CN1686996A - Method for realizing cleansing production of sebacic acid by using clearing resin - Google Patents
Method for realizing cleansing production of sebacic acid by using clearing resin Download PDFInfo
- Publication number
- CN1686996A CN1686996A CN200510038999.XA CN200510038999A CN1686996A CN 1686996 A CN1686996 A CN 1686996A CN 200510038999 A CN200510038999 A CN 200510038999A CN 1686996 A CN1686996 A CN 1686996A
- Authority
- CN
- China
- Prior art keywords
- resin
- sebacic acid
- group
- desorption
- realized
- 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
Links
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003795 desorption Methods 0.000 claims description 21
- 238000010521 absorption reaction Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012609 strong anion exchange resin Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000002000 scavenging effect Effects 0.000 abstract 2
- 239000003085 diluting agent Substances 0.000 abstract 1
- 239000011344 liquid material Substances 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- GAQDIDQMKWSQAH-UHFFFAOYSA-M sodium;10-hydroxy-10-oxodecanoate Chemical compound [Na+].OC(=O)CCCCCCCCC([O-])=O GAQDIDQMKWSQAH-UHFFFAOYSA-M 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000853 cresyl group Chemical class C1(=CC=C(C=C1)C)* 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical group CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for implementing clean production of sebacic acid by using scavenging resin. Said method includes the following procedures: making the neutralized water containing monosodium salt sebacate which is produced after neutralization by using sulfuric acid in the production process of sebacic acid undergo the process of filtration and successively pass through two groups of adsorption towers, every group of adsorption towers is respectively filled with a kind of scavenging resin, firstly removing chromaticity of liquid material, then separating diluent phenol in the production process so as to attain the goal of removing impurity and purifying material, so that it can raise quality of sebacic acid.
Description
One, technical field
The present invention relates to a kind of production method of sebacic acid, particularly, a kind of method that resin is realized the sebacic acid cleaner production of removing of utilizing.
Two, technical background
Sebacic acid is a kind of important Organic Chemicals, about 30,000 tons of China's annual production.Most widely used in the sebacic acid production technique in the world at present is ricinolic acid high temperature alkali cracking, because this technology is thinner with phenol (or cresols), therefore, produces a large amount of processing wastewaters aborning, and 1 ton of product of every production produces 35 tons of processing wastewaters approximately.Phenol in wastewater content is 2000～4000mg/L, COD
CrReach 7000～10000mg/L, also contain 8～12% sodium sulfate in the waste water, and a spot of raw material Viscotrol C and intermediate.Domestic existing manufacturing enterprise without good improvement, has caused severe contamination to environment and rivers to its factory effluent majority.
Three, summary of the invention
1, goal of the invention: the purpose of this invention is to provide a kind of method that resin is realized the sebacic acid cleaner production of removing of utilizing, this method is removed absorption process by increasing in existing manufacturing technique, utilize the complex function adsorption resin of resistant to elevated temperatures decolorizing resin and high adsorption capacity, progressively separate in process of production and remove impurity, thereby can make high-quality sebacic acid product, phenol that again can the Separation and Recovery overwhelming majority, make the wastewater reduction, innoxious of final discharge, realize the target of recycling economy.
2, technical scheme: for achieving the above object, a kind of utilization of the present invention removed the method that resin is realized the sebacic acid cleaner production, may further comprise the steps:
(1) in the sebacic acid production technique in sulfuric acid and after, to contain sebacic acid list sodium salt in and water under the condition of 5～20 ℃ and flow 1～6BV/h (per hour bed volume), successively by two groups of adsorption towers, respectively fill a kind of removing Resin A and B in two groups of adsorption towers, absorb colourity and separating phenol in the feed liquid respectively;
(2) use alkaline solution and water as desorbing agent, will adsorb organic removing resin desorption and regeneration in the adsorption tower, desorption temperature is 40～90 ℃, and the flow of desorbing agent is 0.5～4BV/h;
(3) the high density elutriant that desorption is got off reclaims phenol through distillation, and lower concentration elutriant cover is used for following batch desorption manipulation.
In step (1), described removing Resin A is the high temperature resistant strong anion-exchange resin that has chain alkyl or pyridine group, as NDA280 or NDA288 resin, preferred NDA288 pyridine highly basic decolorizing resin (being Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd produces).Remove resin B on the high-specific surface area resin, having the composite function resin that forms hydrogen bond and complexing group with phenolic hydroxyl group, as NDA7, NDA150, NDA88 or NDA99, preferred NDA99 composite function resin (being Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd produces).
At the alkaline solution described in the step (2) is the sodium hydroxide solution of concentration (quality) 5～20%.
In step (1), the adsorption operations of resin can adopt double-column in series absorption, the operation scheme of single tower desorption, be that every kind of resin is provided with I, II, three adsorption towers of III, with I, II tower series connection following current absorption, the I tower is as first post earlier, the II tower is as stern post, after the absorption of I tower is saturated, switch to II, III tower series connection following current absorption, the II tower is as first post, the III tower is as stern post, the I tower carries out the following current desorption simultaneously, and so cyclical operation can guarantee the operation continuously all the time of whole device.
3, beneficial effect: the present invention compared with prior art, its remarkable advantage is: after one-level was removed resin decolorization, colourity reduced greatly, and makes final sebacic acid product colourity reach the first class product standard (1).(2) phenol content＜0.5mg/L in the feed liquid after secondary is removed resin absorption has reduced the impurity in the product in subsequent technique, and makes final factory effluent contain the phenol amount to reach discharging standards, and COD
Cr＜2000mg/L is for further handling the good condition of having created.(3) phenol of the overwhelming majority in the recyclable production technique is realized changing waste into resources.(4) remove a grade resins ability high temperature that is used to decolour in the resin, long service life, and the same with the complex function adsorption resin that is used for separating phenol all to have regenerability good, reusable advantage.
Four, specific implementation method
Further specify the present invention by the following examples.
Embodiment 1: the NDA288 of each 10mL and NDA99 resin are respectively charged into (Φ 32 * 250mm) in the glass adsorption column of strap clamp cover.Neutralizer after filtering, under 5 ℃ of conditions, at first by the NDA288 resin bed, treatment capacity is that 800mL/ criticizes, one-level effluent color dilution＜20 with the flow of 1BV/h with it
#(platinum cobalt standard colorimetry) is collected in it in container of clean dried.The one-level water outlet is carried out secondary absorption through the NDA99 resin, and treatment capacity is that 400mL/ criticizes, water outlet phenol content＜0.5mg/L.Transfer this material liquid pH to 1～2 with sulfuric acid again, suction filtration, oven dry obtain sebacic acid product 9.3815g/ and criticize, and its quality reaches the first grade standard.The phenol in wastewater content of discharging after the acid out crystallization is lower than discharging standards, COD
Cr＜2000mg/L is for further handling the good condition of having created.
After one-level is removed resin NDA288 absorption 800mL, do not reach saturatedly yet, can need not desorption.Remove resin to adsorbing saturated secondary, using 50mL concentration (quality) successively is that 8% sodium hydroxide solution and 60mL water are under 80 ℃ of conditions, flow with 0.5BV/h carries out desorption by the NDA99 resin bed, the high density elutriant (20mL) that desorption gets off is through distilling recyclable phenol 76%, and lower concentration elutriant cover is used for following batch desorption manipulation.
Embodiment 2: the NDA288 of each 100mL and NDA99 resin are respectively charged into (Φ 96 * 800mm) in the glass adsorption column of strap clamp cover.Neutralizer after filtering, under 10 ℃ of conditions, at first by the NDA288 resin bed, treatment capacity is that 8000mL/ criticizes, one-level effluent color dilution＜20 with the flow of 1BV/h with it
#, it is collected in the container of clean dried.The one-level water outlet is carried out secondary absorption through the NDA99 resin, and treatment capacity is that 4000mL/ criticizes, water outlet phenol content＜0.5mg/L.Transfer this material liquid pH to 1～2 with sulfuric acid again, suction filtration, oven dry obtain sebacic acid product 91.7216g/ and criticize, and its quality reaches the first grade standard.The phenol in wastewater content of discharging after the acid out crystallization is lower than discharging standards, COD
Cr＜2100mg/L is for further handling the good condition of having created.
After one-level is removed resin NDA288 absorption 8000mL, do not reach saturatedly yet, can need not desorption.Remove resin to adsorbing saturated secondary, using 500mL concentration (quality) successively is that 8% sodium hydroxide solution and 600mL water are in 80 ℃, flow with 0.5BV/h carries out desorption by the NDA99 resin bed, the high density elutriant (200mL) that desorption gets off is through distilling recyclable phenol 75%, and lower concentration elutriant cover is used for following batch desorption manipulation.
Embodiment 3: the one-level among the embodiment 1 is removed decolorizing resin replace with the NDA88 resin with the replacement of NDA280 resin, secondary removing separating phenol resin, other operational conditions remain unchanged, and every batch processing amount and effluent quality all slightly are inferior to NDA288 and NDA99 two-stage absorption method for combined use.
Embodiment 4: the one-level among the embodiment 1 is removed decolorizing resin replace with the NDA150 resin with the replacement of NDA280 resin, secondary removing separating phenol resin, other operational conditions remain unchanged, and every batch processing amount and effluent quality all slightly are inferior to NDA288 and NDA99 two-stage absorption method for combined use.
Embodiment 5: the one-level among the embodiment 1 is removed decolorizing resin replace with the NDA7 resin with the replacement of NDA280 resin, secondary removing separating phenol resin, other operational conditions remain unchanged, and every batch processing amount and effluent quality all slightly are inferior to NDA288 and NDA99 two-stage absorption method for combined use.
Embodiment 6: the adsorption temp among the embodiment 1 is substituted with 20 ℃, and desorption temperature substitutes with 40 ℃, and other operational conditions remain unchanged, and every batch processing amount and effluent quality all slightly are inferior to embodiment 1.
Embodiment 7: the absorption flow among the embodiment 1 is substituted with 6BV/h, and the desorption flow substitutes with 4BV/h, and other operational conditions remain unchanged, and every batch processing amount and effluent quality all slightly are inferior to embodiment 1.
Claims (6)
1, a kind of utilization removed the method that resin is realized the sebacic acid cleaner production, it is characterized in that this method may further comprise the steps:
(1) in the sebacic acid production technique in sulfuric acid and after, to contain sebacic acid list sodium salt in and water under the condition of 5～20 ℃ and flow 1～6BV/h, successively by two groups of adsorption towers, be filled with the removing resin of absorbing colourity in the feed liquid in one group of adsorption tower, be filled with the removing resin of separating phenol in another group adsorption tower;
(2) use alkaline solution and water as desorbing agent, will adsorb organic removing resin desorption and regeneration in the adsorption tower, desorption temperature is 40～90 ℃, and the flow of desorbing agent is 0.5～4BV/h;
(3) the high density elutriant that desorption is got off reclaims phenol through distillation, and lower concentration elutriant cover is used for following batch desorption manipulation.
2, a kind of method that resin is realized the sebacic acid cleaner production of removing of utilizing according to claim 1, the removing resin that it is characterized in that colourity in the absorption feed liquid described in the step (1) is the strong anion-exchange resin of high temperature resistant belt length alkyl group or pyridine group, and the removing resin of separating phenol is for having the composite function resin that forms hydrogen bond and complexing group with phenolic hydroxyl group on the high-specific surface area resin.
3, a kind of utilization according to claim 2 removed the method that resin is realized the sebacic acid cleaner production, and the strong anion-exchange resin that it is characterized in that high temperature resistant belt length alkyl group or pyridine group is NDA280 or NDA288 resin.
4, a kind of utilization according to claim 2 removed the method that resin is realized the sebacic acid cleaner production, it is characterized in that the composite function resin that has on the high-specific surface area resin with phenolic hydroxyl group formation hydrogen bond and complexing group is NDA7, NDA150, NDA88 or NDA99.
5, a kind of utilization according to claim 1 removed the method that resin is realized the sebacic acid cleaner production, it is characterized in that at the alkaline solution described in the step (2) be the sodium hydroxide solution of concentration (quality) 5～20%.
6, a kind of utilization according to claim 1 removed the method that resin is realized the sebacic acid cleaner production, it is characterized in that every group of adsorption tower adopts the operation scheme of double-column in series absorption, single tower desorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510038999XA CN1303053C (en) | 2005-04-21 | 2005-04-21 | Method for realizing cleansing production of sebacic acid by using clearing resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510038999XA CN1303053C (en) | 2005-04-21 | 2005-04-21 | Method for realizing cleansing production of sebacic acid by using clearing resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1686996A true CN1686996A (en) | 2005-10-26 |
| CN1303053C CN1303053C (en) | 2007-03-07 |
Family
ID=35305038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510038999XA Expired - Fee Related CN1303053C (en) | 2005-04-21 | 2005-04-21 | Method for realizing cleansing production of sebacic acid by using clearing resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1303053C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362620B (en) * | 2007-08-09 | 2010-09-22 | 谢建中 | Phenolic waste water treatment technology from hydroxyphenylglycine synthesis process |
| CN112724010A (en) * | 2020-12-26 | 2021-04-30 | 衡水京华化工有限公司 | Production method of refined sebacic acid |
| CN113354532A (en) * | 2020-04-02 | 2021-09-07 | 丰益高分子材料（连云港）有限公司 | Method for preparing high-purity sebacic acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1142485A (en) * | 1995-08-04 | 1997-02-12 | 河北省环境保护研究所 | Circulation use of production of phenol from sebacic acid |
| CN1216026C (en) * | 2002-10-15 | 2005-08-24 | 上海焦化有限公司 | Refining method for decanedioic acid |
-
2005
- 2005-04-21 CN CNB200510038999XA patent/CN1303053C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362620B (en) * | 2007-08-09 | 2010-09-22 | 谢建中 | Phenolic waste water treatment technology from hydroxyphenylglycine synthesis process |
| CN113354532A (en) * | 2020-04-02 | 2021-09-07 | 丰益高分子材料（连云港）有限公司 | Method for preparing high-purity sebacic acid |
| CN113354532B (en) * | 2020-04-02 | 2023-04-07 | 丰益高分子材料（连云港）有限公司 | Method for preparing high-purity sebacic acid |
| CN112724010A (en) * | 2020-12-26 | 2021-04-30 | 衡水京华化工有限公司 | Production method of refined sebacic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1303053C (en) | 2007-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10662075B2 (en) | Method and apparatus for the recovery and deep treatment of polluted acid | |
| CN110734178A (en) | coking wastewater membrane concentration salt separation zero-discharge treatment system and method | |
| CN101104533B (en) | Method for treating waste water of H-acid production | |
| CN1204044C (en) | Method for preparing industrial grade and food grade phosphoric acid by wet method phosphoric acid | |
| CN105541017A (en) | Method and device for realizing zero emission of strong brine | |
| CN109019634B (en) | Chemical waste salt refining and resource utilization system and method | |
| CN101235014A (en) | Method for treating and reclaiming waste water of 2-aminopyridine production | |
| CN101269798A (en) | Method for recycling organic resource in waste sulphuric acid and refining waste sulfuric acid | |
| CN101182079B (en) | Citric acid mother liquor treatment process | |
| CN106495404A (en) | A kind of processing method of the high salinity cupric organic wastewater of highly acidity | |
| CN113562924A (en) | Treatment system and method for resource utilization of high-salinity wastewater in ferrous metallurgy | |
| CN1303053C (en) | Method for realizing cleansing production of sebacic acid by using clearing resin | |
| CN205061821U (en) | P hydroxybenzoic acid waste water processing system | |
| CN100415654C (en) | Process for purifying and resource recovery using from waste water of producing H cide | |
| CN111499041A (en) | Novel thiophanate methyl wastewater treatment process | |
| CN112159005A (en) | Treatment process and treatment system for aluminum processing anode waste liquid | |
| CN111498871A (en) | System and method for treating waste salt residues mixed by sodium sulfate and sodium chloride | |
| CN1147437C (en) | Method for treating waste water in dinaphthyl phenol production | |
| CN108117209B (en) | Comprehensive treatment method and device for alkaline residue waste liquid | |
| CN1246234C (en) | Treatment of waste water in producing isophthalic acid dicarbomethoxy-5-sodium sulphonate and its resource utilization method | |
| CN214528548U (en) | Resourceful treatment device for high-salt and high-alcohol wastewater in heparin extraction | |
| CN1858007A (en) | Treating and resourcing method for 4.4-diamido diphenyl propylene-2-disulfonic acid production oxide waste water | |
| CN1176026C (en) | Method of treating phenol-containing effluent and recovering resource in 2-methyl-4-chlorophenoxyacetic acid producing process | |
| CN109133468B (en) | Desulfurization wastewater dechlorination treatment device and process for coal-fired power plant | |
| CN1323041C (en) | Waste water treating and resourcelization method for tobias acid production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070307 Termination date: 20140421 |