CA2029403A1 - Process for acidifying solutions of molasses - Google Patents
Process for acidifying solutions of molassesInfo
- Publication number
- CA2029403A1 CA2029403A1 CA002029403A CA2029403A CA2029403A1 CA 2029403 A1 CA2029403 A1 CA 2029403A1 CA 002029403 A CA002029403 A CA 002029403A CA 2029403 A CA2029403 A CA 2029403A CA 2029403 A1 CA2029403 A1 CA 2029403A1
- Authority
- CA
- Canada
- Prior art keywords
- molasses
- solution
- ion exchanger
- exchanger
- acidified
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/06—Acidifying the wort
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Health & Medical Sciences (AREA)
- Biotechnology (AREA)
- Food Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
Abstract
Abstract A process for acidifying a solution of molasses by treating the solution with an ion exchanger is disclosed.
According to one preferred embodiment of the invention, aqueous solutions of molasses 10 to 70% in strength are treated with weakly acid cation exchanger in the amount of 100 to 700 ml of ion exchanger per kg of molasses. The acidified solutions of molasses so obtained are equally good for fermentation as conventional solutions acidified with sulphuric acid, but in some processes, such as methanization, are superior to the latter, due to the absence of sulphates.
According to one preferred embodiment of the invention, aqueous solutions of molasses 10 to 70% in strength are treated with weakly acid cation exchanger in the amount of 100 to 700 ml of ion exchanger per kg of molasses. The acidified solutions of molasses so obtained are equally good for fermentation as conventional solutions acidified with sulphuric acid, but in some processes, such as methanization, are superior to the latter, due to the absence of sulphates.
Description
~2~ ~3 DEUTSOElE HEFEWERXE GMBH - 1 -- O . Z . 4 4 41 Process for acidifying solutions of molasses The invention relates to a novel process for acidifying dilute solutions of molasses.
The molasses which are obtained as mother liquor in the production of sugar contain approximately 50% ~ugars, 20~ water and furthermore organic and inorganic compounds containing nitrogen and pho~phoru~. It is therefore well suited a~ a nutrient for microorganisms. However, the pH
of the molasses, which is u~ually about 7 to 9, i8 too high for many applications.
In yeast, anaerobic or aerobic metabolism is possible at a pH of between 2 and 7. However, a pH of 4 to 5.5 is usually preferred for yeast fermentation since this pH
range i8 a aelection advantage for yeasts and furthermore guarantees good protection against infection by con-taminants. A certain acid p~ i8 also established when yeast is cultured for baking purposes.
/
After having been diluted with water, the molas~es are therefore acidified with sulphuric acid 80 that the ~esired pH i~ established, before using thQm for the formation of alcohol or for propagating yeast (cf. DRP
641 742 and L. Nacher, Die Hefe, Volume II (1962), 420-23). Sulphuric a~id i8 u~ed because it is extra-ordlnarily inexp4n~lve and, in contrast to other acids,ha~ no effect on the phy~iology of the yeast cells. At the end of the fermentation or yeast culture, the ~ul-phuric acid which has been added remains in the exhausted liquid culture medium in the form of sulphates.
~hese days, yeast waste waters are increasingly purified anaerobically or used for producing methane (bio~as). The sulphates are undesirable in the methanization of the organic material contained in the wa~te water, since they are reduced to hydrogen sulphide and exert a negative ~2~ 3 - 2 - O.Z. 4441 influence on the quality of the biogas (cf. D.8. Archer, Enzyme Microb. Technol. 1983, 162-70, and G. R. Anderson et: al., Process Biochemi~try 1982, 28-32). Indeed, high concentrations of sulphate can lead to an inhibition of tlle formation of bioga~, or bring it to a halt. Moreover, sulphate in waste waters can corrode cement or concrete components and contribute to the destruction of waste water equipment. It is therefore desirable to employ, in the methanization, waste waters whose sulphate concen-trations are as low as possible.
Accordingly, the ob~ect was to reduce the amount of~ulphuric acid when acidifying solutions of mola~ses.
Surpri~ingly, the ob~ect is achieved by treating the dilute solution~ of molas~es with ion exchangers. The fact that sufficient changes in the pH could be brought about with relatively low amount~ of ion exchangers could not have been anticipated.
First, the molasses are converted to preferably 10 to 70~
strength aqueous solution by adding water. Particularly preferred ~olutions of molasses in this context are tho~e fro~ 30 to 60%. The~e percentage~ do not take into account any water contents initially present in the molasses.
The dilute ~olution~ of molasses are treated with lon exchanger~, lt being po~sible to use strongly acid or weakly acid cation exchanger~. Weakly acid cation ex-changers are preferably employed. In this con~ext, use can be made of 811 commercially available cation exchan-ger~.
~he amount of ion exchangers i~ generally 100 to 700 ml relative to 1 kg of undiluted molasse~. Amounts of 120 to 300 ml of ion exchangars per kg of molasses are preferred in this context.
' ~ ' ' ' .
- ' ` ' .
2a~2~
The molasses which are obtained as mother liquor in the production of sugar contain approximately 50% ~ugars, 20~ water and furthermore organic and inorganic compounds containing nitrogen and pho~phoru~. It is therefore well suited a~ a nutrient for microorganisms. However, the pH
of the molasses, which is u~ually about 7 to 9, i8 too high for many applications.
In yeast, anaerobic or aerobic metabolism is possible at a pH of between 2 and 7. However, a pH of 4 to 5.5 is usually preferred for yeast fermentation since this pH
range i8 a aelection advantage for yeasts and furthermore guarantees good protection against infection by con-taminants. A certain acid p~ i8 also established when yeast is cultured for baking purposes.
/
After having been diluted with water, the molas~es are therefore acidified with sulphuric acid 80 that the ~esired pH i~ established, before using thQm for the formation of alcohol or for propagating yeast (cf. DRP
641 742 and L. Nacher, Die Hefe, Volume II (1962), 420-23). Sulphuric a~id i8 u~ed because it is extra-ordlnarily inexp4n~lve and, in contrast to other acids,ha~ no effect on the phy~iology of the yeast cells. At the end of the fermentation or yeast culture, the ~ul-phuric acid which has been added remains in the exhausted liquid culture medium in the form of sulphates.
~hese days, yeast waste waters are increasingly purified anaerobically or used for producing methane (bio~as). The sulphates are undesirable in the methanization of the organic material contained in the wa~te water, since they are reduced to hydrogen sulphide and exert a negative ~2~ 3 - 2 - O.Z. 4441 influence on the quality of the biogas (cf. D.8. Archer, Enzyme Microb. Technol. 1983, 162-70, and G. R. Anderson et: al., Process Biochemi~try 1982, 28-32). Indeed, high concentrations of sulphate can lead to an inhibition of tlle formation of bioga~, or bring it to a halt. Moreover, sulphate in waste waters can corrode cement or concrete components and contribute to the destruction of waste water equipment. It is therefore desirable to employ, in the methanization, waste waters whose sulphate concen-trations are as low as possible.
Accordingly, the ob~ect was to reduce the amount of~ulphuric acid when acidifying solutions of mola~ses.
Surpri~ingly, the ob~ect is achieved by treating the dilute solution~ of molas~es with ion exchangers. The fact that sufficient changes in the pH could be brought about with relatively low amount~ of ion exchangers could not have been anticipated.
First, the molasses are converted to preferably 10 to 70~
strength aqueous solution by adding water. Particularly preferred ~olutions of molasses in this context are tho~e fro~ 30 to 60%. The~e percentage~ do not take into account any water contents initially present in the molasses.
The dilute ~olution~ of molasses are treated with lon exchanger~, lt being po~sible to use strongly acid or weakly acid cation exchanger~. Weakly acid cation ex-changers are preferably employed. In this con~ext, use can be made of 811 commercially available cation exchan-ger~.
~he amount of ion exchangers i~ generally 100 to 700 ml relative to 1 kg of undiluted molasse~. Amounts of 120 to 300 ml of ion exchangars per kg of molasses are preferred in this context.
' ~ ' ' ' .
- ' ` ' .
2a~2~
- 3 - O.Z. 4441 The type and amount of ion exchanger used depend on the de~ired pH. pH value~ in the range of from 5 to 5.5 can readily be ad~usted using weakly acid cation exchanger~
in the preferred amount~.
The acidification can take place at 10 to 80C, tempera-tures of 20 to 30C being preferred. The period in which the treatment with ion exchangers take~ place can be 10 minutes or even 2 hours.
The treatment can be carried out in a stirred reactor. At the end, the ion exchanger can be filtered off, or the ~olution of molasses can be decanted. It is also possible to introduce the ion exchanger into a column and then to pass the solution of molasses through this column. This treatment can be effected batchwise and al~o continuous-ly.
The ~olutions of molasses, which have been acidified inthis way, are highly suitable for producing fermentation products. In particular, the solutions of molasses are used for produc~ng yeast biomass, for example for produc-ing baker's yeast, and also for synthesizing organicsub~tances with the aid of microorgani~ms, such as, for example, for producing alcohol by fermentat~on. The solution~ of molasse~, according to the invention, are certainly equal when compared with conventional, ~ulpha~
tized solutions of molasses. When the fermentation i~
complete, however, exhau~ted fermentat~on solutions which have been prepared u~ing a ~olution of molasses, accord-ing to the inventlon, can advantageou~ly be degraded anaerobically to give bioga~, since the formation of hydrogen ~ulphide is completely absent, or considerably reduced.
The examples which follow are intended to illustrate the invention.
-~ 292~
in the preferred amount~.
The acidification can take place at 10 to 80C, tempera-tures of 20 to 30C being preferred. The period in which the treatment with ion exchangers take~ place can be 10 minutes or even 2 hours.
The treatment can be carried out in a stirred reactor. At the end, the ion exchanger can be filtered off, or the ~olution of molasses can be decanted. It is also possible to introduce the ion exchanger into a column and then to pass the solution of molasses through this column. This treatment can be effected batchwise and al~o continuous-ly.
The ~olutions of molasses, which have been acidified inthis way, are highly suitable for producing fermentation products. In particular, the solutions of molasses are used for produc~ng yeast biomass, for example for produc-ing baker's yeast, and also for synthesizing organicsub~tances with the aid of microorgani~ms, such as, for example, for producing alcohol by fermentat~on. The solution~ of molasse~, according to the invention, are certainly equal when compared with conventional, ~ulpha~
tized solutions of molasses. When the fermentation i~
complete, however, exhau~ted fermentat~on solutions which have been prepared u~ing a ~olution of molasses, accord-ing to the inventlon, can advantageou~ly be degraded anaerobically to give bioga~, since the formation of hydrogen ~ulphide is completely absent, or considerably reduced.
The examples which follow are intended to illustrate the invention.
-~ 292~
- 4 - O.Z. 4441 xample 1 In a 6-litre reactor, 2 kg of molas~e~, con~isting of 25%
of crude molasses and 75% of beet molasses, are diluted with 2 kg of water. The solution of molasses has a pH of 7.40. 500 ml of weakly àcid ion exchanger (type IV, made by Merck, D-6100 Darm~tadt) are now added. The solution i~ then stirred for 30 minutes at 25C. After this, the pH
of the ~olution of molasses is 5.10.
Example 2 The procedure i~ a~ in Example 1, with the difference that 2 kg of wash water from the ion exchanger is u~ed for dilution.
After the treatment with ion exchanger, the solution of mola~ses has a pH of 5.20.
Example 3 3 kg of molasses of Example 1 are diluted with water to give 6 kg of solution of molasses.
500 ml of ion exchanger (LEWATIq~ CNPLF, made by Bayer, D-5090 Leverku~en) are introduced into a chromatography column. The solution of molas~es is then passed through the column at ~ flow rate of 1.70 l/h. This gives 6 kg of ~olutlon of mola~se~ of a pH of 5.08.
Exa~ple 4 The procedure i8 a~ in Example 3, with the difference that 3.5 kg of mola~se~ are diluted to give 7 kg of solution of molas~e~, which are passed through the column at a flow rate of 2.8 l/h. Thi~ give~ 7 kg of solution of mola~ses of a pH of 5Ø
A furth~r 6 kg of ~olution of molasses are passed through -` 2~2~3 - S - O.Z. 4441 the column. This now gives a solution having a pH of 5.35.
ExamPle 5 1.25 kg of beet molasse~ (from Clauen) are diluted with 1.25 kg of water. The solution of molasses now ha~ a pH
of 9.2. The subsequent procedure iB as in Exsmple 3, with the difference that 500 ml of ion exchanger of Example 1 are used. $he flow rate is 1 l/h, and the temperature is 25C.
lQ Thi~ give~ 2.5 kg of solution of molasses having a pH of 5Ø
A further 3.5 kg of the ssme solution of molasses are then passed through the column. This procedure gives a solution having a pH of 5.4.
Example 6 3 kg of beet molasses of Example 5 are diluted with 3 kg of water.
~he conditions of Example 5 are then ad~usted, but the ion exchanger of Example 3 i~ used.
This gives 6 kg of eolution of molas~es havinq a pH of 4.9.
Exsmple 7 1.5 kg of beet molasse~ (from Belgium) are diluted with 1.5 kg of wster. ~he resulting solution of mola~ses has a pH of 8Ø
The procedure is a8 in ~xample 5. Thi~ proces~ giYes 3 kg of ~olution with a pH o~ 5Ø
2~2~ 3 - 6 - 0.2. 4441 A further 3 kg of solution of mola~ses are then pa~sed through the column. This now gives a solution having a pH
of 5.3.
Example 8 Example 6 is repeated with the alteration that beet molasses of Example 7 are employed.
~his gives 6 kg of solution of molasses having a pH of 4.7.
Example 9 Molasses consisting of 25~ cane molasses and 75% beet molasses are diluted with the same amount of water. The pH of the solution of mola3~es is 7.2.
~he procedure is as in Example 6. After 6.9 kg have been put through, the pH is 4.7. A pH of 5.0 is measured after 8.8 kg have been put through.
Rxample 10 Produ¢tion of baker' 8 yeast 5 kg of solution of molasses having a pH of 5.0 are prepared in accordance with Example 4.
In a 20-litre fermenter, 21 g of NH~Cl and 10 ml of concentrated H3P04 are treated with 10 1 of water, and 400 g of perpetuated yeast (strain DHW S-3, by Deut~che Hefewerke, D-4370 Narl) are added. The fermentation takes place at 30~C under aerobic conditions and with molass~s being fed in. The pN is kept constsnt at 5.0 by metering in ammonia solution. After a fermentation time of 24 hours, about 2,400 g of baker's yea~t (43 to 47~
protein, light colour) are harvested. The yeast produced in thi~ way corresponds qualitatively to a baker's yeast - 7 - O.Z. 4441 which is fermented by a solution of mola~ses acidified with ~ulphuric acid (the amount~ of yea~t are based on 27~ dry matter).
Example 11 Production of alcohol In a 20-litre fermenter, 6 kg of solution of molasses from Example 3 are d~luted with 4 kg of water, and a pH
of S.5 is then established with NH3-water. To thi~ there are added 200 ml of a nutrient salt solution containing 25 g of RH2P0~ per litre and 50 g of MgS0~ per litre, and also 100 g of Saccharomyces cerevisiae (27% dry matter, strain DHW S-3, by Deutsche Hefewerke, D-4370 Marl), after which an anaerobic fermentation takes place for 30 hours at 30C and at a p~ of 5.5.
After this period, the concentration of alcohol is 9.45%
by volume, which corresponds to a yield of 750 g of alcohol.
of crude molasses and 75% of beet molasses, are diluted with 2 kg of water. The solution of molasses has a pH of 7.40. 500 ml of weakly àcid ion exchanger (type IV, made by Merck, D-6100 Darm~tadt) are now added. The solution i~ then stirred for 30 minutes at 25C. After this, the pH
of the ~olution of molasses is 5.10.
Example 2 The procedure i~ a~ in Example 1, with the difference that 2 kg of wash water from the ion exchanger is u~ed for dilution.
After the treatment with ion exchanger, the solution of mola~ses has a pH of 5.20.
Example 3 3 kg of molasses of Example 1 are diluted with water to give 6 kg of solution of molasses.
500 ml of ion exchanger (LEWATIq~ CNPLF, made by Bayer, D-5090 Leverku~en) are introduced into a chromatography column. The solution of molas~es is then passed through the column at ~ flow rate of 1.70 l/h. This gives 6 kg of ~olutlon of mola~se~ of a pH of 5.08.
Exa~ple 4 The procedure i8 a~ in Example 3, with the difference that 3.5 kg of mola~se~ are diluted to give 7 kg of solution of molas~e~, which are passed through the column at a flow rate of 2.8 l/h. Thi~ give~ 7 kg of solution of mola~ses of a pH of 5Ø
A furth~r 6 kg of ~olution of molasses are passed through -` 2~2~3 - S - O.Z. 4441 the column. This now gives a solution having a pH of 5.35.
ExamPle 5 1.25 kg of beet molasse~ (from Clauen) are diluted with 1.25 kg of water. The solution of molasses now ha~ a pH
of 9.2. The subsequent procedure iB as in Exsmple 3, with the difference that 500 ml of ion exchanger of Example 1 are used. $he flow rate is 1 l/h, and the temperature is 25C.
lQ Thi~ give~ 2.5 kg of solution of molasses having a pH of 5Ø
A further 3.5 kg of the ssme solution of molasses are then passed through the column. This procedure gives a solution having a pH of 5.4.
Example 6 3 kg of beet molasses of Example 5 are diluted with 3 kg of water.
~he conditions of Example 5 are then ad~usted, but the ion exchanger of Example 3 i~ used.
This gives 6 kg of eolution of molas~es havinq a pH of 4.9.
Exsmple 7 1.5 kg of beet molasse~ (from Belgium) are diluted with 1.5 kg of wster. ~he resulting solution of mola~ses has a pH of 8Ø
The procedure is a8 in ~xample 5. Thi~ proces~ giYes 3 kg of ~olution with a pH o~ 5Ø
2~2~ 3 - 6 - 0.2. 4441 A further 3 kg of solution of mola~ses are then pa~sed through the column. This now gives a solution having a pH
of 5.3.
Example 8 Example 6 is repeated with the alteration that beet molasses of Example 7 are employed.
~his gives 6 kg of solution of molasses having a pH of 4.7.
Example 9 Molasses consisting of 25~ cane molasses and 75% beet molasses are diluted with the same amount of water. The pH of the solution of mola3~es is 7.2.
~he procedure is as in Example 6. After 6.9 kg have been put through, the pH is 4.7. A pH of 5.0 is measured after 8.8 kg have been put through.
Rxample 10 Produ¢tion of baker' 8 yeast 5 kg of solution of molasses having a pH of 5.0 are prepared in accordance with Example 4.
In a 20-litre fermenter, 21 g of NH~Cl and 10 ml of concentrated H3P04 are treated with 10 1 of water, and 400 g of perpetuated yeast (strain DHW S-3, by Deut~che Hefewerke, D-4370 Narl) are added. The fermentation takes place at 30~C under aerobic conditions and with molass~s being fed in. The pN is kept constsnt at 5.0 by metering in ammonia solution. After a fermentation time of 24 hours, about 2,400 g of baker's yea~t (43 to 47~
protein, light colour) are harvested. The yeast produced in thi~ way corresponds qualitatively to a baker's yeast - 7 - O.Z. 4441 which is fermented by a solution of mola~ses acidified with ~ulphuric acid (the amount~ of yea~t are based on 27~ dry matter).
Example 11 Production of alcohol In a 20-litre fermenter, 6 kg of solution of molasses from Example 3 are d~luted with 4 kg of water, and a pH
of S.5 is then established with NH3-water. To thi~ there are added 200 ml of a nutrient salt solution containing 25 g of RH2P0~ per litre and 50 g of MgS0~ per litre, and also 100 g of Saccharomyces cerevisiae (27% dry matter, strain DHW S-3, by Deutsche Hefewerke, D-4370 Marl), after which an anaerobic fermentation takes place for 30 hours at 30C and at a p~ of 5.5.
After this period, the concentration of alcohol is 9.45%
by volume, which corresponds to a yield of 750 g of alcohol.
Claims (10)
1. A process for acidifying a dilute solution of molasses, which comprises treating the solution of molasses with an ion exchanger.
2. A process according to claim 1, wherein 10 to 70 solution of molasses is employed.
3. A process according to claim 1, wherein the ion exchanger is a weakly acid cation exchanger.
4. A process according to claim 1, wherein 100 to 700 ml of ion exchanger are used per kg of molasses.
5. A process according to claim 4, wherein 120 to 300 ml of ion exchanger are used per kg of molasses.
6. Use of a solution of molasses acidified according to claim 1 for producing fermentation products.
7. Use of a solution of molasses acidified according to claim 6 for producing yeast biomass.
8. Use of a solution of molasses, acidified according to claim 6 for producing alcohol by fermentation.
9. A process according to claim 1, wherein the ion exchanger is an acid cation exchanger.
10. A process according to claim 1, wherein the ion exchanger is a strongly acid cation exchanger.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP3937126.3 | 1989-11-08 | ||
DE3937126A DE3937126A1 (en) | 1989-11-08 | 1989-11-08 | METHOD FOR THE ACIDIFICATION OF MELASS SOLUTIONS |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2029403A1 true CA2029403A1 (en) | 1991-05-09 |
Family
ID=6393082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002029403A Abandoned CA2029403A1 (en) | 1989-11-08 | 1990-11-06 | Process for acidifying solutions of molasses |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0426973B1 (en) |
AT (1) | ATE109832T1 (en) |
AU (1) | AU631263B2 (en) |
CA (1) | CA2029403A1 (en) |
DE (2) | DE3937126A1 (en) |
DK (1) | DK0426973T3 (en) |
ES (1) | ES2058712T3 (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2554803B1 (en) * | 1983-11-16 | 1986-03-28 | Sgn Soc Gen Tech Nouvelle | PROCESS FOR THE RECOVERY OF CHARGED LIQUIDS |
JPS60149399A (en) * | 1984-01-12 | 1985-08-06 | Sawao Murao | Measurement of aspartate aminotransferase isozyme |
SE450897B (en) * | 1986-01-31 | 1987-08-10 | Nobel Chematur Ab | PROCEDURE FOR THE PREPARATION OF ETHANOL BY MELASSESHING |
-
1989
- 1989-11-08 DE DE3937126A patent/DE3937126A1/en not_active Withdrawn
-
1990
- 1990-09-10 DK DK90117359.1T patent/DK0426973T3/en active
- 1990-09-10 DE DE59006759T patent/DE59006759D1/en not_active Expired - Fee Related
- 1990-09-10 AT AT90117359T patent/ATE109832T1/en not_active IP Right Cessation
- 1990-09-10 ES ES90117359T patent/ES2058712T3/en not_active Expired - Lifetime
- 1990-09-10 EP EP90117359A patent/EP0426973B1/en not_active Expired - Lifetime
- 1990-11-06 CA CA002029403A patent/CA2029403A1/en not_active Abandoned
- 1990-11-07 AU AU65902/90A patent/AU631263B2/en not_active Ceased
Also Published As
Publication number | Publication date |
---|---|
ATE109832T1 (en) | 1994-08-15 |
AU6590290A (en) | 1991-05-16 |
AU631263B2 (en) | 1992-11-19 |
DK0426973T3 (en) | 1994-12-12 |
EP0426973A1 (en) | 1991-05-15 |
EP0426973B1 (en) | 1994-08-10 |
DE3937126A1 (en) | 1991-05-16 |
ES2058712T3 (en) | 1994-11-01 |
DE59006759D1 (en) | 1994-09-15 |
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