CN102950018B - Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof - Google Patents
Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof Download PDFInfo
- Publication number
- CN102950018B CN102950018B CN201110247325.6A CN201110247325A CN102950018B CN 102950018 B CN102950018 B CN 102950018B CN 201110247325 A CN201110247325 A CN 201110247325A CN 102950018 B CN102950018 B CN 102950018B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- mor
- rare earth
- molecular sieve
- zsm
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst used for a synthesis of methyl acetate through dimethyl ether carbonylation and a preparation method thereof. The catalyst is composed of rare earth ZSM-35/MOR co-crystallized molecular sieve and a matrix which is alumina or silica. The preparation method comprises uniformly mixing the rare earth ZSM-35/MOR co-crystallized molecular sieve, and the alumina or the silica with dilute nitric acid, extruding and molding, exchanging and roasting to prepare the catalyst. The catalyst and the method have advantages of availablity for industrial operations, simple technology and good reaction stability.
Description
Technical field
The present invention relates to heterogeneous catalysis field, be specifically related to a kind of Catalysts and its preparation method of synthesis of acetic acid methyl esters.
Background technology
Methyl acetate is a kind of important basic organic chemical raw material, can be used as the intermediate producing medicine, agricultural chemicals, is also the primary raw material producing food additives, coating, paint etc. simultaneously.Its hydrolysate acetic acid, for the synthesis of products such as vinyl acetate, acetic acid esters and chloracetic acids, is the important source material of synthetic fibers, adhesive, agricultural chemicals and fuel.At present, the synthesis technique of acetic acid mainly comprises direct oxidation of ethylene to method, synthesis gas direct synthesis technique, methyl formate isomerate process and methyl alcohol (or dimethyl ether) carbonylation method.Traditional carbonylation of methanol catalyst is based on loaded by heteropoly acid noble metal.On acidic zeolite material, dimethyl ether carbonylation reaction achieves dimethyl ether Halogen, By Non-precious Metal Catalysts carbonylation process.Wherein acidic mordenites (MOR) shows good reactivity and selectivity of product at low temperatures.
The European patent EP 2292578A1 (2006) being entitled as " acetic acid and synthesis process for dimethyl ether based on molecular sieve catalyst " discloses using acidic molecular sieve as catalyst, utilize methyl alcohol and methyl acetate co-fed come the technique of preparation of dimethyl ether, acetic acid.
The MOR catalyst that the European patent EP 2251082A1 (2006) being entitled as " carbonylating catalyst and process " discloses through alkali treatment modifying has better dimethyl ether carbonylation reaction activity, at 300 DEG C, and GHSV5000h
-1, under 20bar reaction condition, carbon monoxide: hydrogen: dimethyl ether is than during for 76:19:5, and after reaction enters stable state, methyl acetate space-time yield is .250g/kg catalyst/hour.
Patricia etc. are (Angew. Chem. Int. Ed 2006 in article, 45,1617-1620) report, HFER and HMOR molecular sieve at low temperatures (150 DEG C-190 DEG C) has dimethyl ether carbon monoxide carbonylation activity, and under reaction atmosphere, the existence of water is unfavorable for that reaction is carried out.
The US Patent No. 20070238897A1 (2007) being entitled as " carbonylation of alkyl ethers process " discloses to have the molecular sieve of octatomic ring pore passage structure, such as MOR, FER and OFF are as ethers carbonylating catalyst, and the size in octatomic ring duct is greater than 2.5 × 3.6.
The PCT patent WO2008132450A1 (2008) being entitled as " Dimethyl ether carbonylation process " discloses the MOR catalyst of Cu, Ag modification, and compared with the MOR of unmodified, this catalyst is at H
2under atmosphere, in 250 DEG C of-350 DEG C of temperature ranges, there is better carbonylation activity.
The PCT patent WO2009081099A1 (2009) being entitled as " carbonylation produces acetic acid (or methyl acetate) technique " discloses the MOR catalyst of different-grain diameter size, and MOR Size of Zeolite is less, is more conducive to promoting that carbonylation is active.
The PCT patent WO2010130972A2 (2010) being entitled as " carbonylation technique " discloses a kind of MOR catalyst of desiliconization dealumination treatment, by carrying out water treatment, acid treatment and alkali treatment optimum organization to MOR, activity and the reaction stability of MOR catalyst can be significantly improved.
Liu Junlong etc. compared for the difference of Dimethyl ether carbonylation methyl acetate reactivity on MOR and ZSM-35 catalyst in article in (Catal. Lett. (2010) 139 33-37), find that ZSM-35 molecular sieve has better reaction stability and selectivity of product, at 250 DEG C, 1Mpa, DME/CO/N
2under the reaction condition of/He=5/50/2.5/42.5,12.5ml/min, dimethyl ether conversion rate reaches 11%, and methyl acetate is selective reaches 96%.
Compared with pure phase molecular sieve, rare earth ZSM-35/MOR eutectic molecular sieve has the advantage of ZSM-35 and MOR molecular sieve concurrently, and its superior hole link is more conducive to the absorption of reactant molecule and the diffusion of product molecule simultaneously.By optimizing each component ratio in eutectic molecular sieve, the effect of MOR and ZSM-35 in dimethyl ether carbonylation reaction can be given full play to.In addition, the interpolation of cocrystallization molecular sieve rare earth elements improves the stability of ZSM-35/MOR catalyst, makes this catalyst in dimethyl ether carbonylation reaction, possess good regenerability.
Summary of the invention
The object of this invention is to provide a kind of Catalysts and its preparation method of Dimethyl ether carbonylation synthesis of acetic acid methyl esters.
The present invention specifically provides a kind of catalyst for Dimethyl ether carbonylation synthesis of acetic acid methyl esters, it is characterized in that: in this catalyst, each component accounts for the percentage by weight of whole catalyst and is: rare earth ZSM-35/MOR cocrystallization molecular sieve 50-90%, matrix 10-50%, in its middle rare earth ZSM-35/ MOR cocrystallization molecular sieve, ZSM-35 and MOR weight ratio is 0.1-10, produces described catalyst by kneading extruded moulding.
Catalyst for Dimethyl ether carbonylation synthesis of acetic acid methyl esters provided by the invention, in described rare earth ZSM-35/ MOR cocrystallization molecular sieve, ZSM-35 and MOR weight ratio is: 0.1-10, preferred proportion is 1-5..
Catalyst for Dimethyl ether carbonylation synthesis of acetic acid methyl esters provided by the invention, the content of described rare earth ZSM-35/ MOR cocrystallization molecular sieve middle rare earth is 0.01-5.0 wt%.
Catalyst for Dimethyl ether carbonylation synthesis of acetic acid methyl esters provided by the invention, described matrix is aluminium oxide or silica.Wherein alumina source is in boehmite powder or other aluminium sources, and its content is 10-50wt%; Silica source is in Ludox or other silicon sources, and its content is 10-50wt%.
Present invention also offers the preparation method of this kind for Dimethyl ether carbonylation synthesis of acetic acid methyl esters catalyst, it is characterized in that: concrete steps are: by 50-90wt% rare earth ZSM-35/MOR cocrystallization molecular sieve, 10-50 wt% aluminium oxide or silica and dust technology mix, solid in mixture/sour weight ratio=1.0-4.0, extruded moulding, exchange with ammonium nitrate solution, obtained catalyst of the present invention after drying and roasting; Wherein extruded moulding pressure is 0.5-10Mpa, and sintering temperature is 400-650 DEG C, and the time is 2-6 hour.
The present invention has and can supply industrial operation, and technique is simple, the advantages such as carbonylation activity is high, and reaction stability is good.
Detailed description of the invention
The following examples will be further described the present invention, but not thereby limiting the invention.
Comparative example 1
By 80gZSM-35 molecular sieve, (aluminium oxide accounts for boehmite 75.0 wt% to 27g boehmite, identical below, no longer describe) mix rear extruded moulding with 10.0% dust technology, after drying and roasting, exchange three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst A after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst A, wherein the weight content of ZSM-35 molecular sieve and aluminium oxide is respectively 80% and 20%.
Comparative example 2
By 80gMOR molecular sieve, 27g boehmite mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchanges three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, washes twice (1 hour/time), obtained catalyst B after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst B, wherein the weight content of MOR molecular sieve and aluminium oxide is respectively 80% and 20%.
Comparative example 3
By 80g80wt%ZSM-35/20wt%MOR cocrystallization molecular sieve, 27g boehmite mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchanges three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst C after roasting.Wherein extrusion pressure is 1.0 Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst C, wherein the weight content of ZSM-35/MOR cocrystallization molecular sieve and aluminium oxide is respectively 80% and 20%.
Comparative example 4
Catalyst C reaction regeneration is circulated after 5 times, obtain catalyst D.Wherein the online reaction time is 30 hours, and regeneration condition is lower 520 DEG C of air atmosphere, 3 hours.
Embodiment 1
By 80g rare earth 80wt%ZSM-35/20wt%MOR cocrystallization molecular sieve, (rare earth metal is La, content is 1wt%), 27g boehmite mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchange three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst E after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst E, the weight content of its middle rare earth ZSM-35/MOR cocrystallization molecular sieve and aluminium oxide is respectively 80% and 20%.
Embodiment 2
Catalyst D reaction regeneration is circulated after 5 times, obtain catalyst F.Wherein the online reaction time is 30 hours, and regeneration condition is lower 520 DEG C of air atmosphere, 3 hours.
Embodiment 3
By 80g rare earth 70wt%ZSM-35/30wt%MOR cocrystallization molecular sieve, (rare earth metal is La, content is 1.0wt%), 27g boehmite mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchange three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst G after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst G, the weight content of its middle rare earth ZSM-35/MOR cocrystallization molecular sieve and aluminium oxide is respectively 70% and 30%.
Embodiment 4
By 80g rare earth 50wt%ZSM-35/50wt%MOR cocrystallization molecular sieve, (rare earth metal is La, content is 0.5wt%), 27g boehmite mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchange three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst H after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst H, the weight content of its middle rare earth ZSM-35/MOR cocrystallization molecular sieve and aluminium oxide is respectively 80% and 20%.
Embodiment 5
By 80g rare earth 80wt%ZSM-35/20wt%MOR cocrystallization molecular sieve, (rare earth metal is La, content is 1.5wt%), 50g Ludox mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchange three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst I after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst I, the weight content of its middle rare earth ZSM-35/MOR cocrystallization molecular sieve and silica is respectively 80% and 20%.
Embodiment 6
By 70g rare earth 80wt%ZSM-35/20wt%MOR cocrystallization molecular sieve, (rare earth metal is Ce, content is 3wt%), 75g Ludox mixes rear extruded moulding with 10.0% dust technology, after drying and roasting, exchange three times (2 hours/time) with the ammonium nitrate solution of 0.5Mol/L, wash twice (1 hour/time), obtained catalyst J after roasting.Wherein extrusion pressure is 1.0Mpa, and ammonium exchanges and washing temperature is 80 DEG C, and sintering temperature is 540 DEG C, 3 hours.Obtained catalyst J, the weight content of its middle rare earth ZSM-35/MOR cocrystallization molecular sieve and silica is respectively 70% and 30%.
The application of embodiment and comparative example
The application of examples and comparative examples of the present invention in Dimethyl ether carbonylation synthesis of acetic acid methyl esters.At the in-built 7g catalyst of fixed bed reaction pipe, at N
2500 DEG C of activation are warmed up to, then at N under atmosphere
2atmosphere drops to reaction temperature, reacts under condition as shown in table 1, and raw material is dimethyl ether and carbon monoxide mixtures, pass through beds, react under certain air speed and temperature, generate object acetic acid product methyl esters, use online chromatographic quantitative analysis product.
From the result of table 1, adopt ZSM-35(A) as catalyst, dimethyl ether conversion rate is low; Independent employing MOR(B) as catalyst, reaction stability is poor; Compared with rare earth ZSM-35/MOR cocrystallization molecular sieve (F), ZSM-35/MOR cocrystallization molecular sieve (D) repeated regeneration poor performance; Rare earth ZSM-35/MOR catalyst provided by the invention (in table 1 catalyst E, F, G, H, I, J) all has good carbonylation active.
Table 1 dimethyl ether carbonylation reaction evaluating catalyst result
Reaction condition: temperature 200 DEG C; Pressure 1 MPa; Carbon monoxide/dimethyl ether mol ratio 10/1; Dimethyl ether weight space velocity 0.13 h
-1; Fixed bed, catalyst 7 g.
Claims (4)
1. for the catalyst of Dimethyl ether carbonylation synthesis of acetic acid methyl esters, it is characterized in that: this catalyst contains 50-90wt% rare earth ZSM-35/MOR cocrystallization molecular sieve, and all the other are matrix, are produced by kneading extruded moulding; In described rare earth ZSM-35/MOR cocrystallization molecular sieve, ZSM-35 and MOR weight ratio is 0.1-10, and described matrix is aluminium oxide or silica; The content of described rare earth ZSM-35/MOR cocrystallization molecular sieve middle rare earth is 0.01-5.0wt%, and rare earth element used is La, Ce.
2. according to described in claim 1 for the catalyst of Dimethyl ether carbonylation synthesis of acetic acid methyl esters, it is characterized in that: in described rare earth ZSM-35/MOR cocrystallization molecular sieve, ZSM-35 and MOR weight ratio is 1-5.
3. according to described in claim 1 for the catalyst of Dimethyl ether carbonylation synthesis of acetic acid methyl esters, it is characterized in that: described alumina source is in boehmite powder or other aluminium sources; Described silica source is in Ludox or other silicon sources.
4. the preparation method of catalyst described in a claim 1, it is characterized in that: 50-90wt% rare earth ZSM-35/MOR cocrystallization molecular sieve, 10-50wt% aluminium oxide or silica are mixed with dust technology, after extruded moulding, exchange roasting, obtained catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110247325.6A CN102950018B (en) | 2011-08-26 | 2011-08-26 | Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110247325.6A CN102950018B (en) | 2011-08-26 | 2011-08-26 | Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102950018A CN102950018A (en) | 2013-03-06 |
| CN102950018B true CN102950018B (en) | 2014-12-24 |
Family
ID=47759743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110247325.6A Expired - Fee Related CN102950018B (en) | 2011-08-26 | 2011-08-26 | Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102950018B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104138768B (en) * | 2013-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of preparation method for Dimethyl ether carbonylation ZSM-35 molecular sieve catalyst |
| CN104338554B (en) * | 2013-08-01 | 2016-09-07 | 中国科学院大连化学物理研究所 | A kind of green synthesis method of ZSM-35/MOR eutectic molecular sieve |
| CN105817260B (en) * | 2015-01-04 | 2020-11-27 | 中国科学院大连化学物理研究所 | Method for synthesizing FER/MOR eutectic molecular sieve |
| CN106365995B (en) | 2015-07-20 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of production method of methyl acetate |
| CN106365994B (en) | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A kind of production method of lower aliphatic carboxylic acid's Arrcostab |
| CN106946268B (en) * | 2016-01-07 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method |
| WO2020155144A1 (en) | 2019-02-02 | 2020-08-06 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, preparation method therefor, and application thereof |
| CN115591574A (en) * | 2022-10-08 | 2023-01-13 | 扬州晨化新材料股份有限公司（Cn） | Porous alumina-supported metal copper catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517149A (en) * | 2003-01-15 | 2004-08-04 | 中国科学院大连化学物理研究所 | Catalyst containing beta-zeolite and its preparation method and application |
| CN101537369A (en) * | 2008-03-21 | 2009-09-23 | 上海宝钢化工有限公司 | ZSM-5 catalyst and preparation thereof and use thereof |
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2189215A1 (en) * | 2008-11-19 | 2010-05-26 | BP Chemicals Limited | Carbonylation process catalysed by mordenite supported on inorganic oxides |
-
2011
- 2011-08-26 CN CN201110247325.6A patent/CN102950018B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517149A (en) * | 2003-01-15 | 2004-08-04 | 中国科学院大连化学物理研究所 | Catalyst containing beta-zeolite and its preparation method and application |
| CN101537369A (en) * | 2008-03-21 | 2009-09-23 | 上海宝钢化工有限公司 | ZSM-5 catalyst and preparation thereof and use thereof |
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
Non-Patent Citations (2)
| Title |
|---|
| 几种分子筛转晶和混晶的控制及单一晶体的优化合成;彭建彪等;《催化学报》;20020731;第23卷(第4期);363-366 * |
| 稀土分子筛的合成与应用研究进展;李永梅等;《广东化工》;20091231;第36卷(第3期);47-50 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102950018A (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102950018B (en) | Catalyst used for synthesis of methyl acetate through dimethyl ether carbonylation and preparation method thereof | |
| TWI487694B (en) | Process for the carbonylation of dimethyl ether | |
| CN106365995B (en) | A kind of production method of methyl acetate | |
| TWI428319B (en) | Process for the carbonylation of dimethyl ether | |
| CN104119228A (en) | Methyl methoxyacetate (MMAC) synthesis method | |
| CN105358521B (en) | carbonylation method | |
| JP6549793B2 (en) | Process for producing ethylene glycol by directly producing ethylene glycol dimethyl ether from ethylene glycol monomethyl ether | |
| CN108117480A (en) | A kind of catalyzed conversion methanol and alcohol mixeding liquid prepare the new method of isobutanol | |
| CN109574798A (en) | A kind of method that synthesis gas directly produces ethyl alcohol | |
| CN107349956B (en) | Catalyst for hydrogen production by reforming ethanol steam and preparation method thereof | |
| US11292761B2 (en) | Method for directly producing methyl acetate and/or acetic acid from syngas | |
| CN103127945A (en) | Method for preparing catalyst used for preparing acetaldehyde through direct dehydrogenation of ethanol and application of catalyst | |
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| CN107626320A (en) | Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method and application | |
| CN103130625B (en) | Method for preparing acetaldehyde and co-producing acetal by using ethanol | |
| CN103203248A (en) | Preparation method for ZSM-35 molecular sieve carbonylation catalyst | |
| CN106040246A (en) | Nickel-based catalyst and preparation method and application thereof in catalyzing selective hydrogenation of 1,4-butynediol to synthesize 1,4-butylene glycol | |
| CN105669453B (en) | A kind of method for preparing methyl formate co-production dimethyl ether | |
| CN107952439B (en) | Catalyst for catalyzing methanol carbonylation, preparation method thereof, and method for preparing acetic acid and methyl acetate by methanol carbonylation | |
| CN102886269B (en) | Catalyst for synthesizing crotyl alcohol by crotonic aldehyde through gas phase selective hydrogenating and preparation method | |
| CN107519916B (en) | Molecular sieve catalyst, and preparation method and application thereof | |
| US20200231523A1 (en) | Method for directly producing ethanol from syngas | |
| CN104258902A (en) | Catalyst for use in synthesis of dimethyl oxalate through coupling of CO and methyl nitrite | |
| CN113499795B (en) | Hydrochloric acid and 2-methylimidazole hydrochloride modified hydrogen mordenite catalyst, and preparation method and application thereof | |
| CN107519915B (en) | Catalyst for dimethyl ether carbonylation and preparation method and application thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141224 Termination date: 20180826 |