CN101708456B - Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof - Google Patents
Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof Download PDFInfo
- Publication number
- CN101708456B CN101708456B CN 200910227252 CN200910227252A CN101708456B CN 101708456 B CN101708456 B CN 101708456B CN 200910227252 CN200910227252 CN 200910227252 CN 200910227252 A CN200910227252 A CN 200910227252A CN 101708456 B CN101708456 B CN 101708456B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- preparation
- solution
- low
- exchange
- 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.)
- Active
Links
Abstract
The invention provides a molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and a preparation method thereof. The molecular sieve adsorbent comprises the following components based on parts by weight percent: 80-95% of CaLS molecular sieve with SiO2/Al2O3=2.0, and 5-20% of binder. The preparation method comprises the steps of: preparing sodium potassium type low-silicon X type molecular sieve KNaLSX with SiO2/Al2O3=2.0; exchanging 0.5-1.5ml of CaCl2 solution with the KNaLSX molecular sieve at 80-85 DEG C for 1-2h; washing and drying; mixing the molecular sieve with the binder; smashing; wetly stirring with auxiliary binder; drying to be shaped; and roasting at 450-550 DEG C for 1-5h. Compared with the prior art, the adsorbent has high Ca2+exchange degree, high molecular sieve crystallinity, large absorption quantity, fast absorption speed, low cost and good oxygen-nitrogen separation performance.
Description
Technical field
The present invention relates to adsorbent of molecular sieve of a kind of adsorbent of molecular sieve technology, particularly a kind of separating oxygen from air by means of pressure swing adsorption and preparation method thereof.
Background technology
Low-silicon X-shaped molecular screen, referred to as LSX, its SiO
2/ Al
2O
3Be 2.0-2.1, its cation-bit reaches maximum, have maximum adsorption sites, and the cation of synthesis type LSX molecular sieve is Na
+And K
+, directly as the separating oxygen from air by means of pressure swing adsorption adsorbent, its oxygen nitrogen separation than the adsorbent of molecular sieve 5A type molecular sieve of traditional making oxygen by air separation and common X-type molecular sieve without obvious raising.Common X-type molecular sieve, its SiO
2/ Al
2O
3Be 2.35-2.50, cation is Na
+, also claim NaX.Therefore, must be with Na
+And K
+Change into other metal cations, thereby improve oxygen nitrogen separating power.For example, can be with Na
+And K
+Change into calcium ion type low-silicon X-shaped molecular screen, this molecular sieve also is called for short CaLSX.
US Patent No. 4557736 has been reported the X-zeolite of bivalent cation calcium and strontium exchange, claims it to have higher nitrogen adsorbance and nitrogen selectivity preferably when air separation, but the strontium resource scarcity, expensive price.Chinese patent CN1034913 has reported the lithium X zeolite oxygen nitrogen separation of using divalent cation-exchanged and has used adsorbent, has improved oxygen nitrogen separating power, and bivalent cation is selected from Ba
2+, Co
2+, Cu
2+, Cr
2+, Fe
2+, Mg
2+, Mn
2+, Zn
2+, but Li remains main component, the Li expensive price, and preparation process is complicated, and the Li utilization rate is low, makes the adsorbent cost high.US Patent No. 4859217 has been reported the nitrogen selectivity adsorbent that lithium exchange X-zeolite can provide, and the lithium exchange degree is greater than 88%, and initial substance is sodium X-zeolite.
Although the cation exchange X-zeolite that the nitrogen absorption property is improved a lot has had more report in document, the better nitrogen absorption property of especially high exchange degree lithium exchange X-zeolite is known.But prepare relatively difficulty of high exchange degree lithium exchange X-zeolite, and expensive, make the adsorbent cost very high.That reality need to provide is with low cost, oxygen nitrogen separating property separating oxygen from air by means of pressure swing adsorption adsorbent preferably.
Summary of the invention
Technical problem to be solved by this invention provides a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve and preparation method thereof.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, the percentage by weight of each component: SiO
2/ Al
2O
3The Ca of=2.0-2.1
2+The low-silicon X-shaped molecular screen 80-95% of exchange, binding agent is 5-20%.Low-silicon X-shaped molecular screen also claims CaLSX.
A kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its more specifically technical scheme can be: described binding agent is clay, kaolin, carclazyte, bentonite or attapulgite and their two kinds or two or more mixtures, is preferably clay and kaolinic mixture.
A kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its more specifically technical scheme can also be: described CaLSX, its Ca
2+Exchange degree is 80-100%, preferred Ca
2+Exchange degree is 95-98%.
The preparation method of a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its step is as follows:
1, preparation SiO
2/ Al
2O
3The potassium sodium-type low-silicon X-type molecular sieve KNaLSX of=2.0-2.1;
2, use the CaCl of 0.5-1.5M
2Solution and LSX molecular sieve carry out Ca at 80-85 ℃
2+Exchange 1-2 hour, triplicate is washed till without Cl
-, the CaLSX molecular sieve is made in oven dry;
3, CaLSX molecular sieve and binding agent are mixed, pulverize, wet with helping binding agent to mix, moulding, drying;
4, at 450-550 ℃ of lower roasting 1-5 hour, get target product.
Described preparation method, its step 1 preparation SiO
2/ Al
2O
3The low-silicon X-shaped molecular screen LSX of=2.0-2.1, can be according to the method for routine, for example according to the method that provides for " Crystallization of low-silica Faujasite " paper in Zeoliters (1987) 7 phase the 451st page head by Gunter H.Kuhl, prepare SiO
2/ Al
2O
3The potassium sodium-type low-silicon X-type molecular sieve of=2.0-2.1.The KNaLSX molecular sieve of preparation, at 25 ℃, P/P
0In=0.21 the situation, the cyclohexane saturated extent of adsorption is greater than 18.0%.
The preparation method of a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its further concrete technical scheme can be: described CaCl
2The pH value of solution is 6.5-8.5, CaCl
2CaCl in the solution
2With the weight ratio of butt KNaLSX molecular sieve be 0.65: 1.
The preparation method of a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its further concrete technical scheme can also be: described CaCl
2Repeatedly recycle in solution and the KNaLSX molecular sieve exchange process, recycling method is the Ca through exchange
2+The CaCl that content is low
2Solution with contain Na
+Amount and K
+Measure high molecular sieve and contact first, then the Na that contains through replacing
+Amount and K
+Measure low molecular sieve again with contain Ca
2+The CaCl that content is high
2Solution further exchanges.
The preparation method of a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its further concrete technical scheme can also be: the described binding agent that helps is the blue or green powder solution in sodium carboxymethylcellulose, starch solution, field or acrylic based emulsion solution or the two or more mixtures of 1-10%.The acrylic based emulsion solution of preferred 5-8%.
The preparation method of a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention, its further concrete technical scheme can also be: sintering temperature is 500-535 ℃, and the dry air dew point that passes in the roasting process is lower than-40 ℃.
These technical schemes comprise that further concrete technical scheme also can make up mutually or combination, thereby reach better technique effect.
By adopting technique scheme, a kind of separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve of the present invention and preparation method thereof has following beneficial effect:
Adsorbent provided by the invention is compared with known technology, its Ca
2+Exchange degree is high, and molecular sieve crystallinity is high, and adsorption capacity is large, and adsorption rate is fast, and cost is low, and oxygen nitrogen separating property is good.
The specific embodiment
Below by embodiment technology of the present invention is given to illustrate further, but protection scope of the present invention is not limited to these examples.
Raw material used in the embodiments of the invention is:
The KNaLSX molecular sieve: according to the method that provides for " Crystallization of low-silica Faujasite " paper in Zeoliters (1987) 7 phase the 451st page head by Gunter H.Kuhl, preparation SiO
2/ Al
2O
3The potassium sodium-type low-silicon X-type molecular sieve of=2.0-2.1.The KNaLSX molecular sieve of preparation, at 25 ℃, P/P
0In=0.21 the situation, the cyclohexane saturated extent of adsorption is greater than 18.0%.
Ca
2+Switching method is: the CaCl of 600ml45g/l
2Solution (the pH value is 6.5-8.5), the lower KNaLSX molecular sieve 54g that adds of stirring is warming up to 80 ℃, and constant temperature 1 hour filters, repeated exchanged 3 times, washing is extremely without Cl
-, filter cake descended dry 3 hours at 100 ℃, got the CaLSX molecular sieve, Ca
2+Exchange degree greater than 98.0%.
Binding agent: the clay of employing 25% and 75% kaolin.
Help binding agent: adopt 5% acrylic based emulsion solution.
Embodiment 1
First with butt CaLSX molecular sieve 80 grams and binding agent (the sweet soil of 25% sheep and 75% kaolin) 20 gram mixed grindings, cross 120 mesh sieves, then mix wet with 5% an amount of acrylic based emulsion solution, be extruded into the bar of diameter 1.Smm, 100 ℃ of dryings are processed into the cylindrical particle of 2-3mm, and roasting is 3 hours under the condition of 525 ℃ of logical dry airs, get finished product CaLSX adsorbent of molecular sieve, surveying its compressive resistance is 55N/.
Finished product bar 1 is restrained in the BET sample cell of packing into, be warming up to 370 ℃, be evacuated down to simultaneously＜5Pa, kept 1 hour, cool to 25 ℃, pass into N
2, its pressure is 760mmHg, surveys its saturated N
2Adsorbance is 22.35ml/g, and same method is measured O
2Saturated extent of adsorption be 4.26ml/g, be considered as oxygen nitrogen separating power with the ratio of the molal quantity of oxygen nitrification adsorption capacity, then 22.35/4.26 * 28/32=4.59 (28 and 32 are respectively the molecular weight of nitrogen and oxygen).
Embodiment 2:
With embodiment 1 operation, only change the CaLSX molecular sieve into 85g, binding agent changes 15g into, 535 ℃ of sintering temperatures.
The finished product CaLSX adsorbent of molecular sieve that obtains, surveying its compressive resistance is 45N/.
Saturated N
2Adsorption capacity is 26.90ml/g, O
2Saturated adsorption capacity be 5.03ml/g, its oxygen nitrogen separating power is 4.69.
Test condition is also with embodiment 1.
Embodiment 3:
First with 17.5 kilograms of mixed grindings of 82.5 kilograms in butt CaLSX powder and binding agent (the sweet soil of 25% sheep and 75% kaolin), cross 120 mesh sieves, and then add mixed powder on the bowling machine and help the acrylic based emulsion solution of binding agent 5% to be rolled into the bead of 1.5mm, 100 ℃ lower dry, pass into dew point at 530 ℃ and be lower than-40 ℃ dry air, roasting 3 hours, surveying intensity is 51N/.
The saturated N of the upper survey of BET
2Adsorption capacity is 25.5ml/g, saturated O
2Adsorption capacity is 4.65ml/g, and its oxygen nitrogen separating power is 4.80.
Test condition is also with embodiment 1.
The comparative example 1:
First with butt 5A molecular sieve powder 85 grams and binding agent 15 gram mixed grindings, cross 120 mesh sieves, then mix wet with 5% an amount of acrylic based emulsion solution, be extruded into the bar of diameter 1.5mm, 100 ℃ of dryings are processed into the cylindrical particle of 2-3mm, and roasting is 3 hours under the condition of 525 ℃ of logical dry airs, get finished product, surveying its compressive resistance is 50N/.
Finished product bar 1 is restrained in the BET sample cell of packing into, be warming up to 370 ℃, be evacuated down to simultaneously＜5Pa, kept 1 hour, cool to 25 ℃, pass into N
2, its pressure is 760mmHg, surveys its saturated N
2Adsorbance is 12.35ml/g, and same method is measured O
2Saturated extent of adsorption be 3.70ml/g, oxygen nitrogen separating power is 3.0.
The comparative example 2:
First with butt 13X molecular sieve powder 85 grams and binding agent 15 gram mixed grindings, cross 120 mesh sieves, then mix wet with 5% an amount of acrylic based emulsion solution, be extruded into the bar of diameter 1.5mm, 100 ℃ of dryings are processed into the cylindrical particle of 2-3mm, and roasting is 3 hours under the condition of 525 ℃ of logical dry airs, get finished product, surveying its compressive resistance is 45N/.
Finished product bar 1 is restrained in the BET sample cell of packing into, be warming up to 370 ℃, be evacuated down to simultaneously＜5Pa, kept 1 hour, cool to 25 ℃, pass into N
2, its pressure is 760mmHg, surveys its saturated N
2Adsorbance is 12.80ml/g, and same method is measured O
2Saturated extent of adsorption be 4.80ml/g, oxygen nitrogen separating power is 3.05.
The comparative example 3:
In the raw material that comparative example 3 is used and the embodiments of the invention 1 used raw material and operate identical, Ca just
2+Exchange once the Ca of CaLSX powder
2+Exchange degree be 74.5%.Survey its saturated N
2Adsorbance is 15.65ml/g, O
2Saturated extent of adsorption be 3.80ml/g, oxygen nitrogen separating power is 3.60.
The comparative example 4:
In the raw material that comparative example 4 is used and the embodiments of the invention 1 used raw material and operate identical, Ca just
2+The exchange secondary, the Ca of CaLSX powder
2+Exchange degree be 90.64%.Survey its saturated N
2Adsorbance is 20.25ml/g, O
2Saturated extent of adsorption be 4.10ml/g, oxygen nitrogen separating power is 4.30.
The comparative example 5:
In the raw material that comparative example 5 is used and the embodiments of the invention 1 used raw material and operate identical, obstructed dry air when roasting just.Survey its saturated N
2Adsorbance is 19.25ml/g, O
2Saturated extent of adsorption be 3.70ml/g, oxygen nitrogen separating power is 4.55.
Claims (4)
1. the preparation method of a separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve, it is characterized in that: the mass percent of each component of adsorbent of molecular sieve is Ca
2+The low-silicon X-shaped molecular screen CaLSX 80-95% of exchange, binding agent is 5-20%; Ca
2+The Ca of the low-silicon X-shaped molecular screen CaLSX of exchange
2+Exchange degree is 95-98%; Binding agent is clay, kaolin, carclazyte, bentonite or attapulgite and two or more mixtures thereof; Preparation method's step is as follows:
(1), preparation SiO
2/ Al
2O
3The potassium sodium-type low-silicon X-type molecular sieve KNaLSX of=2.0-2.1;
(2), use the CaCl of 0.5-1.5M
2Solution and potassium sodium-type low-silicon X-type molecular sieve KNaLSX carry out Ca at 80-85 ℃
2+Exchange 1-2 hour, be washed till without Cl
-, Ca is made in oven dry
2+The low-silicon X-shaped molecular screen CaLSX of exchange; CaCl
2The pH value of solution is 6.5-8.5;
(3), with Ca
2+The low-silicon X-shaped molecular screen CaLSX of exchange and binding agent mix, and pulverize, and be wet with helping binding agent to mix, moulding, drying; Helping binding agent is the blue or green powder solution in sodium carboxymethylcellulose, starch solution, field or acrylic based emulsion solution or its two or more mixture of 1-10%;
(4), at 500-535 ℃ of lower roasting 1-5 hour, the dry air dew point that passes in the roasting process is lower than-40 ℃, gets target product.
2. the preparation method of described separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve according to claim 1 is characterized in that: described CaCl
2CaCl in the solution
2With the weight ratio of butt potassium sodium-type low-silicon X-type molecular sieve KNaLSX be 0.65: 1.
3. the preparation method of described separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve according to claim 1 is characterized in that: described CaCl
2Repeatedly recycle in solution and the potassium sodium-type low-silicon X-type molecular sieve KNaLSX exchange process, recycling method is the Ca through exchange
2+The CaCl that content is low
2Solution with contain Na
+Amount and K
+Measure high molecular sieve and contact first, then the Na that contains through replacing
+Amount and K
+Measure low molecular sieve again with contain Ca
2+The CaCl that content is high
2Solution further exchanges.
4. the preparation method of described separating oxygen from air by means of pressure swing adsorption adsorbent of molecular sieve according to claim 1, it is characterized in that: the described binding agent that helps is the acrylic based emulsion solution of 5-8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910227252 CN101708456B (en) | 2009-11-23 | 2009-11-23 | Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910227252 CN101708456B (en) | 2009-11-23 | 2009-11-23 | Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101708456A CN101708456A (en) | 2010-05-19 |
| CN101708456B true CN101708456B (en) | 2013-03-06 |
Family
ID=42401276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910227252 Active CN101708456B (en) | 2009-11-23 | 2009-11-23 | Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101708456B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784617B (en) * | 2012-08-14 | 2014-05-07 | 洛阳市建龙化工有限公司 | Adsorbent containing silver molecular sieve as well as preparation method and application of adsorbent |
| CN106622117B (en) * | 2017-01-25 | 2019-04-02 | 洛阳建龙微纳新材料股份有限公司 | A kind of preparation method and applications of HEU type molecular sieve |
| CN107486146B (en) * | 2017-09-06 | 2020-10-23 | 洛阳建龙微纳新材料股份有限公司 | Preparation method and application of mixed cation LiCa-LSX molecular sieve |
| CN113371730A (en) * | 2021-06-02 | 2021-09-10 | 昊华化工科技集团股份有限公司 | Modified calcium low-silicon zeolite molecular sieve and preparation method thereof |
| CN113697824B (en) * | 2021-08-26 | 2023-08-25 | 中国地质科学院郑州矿产综合利用研究所 | Preparation process and application of modified 3A molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146374A (en) * | 1995-09-27 | 1997-04-02 | 环球油品公司 | Nitrogen-selective zeolitic adsorbent for use in air separation process |
| CN1341474A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp.-change adsorptive process |
| CN101524638A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | Preparation method of submicron molecular sieve carbon dioxide absorbent |
-
2009
- 2009-11-23 CN CN 200910227252 patent/CN101708456B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146374A (en) * | 1995-09-27 | 1997-04-02 | 环球油品公司 | Nitrogen-selective zeolitic adsorbent for use in air separation process |
| CN1341474A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp.-change adsorptive process |
| CN101524638A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | Preparation method of submicron molecular sieve carbon dioxide absorbent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101708456A (en) | 2010-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101708456B (en) | Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof | |
| KR102173543B1 (en) | Zeolitic adsorbents, process for preparing same and uses thereof | |
| US6918948B2 (en) | Process for use of molecular sieve adsorbent blends | |
| KR101947248B1 (en) | Zeolitic adsorbents with large external surface area, process for preparing same and uses thereof | |
| CN108854945A (en) | Agglomerated zeolitic absorbents, their production method and their purposes | |
| JP2014516305A (en) | Binderless zeolite adsorbent, method for producing binderless zeolite adsorbent, and adsorption separation method using binderless zeolite adsorbent | |
| CN105339082A (en) | Zeolite adsorbents comprising EMT zeolite, method for preparing same and uses thereof | |
| JP2005515876A6 (en) | Method for producing molecular sieve adsorbent blend | |
| CN102861551B (en) | Bax type zeolite granule and process for preparing the same | |
| JPS6128606B2 (en) | ||
| US20050119112A1 (en) | Process for production of molecular sieve adsorbent blends | |
| US3979335A (en) | Process for the preparation of synthetic zeolites | |
| KR20170083116A (en) | Zeolite adsorbents made from x zeolite with low binder content and low external surface area, method for preparation of same and uses thereof | |
| CN105800638A (en) | Low-potassium type 3A zeolite molecular sieve and preparation method thereof | |
| CN109485058A (en) | Preparation method of binder-free LSX molecular sieve | |
| CN101289196B (en) | Method for preparing LiLSX molecular screen | |
| CN113371730A (en) | Modified calcium low-silicon zeolite molecular sieve and preparation method thereof | |
| US20070062369A1 (en) | Method for the production of shaped zeolites, and method for eliminating impurities from a gas stream (as amended) | |
| CN1663675A (en) | Formulation of dry filter core for refrigerating system | |
| CN109562351A (en) | The zeolite adsorbents of the agglomerate form of low tortuosity | |
| CN106698458B (en) | The low silicon faujasite of lithium type, preparation method and the usage | |
| JPH11246214A (en) | A-type zeolite bead compact and its production | |
| JPH11246282A (en) | X-zeolite bead compact and its production | |
| JPH0443696B2 (en) | ||
| JPS6240283B2 (en) |
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 | ||
| C56 | Change in the name or address of the patentee |
Owner name: LUOYANG JIANLONG MICRO-NANO NEW MATERIAL CO., LTD. Free format text: FORMER NAME: LUOYANG JIANLONG CHEMICAL INDUSTRY CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 471900 Yanshi City, Henan Province Industrial Agglomeration Area (Industrial Zone, military and civilian road) Patentee after: LUOYANG JIANLONG MICRO-NANO NEW MATERIALS CO., LTD. Address before: 471039 new walled Industrial Park, Chengguan Town, Henan, Luoyang Patentee before: Luoyang Jianlong Chemical Industry Co., Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Molecular sieve adsorbent for separating oxygen from air by means of pressure swing adsorption and preparation method thereof Effective date of registration: 20170220 Granted publication date: 20130306 Pledgee: Industrial Commercial Bank of China Ltd Yanshi branch Pledgor: LUOYANG JIANLONG MICRO-NANO NEW MATERIALS CO., LTD. Registration number: 2017990000115 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20200407 Granted publication date: 20130306 Pledgee: Industrial Commercial Bank of China Ltd Yanshi branch Pledgor: LUOYANG JIANLONG MICRO-NANO NEW MATERIALS Co.,Ltd. Registration number: 2017990000115 |