CN101328109A - Method for separating and purifying 1,3-propanediol in fermentation liquor by means of five-region simulated moving bed - Google Patents
Method for separating and purifying 1,3-propanediol in fermentation liquor by means of five-region simulated moving bed Download PDFInfo
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- CN101328109A CN101328109A CNA2008100230101A CN200810023010A CN101328109A CN 101328109 A CN101328109 A CN 101328109A CN A2008100230101 A CNA2008100230101 A CN A2008100230101A CN 200810023010 A CN200810023010 A CN 200810023010A CN 101328109 A CN101328109 A CN 101328109A
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Abstract
The invention discloses a method for separating and purifying the 1,3-propylene glyol in the fermentation broth in a simulated moving bed at five zone comprising the specific steps: (1) removing cells, proteins and polysaccharide impurities by flocculation, ultrafiltration and centrifugation of the 1,3-propylene glyol yeast fermentation broth; (2) decoloring the fermentation broth by passing active carbon after ultrafiltration; (3) concentrating the decolored 1,3-propylene glyol fermentation broth under vacuum at 60 DEG C till the volume accounts for 15% of the original volume, obtaining the fermentation broth crude extracts after crystallization and desalination when the temperature is 10 DEG C while the concentration of 1,3-propylene glyol is 5%-40%; (4) separating and purifying the 1,3-propylene glyol fermentation broth crude extracts in a simulated moving bed at five zone filling with UBK555 type cation exchange resin. The method of the invention utilizes the property difference in physics, chemical and biology between the target product and coexisting impurities in the solution and achieves the purpose of separation and purification of 1,3-propylene glyol by means of simulated moving bed, wherein the product purity can reach more than 99% and the yield can reach more than 70%.
Description
Technical field
The invention belongs to industrial chemicals product manufacture field, relate in the five-region simulated moving bed separation and purification fermented liquid 1, the method for ammediol.
Background technology
1, ammediol (1,3-PD) be colourless, tasteless, transparent liquid, it is a kind of important chemical material, be mainly used in the synthetic of thickening material, washing composition, sanitas, emulsifying agent, also be used for industries such as food, makeup and pharmacy, its topmost purposes is the macromolecular material as the synthetic excellent performance of polymer monomer.
Present 1, the preparation method of ammediol has two kinds of chemical synthesis and microbe fermentation methods.Chemical synthesis has acrolein hydration method, epoxyethane method, formaldehyde and acetaldehyde condensation method, 1,3-propylene dichloride hydrolysis method ..., but big owing to energy consumption, cost is high, by product is many, purity is low and reason such as technology controlling and process difficulty, has limited large-scale production.
Current biological process produces 1, and ammediol enjoys the whole world to pay close attention to.Compare with traditional chemical synthesis, fermentative Production 1, ammediol has advantages such as raw material sources are renewable, reaction conditions is gentle, selectivity is good, by product is few, environmental pollution is low, effectively extracts 1 from fermented liquid, and ammediol is the key that biological process is produced.
Hu Gu etc. adopt multiple-effect evaporation to concentrate 1, and the method for ammediol dilute solution prepares high purity product, but energy consumption is too big; Utilize liquid-liquid extraction method to separate 1, the effect that ammediol is not obtained to great waves etc.
" four-area simulated moving bed separation 1, the method for ammediol " of number of patent application 2007100229044 obtained effect preferably, but purity and productive rate are lower.
Summary of the invention
The objective of the invention is to: provide in the five-region simulated moving bed separation and purification fermented liquid 1, the method of ammediol, adopt five-region simulated moving bed chromatographic separation 1, ammediol, the realization serialization is produced, under the condition that guarantees product purity, reach the higher rate of recovery and production intensity, and reduce pollution effectively environment.
Technical solution of the present invention is: adopt in the five-region simulated moving bed separation and purification fermented liquid 1, and ammediol, step is as follows:
(1) with 1, the ammediol yeast fermentation broth is by flocculation, ultrafiltration and centrifugal removal thalline, protein and polysaccharide impurity;
(2) fermented liquid after the ultrafiltration is passed through activated carbon decolorizing;
(3) 1 after will decolouring, the ammediol fermented liquid is concentrated into 15% of original volume by 60 ℃ of vacuum decompressions, and be cooled to 10 ℃ of crystallization desalinations and get fermentation broth coarse extract, 1, ammediol concentration is 5%--40%;
(4) adopt the simulation moving-bed separation and purification 1 that is filled with UBK555 type Zeo-karb, the ammediol fermentation broth coarse extract gets 1, the ammediol refined solution.
In the five-region simulated moving bed separation and purification fermented liquid of the present invention 1, in the method for ammediol, five-region simulated moving bed initial time called after district 0, district I, district II, district III, the district IV of respectively distinguishing, each switching instant just periodically by turns once, be transformed to district I, district II, district III, district IV successively, district 0; Each district is composed in series by 1-4 root fixed-bed ion exchanger, every root chromatogram column is of a size of L1500mm * D100mm, exit end by last root chromatogram column is connected by check valve successively with the entrance end of back one root chromatogram column, and the exit end of last root chromatogram column is connected with the entrance end of first root chromatogram column; Wherein distinguish 0 between No. 1 elutriant inlet and No. 2 extracting liquid outlets, distinguishing in 0 impurity in the desorb fermented liquid; District I between No. 2 elutriants inlet and No. 1 extracting liquid outlet, in distinguishing I in the purified fermentation broth 1, ammediol; District II between No. 1 extracting liquid outlet and injection port, the impurity in absorption repeatedly in district II, desorb, the concentrated broth; District III separates weak absorption impurity in district III between injection port and raffinate outlet; District IV is between No. 3 elutriants inlet and elutriant loop exit, and elutriant is cleaned the back and enters district's 0 recycle with fresh elutriant on the one hand, will distinguish IV on the other hand and distinguish 0 and separate the component that prevents in the raffinate and enter and distinguish 0 and pollute.
In the five-region simulated moving bed separation and purification fermented liquid of the present invention 1, in the method for ammediol, adopt the 0.1-0.5M NaOH aqueous solution as elutriant, elutriant flow 200-800ml/min, pressure 1-10Mpa; Sample introduction flow 50-300ml/min, pressure 1-10Mpa; Extracting solution and raffinate flow velocity are controlled by pressure regulating valve, pressure 1-10Mpa; Valve switching time is 5-30min; Whole simulation moving-bed temperature is 20-60 ℃, 20-60 ℃ of sample introduction liquid, elutriant temperature; Collect 1 from No. 1 extracting liquid outlet, the ammediol refined solution obtains impurity from No. 2 extracting liquid outlets and raffinate outlet.
Beneficial effect of the present invention: 1. five-region simulated moving bed is by the many identical cation exchange resin column series connection of character, the switching in order in difference in functionality district between i.e. absorption by the strong and weak absorbed component in the ion exchange process, refining, desorb, the resin regeneration, according to 1, ammediol separates with the different principle of impurity equilibrium system on separating medium, and the position that the switching of employing combination valve changes opening for feed, raffinate outlet, moving phase inlet, extracting liquid outlet obtains target product; 2. be based upon inwardly isolating continuously, utilize in the solution between the target product and coexistent impurity difference in physics, chemistry and biological property, make it in lock out operation, have different rate of mass transfer and equilibrium state, by simulation moving-bed realization 1, the ammediol separation and purification, good product purity, yield height, output are big, and product purity can reach more than 99%, yield reaches more than 70%.
Description of drawings
Fig. 1 is the schematic block diagram of five-region simulated moving bed clastotype of the present invention.
Among the figure: 1. distinguish 0,2. district I3. district II, 4. district III, 5. district IV, 6.1 number elutriant inlet, No. 7.2 extracting liquid outlets, No. 8.2 elutriant inlets, No. 9.1 extracting liquid outlets, 10. injection port, the outlet of 11. raffinates, No. 12.3 elutriant inlets, 13. elutriant loop exits.
Embodiment
Adopt in the five-region simulated moving bed separation and purification fermented liquid 1, ammediol, step is as follows:
(1) with 1, the ammediol yeast fermentation broth is by flocculation, ultrafiltration and centrifugal removal thalline, protein and polysaccharide impurity;
(2) fermented liquid after the ultrafiltration is passed through activated carbon decolorizing;
(3) 1 after will decolouring, the ammediol fermented liquid is concentrated into 15% of original volume by 60 ℃ of vacuum decompressions, and be cooled to 10 ℃ of crystallization desalinations and get fermentation broth coarse extract, 1, ammediol concentration is 5%--40%;
(4) adopt the simulation moving-bed separation and purification 1 that is filled with UBK555 type Zeo-karb, the ammediol fermentation broth coarse extract gets 1, the ammediol refined solution.
As shown in Figure 1, in the five-region simulated moving bed separation and purification fermented liquid of the present invention 1, in the method for ammediol, five-region simulated moving bed initial time called after district 0, district I, district II, district III, the district IV of respectively distinguishing, each switching instant just periodically by turns once, be transformed to district I, district II, district III, district IV successively, district 0; Each district is composed in series by 1-4 root fixed-bed ion exchanger, every root chromatogram column is of a size of L1500mm * D100mm, exit end by last root chromatogram column is connected by check valve successively with the entrance end of back one root chromatogram column, and the exit end of last root chromatogram column is connected with the entrance end of first root chromatogram column; Wherein distinguish 0 between 6 and No. 2 extracting liquid outlets 7 of No. 1 elutriant inlet, impurity in the desorb fermented liquid in district 0; District I between 8 and No. 1 extracting liquid outlets 9 of No. 2 elutriants inlet, in distinguishing I in the purified fermentation broth 1, ammediol; District II between No. 1 extracting liquid outlet 9 and injection port 10, the impurity in absorption repeatedly in distinguishing II, desorb, the concentrated broth; District III separates weak absorption impurity in district III between injection port 10 and raffinate outlet 11; District IV is between No. 3 elutriants inlet 12 and elutriant loop exit 13, and elutriant is cleaned the back and enters district's 0 recycle with fresh elutriant on the one hand, will distinguish IV on the other hand and distinguish 0 and separate the component that prevents in the raffinate and enter and distinguish 0 and pollute.
In the five-region simulated moving bed separation and purification fermented liquid of the present invention 1, in the method for ammediol, adopt the 0.1-0.5M NaOH aqueous solution as elutriant, elutriant flow 200-800ml/min, pressure 1-10Mpa; Sample introduction flow 50-300ml/min, pressure 1-10Mpa; Extracting solution and raffinate flow velocity are controlled by pressure regulating valve, pressure 1-10Mpa; Valve switching time is 5-30min; Whole simulation moving-bed temperature is 20-60 ℃, 20-60 ℃ of sample introduction liquid, elutriant temperature; Collect 1 from No. 1 extracting liquid outlet 9, the ammediol refined solution obtains impurity from No. 2 extracting liquid outlets 7 and raffinate outlet 11.
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these embodiment just in order to demonstrate the invention, but not limit the scope of the invention by any way.
Example 1: will anticipate over-richness and be 5% 1, the ammediol fermentation broth coarse extract, purifying preparation 1 on Hanbon Sci. ﹠ Tech. Co., Ltd. five-region simulated moving bed, ammediol, the chromatographic column that the configuration of every district is filled with Zeo-karb is respectively 2-4-2-4-2, flow rate of mobile phase in five districts is respectively 200,200,250,300,350ml/min, valve switching time is 5min, whole simulation moving-bed temperature is 20 ℃, feeding liquid, 20 ℃ of elutriant temperature, NaOH concentration is 0.1M in the elutriant, the sample introduction flow is: III flow in district subtracts district II flow, be 300-250=50mL/min, down together.Finally obtain 1, the purity of ammediol is 99.4%, the rate of recovery is 70%.
Example 2: will anticipate over-richness and be 20% 1, the ammediol fermentation broth coarse extract, purifying preparation 1 on Hanbon Sci. ﹠ Tech. Co., Ltd. five-region simulated moving bed, ammediol, the chromatographic column that the configuration of every district is filled with Zeo-karb is respectively 2-2-2-2-2, flow rate of mobile phase in five districts is respectively 300,250,300,400,550ml/min, valve switching time is 10min, whole simulation moving-bed temperature is 35 ℃, 35 ℃ of feeding liquid, elutriant temperature, NaOH concentration is 0.2M in the elutriant, and the sample introduction flow is 100mL/min.Finally obtain 1, the purity of ammediol is 99.3%, the rate of recovery is 78%.
Example 3: will anticipate over-richness and be 15% 1, the ammediol fermentation broth coarse extract, purifying preparation 1 on Hanbon Sci. ﹠ Tech. Co., Ltd. five-region simulated moving bed, ammediol, the chromatographic column that the configuration of every district is filled with Zeo-karb is respectively 2-4-2-4-2, flow rate of mobile phase in five districts is respectively 400,250,300,500,550ml/min, valve switching time is 15min, whole simulation moving-bed temperature is 40 ℃, 40 ℃ of feeding liquid, elutriant temperature, NaOH concentration is 0.3M in the elutriant, and the sample introduction flow is 200mL/min.Finally obtain 1, the pure of ammediol is 99.5%, the rate of recovery is 79%.
Example 4: will anticipate over-richness and be 25% 1, the ammediol fermentation broth coarse extract, purifying preparation 1 on Hanbon Sci. ﹠ Tech. Co., Ltd. five-region simulated moving bed, ammediol, the chromatographic column that the configuration of every district is filled with Zeo-karb is respectively 2-4-2-4-2, flow rate of mobile phase in five districts is respectively 600,450,300,550,750ml/min, valve switching time is 25min, whole simulation moving-bed temperature is 60 ℃, 60 ℃ of feeding liquid, elutriant temperature, NaOH concentration is 0.4M in the elutriant, and the sample introduction flow is 250mL/min.Finally obtain 1, the purity of ammediol is 99.4%, the rate of recovery is 81%.
Example 5: will anticipate over-richness and be 40% 1, the ammediol fermentation broth coarse extract, purifying preparation 1 on Hanbon Sci. ﹠ Tech. Co., Ltd. five-region simulated moving bed, ammediol, the chromatographic column that the configuration of every district is filled with Zeo-karb is respectively 4-4-4-4-4, flow rate of mobile phase in five districts is respectively 500,450,450,750,800ml/min, valve switching time is 30min, whole simulation moving-bed temperature is 55 ℃, 55 ℃ of feeding liquid, elutriant temperature, NaOH concentration is 0.5M in the elutriant, and the sample introduction flow is 300mL/min.Finally obtain 1, the pure of ammediol is 99.3%, the rate of recovery is 77%.
Claims (4)
1. in the five-region simulated moving bed separation and purification fermented liquid 1, the method for ammediol is characterized in that step is:
(1) with 1, the ammediol yeast fermentation broth is by flocculation, ultrafiltration and centrifugal removal thalline, protein and polysaccharide impurity;
(2) fermented liquid after the ultrafiltration is passed through activated carbon decolorizing;
(3) 1 after will decolouring, the ammediol fermented liquid is concentrated into 15% of original volume by 60 ℃ of vacuum decompressions, and be cooled to 10 ℃ of crystallization desalinations and get fermentation broth coarse extract, 1, ammediol concentration is 5%--40%;
(4) adopt the five-region simulated moving bed separation and purification 1 that is filled with UBK555 type Zeo-karb, the ammediol fermentation broth coarse extract gets 1, the ammediol refined solution.
2. in the five-region simulated moving bed separation and purification fermented liquid according to claim 11, the method of ammediol, it is characterized in that: five-region simulated moving bed initial time called after district 0 (1), district I (2), district II (3), district III (4), the district IV (5) of respectively distinguishing, each switching instant just periodically by turns once, be transformed to district I, district II, district III, district IV successively, district 0; Each district is composed in series by 1-4 root fixed-bed ion exchanger, is connected successively by check valve by the exit end of the last root chromatogram column entrance end with back one root chromatogram column, and the exit end of last root chromatogram column is connected with the entrance end of first root chromatogram column; Wherein distinguish 0 and be positioned between No. 1 elutriant inlet (6) and No. 2 extracting liquid outlets (7), impurity in the desorb fermented liquid in district 0; District I is positioned between No. 2 elutriants inlet (8) and No. 1 extracting liquid outlet (9), in distinguishing I in the purified fermentation broth 1, and ammediol; District II is positioned between No. 1 extracting liquid outlet (9) and the injection port (10), the impurity in absorption repeatedly in district II, desorb, the concentrated broth; District III is positioned between injection port (10) and the raffinate outlet (11), separates weak absorption impurity in district III; District IV is positioned at No. 3 wash-outs and washes between mouthful (12) and the elutriant loop exit (13), on the one hand elutriant is cleaned the back and enters district's 0 recycle with fresh elutriant, will distinguish IV and district 0 on the other hand and separate the component that prevents in the raffinate and enter and distinguish 0 and pollute.
3. in the five-region simulated moving bed separation and purification fermented liquid according to claim 21, the method for ammediol is characterized in that: adopt the 0.1-0.5M NaOH aqueous solution as elutriant, elutriant flow 200-800ml/min, pressure 1-10Mpa; Sample introduction flow 50-300ml/min, pressure 1-10Mpa; Extracting solution and raffinate flow velocity are controlled by pressure regulating valve, pressure 1-10Mpa; Valve switching time is 5-30min; Whole simulation moving-bed temperature is 20-60 ℃, 20-60 ℃ of sample introduction liquid, elutriant temperature; Obtain 1 from No. 1 extracting liquid outlet (9) collection, the ammediol refined solution obtains impurity from No. 2 extracting liquid outlets (7) and raffinate outlet (11).
4. in the five-region simulated moving bed separation and purification fermented liquid according to claim 21, the method for ammediol is characterized in that: chromatographic column is of a size of L1500mm * D100mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100230101A CN101328109A (en) | 2008-07-07 | 2008-07-07 | Method for separating and purifying 1,3-propanediol in fermentation liquor by means of five-region simulated moving bed |
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| CNA2008100230101A CN101328109A (en) | 2008-07-07 | 2008-07-07 | Method for separating and purifying 1,3-propanediol in fermentation liquor by means of five-region simulated moving bed |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795962A (en) * | 2012-09-06 | 2012-11-28 | 厦门大学 | Method for adsorbing and extracting 1,3-propanediol from zymotic fluid by using cationic resin |
| CN103304374A (en) * | 2012-03-14 | 2013-09-18 | 江苏汉邦科技有限公司 | Method for separating and purifying 1, 3-propylene glycol in fermentation liquor by five-region simulated moving bed |
| CN106117012A (en) * | 2016-06-22 | 2016-11-16 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid |
| CN112979419A (en) * | 2021-02-25 | 2021-06-18 | 中国科学院过程工程研究所 | Method for separating dihydric alcohol by sequential simulated moving bed |
| CN112979418A (en) * | 2019-12-17 | 2021-06-18 | 南京凯通粮食生化研究设计有限公司 | Method for separating ethylene glycol and butanediol |
| CN114276217A (en) * | 2021-12-17 | 2022-04-05 | 苏州苏震生物工程有限公司 | Desalination and purification method of 1, 3-propylene glycol fermentation liquor |
-
2008
- 2008-07-07 CN CNA2008100230101A patent/CN101328109A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304374A (en) * | 2012-03-14 | 2013-09-18 | 江苏汉邦科技有限公司 | Method for separating and purifying 1, 3-propylene glycol in fermentation liquor by five-region simulated moving bed |
| CN102795962A (en) * | 2012-09-06 | 2012-11-28 | 厦门大学 | Method for adsorbing and extracting 1,3-propanediol from zymotic fluid by using cationic resin |
| CN102795962B (en) * | 2012-09-06 | 2014-09-10 | 厦门大学 | Method for adsorbing and extracting 1,3-propanediol from zymotic fluid by using cationic resin |
| CN106117012A (en) * | 2016-06-22 | 2016-11-16 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid |
| CN106117012B (en) * | 2016-06-22 | 2018-07-31 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination |
| CN112979418A (en) * | 2019-12-17 | 2021-06-18 | 南京凯通粮食生化研究设计有限公司 | Method for separating ethylene glycol and butanediol |
| CN112979419A (en) * | 2021-02-25 | 2021-06-18 | 中国科学院过程工程研究所 | Method for separating dihydric alcohol by sequential simulated moving bed |
| CN114276217A (en) * | 2021-12-17 | 2022-04-05 | 苏州苏震生物工程有限公司 | Desalination and purification method of 1, 3-propylene glycol fermentation liquor |
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Open date: 20081224 |