CA2271519A1 - Process for the separation of tetrahydropyrimidine derivatives - Google Patents
Process for the separation of tetrahydropyrimidine derivatives Download PDFInfo
- Publication number
- CA2271519A1 CA2271519A1 CA 2271519 CA2271519A CA2271519A1 CA 2271519 A1 CA2271519 A1 CA 2271519A1 CA 2271519 CA2271519 CA 2271519 CA 2271519 A CA2271519 A CA 2271519A CA 2271519 A1 CA2271519 A1 CA 2271519A1
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- CA
- Canada
- Prior art keywords
- process according
- adsorption
- compounds
- solution
- zeolites
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/16—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention relates to a process for the separation of tetrahydropyrimidine derivatives, especially 2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (ectoines)and 2-methyl,5-hydroxyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (hydroxyectoines), which are present together in aqueous solutions, especially fermentation broths, by selective adsorption of one component on zeolites.
Description
Process for the separation of tetrahydropyrimidine derivatives The invention relates to a process for the separation of tetrahydropyrimidine derivatives, especially 2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (ectoines) and 2-methyl,5-hydroxyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (hydroxyectoines), which are present together in aqueous solutions, by selective adsorption of one component on zeolites.
Tetrahydropyrimidine derivatives refer in particular to the compounds known from EP-A1-0553884.
Structurally, ectoines are cyclic amino acid derivatives, which belong to the class of so-called "compatible solutes". They are also compatible with cytoplasm in high concentration and stabilise the cell components in a medium with low water activity. This action indicates a broad field of application in medical and cosmetic sectors.
Owing to new biotechnological processes it has become possible to culture halophilic eubacteria, e.g. of the Halomonas species, and to cause these organisms to separate out the ectoines into the medium surrounding them (T. Sauer et al. GIT Fachz. Lab. 10/95).
Since both ectiones [sic] and hydroxyectoines are produced, depending on the fermentation conditions, it is necessary to separate these two components in the subsequent processing steps in order to obtain the pure components.
This separation may take place for instance by extraction with methanol, utilising the different solubilities of ectoine and hydroxyectoine (T. Sauer and Erwin A. Galinski.
Biotechnology and Bioengineering, VOL. 57, NO 3, 1998).
Tetrahydropyrimidine derivatives refer in particular to the compounds known from EP-A1-0553884.
Structurally, ectoines are cyclic amino acid derivatives, which belong to the class of so-called "compatible solutes". They are also compatible with cytoplasm in high concentration and stabilise the cell components in a medium with low water activity. This action indicates a broad field of application in medical and cosmetic sectors.
Owing to new biotechnological processes it has become possible to culture halophilic eubacteria, e.g. of the Halomonas species, and to cause these organisms to separate out the ectoines into the medium surrounding them (T. Sauer et al. GIT Fachz. Lab. 10/95).
Since both ectiones [sic] and hydroxyectoines are produced, depending on the fermentation conditions, it is necessary to separate these two components in the subsequent processing steps in order to obtain the pure components.
This separation may take place for instance by extraction with methanol, utilising the different solubilities of ectoine and hydroxyectoine (T. Sauer and Erwin A. Galinski.
Biotechnology and Bioengineering, VOL. 57, NO 3, 1998).
However, this process is expensive on an industrial scale owing to the considerable quantities of methanol required.
The object of the invention is to provide an alternative process which permits an effective separation of tetrahydropyrimidine derivatives, especially ectoines and hydroxyectoines, from an aqueous solution optionally contained [sic] other organic and inorganic compounds without the use of solvents.
The invention provides a process for the separation of tetrahydropyrimidines present in aqueous solution from the corresponding hydroxy compounds, especially of 2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (ectoines (I)) 2-methyl,5-hydroxyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (hydroxyectoines)(II) which are present together in aqueous solutions, characterised in that the aqueous solutions containing the two components are brought into contact with a preferably acidic zeolite having a modulus of 15 to 1000 at a pH of 1.5 to 7Ø This results in a kinetically preferential adsorption of ectoine compared with hydroxyectoine. By adjusting the contact time between zeolite and solution to an optimum value to be determined experimentally, a selective depletion of ectoine from the starting solution occurs, while the hydroxyectoine remains in solution initially and is adsorbed in significant quantity only with prolonged contact times. The ectoine derivatives bonded to the zeolite are desorbed from the zeolite used by adjusting the pH to >8.0, especially using an ammonium hydroxide solution. The solution may also be adjusted to this pH value by adding another basic, optionally organic component, especially lysine.
Depending on the required purity of the derivatives to be isolated, the purification process may optionally be carried out in multiple consecutive steps.
The object of the invention is to provide an alternative process which permits an effective separation of tetrahydropyrimidine derivatives, especially ectoines and hydroxyectoines, from an aqueous solution optionally contained [sic] other organic and inorganic compounds without the use of solvents.
The invention provides a process for the separation of tetrahydropyrimidines present in aqueous solution from the corresponding hydroxy compounds, especially of 2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (ectoines (I)) 2-methyl,5-hydroxyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (hydroxyectoines)(II) which are present together in aqueous solutions, characterised in that the aqueous solutions containing the two components are brought into contact with a preferably acidic zeolite having a modulus of 15 to 1000 at a pH of 1.5 to 7Ø This results in a kinetically preferential adsorption of ectoine compared with hydroxyectoine. By adjusting the contact time between zeolite and solution to an optimum value to be determined experimentally, a selective depletion of ectoine from the starting solution occurs, while the hydroxyectoine remains in solution initially and is adsorbed in significant quantity only with prolonged contact times. The ectoine derivatives bonded to the zeolite are desorbed from the zeolite used by adjusting the pH to >8.0, especially using an ammonium hydroxide solution. The solution may also be adjusted to this pH value by adding another basic, optionally organic component, especially lysine.
Depending on the required purity of the derivatives to be isolated, the purification process may optionally be carried out in multiple consecutive steps.
The tetrahydropyrimidine derivatives to be separated according to the invention are understood to be in particular compounds of the formula s , ~. .2 COOL C H COO"
CH
wherein R1: H and R2: OH.
The solutions from which these substances are separated are generally aqueous or organic by nature.
Suitable zeolites for the adsorption of the compounds to be separated according to the invention are those of the types Y, DAY, mordenite, dealuminised mordenite, ZSM-5, ' dealuminised ZSM-5, (3 or VPIS and with a modulus of 10 to 1000, especially of 15 to 200, preferably of 15 to 45. The ZSM-5 type is preferably used in the H-, ,ammonium- or Na form.
The process generally takes place in a temperature range of between 15 and 80°C, preferably 20 to 40° C.
The concentrations of the ectoines or hydroxyextoines [sic]
to be separated vary within the known solubility range. The (molar) concentration ratios of the compounds to be separated which are common in the prior art may be worked up by the process according to the invention and provide the desired product in the required purity. The adsorbents are used in powder form, as mouldings or fixed on substrates. The batch, fixed bed or cross-flow filtration processes, conducted continuously or in batches, are available for the technical implementation of the process.
In an advantageous embodiment, the adsorption on zeolite is combined with cross-flow filtration in which a solution containing the tetrahydropyrimidine derivatives, optionally freed from the biomass, is brought into contact with the suspensions of an acidic zeolite for a period of time appropriate to the adsorption kinetics and then the hydroxytetrapyrimidine derivatives present in the supernatant liquid are separated by cross-flow filtration, in which a) the charged zeolites in the form of suspensions are made to flow past a porous surface/membrane, b) a pressure difference being set up between the side of the surface/membrane subject to the flow and the opposite side, so that c) part of the solution containing the hydroxy compounds, completely or partially freed from the adsorbed compounds, flowing over the surface/membrane flows through the surface/membrane transverse to the direction of flow (filtrate flow) d) in a washing step the solution freed from the adsorbed compounds, which contains the hydroxy compounds, is separated off, and e) the adsorbed compounds are then desorbed.
The latter takes place at an appropriate pH, especially at a pH >8Ø
Fine particle size zeolite powders of the types mentioned above with a particle diameter of 1 to 100 Vim, especially 2 to 20 Vim, are particularly suitable as adsorbents. The short intraparticle diffusion paths permit high adsorption selectivities and thus high separation factors.
The purities achieved for hydroxyectoine in the supernatant liquid (based on total ectoine) are 100% when using e.g.
CH
wherein R1: H and R2: OH.
The solutions from which these substances are separated are generally aqueous or organic by nature.
Suitable zeolites for the adsorption of the compounds to be separated according to the invention are those of the types Y, DAY, mordenite, dealuminised mordenite, ZSM-5, ' dealuminised ZSM-5, (3 or VPIS and with a modulus of 10 to 1000, especially of 15 to 200, preferably of 15 to 45. The ZSM-5 type is preferably used in the H-, ,ammonium- or Na form.
The process generally takes place in a temperature range of between 15 and 80°C, preferably 20 to 40° C.
The concentrations of the ectoines or hydroxyextoines [sic]
to be separated vary within the known solubility range. The (molar) concentration ratios of the compounds to be separated which are common in the prior art may be worked up by the process according to the invention and provide the desired product in the required purity. The adsorbents are used in powder form, as mouldings or fixed on substrates. The batch, fixed bed or cross-flow filtration processes, conducted continuously or in batches, are available for the technical implementation of the process.
In an advantageous embodiment, the adsorption on zeolite is combined with cross-flow filtration in which a solution containing the tetrahydropyrimidine derivatives, optionally freed from the biomass, is brought into contact with the suspensions of an acidic zeolite for a period of time appropriate to the adsorption kinetics and then the hydroxytetrapyrimidine derivatives present in the supernatant liquid are separated by cross-flow filtration, in which a) the charged zeolites in the form of suspensions are made to flow past a porous surface/membrane, b) a pressure difference being set up between the side of the surface/membrane subject to the flow and the opposite side, so that c) part of the solution containing the hydroxy compounds, completely or partially freed from the adsorbed compounds, flowing over the surface/membrane flows through the surface/membrane transverse to the direction of flow (filtrate flow) d) in a washing step the solution freed from the adsorbed compounds, which contains the hydroxy compounds, is separated off, and e) the adsorbed compounds are then desorbed.
The latter takes place at an appropriate pH, especially at a pH >8Ø
Fine particle size zeolite powders of the types mentioned above with a particle diameter of 1 to 100 Vim, especially 2 to 20 Vim, are particularly suitable as adsorbents. The short intraparticle diffusion paths permit high adsorption selectivities and thus high separation factors.
The purities achieved for hydroxyectoine in the supernatant liquid (based on total ectoine) are 100% when using e.g.
5 ZSMS/28 after a contact time of 1 h (Example 1). In the case of mordenite 30 the purities are approx. 60% after 24 h owing to slower kinetics (Example 2). However, they can be increased with an appropriate combination of the process steps.
To increase the purity, the solutions are transferred into the purification process according to the invention one or more times. A variant of the process according to the invention consists in combining it with purification processes known from the prior art by using organic cation exchangers and other purification steps.
An appropriate adsorption and desorption step takes place before and/or after a purification step by adsorption on one of the zeolites used according to the invention, which has been followed by desorption.
To increase the purity, the solutions are transferred into the purification process according to the invention one or more times. A variant of the process according to the invention consists in combining it with purification processes known from the prior art by using organic cation exchangers and other purification steps.
An appropriate adsorption and desorption step takes place before and/or after a purification step by adsorption on one of the zeolites used according to the invention, which has been followed by desorption.
Example 1 Adsorption of an ectione [sic]/hydroxyectoine mixture on Time-related concentration curves for ectoine and hydroxyectoine and the purities for hydroxyectoine (based on total ectoine) Starting solution composition Volume of liquid [ml~ 30 Zeolite concentration [wt. %7 10 Ectoine concentration 1.5 Lg/11 Hydroxyectoine concentration 0.14 Lg/11 Other impurities [g/1] ca. 1 l.o0 loo.oo o.so O o Ectoine x.00 p O Hyd~oxyectoine O '~~p Hydroxyectoine purity O O
0.60 60.00 v L
C/CO y, 0.40 ~ 40.00 c m ~o 0.20 20.00 0.00 ~ 0. 6~:r Q ' ~ ~ 0.00 Time [hJ
0.60 60.00 v L
C/CO y, 0.40 ~ 40.00 c m ~o 0.20 20.00 0.00 ~ 0. 6~:r Q ' ~ ~ 0.00 Time [hJ
Example 2 Adsorption of an ectione [sic]/hydroxyectoine mixture on mordenite 30 Time-related concentration curves for ectoine and hydroxyectoine and the purities for hydroxyectoine (based on total ectoine) in the supernatant liquid Starting solution composition Volume of liquid [ml] 30 Zeolite concentration [wt. ~] 10 Ectoine concentration 1.5 [g/11 Hydroxyectoine concentration 0.14 Ig/11 .
Other impurities [g/1] ca. 1 '.°° 0 0 0 '°°.°°
a Ectoine O hlydroxyectoine O
O Hydroxyectoine pu~ty , 0.80 80.00 0.60 ~ a ~ 80.00 O
a CICo a m 0.40 40.00 c O
a m a x a 0.20 C 20.00 a 0.00 , ~ 0.oa Tlme (h]
Other impurities [g/1] ca. 1 '.°° 0 0 0 '°°.°°
a Ectoine O hlydroxyectoine O
O Hydroxyectoine pu~ty , 0.80 80.00 0.60 ~ a ~ 80.00 O
a CICo a m 0.40 40.00 c O
a m a x a 0.20 C 20.00 a 0.00 , ~ 0.oa Tlme (h]
Claims (14)
1. Process for the separation of tetrahydropyrimidines present in aqueous solution from the corresponding hydroxy compounds, characterised in that the aqueous solutions of these compounds are brought into contact with an acidic zeolite having a modulus of 15 to 1000 at a pH of 1.0 to 7.0, the supernatant liquid preferentially containing the hydroxy compounds is separated after adsorption is complete and the adsorbed derivatives are desorbed from the zeolites with an aqueous solution adjusted to a pH of >8.0 optionally by adding a basic organic component.
2. Process according to claim 1, characterised in that a mixture of 2-methyl-1,4,5,6-tetrahydropyrimidine-4-carboxylic acids (ectoines) of the general formula wherein R1:H and R2:OH, present in aqueous solution, is separated.
3. Process according to claims 1 and 2, characterised in that the supernatant liquid obtained after adsorption is again brought into contact with one of the above mentioned types of zeolite, the adsorbent is then separated off and these steps are optionally repeated one or more times.
4. Process according to claims 1 to 3, characterised in that a fermentation solution is used as the aqueous solution.
5. Process according to claim 4, characterised in that before the adsorption the micro-organisms are at least partly separated out of the fermentation solution.
6. Process according to claims 4 and 5, characterised in that before the adsorption the soluble proteins are at least partly separated out of the fermentation solution.
7. Process according to one or more of claims 1 to 6, characterised in that acid zeolites of the types Y, DAY, mordenite, dealuminised mordenite, ZSM-5, dealuminised ZSM-5, .beta. or VPI-5 with a modulus of 15 to 1000 are used as adsorbents.
8. Process according to claim 6, characterised in that zeolites of the ZSM5 type or mordenite are used in the H-, ammonium or Na form.
9. Process according to one or more of claims 1 to 8 for the separation of the tetrahydropyrimidine derivatives
10 mentioned above, especially according to formula (I), characterised in that it is combined with a cross-flow filtration, wherein a) the charged zeolites in the form of suspensions are made to flow past a porous surface/membrane, b) a pressure difference being set up between the side of the surface/membrane subject to the flow and the opposite side, so that c) part of the solution containing the hydroxy compounds, completely or partially freed from the adsorbed compounds, flowing over the surface/membrane flows through the surface/membrane transverse to the direction of flow (filtrate flow) d) in a washing step the solution freed from the adsorbed compounds, which contains the hydroxy compounds, is separated off, and e) the adsorbed compounds are then desorbed.
10. Process according to claim 9, characterised in that zeolites with an average particle diameter of 1 to 100 µm are used.
10. Process according to claim 9, characterised in that zeolites with an average particle diameter of 1 to 100 µm are used.
11. Process according to claims 9 and 10, characterised in that a trans-membrane pressure of 0.2 to 3 bar is established.
12. Process according to claims 9 to 11, characterised in that ceramic or organic membranes/porous surfaces with ultrafiltration or micro- or nanofiltration properties are used.
13. Process according to one or more of the above claims, characterised in that the desorbed solution is subjected to adsorption and desorption one or more times.
14. Process according to one or more of the above claims, characterised in that the process for the separation of compounds (A) is combined with adsorption on cation exchangers or other purification steps and the solutions obtained therefrom, optionally repeatedly, by desorption.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1998121378 DE19821378A1 (en) | 1998-05-13 | 1998-05-13 | Process for the separation of tetrahydropyrimidine derivatives |
| DE19821378.6 | 1998-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2271519A1 true CA2271519A1 (en) | 1999-11-13 |
Family
ID=7867601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2271519 Abandoned CA2271519A1 (en) | 1998-05-13 | 1999-05-12 | Process for the separation of tetrahydropyrimidine derivatives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0957174A1 (en) |
| JP (1) | JPH11349574A (en) |
| CA (1) | CA2271519A1 (en) |
| DE (1) | DE19821378A1 (en) |
| SK (1) | SK62599A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669560A (en) * | 2016-01-12 | 2016-06-15 | 天津科技大学 | Method for separating and extracting tetrahydropyrimidine from fermentation broth |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10047444A1 (en) * | 2000-09-21 | 2002-04-11 | Bitop Gmbh | Process for the separation and high-purity isolation of low-molecular, structurally similar compounds, in particular of tetrahydropyrimidine derivatives such as e.g. 1,4,5,6-tetrahydro-2-methyl-4-pyrimidinecarboxylic acids (ectoins) and their cleavage products |
| DE10200068A1 (en) * | 2002-01-03 | 2003-07-17 | Merck Patent Gmbh | Process for the chromatographic separation of ectoin |
| CN104557729B (en) * | 2014-12-11 | 2017-02-22 | 山东福田科技集团有限公司 | Tetrahydropyrimidine extraction process |
| CN109053587A (en) * | 2018-08-31 | 2018-12-21 | 山东福田药业有限公司 | A method of the separation and Extraction tetrahydropyrimidine from halophilic microorganism fermentation liquid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4910336A (en) * | 1988-11-25 | 1990-03-20 | Uop | Process for separating phenylalanine from salts |
| IL100810A (en) * | 1992-01-30 | 1996-12-05 | Yeda Res & Dev | Pharmaceutical compositions comprising 2-methyl-4-carboxy-5-hydroxy-tetrahydropyrimidine and/or 2-methyl-4-carboxy-tetrahydropyrimidine methods for the isolation and purification of said compounds and substantially pure 2-methyl-4-carboxy-5-hydroxy-3, 4, 5, 6-tetrahydropyrimidine salts 5-ethers and 5-esters thereof |
| DE4217203C2 (en) * | 1992-05-23 | 1995-09-21 | Degussa | Process for separating amino acids from aqueous solutions |
| DE19617729A1 (en) * | 1996-05-03 | 1997-11-13 | Degussa | Crossflow filtration process for the separation of organic compounds after adsorption on inorganic solids |
| DE19711082A1 (en) * | 1997-03-18 | 1998-09-24 | Degussa | Process for the separation of tetrahydropyrimidines from aqueous solutions |
-
1998
- 1998-05-13 DE DE1998121378 patent/DE19821378A1/en not_active Withdrawn
-
1999
- 1999-05-03 EP EP99108790A patent/EP0957174A1/en not_active Withdrawn
- 1999-05-10 SK SK62599A patent/SK62599A3/en unknown
- 1999-05-12 CA CA 2271519 patent/CA2271519A1/en not_active Abandoned
- 1999-05-13 JP JP13297499A patent/JPH11349574A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669560A (en) * | 2016-01-12 | 2016-06-15 | 天津科技大学 | Method for separating and extracting tetrahydropyrimidine from fermentation broth |
| CN105669560B (en) * | 2016-01-12 | 2019-02-19 | 天津科技大学 | A method of the separation and Extraction tetrahydropyrimidine from fermentation liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0957174A1 (en) | 1999-11-17 |
| SK62599A3 (en) | 2000-02-14 |
| DE19821378A1 (en) | 1999-11-18 |
| JPH11349574A (en) | 1999-12-21 |
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