CN100497289C - Method and device for preparing methyl formate by methanol carbonylation - Google Patents
Method and device for preparing methyl formate by methanol carbonylation Download PDFInfo
- Publication number
- CN100497289C CN100497289C CNB2006100270167A CN200610027016A CN100497289C CN 100497289 C CN100497289 C CN 100497289C CN B2006100270167 A CNB2006100270167 A CN B2006100270167A CN 200610027016 A CN200610027016 A CN 200610027016A CN 100497289 C CN100497289 C CN 100497289C
- Authority
- CN
- China
- Prior art keywords
- methyl
- formiate
- condenser
- disengaging zone
- reactor
- 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.)
- Expired - Fee Related
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 120
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000006315 carbonylation Effects 0.000 title claims abstract description 19
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000008676 import Effects 0.000 claims description 28
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000012043 crude product Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention discloses methanol carbonylation way preparing methyl formate method and its equipment. According to weight percentage, 62-68 percent methanol, 31-38 percentage carbon monoxide and 0.15-0.2 percent catalyst are filled into reactor, methyl formate synthesis reaction is done under condition of temperature 75-95 degrees centigrade, reaction system pressure is 2.0-4.0MPa. Reaction product vapor through methyl formate separating area, condenser and tail condenser, methyl formate crude product mixed liquor is got from gas phase condensation separating. Large methanol circulation and high catalyst consumption in existing technique is solved in this invention, and in existing method, methyl formate content maintains balance concentration in liquor phase, so the synthesis reaction driving force is not strong, and crude methyl formate content is low.
Description
Technical field
The present invention relates to a kind of preparation method and device thereof of methyl-formiate, relate in particular to a kind of method and device thereof of preparing methyl formate by methanol carbonylation.
Background technology
(methyl formate, MeF MF) are one of important carbinol derivatives and important chemical material to methyl-formiate.The traditional preparation process method of methyl-formiate is the esterification synthetic by formic acid and methyl alcohol.Since the eighties in 20th century, new methyl-formiate synthetic method is continually developed research, the methanol carbonylation and the methanol dehydrogenation legal system that particularly are applied to suitability for industrialized production are equipped with methyl-formiate, the cost of producing methyl-formiate is declined to a great extent, also promoted the continuous expansion of methyl-formiate Application Areas simultaneously.
At present, the technology of methanol carbonylation production methyl-formiate is divided into the rectifying separation of the synthetic and methyl-formiate of methyl-formiate.Owing to be subjected to the restriction of molecular balance, reaction solution is from the reactor bottom recycle stock during extraction, exist in the extraction material methyl-formiate content too low, wherein by weight percentage, the content of methyl-formiate is 18～25%, and the content of methyl alcohol is 75～82%, the isolating load of methanol loop is bigger than normal in the methyl-formiate separation system, and catalyzer is along with material is discharged synthesis system together, and the catalyst consumption height causes certain pollution to system and environment.This technology causes the impellent of methyl-formiate building-up reactions little owing to methyl-formiate content in the liquid phase is remaining near equilibrated concentration, and the equipment of production equipment is huge relatively, usefulness is lower, complicated operation, and the production energy consumption of unit product is very high.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of and overcome above-mentioned deficiency, under the certain prerequisite of methanol carbonyl synthesis system catalyzer recoverable amount, improve the preparation method and the device thereof of methyl-formiate content in the production.
Technical scheme of the present invention is:
A kind of method of preparing methyl formate by methanol carbonylation, by weight percentage, 62～68% methyl alcohol, 31～38% carbon monoxide and 0.15～0.2% catalyzer enter reactor, carry out the methyl-formiate building-up reactions under the condition of 75～95 ℃ of temperature of reaction, reacting system pressure 2.0～4.0MPa; Reaction product steam is successively by methyl-formiate disengaging zone, condenser, tail condenser in the rectification zone of reactor top, through vapor condensation separate the thick product mixed solution of methyl-formiate.
Described methyl-formiate reactor bottom connects a cycle heat exchange device; Through the recycle stock part extraction that contains methyl-formiate and methyl alcohol of condenser, the condensation of tail condenser, another part enters the methyl-formiate reactor by U type pipe.
The temperature of described methyl-formiate disengaging zone is 80～105 ℃, and the condensing temperature in the condenser is 25～45 ℃.
Described catalyzer is sodium methylate or potassium methylate.
Described methyl-formiate is provided with structured packing or column plate in the disengaging zone.
Described methyl-formiate is provided with the disc type flasher in the disengaging zone.
As the first kind of technical scheme that realizes aforesaid method be:
A kind of device of preparing methyl formate by methanol carbonylation, comprise the methyl-formiate reactor, be provided with the methyl-formiate disengaging zone in the top of described methyl-formiate reactor, the bottom is connected with the outlet of CO cyclic spray device and a port of cycle heat exchange device respectively, and described bottom also is provided with the CO import; Described methyl-formiate disengaging zone links to each other with condenser, tail condenser gas phase successively, and the liquid phase outlet of described condenser links to each other with the liquid phase outlet of tail condenser and communicates with described methyl-formiate reactor by U type pipe, and links to each other with the import of medial launder; Another outlet of described tail condenser communicates with tail gas emptying Controlling System, and links to each other with the import of CO cyclic spray device; The another port of described cycle heat exchange device communicates with the bottom of described methyl-formiate disengaging zone.
Described methyl-formiate is provided with structured packing or column plate in the disengaging zone.
As the second kind of technical scheme that realizes aforesaid method be:
A kind of device of preparing methyl formate by methanol carbonylation is provided with the methyl-formiate disengaging zone outside the top of described methyl-formiate reactor, the bottom is connected with the outlet of CO cyclic spray device and a port of cycle heat exchange device respectively, and described bottom also is provided with the CO import; Described methyl-formiate disengaging zone links to each other with condenser, tail condenser gas phase successively, the liquid phase outlet of described condenser links to each other and links to each other with the import of medial launder with the liquid phase outlet of tail condenser, the outlet of described medial launder communicates by the bottom of U type pipe with described methyl-formiate disengaging zone, another outlet of described tail condenser communicates with tail gas emptying Controlling System, and links to each other with the import of CO cyclic spray device; The another port of described cycle heat exchange device communicates with the bottom of described methyl-formiate disengaging zone.
Described methyl-formiate is provided with the disc type flasher in the disengaging zone.
Beneficial effect of the present invention is:
Adopt the method and the device thereof of preparing methyl formate by methanol carbonylation of the present invention, separate to such an extent that the content of methyl-formiate is 65～85% the thick product mixed solution of methyl-formiate, the content of methyl alcohol is 35～15% from vapor condensation, under equal methyl-formiate production capacity, the methyl alcohol of unit methyl-formiate is gone into the tower amount and is descended 50～85%, and catalyst levels descends 50～85%; Reaction product methyl-formiate and part methyl alcohol are by the vapor condensation extraction, catalyzer is retained in the reactor, improved the utilization ratio of catalyzer, avoided the loss of catalyzer when the material extraction, reduced the consumption of catalyzer, avoided the catalyzer salt slurry to stop up the environmental pollution that the cleaning carried out brings to the pollution threat of environment with because of catalyzer.Separated methyl-formiate content≤5% in the circulation fluid behind the methyl-formiate through reactive distillation, methyl-formiate concentration≤4.5% after the additional fresh methanol, the impellent of methyl-formiate building-up reactions is bigger, and system device is less relatively, reduce the investment cost of device, saved investment about 50%.Energy efficient is about 60%, reduces the production scale of investment.
The present invention is further illustrated below by drawings and Examples, but the present invention is not limited only to content related among the embodiment.
Description of drawings
Fig. 1 is first kind of technical process of preparing methyl formate by methanol carbonylation of the present invention.
Fig. 2 is second kind of technical process of preparing methyl formate by methanol carbonylation of the present invention.
Embodiment
The present invention adopts reactive distillation process to pass through preparing methyl formate by methanol carbonylation.
With reference to the accompanying drawings 1, on the basis of existing methyl-formiate reactor, be provided with the MF disengaging zone of band structured packing or column plate in the top of reactor, the top exit of MF disengaging zone links to each other with the import of condenser, the gaseous phase outlet of condenser links to each other with the gas phase import of tail condenser, its liquid phase outlet communicates with the liquid phase outlet of tail condenser, links to each other with the import of medial launder, and links to each other with reactor by U type pipe; Another outlet of tail condenser communicates with tail gas emptying Controlling System, and link to each other with the import of CO cyclic spray device, one outlet of CO cyclic spray device communicates with reactor bottom one import, the reactor bottom outlet links to each other with the import of cycle heat exchange device, and the outlet of cycle heat exchange device communicates with below, MF disengaging zone part in the reactor.
Under the condition of 75～95 ℃ of temperature of reaction, reacting system pressure 2.0～4.0MPa, by by weight percentage, 64% methyl alcohol, 0.15% sodium methylate are sent into reactor, and 35.85% CO enters reactor by the cyclic spray device from another import of reactor bottom.The liquid phase recycle stock that contains concentration 18～25% methyl-formiates enters 80～105 ℃ MF disengaging zone, under the effect of CO cyclic spray device, methyl-formiate in the gas phase and methyl alcohol saturation steam are brought in 25～45 ℃ the condenser thereupon and are condensed, separate do not contain catalyzer content be that 65～85% methyl-formiates and content are the phlegma of 15～35% methyl alcohol, by the medial launder extraction.
With reference to the accompanying drawings 2, the top exit of reactor links to each other with the import of MF disengaging zone, and an outlet of MF disengaging zone links to each other with the import of condenser, and the gaseous phase outlet of condenser links to each other with the gas phase import of tail condenser, its liquid phase outlet communicates with the liquid phase outlet of tail condenser, and links to each other with the import of medial launder; The outlet of medial launder links to each other with another outlet of MF disengaging zone by U type pipe; Another outlet of tail condenser communicates with tail gas emptying Controlling System, and link to each other with the import of CO cyclic spray device, one outlet of CO cyclic spray device communicates with reactor bottom one import, another import of reactor bottom links to each other with the outlet of cycle heat exchange device, and the import of cycle heat exchange device communicates with the outlet of MF disengaging zone.Wherein be provided with the disc type flasher in the MF disengaging zone.
Under the condition of 75～95 ℃ of temperature of reaction, reacting system pressure 2.0～4.0MPa, by weight percentage, 66% methyl alcohol, 0.2% potassium methylate are sent in the pipe connecting between MF disengaging zone and the cycle heat exchange device, and 33.8% CO enters reactor by the import of reactor bottom.The liquid phase recycle stock that contains concentration 18～25% methyl-formiates enters 85～95 ℃ MF disengaging zone, under the effect of CO cyclic spray device, methyl-formiate in the gas phase and methyl alcohol saturation steam are brought in 25～45 ℃ the condenser thereupon and are condensed, separate do not contain catalyzer content be that 65～85% methyl-formiates and content are the phlegma of 15～35% methyl alcohol, by the medial launder extraction.
Claims (10)
1, a kind of method of preparing methyl formate by methanol carbonylation, by weight percentage, 64～66% methyl alcohol, 33.8～35.85% carbon monoxide and 0.15～0.2% catalyzer enter reactor, carry out the methyl-formiate building-up reactions under the condition of 75～95 ℃ of temperature of reaction, reacting system pressure 2.0～4.0MPa; Reaction product steam is successively by methyl-formiate disengaging zone, condenser, tail condenser in the rectification zone of reactor top, through vapor condensation separate the thick product mixed solution of methyl-formiate.
2, according to the method for the described preparing methyl formate by methanol carbonylation of claim 1, it is characterized in that: described methyl-formiate reactor bottom connects a cycle heat exchange device; Through the recycle stock part extraction that contains methyl-formiate and methyl alcohol of condenser, the condensation of tail condenser, another part enters the methyl-formiate reactor by U type pipe.
3, according to the method for the described preparing methyl formate by methanol carbonylation of claim 1, it is characterized in that: the temperature of described methyl-formiate disengaging zone is 80～105 ℃, and the condensing temperature in the condenser is 25～45 ℃.
4, according to the method for the described preparing methyl formate by methanol carbonylation of claim 1, it is characterized in that: described catalyzer is sodium methylate or potassium methylate.
5, according to the method for the described preparing methyl formate by methanol carbonylation of claim 1, it is characterized in that: described methyl-formiate is provided with structured packing or column plate in the disengaging zone.
6, according to the method for the described employing preparing methyl formate by methanol carbonylation of claim 1, it is characterized in that: described methyl-formiate is provided with the disc type flasher in the disengaging zone.
7, a kind of device for preparing methyl-formiate according to the described method of claim 1, comprise the methyl-formiate reactor, it is characterized in that: be provided with the methyl-formiate disengaging zone in the top of described methyl-formiate reactor, the bottom is connected with the outlet of CO cyclic spray device and a port of cycle heat exchange device respectively, and described bottom also is provided with the CO import; Described methyl-formiate disengaging zone links to each other with condenser, tail condenser gas phase successively, and the liquid phase outlet of described condenser links to each other with the liquid phase outlet of tail condenser and communicates with described methyl-formiate reactor by U type pipe, and links to each other with the import of medial launder; Another outlet of described tail condenser communicates with tail gas emptying Controlling System, and links to each other with the import of CO cyclic spray device; The another port of described cycle heat exchange device communicates with the bottom of described methyl-formiate disengaging zone.
8, according to the device of the described preparation methyl-formiate of claim 7, it is characterized in that: described methyl-formiate is provided with structured packing or column plate in the disengaging zone.
9, a kind of device for preparing methyl-formiate according to the described method of claim 1, comprise the methyl-formiate reactor, it is characterized in that: be provided with the methyl-formiate disengaging zone outside the top of described methyl-formiate reactor, the bottom is connected with the outlet of CO cyclic spray device and a port of cycle heat exchange device respectively, and described bottom also is provided with the CO import; Described methyl-formiate disengaging zone links to each other with condenser, tail condenser gas phase successively, the liquid phase outlet of described condenser links to each other and links to each other with the import of medial launder with the liquid phase outlet of tail condenser, the outlet of described medial launder communicates by the bottom of U type pipe with described methyl-formiate disengaging zone, another outlet of described tail condenser communicates with tail gas emptying Controlling System, and links to each other with the import of CO cyclic spray device; The another port of described cycle heat exchange device communicates with the bottom of described methyl-formiate disengaging zone.
10, according to the device of the described preparation methyl-formiate of claim 9, it is characterized in that: described methyl-formiate is provided with the disc type flasher in the disengaging zone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100270167A CN100497289C (en) | 2006-05-29 | 2006-05-29 | Method and device for preparing methyl formate by methanol carbonylation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100270167A CN100497289C (en) | 2006-05-29 | 2006-05-29 | Method and device for preparing methyl formate by methanol carbonylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1850777A CN1850777A (en) | 2006-10-25 |
| CN100497289C true CN100497289C (en) | 2009-06-10 |
Family
ID=37132279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100270167A Expired - Fee Related CN100497289C (en) | 2006-05-29 | 2006-05-29 | Method and device for preparing methyl formate by methanol carbonylation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100497289C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY169033A (en) * | 2012-11-26 | 2019-02-04 | Basf Se | Method for producing methyl formate by reacting methanol with carbon monoxide in the presence of a catalyst system which comprises alkali formate and alkali alcoholate |
| CN103044189B (en) * | 2012-12-21 | 2015-04-22 | 巨化集团技术中心 | Preparation device and method of 2-bromo heptafluoropropane |
| CN103951558B (en) * | 2014-04-10 | 2015-07-15 | 中国科学院福建物质结构研究所 | Device for producing methyl formate by gas phase methanol carbonylation, process and catalyst on-line evaluation method |
| CN106380392B (en) * | 2016-08-29 | 2019-06-18 | 成都天成碳一化工有限公司 | A kind of formic acid preparation facilities and preparation method thereof |
| CN107353193A (en) * | 2017-07-17 | 2017-11-17 | 衡阳屹顺化工有限公司 | A kind of preparation method of anhydrous formic acid |
| CN112409163B (en) * | 2020-12-18 | 2022-12-20 | 贵州天福化工有限责任公司 | Separation method of by-product in process of preparing methyl formate by carbonylation of methanol |
-
2006
- 2006-05-29 CN CNB2006100270167A patent/CN100497289C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1850777A (en) | 2006-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103012062B (en) | Process for indirectly producing alcohol with synthetic gas and application of process | |
| CA2648779C (en) | Production of dry alcohol | |
| CN100497289C (en) | Method and device for preparing methyl formate by methanol carbonylation | |
| CN203033918U (en) | Process system for indirectly producing ethanol by using synthesis gases | |
| CN1830934A (en) | Method for producing dimethyl ether using methanol as raw material | |
| CN110218151B (en) | Device and method for preparing propyl propionate through tower kettle flash evaporation type heat pump reaction rectification | |
| CN2621805Y (en) | Shell external cooling-thermal insulating and combined fixed bed catalyst chember | |
| CN102068945B (en) | Reactive distillation device and method for separating and purifying methylal | |
| CN101058534B (en) | Device and method for preparing dimethyl ether from methanol | |
| CN101570469A (en) | Method for continuously producing isobutyl alcohol through hydrogenation of methylacrolein | |
| CN213050530U (en) | High-efficiency energy-saving ethyl lactate reaction rectification production device | |
| CN103420752B (en) | Separation refinement method for ethylene preparation through biomass ethanol dehydration | |
| CN112979516B (en) | Energy-saving methyl mercaptan synthesis device | |
| CN102311321B (en) | Method for preparing butyraldehyde from propylene and synthesis gas | |
| CN101481295A (en) | Methanol fluidized bed synthetic process | |
| CN101168506B (en) | Preparation method for sec-butyl acetate with product separating technique | |
| CN101928206B (en) | Method for producing dimethyl ether by synthesis gas and equipment thereof | |
| CN109824498B (en) | Diacetone alcohol continuous production device and production process | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN1202061C (en) | Method for catalytic synthesising dimethyl ether in combined bed | |
| CN1331833C (en) | Process for preparing dimethyl ether | |
| CN110698340A (en) | Process method for producing ethyl lactate by reactive distillation dividing wall tower technology | |
| CN2576323Y (en) | Internal-cooling pipe-casing compound fixed-bed combined catalytic reactor | |
| CN103012089B (en) | Method for carbonyl synthesis of propylene | |
| CN220861410U (en) | Methyl chloride synthesis system without byproduct hydrochloric acid |
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 | ||
| ASS | Succession or assignment of patent right |
Owner name: HANGZHOU HUAJIE GREEN ENERGY CO., LTD. Free format text: FORMER OWNER: SUN JIANMIN Effective date: 20100525 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 324100 NO.6, NINGXIU MOUNTAIN VILLA, JIANGSHAN CITY, ZHEJIANG PROVINCE TO: 310012 4-405, JIJIN HOTEL, XUEYUAN ROAD, XIHU DISTRICT, HANGZHOU CITY, ZHEJIANG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100525 Address after: 310012, Xihu District, Zhejiang province Xueyuan Road Hangzhou highlights Hotel 4-405 Patentee after: Hangzhou Hua Jie green energy Co., Ltd. Address before: 324100, 6, Sau Sau villa, Jiangshan City, Zhejiang Province Patentee before: Sun Jianmin |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090610 Termination date: 20150529 |
|
| EXPY | Termination of patent right or utility model |