EP2111466A2 - Alcalisation de jus brut - Google Patents

Alcalisation de jus brut

Info

Publication number
EP2111466A2
EP2111466A2 EP08707168A EP08707168A EP2111466A2 EP 2111466 A2 EP2111466 A2 EP 2111466A2 EP 08707168 A EP08707168 A EP 08707168A EP 08707168 A EP08707168 A EP 08707168A EP 2111466 A2 EP2111466 A2 EP 2111466A2
Authority
EP
European Patent Office
Prior art keywords
raw juice
juice
alkalization
preliming
alkalinity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08707168A
Other languages
German (de)
English (en)
Other versions
EP2111466B1 (fr
Inventor
Stefan Frenzel
Mohsen Ajdari Rad
Azar Shahidizenouz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suedzucker AG
Original Assignee
Suedzucker AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suedzucker AG filed Critical Suedzucker AG
Priority to PL08707168T priority Critical patent/PL2111466T3/pl
Publication of EP2111466A2 publication Critical patent/EP2111466A2/fr
Application granted granted Critical
Publication of EP2111466B1 publication Critical patent/EP2111466B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/02—Purification of sugar juices using alkaline earth metal compounds
    • C13B20/04—Purification of sugar juices using alkaline earth metal compounds followed by saturation
    • C13B20/06—Purification of sugar juices using alkaline earth metal compounds followed by saturation with carbon dioxide or sulfur dioxide
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/02—Purification of sugar juices using alkaline earth metal compounds

Definitions

  • the invention relates to an improved process for the purification of sugar beet raw juice, which is obtained by extraction of sugar beet, as well as apparatus for the purification of sugar beet
  • the present invention further relates to processes for the production of sucrose syrup or sucrose from sugar beet raw juice.
  • sugar is made from beets
  • the sugar beet raw juice obtained during the extraction is then fed to a juice purification stage, which is also referred to as extract purification. It should in the raw juice contained contaminants, which are referred to as non-sucrose substances are removed. Usually, the juice is purified as lime-carbonic acid extract cleaning; this contains the process steps Precalculation and Main liming. Subsequently, a first and optionally a second or a further finds
  • Carbonatation takes place, wherein by means of filtration, the precipitate formed during the carbonation is separated from the clarified raw juice.
  • the purified in the juice purification raw juice which is also referred to as a thin juice contains about 12 to 18%, especially about 15 to 17% sucrose.
  • the purity of the raw juice is normally between 90 and 92%. It is then thickened by dehydration to a thick juice with a sucrose content of about 65 to 70% and then further thickened in crystallizers until a viscous mass, the so-called cooking mass, forms with about 85% sucrose. By centrifuging the molasses, finally, crystalline white sugar is obtained, which can then optionally be refined.
  • the non-sucrose substances contained in the sugar beet raw juice are degraded only to such an extent that they can be separated off by means of appropriate separation methods.
  • the non-sucrose substances are partially degraded to low molecular weight compounds; these can no longer be completely removed from the raw juice.
  • Known problems are the associated adverse color development of the obtained from the juice cleaning Dünnsafts and the disadvantageous high calcium salt content of the Dünnsaft.
  • the presence of nonsugar substances deteriorates the production result, especially those from the raw juice after thickening of the Dünnsaft and subsequent crystallization and centrifugation recovered crystalline sucrose or the sucrose syrup.
  • the raw juice obtained from the pulp extraction usually has a pH of about 5.8 to 6.2 and a temperature of about 20 to 30 0 C. After extraction, the
  • Raw juice optionally doused and / or sanded and known to be heated with the aid of Rohsafchtmaschinerärmem to the known preliming temperature of about 55 to 75 0 C.
  • Acid amides such as glutamine instead.
  • These components as well as the invert sugar formed by undesirable sucrose hydrolysis must be separated or degraded in an early phase of sucrose recovery. Otherwise, the subsequent juice thickening leads to the disadvantageous formation of acids and to
  • unused lime is converted into calcium carbonate by introducing carbon dioxide as the carbonation gas in the main liming process.
  • Calcium carbonate is a strong adsorbent for soluble non-sucrose substances. Calcium carbonate thus also serves as an adsorption and filtration aid.
  • Carbon dioxide and the quicklime for the production of lime are usually obtained in the sugar factory in coke ovens, where limestone is burned with coke.
  • the calcium carbonate sludges (so-called sludge juice concentrates) concentrated via the filters in the first and preferably second and optionally further carbonation stages are usually combined and pressed off via membrane filter presses. The result is the so-called Carbokalk.
  • This Carbokalk is a storable product with a
  • a disadvantage of the conventional lime-carbonic acid extract cleaning is, above all, that a cleaning effect that is still too low is achieved since only about a maximum of 40% of all non-sucrose substances can be removed from the sugar beet raw juice.
  • invert sugar is formed by hydrolysis of the sucrose, which reduces the quality of the resulting thin juice; above all, this has a detrimental effect on the color development of the Dünnsaft (Dünnsaftnote).
  • Dünnsaft Dünnsaft
  • the calcium carbonate formed acts as a filtering agent. If the Kalkmilcheintrag be lowered, not only worsened
  • the present invention is based on the technical problem of providing an alternative and improved method of purifying sugar beet raw juice.
  • the present invention solves the underlying technical problem essentially by providing a method for purifying sugar beet raw juice, which contains at least the following method steps:
  • Step (a) recovering the raw juice by extraction of
  • Step (b) first (or so-called early) alkalization of the raw juice after extraction to a first alkalinity c;
  • Step (c) heating the alkalized raw juice to the preliming temperature T;
  • Step (d) precalcification of the alkalized raw juice by a second alkalization to a second alkalinity to flocculate the non-sucrose substances.
  • a value interval of 0.07 to 0.12 applies to factor a, and a value interval of 2 to 4 applies to addend b.
  • a is approximately 0.1.
  • B is preferably about 3.
  • the temperature T is preferably 80 ° C. or less.
  • the first alkalinity c in step (b) is always lower (lower pH) than the second alkalinity (higher pH) than in step (d). It has been shown that pH (from about 5.8 to about 6.2) and temperature (from about 20 to about 30 0 C) of the raw juice, as he obtained directly after the conventional beet extraction and introduced directly into the preliming stage in conventional extract purification processes, favoring chemical, enzymatic and microbiological degradation reactions of the sucrose and other non-sucrose substances contained. The prevailing acidic environment also reduces the susceptibility of the raw juice to the issue, so that the heating of the raw juice before or during the preliming stage leads to the formation of further non-sucrose substances, especially invert sugar.
  • Raw juice before and during preliming has a major influence on the quality of the thin or thick juice, especially on color and calcium salt content. This leads directly to the reduction of sugar yield in the process.
  • a preferred embodiment of the method according to the invention provides that the alkalization of the raw juice in step (b) a first alkalinity c is selected as a function of the preliming temperature T in step (d).
  • c takes values of about 7 to about 11.
  • c is pH 9 or less.
  • steps (c) and / or (d) the preliming T 80 0 C or less, or 75 ° C or less and preferably of 50 to 75 0 C.
  • the first alkalization according to the invention preferably takes place in step (b) immediately after the extraction, preferably immediately after the mash.
  • the first takes place in step (b)
  • the subsequent (conventional) second alkalization takes place in the form of the preliming by adding lime milk to a total concentration of 0.1 to 0.3 g CaO / 100 ml.
  • the second alkalization progressive to an alkalinity of pH 1 1 or more.
  • the second alkalization proceeds progressively until the optimum is reached Flocculation point at which the non-sucrose substances coagulate and / or precipitate.
  • recycled already alkalized raw juice for example sludge juice concentrate from the carbonation and / or grosskalkalkter raw juice occurs.
  • sugar beet raw juice or “raw juice” is understood to mean the juice which is preferably extracted from sugar beet pulp by countercurrent extraction.
  • this sugar-rich raw juice contains other organic and inorganic constituents of the turnip, which are referred to as non-sucrose substances or non-sugar substances.
  • non-sucrose substances refers above all to high-molecular substances such as proteins, polysaccharides and cell wall components as well as low-molecular compounds such as inorganic or organic acids, amino acids and mineral salts
  • Hemicellulose Hemicellulose. These substances, like the proteins, which include proteins, in particular nucleoproteids, are present as hydrophilic macromolecules in colloidally disperse form.
  • the organic acids are, for example, lactate, citrate and oxalate.
  • the inorganic acids / salts are, in particular, sulfates and phosphates.
  • "Lime milk” is understood to mean calcium hydroxide, which is formed in the highly exothermic reaction of quick lime (calcium oxide) with water and used as liming agent in the preliming and main liming The addition of lime to the raw juice in the preliming causes the precipitation or coagulation of
  • Non-sucrose substances in the form of a coagulum in the form of a coagulum.
  • the addition of lime milk for preliming the raw juice is carried out according to the invention preferably as a progressive preliming.
  • the progressive preliming by a gradual increase in the alkalinity or the pH of the raw juice is preferably carried out by slow
  • Inlet of the lime-liming agent or by small broken lime milk individual additions, in particular, the pH optimum is passed slowly.
  • the progressive alkalization is preferably carried out in countercurrent, wherein the recirculated juice of higher alkalinity is mixed as quickly as possible with a juice of lower alkalinity, without that different alkalinity gradients can build up within the mixing zone.
  • suitable transport systems in the preliming apparatus it is ensured within the system that the required recirculation quantity is guided with high constancy counter to the main flow direction.
  • step (e) is followed by at least one main liming stage, in which the pre-limbed raw juice is main caked.
  • This is preferably characterized by the fact that the preliming juice obtained is further alkalized.
  • more milk of lime is added, so that a concentration of preferably 1, 0 g CaO / 100 ml is achieved.
  • the main liming is carried out in two stages. The inventors found, surprisingly, that the effectiveness of the separation and splitting of non-sucrose substances during the main liming stage can be improved by a first cold main liming and a subsequent second hot main liming.
  • Main liming can be reduced.
  • step (e1) a first main calcification takes place and in a, preferably immediately following, step (e2) a second main calcification takes place.
  • step (e1) further lime milk is preferably added to the preliming juice until a
  • the first main calcification as a "cold main liming" at low temperature that is at a temperature of 75 0 C or less, preferably 70 0 C 1 preferably 65
  • the second main liming of the main limed raw juice takes place, with further lime milk optionally being added up to a concentration of preferably 0.1 CaO / 100 ml.
  • the second main calcification as "hot Hauptkalkung" at high temperature that is at a temperature of more than 75 0 C, preferably 80 0 C or more, preferably 85 0 C or more, more preferably in a temperature range from 85 to 95 0th C.
  • the elevated temperature in the second main liming is achieved by connecting a heat exchanger or Instantaneous water heater, which is flowed through by the main liming juice, reaches.
  • the method according to the invention is also advantageously suitable for processing beet material of inferior quality, especially of altered beets. This means above all that the campaign time, that is, the time in which the harvested and intermediate beets are processed in the sugar factory, can be extended.
  • At least one flocculant is added after the, preferably first, principal calcination and prior to clarification of the limed crude juice to improve settling of the non-nonsucrose fraction in sludge.
  • the flocculant is added to a concentration of 1 to 8 ppm.
  • the flocculant is selected from polyanionic macromolecules, preferably from acrylamide and copolymers of acrylamide and sodium acrylate.
  • the flocculant has an average molecular weight of about 5x10 6 to 22x10 6 g / mol on average.
  • the separated non-sucrose substances or the non-sucrose substance-containing fraction are further concentrated as so-called thin sludge.
  • a sucrose-containing fraction is separated therefrom in at least one further step in one or more separation devices, whereby the non-sucrose substance-containing fraction is further concentrated.
  • a centrifuge is used as separation device.
  • the centrifuge is preferably selected from disk centrifuges or disk separators and decanter centrifuges.
  • the separation devices are optionally connected directly one behind the other; However, it is also envisaged that the sludge outlet of a first separation device is connected via a mixing container or a similar device to the inlet of a second further separation device.
  • the sucrose-containing clarified juices or desiccating juices separated from the second and further separating apparatuses are again in the inventive compositions
  • the chalked raw juice is fed to the main liming in the carbonation.
  • at least one carbonation is preferably carried out by introducing carbon dioxide into the main liming juice in a step which is preferably immediately following. Following the carbonation, a filtration of the resulting sludge takes place. This gives a clear sucrose syrup. The carbonation takes place in
  • the carbonation is formed as a two- or multi-stage carbonation.
  • a first carbonation and first filtration takes place in step and, preferably immediately followed by a second carbonation and second filtration.
  • a third and further carbonation and filtration may follow, depending on the field of application and convenience.
  • Another object of the invention is a method for
  • sucrose syrup from sugar beet raw juice comprises according to the invention in a first step, the provision of the raw sugar beet juice, as it is preferably obtained from the countercurrent extraction of sugar beet cossettes. Thereafter, the extract purification method of the present invention is carried out with at least steps (a) to (d), preferably (a) to (e), as described above. Thereafter, in a further step, a sucrose syrup freed from nonsugar substances and clarified is obtained. This can optionally be crystallized in a further step in a conventional manner, so that crystalline sucrose is obtained.
  • Another object of the invention is a device for carrying out the extract cleaning method according to the invention, this has at least the following elements: a first alkalization (10), a
  • Precalcification device (30) and a first heat exchanger (20) connected therebetween see FIGS. 1 and 2).
  • the first alkalizing device (10) serves to alkalize the crude juice and has at least one inlet (1 1) for the raw juice, at least one metering device (13) for the dosing of alkalis and at least one outlet (12) for the alkalized raw juice.
  • the first alkalization device (10) is static Mixer trained.
  • the feed (11) of the first alkalization device (10) is in fluid communication directly with a mash container of the extraction stage for the extraction of sugar beets.
  • the preliming device (30) serves for preliming of the alkalized raw juice and has at least one feed (21) for the alkalized raw juice, at least one metering device (23) for the metering of lime and at least one discharge (22) for the pre-limed raw juice.
  • the first heat exchanger (20) serves for heating the crude juice which has become alkalized in the first alkalizing device (10) and has at least one inlet (21) for the alkalized raw juice and at least one outlet (22) for the heated, limed raw juice; the inlet (21) is in fluid communication with the outlet (12) of the first alkalizing device (10), and the outlet (52) is in fluid communication with the inlet (31) of the preliming device (30).
  • the device according to the invention has at least the following further elements: a first main liming device (40); a second
  • the first main limiter (40) serves the first one
  • Main liming in particular the cold main liming, the limed raw juice and has at least one inlet (41) for the raw juice, at least one metering device (43) for the dosage of Lime milk and at least one outlet (42) for the main lime raw juice.
  • the second main liming device (60) serves for the second main liming, in particular of the hot main liming, of the main limed raw juice and has at least one inlet (61) for the raw juice, optionally at least one metering device (63) for the metering of lime, and at least one outlet (62). for the main lime juice.
  • the second heat exchanger (50) is used for heating the raw juice which has been fully calcified in the first main liming means (40) and has at least one inlet (51) for the main-limed raw juice and at least one outlet (52) for the heated main-limed raw juice; the inlet (51) is connected to the drain
  • Main liming device (60) in fluid communication.
  • FIG. 1 shows the schematic structure of a preferred device according to the invention.
  • the device comprises a first alkalization device (10), a preliming device (30) and a first heat exchanger (20) connected therebetween;
  • the first alkalization device (10) has an inlet (11) for the raw juice, a metering device (13) and a drain (12) for the alkalized raw juice;
  • the preliming device (30) has an inlet (31) for the alkalized raw juice, a metering device (33) and a discharge (32) for the precalked raw juice;
  • the (first) heat exchanger (20) has an inlet (21) for the alkalized raw juice and at least one outlet (22) for the heated limed raw juice;
  • the device comprises a first alkalization device (10), a prelim
  • Preliming device (30) in fluid communication.
  • FIG. 2 shows a further preferred arrangement of the device according to the invention.
  • the apparatus comprises a first alkalizing device (10), a preliming device (30) and a first heat exchanger (20) connected therebetween, and a first main liming device (40); a second
  • the first alkalization device (10) has an inlet (11), a metering device (13) and a drain (12);
  • the preliming device (30) has an inlet (31), a metering device (33) and a drain (32);
  • the (first) heat exchanger (20) has an inlet (21) and a drain (22); the inlet (21) is connected to the drain
  • the first alkalization device (10) in fluid communication and the drain (22) is in fluid communication with the inlet (31) of the preliming device (30);
  • the first main limiter (40) has a Feed (41) for the raw juice, a metering device (43) and a discharge (42) for the main lime raw juice;
  • the second main liming device (60) has a feed (61) for the raw juice and a discharge (62) for the main limed raw juice;
  • (50) has an inlet (51) for the main lime raw juice and a discharge (52) for the heated Hauptkkalkten raw juice; the inlet (51) is in fluid communication with the outlet (42) of the first main limiter (40) and the outlet (52) communicates with the inlet
  • FIG. 3 shows the graphical representation of the dependence of the thin juice color on the selected alkalinity in the first (early) raw juice alkalization according to the invention.
  • FIG. 4 shows the graphical representation of the dependence of the calcium salt content of the dilute juice on the selected alkalinity in the first (early) raw juice alkalization according to the invention.
  • Figure 5 shows the graphical representation of the dependence of
  • Invert sugar increase in the raw juice from the preliming temperature and from the selected alkalinity in the first (early) raw juice alkalization according to the invention.
  • FIG. 6 shows the graphical representation of the dependence of the FK
  • Sugar beets that have been freshly harvested or stored for some time are washed and then chopped in a cutting machine with a cutting unit.
  • the crushed beet pulp are fed via a mash tank of a countercurrent extraction plant and extracted in this.
  • the temperature during the extraction is about 75 ° C.
  • the extractor used is a tower extractor, in which the chips are extracted in countercurrent with the heated fresh water.
  • the extract is the so-called sugar beet raw juice.
  • the raw technical juice is alkalized in a separate step in a separate alkalization by adding lime to a pH of 6.0 to 11, 0;
  • the alkalisation container is a heatable container with stirrer, CO 2 inlet tube and pH
  • flocculation of non-sucrose substances occurs by coagulation of the non-sucrose substances with each other and by precipitation by the added milk of lime.
  • the precalcified raw juice is subjected in a downstream further alkalization a first cold main liming.
  • the alkalinity is increased to 1.0 g CaO / 100 ml by further addition of lime milk.
  • the temperature at the hot main liming is about 85 0 C; this is held for about 20 minutes.
  • the first carbonation takes place at 85 ° C with the addition of carbon dioxide. During dosing, the pH is monitored as described above. The carbonation takes place within 15 min to a pH of 1 1, 20. 2.5 Second Carbonation
  • the sludge juice 1 obtained from the first carbonation is filtered off with a suction bottle via a Buchner funnel.
  • the filter material used is a round filter from Schleicher & Schuell 589/1, black band filter, ashless (12 ⁇ m).
  • Carbonation is returned to the purified reactor and further heated to about 88 0 C. This is followed by the renewed addition of carbon dioxide until the pH of the juice reaches 9.25 (within 10 minutes). Thereafter, the dosage is stopped. After a post-reaction time of 10 minutes, the sludge juice 2 obtained in the second carbonation is likewise filtered (round filter Fa. Schleicher & Schuell 5893, Blauband, ashless, 2 ⁇ m). The thin juice is obtained. The color and the calcium salt content of the thin juice are determined.
  • the precipitated calcium carbonate is removed from the clarified raw juice after the first carbonation in the first filtration or after the second carbonation in the second filtration, so that a clarified purified raw juice is obtained.
  • the retentate contained in the first and second filtration is collected in a sludge tank and then via a
  • Thin juice color increases with increasing preliming temperature.
  • the thin juice color is reduced by alkalization of the raw juice.
  • the influence of the raw juice to the decrease of the thin juice color is dependent on the preliming: A decrease in the thin juice color of about 200 IU (for a preliming of 50 0 C) and a decrease in
  • Thin juice color of about 500 IU (at a preliming temperature of 80 0 C).
  • the calcium salt content of the thin juice increases as the preliming temperature increases.
  • the calcium salt content of the thin juice decreases with the alkalization of the raw juice to an optimum pH.
  • the required pH of the raw juice prior to its heating to achieve the minimum calcium salt content of the thin juice is consistent with the required pH of the raw juice for the optimum thin juice color.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Non-Alcoholic Beverages (AREA)
  • Saccharide Compounds (AREA)
  • Dairy Products (AREA)

Abstract

L'invention concerne un procédé amélioré de purification de jus brut de betteraves sucrières obtenu par extraction à partir de betteraves sucrières, ainsi que des dispositifs pour la purification de jus brut de betteraves sucrières. L'invention concerne en outre des procédés de fabrication de sirop de saccharose, ou bien de saccharose à partir de jus brut de betteraves sucrières.
EP08707168.4A 2007-01-24 2008-01-22 Alcalisation de jus brut Active EP2111466B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08707168T PL2111466T3 (pl) 2007-01-24 2008-01-22 Alkalizacja soku surowego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007003463A DE102007003463B4 (de) 2007-01-24 2007-01-24 Rohsaftalkalisierung
PCT/EP2008/000435 WO2008089946A2 (fr) 2007-01-24 2008-01-22 Alcalisation de jus brut

Publications (2)

Publication Number Publication Date
EP2111466A2 true EP2111466A2 (fr) 2009-10-28
EP2111466B1 EP2111466B1 (fr) 2020-01-15

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08707168.4A Active EP2111466B1 (fr) 2007-01-24 2008-01-22 Alcalisation de jus brut

Country Status (9)

Country Link
US (1) US9133528B2 (fr)
EP (1) EP2111466B1 (fr)
CN (1) CN101636508B (fr)
CA (1) CA2676356C (fr)
DE (1) DE102007003463B4 (fr)
EA (1) EA015385B1 (fr)
PL (1) PL2111466T3 (fr)
UA (1) UA98134C2 (fr)
WO (1) WO2008089946A2 (fr)

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CN103173580B (zh) * 2013-04-07 2014-07-02 佐源集团有限公司 一种双碳酸法原糖加工的溶糖工艺
DE102014006046A1 (de) * 2014-04-24 2015-10-29 Richard Hartinger Verfahren und Vorrichtung zur Herstellung eines Gemüse-Süßungsmittels
ES2625737T3 (es) * 2014-05-16 2017-07-20 Sociedade Portuguesa Do Ar Líquido Método para la carbonatación
CN107488753A (zh) * 2017-07-24 2017-12-19 广西柳城县成霖农业科技有限公司 一种生产红糖的方法
DE102017215243A1 (de) * 2017-08-31 2019-02-28 Südzucker AG Verfahren zur Herstellung von funktionsverbessertem Carbokalk
BE1026862B1 (fr) * 2018-12-13 2020-07-13 Isera & Scaldis Sugar Procédé pour chaine de production de sucre

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Also Published As

Publication number Publication date
US9133528B2 (en) 2015-09-15
CA2676356C (fr) 2015-03-17
DE102007003463B4 (de) 2012-12-13
EP2111466B1 (fr) 2020-01-15
CA2676356A1 (fr) 2008-07-31
EA200900953A1 (ru) 2010-02-26
US20100043783A1 (en) 2010-02-25
WO2008089946A2 (fr) 2008-07-31
CN101636508B (zh) 2014-05-14
EA015385B1 (ru) 2011-08-30
CN101636508A (zh) 2010-01-27
WO2008089946A3 (fr) 2008-11-20
DE102007003463A1 (de) 2008-07-31
UA98134C2 (en) 2012-04-25
PL2111466T3 (pl) 2020-06-29
WO2008089946A8 (fr) 2008-10-02

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