CN104774002A - Porous cordierite with catalytic activity and preparation method of porous cordierite - Google Patents
Porous cordierite with catalytic activity and preparation method of porous cordierite Download PDFInfo
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- CN104774002A CN104774002A CN201510158376.XA CN201510158376A CN104774002A CN 104774002 A CN104774002 A CN 104774002A CN 201510158376 A CN201510158376 A CN 201510158376A CN 104774002 A CN104774002 A CN 104774002A
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- CN
- China
- Prior art keywords
- diatomite
- hours
- preparation
- porous cordierite
- grinding
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Links
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052878 cordierite Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000454 talc Substances 0.000 claims abstract description 12
- 229910052623 talc Inorganic materials 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 235000012222 talc Nutrition 0.000 claims description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to porous cordierite with catalytic activity and a preparation method of the porous cordierite. The porous cordierite comprises the following components in percentage by mass: 36.6% of talc, 43.1% of kaolin, 14.1% of aluminum oxide, 5.6% of carbon containing diatomite based on diatomite, 0.2% of La2Ce2O7, 0.3% of BaNb2O6 and 0.1% of BaTiO3. The preparation method comprises the following steps: mixing and grinding the raw materials and drying for 10 hours at 110 DEG C; then raising the temperature at a speed of 1 DEG C/minute to 800 DEG C in a nitrogen atmosphere and insulating for 5 hours; and then further raising the temperature at a speed of 1 DEG C/minute to 1350 DEG C in an air atmosphere and insulating for 10 hours. The cordierite is high in specific surface and low in coefficient of thermal expansion and has the catalytic activity.
Description
Technical field
The present invention relates to support of the catalyst technical field, be specifically related to a kind of porous cordierite with catalytic activity and preparation method thereof.
Background technology
While Economic development, current environment and energy shortage problem more and more receive publicity.As adopted the automobile of gasoline and diesel oil, needing to install catalyzer exhaust purifier additional and coming in cleaning of off-gas the poisonous and hazardous pollutent of human body.The objectionable impurities of a lot of chemical industry discharge also needs to be processed by catalyzer.And to make the indispensable carrier of catalyzer be the honeycomb substrate that cordierite material is fired, it is low that trichroite has thermal expansivity, the feature that void content is high.Just because of cordierite material, there is excellent thermal shock resistance, be widely used in the field such as catalyst field and heat-storing material.
Because natural trichroite is little, the industrial artificial synthesis that all adopts prepares trichroite.Owing to adopting, the raw materials cost that corresponding pure-oxide carrys out synthesis of high purity trichroite in trichroite is high, firing temperature is high, firing temperature window narrows, causes the cost of high purity trichroite very high, industrially cannot large-scale promotion use.Therefore, many employing natural matters are main synthesis of dichroite at present, as adopted the natural matter such as talcum, kaolin.In cordierite material synthesis field, if reducing the thermal expansivity of material is an important index, reduces thermal expansivity except synthesis technique, depend primarily on the method for adding auxiliary agent.In addition, because cordierite material is mainly used in purifying vehicle exhaust, industrial organic exhaust gas process field, if add auxiliary agent in cordierite material building-up process, not only can reduce the thermal expansivity of material, there is again certain catalytic performance, will greatly expand the Application Areas of cordierite material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of porous cordierite with catalytic activity and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Have a porous cordierite for catalytic activity, this trichroite is by talcum, kaolin, aluminum oxide, carbon containing diatomite, La
2ce
2o
7, BaNb
2o
6and BaTiO
3composition, the mass percentage of each composition is: talcum 36.6%; Kaolin 43.1%; Aluminum oxide 14.1%; With the carbon containing diatomite 5.6% of diatomite metering; La
2ce
2o
70.2%; BaNb
2o
60.3%; BaTiO
30.1%.
By raw material according to mass percentage: talcum 36.6%; Kaolin 43.1%; Aluminum oxide 14.1%; Carbon containing diatomite (in diatomite) 5.6%; La
2ce
2o
70.2%; BaNb
2o
60.3%; BaTiO
30.1%, after mixing, grinding, 110 DEG C are dried 10 hours, then with the temperature rise rate of per minute 1 DEG C, be warmed up to 800 DEG C in a nitrogen atmosphere, be incubated 5 hours, then switch to air atmosphere, continue with the temperature rise rate of per minute 1 DEG C, be warmed up to 1350 DEG C, be incubated and burn till for 10 hours.
The diatomaceous preparation method of described carbon containing is that diatomite selects SiO
2the high purity diatomite essence soil that content is greater than 90%, according to sucrose: diatomite mass ratio=1:2, take corresponding sucrose and diatomite, the sucrose water dissolution of twice quality, then mix with diatomite, flood after 2 hours, evaporation removing moisture at 100 DEG C, then in 500 DEG C of nitrogen atmosphere roastings 4 hours.
Described La
2ce
2o
7preparation method: be 1 according to La and Ce mol ratio, take corresponding La
2o
3with Ce (CO
3)
2, grinding after mixing, then 1400 DEG C of air atmosphere roastings 8 hours.
Described BaNb
2o
6preparation method: be 1 according to Ba and Nb mol ratio, take corresponding BaCO
3and Nb
2o
5, grinding after mixing, then 1000 DEG C of air atmosphere roastings 8 hours.
Described BaTiO
3preparation method: be 1 according to Ba and Ti mol ratio, take corresponding BaCO
3and TiO
2, grinding after mixing, then 1000 DEG C of air atmosphere roastings 8 hours.
Cordierite material is mainly used in purifying vehicle exhaust, the support of the catalyst of industrial organic exhaust gas process field, if cordierite material has certain catalytic activity, plays help to the performance improving load active component rear catalyst.The present invention, by the adjustment of trichroite synthesizing formula, to reduce the thermal expansivity of material, and makes cordierite material itself have catalytic activity.The trichroite specific surface adopting preparation method of the present invention to obtain is high, thermal expansivity is low, have catalytic activity simultaneously.
Embodiment
Below in conjunction with embodiment the present invention made and further illustrating, but the present invention is not limited to these embodiments.
Embodiment 1
(1) the diatomaceous preparation of carbon containing: diatomite selects SiO
2the high purity diatomite essence soil that content is greater than 90%, according to quality than sucrose: diatomite=1:2, takes corresponding sucrose and diatomite.The sucrose water dissolution of twice quality, then mixes with diatomite, floods after 2 hours, and evaporation removing moisture at 100 DEG C, then in 500 DEG C of nitrogen atmosphere roastings 4 hours, sucrose, through carbonization, generates carbon containing diatomite.
(2) La
2ce
2o
7preparation: be 1 according to La and Ce mol ratio, take corresponding La
2o
3with Ce (CO
3)
2, grinding after mixing, then 1400 DEG C of air atmosphere roastings 8 hours.
(3) BaNb
2o
6preparation: be 1 according to Ba and Nb mol ratio, take corresponding BaCO
3and Nb
2o
5, grinding after mixing, then 1000 DEG C of air atmosphere roastings 8 hours.
(4) BaTiO
3preparation: be 1 according to Ba and Ti mol ratio, take corresponding BaCO
3and TiO
2, grinding after mixing, then 1000 DEG C of air atmosphere roastings 8 hours.
(5) with selected talcum, selected kaolin, aluminum oxide, carbon containing diatomite, La
2ce
2o
7, BaNb
2o
6and BaTiO
3for raw material.Raw material is according to following mass percent: selected talcum 36.6%; Selected kaolin 43.1%; Aluminum oxide 14.1%; Carbon containing diatomite (in diatomite) 5.6%; La
2ce
2o
70.2%; BaNb
2o
60.3%; BaTiO
30.1%.The compression moulding after mixing, grinding of above raw material, dry 10 hours with 110 DEG C, then with the temperature rise rate of per minute 1 DEG C, be warmed up to 800 DEG C in a nitrogen atmosphere, be incubated 5 hours, then switch to air atmosphere, continue with the temperature rise rate of per minute 1 DEG C, be warmed up to 1350 DEG C, be incubated and burn till for 10 hours.
(6) specific surface area of sample adopts the BET method of nitrogen adsorption under liquid nitrogen temperature to measure, and the results are shown in Table 1.
(7) sample MEASURING THE THERMAL EXPANSION COEFFICIENT, to trichroite sample after grinding, carries out MEASURING THE THERMAL EXPANSION COEFFICIENT, the results are shown in Table 1 within the scope of 50-800 DEG C.
(8) the catalytic performance test of sample, to trichroite sample broke, selects 20 ~ 40 order trichroite 2ml, installs in catalyticreactor.Using propane combustion reactions as simulation reaction, Propane-air is reactant gases, and propane concentration is 1000ppm, and by catalyzer, reaction gas flow is 670ml/min.The transformation efficiency of propane at analytical reaction temperature.The results are shown in Table 1.
Comparative example 1
(1) with selected talcum, selected kaolin, aluminum oxide, Primary Study of Choosing Diatomite for raw material.Raw material is according to following mass percent: selected talcum 36.9%; Selected kaolin 43.4%; Aluminum oxide 14.1%; Primary Study of Choosing Diatomite 5.6%.The compression moulding after mixing, grinding of above raw material, dry 10 hours with 110 DEG C, then with the temperature rise rate of per minute 1 DEG C, be warmed up to 800 DEG C in a nitrogen atmosphere, be incubated 5 hours, then switch to air atmosphere, continue with the temperature rise rate of per minute 1 DEG C, be warmed up to 1350 DEG C, be incubated and burn till for 10 hours.
(2) sample MEASURING THE THERMAL EXPANSION COEFFICIENT is identical with embodiment 1 with catalytic performance test, the results are shown in Table 1.
The thermal expansivity of table 1 embodiment and comparative example's catalyzer and catalytic performance
As can be seen here, to have thermal expansivity low and propane is had to the feature of oxidation activity for cordierite material of the present invention.
Claims (6)
1. there is a porous cordierite for catalytic activity, it is characterized in that: this trichroite is by talcum, kaolin, aluminum oxide, carbon containing diatomite, La
2ce
2o
7, BaNb
2o
6and BaTiO
3composition, the mass percentage of each composition is: talcum 36.6%, kaolin 43.1%, aluminum oxide 14.1%, with the carbon containing diatomite 5.6%, La of diatomite metering
2ce
2o
70.2%, BaNb
2o
60.3%, BaTiO
30.1%.
2. there is a preparation method for the porous cordierite catalyzer of catalytic activity, to it is characterized in that raw material according to mass percentage: talcum 36.6%, kaolin 43.1%, aluminum oxide 14.1%, with the carbon containing diatomite 5.6%, La of diatomite metering
2ce
2o
70.2%, BaNb
2o
60.3%, BaTiO
3after 0.1% mixing, grinding, dry 10 hours, then with the temperature rise rate of per minute 1 DEG C through 110 DEG C, be warmed up to 800 DEG C in a nitrogen atmosphere, be incubated 5 hours, then switch to air atmosphere, continue with the temperature rise rate of per minute 1 DEG C, be warmed up to 1350 DEG C, be incubated and burn till for 10 hours.
3. porous cordierite according to claim 1, is characterized in that the diatomaceous preparation method of described carbon containing is that diatomite selects SiO
2the high purity diatomite essence soil that content is greater than 90%, according to sucrose: diatomite mass ratio=1:2, take corresponding sucrose and diatomite, the sucrose water dissolution of twice quality, then mix with diatomite, flood after 2 hours, evaporation removing moisture at 100 DEG C, then in 500 DEG C of nitrogen atmosphere roastings 4 hours.
4. porous cordierite according to claim 1, is characterized in that described La
2ce
2o
7preparation method: be 1 according to La and Ce mol ratio, take corresponding La
2o
3with Ce (CO
3)
2, grinding after mixing, then 1400 DEG C of air atmosphere roastings 8 hours.
5. porous cordierite according to claim 1, is characterized in that described BaNb
2o
6preparation method: be 1 according to Ba and Nb mol ratio, take corresponding BaCO
3and Nb
2o
5, grinding after mixing, then 1000 DEG C of air atmosphere roastings 8 hours.
6. porous cordierite according to claim 1, is characterized in that described BaTiO
3preparation method: be 1 according to Ba and Ti mol ratio, take corresponding BaCO
3and TiO
2, grinding after mixing, then 1000 DEG C of air atmosphere roastings 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510158376.XA CN104774002B (en) | 2015-04-03 | 2015-04-03 | Porous cordierite with catalytic activity and preparation method of porous cordierite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510158376.XA CN104774002B (en) | 2015-04-03 | 2015-04-03 | Porous cordierite with catalytic activity and preparation method of porous cordierite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104774002A true CN104774002A (en) | 2015-07-15 |
| CN104774002B CN104774002B (en) | 2017-02-22 |
Family
ID=53615812
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|---|---|---|---|
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| Country | Link |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802714A (en) * | 2003-04-09 | 2006-07-12 | Mra实验室有限公司 | High dielectric constant very low fired X7R ceramic capacitor, and powder for making |
| CN101423392A (en) * | 2008-10-08 | 2009-05-06 | 东莞华科电子有限公司 | Low-temperature co-fired microwave dielectric ceramic material and preparation method thereof |
| CN102600910A (en) * | 2012-02-17 | 2012-07-25 | 江苏省宜兴非金属化工机械厂有限公司 | High-water absorption flue gas denitration honeycomb ceramic support and preparation method thereof |
| CN104030720A (en) * | 2014-06-24 | 2014-09-10 | 北京奥福(临邑)精细陶瓷有限公司 | Zero-firing-shrinkage cordierite honeycomb ceramic carrier and preparation method thereof |
-
2015
- 2015-04-03 CN CN201510158376.XA patent/CN104774002B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1802714A (en) * | 2003-04-09 | 2006-07-12 | Mra实验室有限公司 | High dielectric constant very low fired X7R ceramic capacitor, and powder for making |
| CN101423392A (en) * | 2008-10-08 | 2009-05-06 | 东莞华科电子有限公司 | Low-temperature co-fired microwave dielectric ceramic material and preparation method thereof |
| CN102600910A (en) * | 2012-02-17 | 2012-07-25 | 江苏省宜兴非金属化工机械厂有限公司 | High-water absorption flue gas denitration honeycomb ceramic support and preparation method thereof |
| CN104030720A (en) * | 2014-06-24 | 2014-09-10 | 北京奥福(临邑)精细陶瓷有限公司 | Zero-firing-shrinkage cordierite honeycomb ceramic carrier and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN104774002B (en) | 2017-02-22 |
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Address after: 332000 No. 2, Yugang Road, chengxigang Industrial Park, Jiujiang Economic and Technological Development Zone, Jiujiang City, Jiangxi Province Patentee after: Jiangxi Antan high tech Material Co.,Ltd. Address before: 332000 chengxigang Industrial Park, Jiujiang Economic Development Zone, Jiangxi Province Patentee before: JIANGXI ANTIAN ADVANCED MATERIALS CO.,LTD. |