WO2009043715A1 - Method for dosing dialkyl dicarbonates in beverages - Google Patents

Abstract

The invention relates to a method for the production of microbially stabilized beverages by means of a dialkyl dicarbonate, characterized in that the dialkyl dicarbonate is added to the beverage in the form of an aqueous and/or organic solution.

Description

 Method for dosing dialkydicarbonates in drinks

The invention relates to a novel method and the use of a device for dosing of dialkyl dicarbonates in drinks.

Dialkyl dicarbonates are used in the beverage industry for the cold sterilization of non-alcoholic carbonated or still fruit juice drinks, fruit juices, wines, non-alcoholic wines, ciders, ice teas and other beverages. This technology of beverage stabilization has a number of advantages. The outstanding advantage lies in the fact that taste and color are not affected in contrast to hot filling. Persistent preservatives such as benzoate or benzoic acid or sorbate or sorbic acid also have the advantage, especially in the absence of any taste impairments. Compared to a cold aseptic filling especially the very much lower investment costs in plant technology are known as an advantage in the use of dialkyldicarbonates.

The substance class of dialkyl dicarbonates has the special property of hydrolyzing in contact with corresponding (aqueous) beverages in the derived alcohols and carbon dioxide. For this reason, dialkyl dicarbonates are always transported, stored and used as pure substances and can not be used in, for example, aqueous

Solutions are pre-formulated or handled as such. In addition, the solubility of some dialkyl dicarbonates in water is relatively low. Furthermore, unfortunately, some dialkyl dicarbonates are at the beverage bottling temperatures commonly used in the beverage industry of 0 -

15 ⁰ C in solid state before. Finally, when metering into the beverage stream, ensure that a quantity proportional to the beverage flow rate is metered.

For these reasons, it is imperative that the dosage of dialkyldicarbonates in the beverage stream in general a special mechanical metering device is necessary. The devices usually used in the prior art are apparatuses which include a dialkyl dicarbonate storage vessel, a metering pump, a nozzle head in the beverage line, a flow meter in the beverage line, a temperature control unit, a ventilation unit and of course the necessary connections and contain an electronic control. According to the prior art, these devices always dosed pure dialkyl dicarbonate into the beverage stream. According to the prior art electromagnetic diaphragm pumps are used with linear drive. Improvements of corresponding pumps have been described for example in DE-A-2910328 and DE-A-2930765. These pumps dispense discontinuously, in portions (intermittently), and are coupled to the inductive flowmeter to ensure a proportional beverage flow rate. The Dosierang the dialkyl dicarbonates is carried out according to the prior art under high pressure in front of the nozzle, usually well> 20 bar. This pressure is necessary to ensure adequate atomization and uniform distribution of the pure dialkyl dicarbonates in the beverage stream. In addition, the nozzle must be heated in the rule, since the beverage filling temperature may be below the melting point of dialkyl dicarbonates, and thus could crystallize the pure dialkyldicarbonates on or in the nozzle.

The described devices thus have a number of disadvantages:

The dosage is discontinuous. In the sense of a uniform distribution of dialkyl dicarbonates in the drink, this is not optimal.

In addition, you need a heater in the nozzle. A corresponding device is technically complex and, moreover, the temperature prevailing at the nozzle is critical. Because, if the nozzle is overheated, it can lead to premature, unwanted decay of the Dialkyldicarbonate within the nozzle, and the resulting gas can change the dosing permanently. However, a temperature monitoring in the nozzle is very expensive.

Furthermore, the metering must be done under high pressure and therefore the pump must have the appropriate capacity. In order to guarantee the necessary operating time, therefore, expensive, especially resilient materials are required.

The object of the present invention was to find a way of adding dialkydicarbonate which overcomes the disadvantages of the prior art.

There has now been found a method and a device for dosing, which brings significant benefits and is much easier to operate.

The invention therefore relates to a process for the preparation of microbially stabilized (sterilized) beverages by means of a dialkyl dicarbonate, characterized in that the dialkyl dicarbonate is added to the beverage in the form of an aqueous and / or organic solution.

The dialkydicarbonate used is preferably dimethyl carbonate (DMDC) and diethyl dicarbonate, in particular the DMDC.

Preferred solvents of the aqueous and / or organic solution of dialkyl dicarbonates are water, aliphatic monoalcohols, in particular C 1 -C 6 -alcohols, such as, for example, ethanol, n-propanol or isopropanol, glycols, in particular ethylene glycol or

Diethylene glycol and dimethyl sulfoxide (DMSO) to name the drink itself and mixtures thereof. Ethanol or water is particularly preferably used as the solvent. The mixing ratio of solvent: dialkyl dicarbonate is particularly preferably 1: 2 to 20: 1, very particularly preferably from 1: 1 to 10: 1.

In addition to green tea, black tea and other types of tea and tea-based beverages, drinks that are usually acidified (pH <4.2) are also usually to be mentioned as drinks. Carbonated and non-carbonated non-alcoholic soft drinks, fruit juices, fruit nectars, wines, soft drinks, ciders, ice teas, mixed alcoholic drinks, flavored waters or sports drinks should also be mentioned in this context.

The process according to the invention is preferably characterized in that the dialkyl dicarbonate solution is prepared by mixing dialkyl dicarbonate and water and / or an organic solvent and after a few hours, preferably within 5 hours, preferably within 30 minutes, in particular within 10 minutes, of the beverage is added to the mixing.

The dialkyl dicarbonate and the solvent or solvent mixture are initially preferably in separate storage vessels

These are preferably connected via corresponding supply lines with the mixing control unit, wherein the proportions can be adjusted for example via a compressed air unit with controllable pressure control from a suitable arrangement.

The mixing chamber, as the location of the mixing unit, where the solvent and the dialkyl dicarbonate, especially the DMDC are mixed and then coexist, can have a variety of configurations.

An embodiment of the mixing chamber is, for example, a preferably about 0.5 to 100 ml small container in which the solvent (mixture) and dialkyl dicarbonate are introduced, for example by compressed air. In this case, the chamber is advantageously shaped such that already takes place during the entry or injection of the two components, a good mixing.

Another embodiment of the mixing chamber is, for example, a tube into which the solvent or solvent mixture and dialkyl dicarbonate flow together or in series and are appropriately swirled or mixed during this. Preferably, the time between the preparation of the dialkyl dicarbonate solution and the

Adding the dialkyl dicarbonate solution to the beverage less than 50% of the half-life of the dialkyl dicarbonate in the solvent used at the prevailing temperature, more preferably less than 25% of the corresponding half-life.

The mixing takes place in particular at a temperature around or slightly above the

Beverage filling temperature, in practice usually at -2 to +35 ⁰ C, preferably at 4 to 25 ⁰ C, in particular at 6 to 22 ⁰ C.

The inventive method is preferably characterized in that the additions to the beverage by means of nozzles, in particular with a pressure of 0.1 to 15 bar relative to the beverage pressure.

Preferably, a pressure relative to the pressure of the beverage stream of 0.1 to 10 bar, in particular from 0.1 to 5 bar used.

A preferred embodiment of the nozzle entry is characterized by an arrangement of 2-20, in particular 3-10 nozzles, which are connected via a common feed system. The arrangement of the nozzles in the beverage stream can be linear or spiral, for example. The nozzles preferably have a different, each slightly increasing opening pressure, i. the pressure at which a passage of the liquid into the beverage stream can take place. This can be achieved, for example, in that a correspondingly configured steel spring presses on a sealing plate with a corresponding pressure within the nozzle. Therefore, if the dialkyl dicarbonate solution is pressed into the arrangement, more and more nozzles are opened successively, thus allowing the uniform introduction of increasing or decreasing quantities of liquid.

In a further preferred embodiment of the method according to the invention, a flow meter is usually used, for example an inductive flow meter to adjust the metering rate to the beverage flow. Other eg mechanical

Flowmeters are also possible. Optionally, another inductive or mechanical flow meter can also be attached to the dialkyl dicarbonate / solvent line upstream of the injection area in order to be able to perform a direct electronic / direct balance electronically.

The flow meter preferably registers the beverage flow continuously. By means of an electronic control, the necessary amount of solution to be dispensed is preferably calculated therefrom. If beverage flow is reported by the flow meter, then solvent and dialkyl dicarbonate are introduced into the mixing chamber by compressed air and / or corresponding valves and pressed from there into the injection area. Depending on Applied pressure open an increasing number of nozzle heads and allow a uniform introduction even at high beverage flow rates. If the flowmeter registers a standstill in the beverage line, the pressure is reduced and

the nozzles close. Advantageously, no or only a small amount of residual remains

Solution in the mixing chamber. If so, a possibly forming overpressure through the injection area can easily escape at any time.

The temperature of the beverage stream is preferably -2 to 35 ⁰ C, in particular 4 to 25 ⁰ C.

The inventive method is preferably characterized in that

a) the preparation of the dialkyl dicarbonate solution is carried out in a mixing unit, the

- At least one inlet for the dialkyl dicarbonate and

- at least one inlet for the solvent and

- Has a mixing chamber into which the components of the dialkyl dicarbonate solution

can be mixed and

b) the dialkyl dicarbonate solution by means of nozzles in the drink, preferably the

Beverage stream.

The point of addition to the beverage stream is preferably located shortly before being filled into the individual containers, in particular bottles.

The inventive method is characterized by the fact that you do not need high pressure nozzle systems and the pressure only slightly above the pressure in the

Beverage line must lie. There is no need for extremely fine atomization of the dialkyl dicarbonates.

As a rule, no heating of the nozzles is required. The dosing method allows bottling even at low beverage temperature. The dosage can now be continuous and does not have to be intermittent.

The described method thus comes in one embodiment using

Compressed air completely without actual mechanical pump.

The invention further relates to the use of dialkyl dicarbonate dissolved in water and / or organic solvents for the production of microbially stabilized beverages. A very important advantage of this approach is also that solutions such as aqueous-alcoholic solutions are much easier to distribute in the drink than pure dialkyl dicarbonates. Therefore, you can work on the nozzle with much lower pressures.

Another advantage is that suitable solutions of dialkyl dicarbonates at 0-15 ⁰ C present in the liquid state and thus can be dispensed with the conventionally required nozzle head heating.

To implement the method according to the invention, it is, for example, advantageous to use the device described below. Of course, however, the dosage according to the invention can also be carried out with existing metering devices according to the prior art, wherein a corresponding mixing device is to be inserted. Likewise, the dosage of solvent or a solvent mixture and dialkyl dicarbonate can be carried out with one separate pump each. Care should be taken that pressure build-up not caused by hydrolysis or alcoholysis can destroy components of the pump. One way to prevent this are, for example, correspondingly attached pressure relief valves.

The invention further relates to the use of a device for introducing dialkyl dicarbonate solutions into a beverage stream, preferably for the purpose of producing microbially stabilized drinks, the device at least comprising

a) a mixing unit, the

at least one feed for dialkyl dicarbonate,

at least one feed for water, an organic solvent or

Mixtures thereof

- An inlet control unit and

- Has a mixing chamber

and

b) a dosing unit for dissolved dialkyl dicarbonate, the

- Has at least one nozzle and

- Is attached to a Flüssigkeitsdurchströmeinheit

and if necessary c) a flow meter that measures the flow rate of the liquid in the

Fluid Durchströmeinheit measures and depending on the amount of addition of the dissolved dialkyl dicarbonate controlled by the metering unit.

The preferred embodiments of the mixing unit and the dosing unit are already described above and also apply to the device.

The invention further relates to the use of dialkyl dicarbonate dissolved in water and / or organic solvents for the production of microbially stabilized beverages.

Examples:

example 1

A mixture of dimethyl dicarboante and ethanol pa is well mixed in a 100 ml flask and cooled by solid CO ₂ . Then it is heated slowly and the

Temperature determines at which a clear solution is obtained.

Dimethyldicarbonate-ethanol = 1: 10-1 ^° C

Dimethyldicarbonate Ethanol: Water = 1: 5: 50 + 2 ⁰ C

Dimethyl dicarbonate +17 ⁰ C

Example 2

One apple juice (40 ml) was preserved with each 250 ppm of dimethyl dicarbonate and sealed at 26 ⁰ C stored. In the first case (a), the pure dimethyl dicarbonate was added to the drink and shaken gently. In the second case (b), the dimethyl dicarbonate was previously dissolved in ethanol in a ratio of 1:10 and added to the beverage after about 10 minutes and shaken gently. In the third case (c), a solution of dimethyl dicarbonate / ethanol / water in the ratio of 1: 5: 50 was used and gently shaken.

As a comparative experiment (d), the same apple juice was left unpreserved.

Results: Shown are the durability of the samples.

(a) 10 days

(b)> 4 weeks

(c)> 4 weeks

(d) 3 days

The example illustrates that a previous solution of dialkyl dicarbonate is surprisingly more effective against microorganisms than undiluted dialkyl dicarbonate.

The table gives the results of the microbiological count of colonies. For this purpose, a membrane-filled beverage matrix (commercial flavored water, apple) was used seedlings were then seeded on P. glabrum, then mixed with DMDC / EtOH, the samples were shaken well, and after the indicated times on agar plates the respective bacterial counts were determined (twice each twice, ie quadruple determination). The YM agar plates were incubated at 26 ° C for 7 days.

table

* in colony-forming units per 1 ml of beverage sample tested ** - means that no more germs could be detected

Example 3

Description of a metering device according to the invention:

The device contains two storage vessels: The dialkyl dicarbonate is in a 3 liter container, a 25 liter container contains a 1: 1 ethanol-water mixture. Both storage vessels are housed in a stainless steel cabinet. In each vessel dives a lance just to the ground. The lances consist of a stainless steel tube with 4 mm inner diameter. In addition, both vessels are provided with compressed air supply, 5 bar. The two lances from the vessels meet as two inputs in an electronically controlled valve, which can connect or disconnect three paths together. The third way is the outlet The valve leads through a short tube with nubs on the inner wall as a mixing section and through a small additional mechanical flow meter and flows into three nozzles, which stir directly into the beverage stream. The nozzles open successively at 0.5, 0.6 and 0.7 bar overpressure. In the beverage stream is the central inductive flow meter (company: Endress & Hauser). Through this flow meter in the beverage flow is depending on the flow

Beverage a setpoint for the introduced dialkyl dicarbonate solution amount determined and mediated to the control loop. The three-way valve regulates to this setpoint with the aid of the smaller flow meter after the mixing section. The mixing ratio is determined by the geometry or the pipe diameter in the valve and is 1: 5 (dialkyl dicarbonate to solvent mixture). For electronic control, a simple control loop is used.

The design of the supply lines is in V4A steel.

Example 4

The dosing device described in Example 3 was used to fill a Schorlengetränkes (50% apple juice content). The dosing device was placed directly in front of the filler in the

Integrated filling line. The amount of bottled product was 10,000. The mass flow rate was 3,000 liters per hour. The drink was bottled in PET bottles and was microbiologically stable after filling for> 3 months.

Claims

claims 1. A process for the preparation of microbially stabilized drinks by means of a dialkyl dicarbonate, characterized in that one adds the dialkyl dicarbonate in the form of an aqueous and / or organic solution to the drink. 2. The method according to claim 1, characterized in that as dialkyldicarbonate dimethyldicarbonate or diethyldicarbonate, in particular dimethyldicarbonate is used. 3. The method according to claim 1, characterized in that is used as the solvent of the aqueous and / or organic solution of water, at least one aliphatic monoalcohol, in particular Ci-Cβ-alcohol, glycols, DMSO, the beverage itself or mixtures thereof. 4. The method according to claim 1, characterized in that the solvent of the aqueous and / or organic solution is selected from the group consisting of water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol and Dimethyl sulfoxide (DMSO). 5. The method according to claim 1, characterized in that the dialkyl dicarbonate solution prepared by mixing dialkyl dicarbonate and water and / or an organic solvent and added to the beverage within 5 hours, preferably within 30 minutes, in particular within 15 minutes, after mixing becomes. 6. The method according to claim 1, characterized in that the time between the preparation of the dialkyldicarbonate solution and addition to the beverage less than 50% of the half-life of the dialkyl dicarbonate in the respective solvent at the prevailing temperature, more preferably less than 25% of the corresponding Half-life is. 7. The method according to claim 1, characterized in that the addition to the beverage by means of nozzle, in particular with a pressure of 0.1 to 15 bar relative to the beverage pressure. 8. The method according to claim 1, characterized in that a) the preparation of the dialkyl dicarbonate solution is carried out in a mixing unit, the - At least one inlet for the dialkyl dicarbonate and - At least one inlet for the solvent and - has a mixing chamber in which the components of the Dialkyldicarbonat- Solution can be mixed and b) brings the dialkydicarbonate solution by means of nozzles in the drink, preferably the beverage stream. 9. Use of a device for introducing dialkyl dicarbonate solutions into a beverage stream, preferably for the purpose of producing microbially stabilized drinks, wherein the device comprises at least a) a mixing unit, the at least one feed for dialkyl dicarbonate, at least one feed for water, an organic solvent or Mixtures thereof - An inlet control unit and - Has a mixing chamber and b) a dosing unit for dissolved dialkyl dicarbonate, the - Has at least one nozzle and - Is attached to a Flüssigkeitsdurchströmeinheit and possibly c) a flow meter which measures the flow rate of the liquid in the liquid flow unit and, depending on this, regulates the amount of addition of the dissolved dialkyl dicarbonate by means of the metering unit. 10. Use of dissolved in water and / or organic solvents dialkydicarbonate for the production of microbially stabilized drinks.