 / P- I - 5 - A 28 222 ï j i * The following explanations relate to the application of the invention to tobacco, but with the restrictions just made, they can be used analogously for the treatment of relevant foods and other luxury foods.

5

The assimilation caused by the preparation is preferably carried out using an inoculum of 30 to 100 g. 1 ~ 1 (grams of culture volume per liter of working mix serving). The assimilation is preferably carried out using a microorganism culture from the standard strains listed below:

Candida utilis NCYC 707; Candida Berthetii CBS 5452; Candida utilis NCYC 321; Candida utilis NCYC 359, corresponds to DSM 70167; Enterobacter aerogenes ATCC 13048, corresponds to DSM 30053.

15

These strains are available at the depository locations indicated by the abbreviations in the form required for patent law disclosure under the number given.

Abbreviations mean: 2o NCYC National Collection of Yeast Cultures, Brewing Industry Research Foundation; CBS Centraal Bureau voor Schimmelcultures; ATCC American Type Culture Collection; DSM German collection of microorganisms.

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The description of the strains follows from the following * lists I, II and III. In these lists, "+ M good;" weak; absent.

S - 30 List I: Characterization of Candida yeasts j!

Plasmodium or Pseudoplasmodium mobile cells -; Ballistospores -; monopolar sprout -; bipolar shoot -; Sprouts on stem -; triangular cells -; moon-shaped 35 cells -; short-lived cells with slow growth on malt agar and strong acetic acid production formation of a real * Mycelius formation of pseudomycelia +; Cultures red or / orange -.

rr - 6 - A 28 222 LIST XI: Characterization of Candida utilis NCYC 707, NCYC 359 and CBS 321 by the characters before the slash and Candida berthetii CBS 5452 by the characters after the slash.

5

Fermentation: glucose + / +; Galactose - / -; Sucrose +/-;

Maltose - / -; Cellobiose - / -; Trehalose - / -; Lactose melibiosis raffinose +/-; Melecitosis inulin

Io assimilation: glucose + / +; Galactose - / -; L-sorbose

Sucrose +/-; Maltose +/-; Cellobiose + / +; Trehalose +, -> / -; Lactose - / -; Melibiosis Raffinose +/-; Melezitosis +/-;

Inulin + / - * »soluble starch D-xylose +,; L-arabinose D-arabinose - / -; D-Ribose L-Rhamnose - / -; 15 ethanol +, ^ / +; Glycerin + / +; Erythrol ribitol

Galactitol D-Mannitol +, -, «*> / -; D-glucitol oC-methyl-D-glucoside salicin + / +; DL lactate +/-;

Succinate; Citrate inositol - / -;

Assimilation of potassium nitrate + / +; Growth in vitamin-free 2o medium +, ^ / +] growth-promoting vitamins thiamine / absent; Naci tolerance% (w / v) 6-8 / 6-7; maximum growth temperature in ° C 39-43 / 40-41.

POSITION III: Characterization of ATCC 13048 25

Short chopsticks; Flagellation peritrich; Agility +; Spore formation pigment grief reaction 02 behavior aerobic +; anaerobic +; Catalase +; Oxidase nitrite formation from nitrate +; Indole Methyl Red 3o Vosges-Proskauer +; Citrate +; H2S -; Urease gelatin lysine decarboxylase +; Arginine dihydrolase ornithinde carboylase +; Phenylalanine deaminase malonate +; Gas from glucose +; Lactose +; Sucrose +; Mannitol +; Dulcit salicin +; Adonit +; Inositol +; Sorbitol +; Arabinose +; 35, raffinose +; Rhamnose +.

j «· - 7 - A 28 222 - The invention will now be explained in more detail with reference to the accompanying drawing and some examples.

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The drawing shows, for example, a generalized flow scheme for the inventive method. The reference numbers used in the drawing have the meaning shown in the following list IV.

POSITION IV: Product stock 1; Water tank 2; Stock for To Accessories 3; Washer with separator 4; Mixer 5; Treatment branch 6; Treatment branch 7; Mixer 8; Dosing pump 9; Working container i0; Centrifuge 13; Treatment branch 14; Playback device 15; Control device 16; pH controller 17; Temperature controller 18; Aerator 19; Stirrer 20; Anti-foam additive 21; Reconstitution facility 22 and dryer 23.

From the product supply 1, product, for example tobacco ribs, reaches the washer 4 with water from the water tank 2, where the soluble constituents are washed out and reach the treatment branch 6 as a 2o product solution. In the treatment branch, sterilization is carried out by heating and then cooling again .

The necessary additives, primarily phosphates and glucose, 25 get from the supply 3 with water into the mixer 5 and as a solution in the treatment branch 7, where they can be sterilized by heating and then cooled.

I In the mixer 8, the solutions from the two treatment branches 6 and 7 are then mixed — and now reach the working container 10 via the metering pump 9. The devices 17 to 20 remove the ar in the working container 10 - * Mixing portion continuously adjusted with regard to pH and temperature, dosed, aerated and stirred intensively.

! 35 The working mix from the working | container 10 is withdrawn, possibly pasteurized, which is not shown in the I drawing, and then reaches the Zen-trifuge 13. There the biomass is withdrawn and further var.

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Turned supplied, while the remaining liquid as a target solution in the treatment branch 14, where it is concentrated. This target solution, which essentially contains all components of the product solution, with the exception of the nitrates, nitrite and ammonium compound, which have been completely removed, can now be used as required, for example according to the flow diagram of the washed out, in the dryer 23 dried to the original moisture content of the product from the product supply 1 or, alternatively, in the reconstitution device 22, the product reconstituted into tobacco leaf-like pieces of film can be added in the re-adding device 15 by spraying or in some other way.

To start up, a working portion of the working mixture 10 is given from the product solution with the necessary additives and an inoculum of the microorganism in question. After about 8 to 20 hours, all nitrates, nitrites and ammonium compounds are broken down in this working mixture portion and the continuous operation can begin by switching on the metering pump 9 according to the desired dilution rate and controlled so that the volume of the filling of the working container 10, that is, the working mix portion remains constant.

25 Treatment in treatment branches 6 and 7 is carried out by preheating to 100 ° C, sterilizing at 110 ° C for 40 minutes. and then cooling to 30 ° C. Vacuum evaporation takes place in the treatment branch 14. The dosing pump 9 has a delivery capacity of 50 to 200 l. "" 1.h ~ 1. The working container 10 has a capacity of 750 l and is 2/3 full during operation. Accordingly, the volume of a working mixture portion is 500 l.

Depending on the products to be processed and the microorganisms used, the operating conditions are set so that the nitrates, nitrites and ammonium compounds contained in the product solution are completely eliminated and 1 the additives 5 added in the mixer are just used for this assimilation .

-9-, A 28 222 * Favorable operating conditions result from the examples listed in the following list V. In these examples, tobacco stems are used and Candida utilis NCYC 707 is used as a microorganism. For other 5 tobacco plant parts as the starting product and / or other microorganisms, the operating conditions must be modified within the scope of the information given at the beginning.

In the table as concentration, a "chemically" 10 content that is no longer perceptible under normal analysis conditions means that it is less than 10 ppm each for carbon and phosphate and less than 1 ppm each for nitrate, nitrite and ammonium compounds.

15 POSITION V:

Example 1 ; 2; 3; 4; 5; '6; 7; 8th; 9; 10;

Concentration of the additional solution in g.l-1:

Nitrate 5 * 0; 5> Q; 5 * 0; 5 * 0; 5 * 0; 4.1; 4.9; 7 * 5; 3 * 0; 1 * 0 20 nitrite °; °; °; °; °;

Ammonium Ver- o * 08 0.08; 0.08; 0 * 08 0.08, * 0.1; 0.1; 0.1; 0.1; 0.1

bindings I I I I I

Phosphate 1 »25; 1.25 * 10.0; 1.25; 1 * 25; 1» 25; 1 »25; 1» 6; 0.755 0 ^^ 5 *

Glucose 40; | 40; | 40 * | 40 * | 40? 40; 40; 60, 2.4, 0.8

Operating conditions of assimilation: 25 temperature (° C) 30; 30; 30; 30; 30; 37; 26; 30; 30; 30 pH 5 * 5; 3.9; 5 * 5 »5 * 5 * 5 * 5 * 5 * 5; 5.5; 5 * 5; 5 * 5 * 5 * 5

Degree of ventilation 1> 5 »1 * 5; 1 * 5 »1 * 5; 1 * 5; 1 * 5; 1.5, 2.0, 1.0; 0.5 (l.l ”.min.)

Dilution rate 0.2; 0.2; 0.2, 0.01, 0.34; 0.2; 0.2; 0.2; 0.2; 0.2 30 (x.i ~ 1, h ~ T) _i l l l_______

Concentration of the target solution in g.! ”1 to:

Nitrate. ο; ο; ο; ο; ο; ο; ο; ö; ο; O;

Nitrite '; ο; ο; ο; ο; ο; ο; ο; ο; O;

Ammonium ver 0 0. 0; ο; ο; ο; ο; O; bindings »» »,» 35 phosphate 0.1; 0.1; 8.4; 0.1; 0.1; 0.1; 0.1; ο; ο; O;

Glucose_o; O; O; O; O; O; O; O; O; o î

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Claims (11)

1. Process for obtaining a target solution essentially free of nitrates, nitrites and ammonium compounds from an aqueous product solution obtained by washing out tobacco plant parts as a tobacco extract by eliminating the nitrates, nitrites and ammonium compounds with metabolic, aerobic assimilation caused by microorganisms with largely gentle transfer of the remaining solution components of the 1 o product solution in the target solution, characterized in that a predetermined working mixture portion of a working mixture obtained from product solution and additives and mixed with the microorganisms is kept in a nitrate, nitrite and ammonium compounds degrading assimilation state, prevent this working mixture portion from one to one —1 nitrate concentration from 3 to 7.5 g. 1, a phosphate concentration of 1.0 to 10 g. 1 and a carbon source with a concentration of 16.5-10 assimilable carbon atoms per nitrate molecule adjusted from the product solution and additives obtained continuously from the product solution and additives while maintaining a dilution rate of 0.1 to 0, 35 1 · 1. h charged and in the ventilation range from 0.8 to 2.5 1.1. min. , in the pH range from 3.5 to 6 and in the temperature range from 25 ° C to 37 ° C each on a triplet of values, which is favorable in terms of a large ratio of degraded nitrate to carbon used, and ♦ in ongoing treated mixture is removed from the working mixture portion at such a decrease rate that the volume of the working mixture portion remains constant; and that the target solution is obtained by withdrawing the biomass from the removed, treated mixture. > - -11.- A 28 222 • · « 2. The method according to claim 1, characterized in that the assimilation by using a Candida from the group consisting of the Candida utilis NCYC 707 »Candida Berthetii CBS 5452, Candida utilis NCYC'321 and Candida utilis NCYC 359 and 5 that the working mixture portion with one from the to a Ni-tread concentration of 4.5 to 5.5 g. 1 and a phosphate concentration of 1.1 to 1.5 g. l ”” 5 set additional solution continuously while maintaining a dilution rate of 0.18 to 0.22 1. 1 ~ 1. h ”1 loaded, running 1.4 to 1.6 —1. -1 . + 1o 1. 1 . mm. ventilated and kept at a pH of 5 »5 - 0.3 and a temperature of 30 ° C - 3 ° C. 3. The method according to claim 2, characterized in that the working mixture portion with a from the on a nitrate concentration -1 15 g of 5.0 g. 1 and to a phosphate concentration “1–1 of 1.25 g. 1 and a glucose concentration of 40 g. 1 adjusted additional solution continuously while maintaining a dilution rate of 0.2 1 .1. h charged, continuously aerated with 1.5 1 · 1 "1. min.-1 and kept at a pH of 5.5 2o and a temperature of 30 ° C. 4. The method according to claim 1, characterized in that the assimilation by using a Candida from the group consisting of the Candida utilis NCYC 707, Candida Berthetii CBS 5452, 25 Candida utilis NCYC 321 and Candida utilis NCYC 359 and that a carbon from the group consisting of glucose, sucrose, maltose, cellobiose, ethanol, glycerol and citrate is used as the carbon source. 5. The method according to claim 1, characterized in that the assimilation is carried out by using the Enterobacter aerogenes ATCC 13048 and that the working mixture portion with a from to a nitrate concentration of 4.5 to 5.5 g. 1 ”and a phosphate concentration of 1.1 to 1.5 g. 1 set 35 additional solution continuously with a dilution rate of 0.18 to 0.22 1. I-1. h ”1 loaded, continuously with 1.4 to 1.6 J _ * i I 1.1. min. aerated and kept at a pH between 5.5 - ~ 4 * · to 6.0 and a temperature between 35 ° C and 37 ° C. Γ 'k v 12. A 28 222 6. The method according to claim 5, characterized in that the working mixture portion with a from the to a nitrate concentration - _-i concentration of 5.0 g. 1 and to a phosphate concentration -1-1 of 1.2 g .. 1 and a glucose concentration of 40 g. 1 5 set additional solution continuously while maintaining a dilution rate of 0.2 1 .1. h charged, continuously aerated with 1.5 1 · l "1 min." "1 and kept at a pH of 6.0 and a temperature of 37 ° C. 107. The method according to claim 5, characterized in that the assimilation is carried out by using the Enterobacter aerogenes ATCC 13048 and that a carbon is used as a carbon source from the group consisting of glucose, sucrose, maltose, cellobiose, ethanol, glycerol, citrate and lactose. 15 8. The method according to claim 2 or 5, characterized in that the additional solution has a phosphate concentration of 1.2 g. 1 has. 209. Process for recovering one of nitrates, nitrites and. Anunonium compounds essentially free target solution from a product solution containing nitrates, nitrites and / or ammonium compounds by eliminating the nitrates, nitrites and ammonium compounds with me-25 tabular, aerobic assimilation caused by microorganisms with largely gentle transfer of the remaining solution components of the product solution Λ in'dié target solution , characterized in that, in accordance with claim 1, a predetermined working mixture portion of a working mixture obtained from product solution and additives and mixed with the microorganisms is kept in a state of assimilation which decomposes nitrate, nitrite and ammonium compounds by this working mixture portion having a concentration to be eliminated Compounds from 3 to 7.5-1-1 g. 1, a phosphate concentration of 1.0 to 10 g. 1 + 35 as a carbon source in a concentration of 16.5 - 10 / assimilable carbon atoms per molecule of the compound to be eliminated adjusted from the product solution and additives obtained continuously in compliance with s - · '\ - 13 - A 28 222 iit * —1 —1 î at a dilution rate of 0.1 to 0.35 1 · 1 «h I _ · ι j. ^ and in the ventilation range from 0.8 to 2.5 1. 1 . min. , in the pH range from 3.5 to 6 and in the temperature range from 25 ° C. to 37 ° C. in each case on a triplet of values which is favorable with regard to a large ratio of the degraded compound to be eliminated to the carbon used, and in continuously treated mixture is removed from the working mixture portion at such a decrease rate that the volume of the working mixture portion remains constant; and that the target solution is obtained by withdrawing the biomass from the removed, treated mixture. ___ '