CN102557060B - Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same - Google Patents
Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same Download PDFInfo
- Publication number
- CN102557060B CN102557060B CN201010610682.XA CN201010610682A CN102557060B CN 102557060 B CN102557060 B CN 102557060B CN 201010610682 A CN201010610682 A CN 201010610682A CN 102557060 B CN102557060 B CN 102557060B
- Authority
- CN
- China
- Prior art keywords
- rho
- molecular sieve
- sapo molecular
- synthetic method
- organic amine
- 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
Images
Abstract
The invention relates to a synthesizing method for an RHO-SAPO molecular sieve and a catalyst prepared with the same. The method is characterized in that: organic amine is directly taken as a main solvent and a temperate agent of a synthesizing system, and the solvent is thermally synthesized into the RHO-SAPO molecular sieve at a high organic amine/water molar proportion.
Description
Technical field
The present invention relates to a kind of synthetic method of RHO-SAPO molecular sieve.
The invention still further relates to the application of the RHO-SAPO obtained under this synthetic method.
Background technology
Since nineteen eighty-two, in the patent US 4310440 of U.S.'s union carbide corporation application, since successfully synthesizing a series of aluminium phosphate molecular sieve and derivative thereof, aluminium phosphate molecular sieve and heteroatoms substitutive derivative thereof are one of study hotspots of material circle and catalytic field always.The technical characterstic of this class SAPO Zeolite synthesis is to adopt ,Lin source, ,Lv source, silicon source and different template to synthesize, and structural unit is by PO
2+, AlO
2-and SiO
2tetrahedron forms.In this molecular sieve analog, the molecular sieve of some small structures has been successfully applied to the processes such as MTG, MTO as SAPO-34 etc., and demonstrates good catalytic performance.
Molecular sieve with RHO skeleton structure is to be connected to form by two octatomic rings by the α cage, belongs to isometric system, and the main aperture road consists of two octatomic rings, port size 0.36nm * 0.36nm.1973, Robson, the reported first such as H.E. with Na
+, Cs
+for structure directing agent synthesize Si-Al zeolite molecular sieve with RHO structure (Adv.Chem.Ser., 121,106-115).1987, Rouse, the reports such as R.C. found a class have the natural crystal of RHO structure (N.Jb.Miner.Mh., 1987,433-440).After this, people use Na
+, Cs
+for structure directing agent synthesizes again BePO (Stud.Surf.Sci.Catal., 1989,49 with RHO structure in succession, 411-420), AlGeO (MicroporousMesoporous Mat., 1999,28,139-154), BeAsO (1991, Nature, 349,508-510), GaSiO (J.Phys.Chem., 1995,99,9924-9932) molecular sieve.1998, Feng, P.Y. wait and reported with N, N '-di-isopropyl-1,3-propylene diamine (N, N '-diisopropyl-1,3-propanediamine) synthesizes CoAPO-RHO, MgAPO-RHO, MnAPO-RHO molecular sieve (Microporous Mesoporous Mat. for template, 23,315-322).Hee-Young Jeon etc. is applied to synthesis of methylamines, dimethylamine (Appl.Catal.A by several micro porous molecular sieves with octatomic ring duct, 2006,305,70-78), contrast finds that the RHO zeolite reaches more than 90% the selectivity of methylamine and dimethylamine, has best methylamine, dimethylamine catalytic selectivity in several molecular sieves of research.Over the past two years, Mohamed H, Farid Nouar, Tao W philosophy had been reported RHO-MOFs be applied to hydrogen storage material, and obtained a series of progress (J.AM.CHEM.SOC.2008,130,12639-12641; J.AM.CHEM.SOC.2009,131,2864-2870; J.AM.CHEM.SOC.2009,131,6111-6113).
The synthetic method of RHO-SAPO molecular sieve mainly comprises at present: the xerogel synthesis method (see and apply for a patent 200910169329.X) under the Hydrothermal Synthesis RHO-SAPO under tensio-active agent participates in and surfactant-free participate in.
In hydrothermal synthesis method under surfactant participates in, on the one hand because building-up process has adopted external phase and the main body solvent of water as synthetic system, after synthesizing, can produce and be difficult in a large number the waste liquid utilized, increase the pressure of environmental protection treatment; Building-up process has been used relatively costly tensio-active agent on the other hand, has increased synthetic cost.
In xerogel synthesis method under surfactant-free participates in, at first to configure silicon phosphorus aluminium xerogel, complex process; And the RHO-SAPO Crystallization of Zeolite degree that this kind of synthetic method obtains is not high, the RHO-SAPO molecular sieve obtained often separates by modes such as washings with non-crystallized silicon phosphorus aluminium xerogel is more difficult.
1985, (Nature 1985 for Bibby and Dale, V317,157) reported and successfully synthesized sial and silica-sodalite molecular sieve, the brand-new research field of having opened solvent thermal synthesis of molecular sieve and molecular sieve type containing Microporous Compounds in ethylene glycol and propyl alcohol solvent.With traditional hydrothermal synthesis method, compare, the advantage of non-aqueous solvent thermal synthesis is its structured material that synthesizing new may be provided and improves the approach of the performance of known materials.Up to now, in the exploration of solvent thermal synthesis of molecular sieve, many employings alcoholic solvent close with aqueous polar.
Water is one of indispensable composition in Zeolite synthesis, even in the system of organic solvent thermal synthesis, the existence of a small amount of water is also necessary.Bibliographical information, during solvent thermal is synthetic, in low water consumption scope, crystallization process (J.Am.Chem.Soc.2008, V130,8120) can be obviously accelerated in a small amount of interpolation of water.Up to now, there is not yet the report of non-aqueous solvent thermal synthesis RHO-SAPO molecular sieve.Technical scheme of the present invention, adopt organic solvent and the template of organic amine as the solvent thermal synthetic system, only, in the presence of a small amount of water, synthesizes the RHO-SAPO molecular sieve.
Summary of the invention
The object of the present invention is to provide the synthetic method of RHO-SAPO molecular sieve under a kind of non-aqueous solvent hot system.
For achieving the above object, the present invention adopts organic solvent and the template of organic amine as the solvent thermal synthetic system, successfully synthesizes the RHO-SAPO molecular sieve.
Method of the present invention is not limited to synthetic RHO-SAPO molecular sieve, and the kind that changes organic amine will likely be synthesized other structure type SAPO molecular sieve.
The synthetic method that technical scheme of the present invention is a kind of RHO-SAPO molecular sieve, is characterized in that, adopts solvent process for thermosynthesizing, and key step is as follows:
A) by organic amine, ,Gui source, ,Lin source, aluminium source and water according to 6～30: 1: 0.5～5: 0.01～1.0: the mixed in molar ratio of 0.1-10, obtain preparing the original mixture of RHO-SAPO molecular sieve, wherein the molar ratio of water and described organic amine is less than 2;
B) 160～210 ℃ of lower crystallization of the original mixture described step a) obtained 0.5～15 day.
In the present invention, described aluminium source is any one or any several mixture in aluminum isopropylate, aluminum oxide, aluminium hydroxide, aluminum chloride, Tai-Ace S 150; Described phosphorus source is any one or any several mixture in ortho-phosphoric acid, metaphosphoric acid, phosphoric acid salt, phosphite; Described silicon source is any one or any several mixture in silicon sol, tetraethoxy, white carbon black, silicon-dioxide.
Described organic amine is diethylamine, the mixture of diethylamine and triethylamine, or the mixture of diethylamine and morpholine.Wherein triethylamine or morpholine and diethylamine molar ratio are less than 0.5.Building-up process of the present invention organic amine used is the organic amine mixture that diethylamine or diethylamine are main body.Change consumption and the ratio of organic amine, may cause the generation of stray crystal or other SAPO molecular sieve.
The molar ratio of described organic amine and water is 0.51～300, preferably 1～300, more preferably 1.5～300.
In the present invention, after end of synthesis, can adopt the mode of distillation that main body solvent organic amine is separated from crystallization liquid, the waste liquid growing amount is low, and organic amine can be reused simultaneously, not only reduces synthetic cost, and is a kind of synthetic method of environment-friendly and green.
Described step b) in, crystallization temperature is 180～200 ℃, and crystallization time is 1～3 day.
Described step prepares the process of original mixture in a), and its material addition sequence can be for first mixing phosphorus source and organic amine, then add ,Gui source, aluminium source and water.
The order of addition(of ingredients) of the layoutprocedure by controlling original mixture, make its mixing of materials sequentially for first mixing phosphorus source and organic amine, then add ,Gui source, aluminium source and water, can avoid generating stray crystal, obtains highly purified RHO-SAPO product simultaneously.
The synthetic method of RHO-SAPO molecular sieve of the present invention can also comprise step c): until described step b) after crystallization completes, solid product is separated, washing, drying, to obtain the RHO-SAPO molecular screen primary powder.
Synthetic RHO-SAPO molecular sieve, after roasting in 400～700 ℃ of air, can be used as the catalyzer of acid catalyzed reaction.
The beneficial effect that the present invention can produce comprises:
(1) provide a kind of synthetic method of new RHO-SAPO molecular sieve.
(2) in the solvent thermal synthetic system, the main body solvent diethylamine boiling point adopted is low, and thermal capacitance is little, can after end of synthesis, adopt the method for distillation that it is steamed, and the residual waste solution amount is few, and organic amine is reusable, is a kind of synthetic method of environment-friendly and green.
The accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of synthetic product in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of synthetic product in the embodiment of the present invention 3.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
Embodiment 1 (FDZ-39-6)
By 10.37g ortho-phosphoric acid (H
3pO
4quality percentage composition 85%) join in the 60ml diethylamine under the condition of ice-water bath, and add wherein successively 8.34g activated alumina (Al under whipped state
2o
3quality percentage composition 72.5%), 5.69g silicon sol (SiO
2quality percentage composition 28.2%), and the 0.2g deionized water, after vigorous stirring mixes it, gel is transferred in stainless steel cauldron, under the crystallization temperature of 200 ℃, dynamically synthesize 48 hours.After crystallization finishes, solid product is centrifugal, washing, after drying in 100 ℃ of air, sample is done XRD analysis.The XRD data are in Table 1, and result shows that synthetic product is for having the RHO structure.Its that sample is done to XRF analysis consists of Al
0.489p
0.306si
0.205, this shows that the gained sample is the RHO-SAPO molecular sieve.The gained sample is done to scanning electron microscope and characterize, the electromicroscopic photograph obtained is shown in Fig. 1.
Comparative Examples 1
By 8.34g activated alumina (Al
2o
3quality percentage composition 72.5%) mix and stir evenly with the diethylamine of 60ml, and add wherein successively 10.37g ortho-phosphoric acid (H under whipped state
3pO
4quality percentage composition 85%), 5.69g silicon sol (SiO
2quality percentage composition 28.2%) and the 0.2g deionized water, after vigorous stirring mixes it, gel is transferred in stainless steel cauldron under the crystallization temperature of 200 ℃ dynamically synthetic 48 hours.After crystallization finishes, solid product is centrifugal, washing, after drying in 100 ℃ of air, sample is done XRD analysis.The XRD result shows the mixed crystal that synthetic product is RHO-SAPO and SAPO-34 molecular sieve.
Comparative Examples 2
By 8.34g activated alumina (Al
2o
3quality percentage composition 72.5%), 10.37g ortho-phosphoric acid (H
3pO
4quality percentage composition 85%), 5.69g silicon sol (SiO
2quality percentage composition 28.2%) mix and stir evenly with the deionized water of 45ml, and add the 10mi diethylamine under whipped state, after vigorous stirring mixes it, gel is transferred in stainless steel cauldron, dynamically synthesized 48 hours under the crystallization temperature of 200 ℃.After crystallization finishes, solid product is centrifugal, washing, after drying in 100 ℃ of air, sample is done XRD analysis, and result shows that synthetic product is the SAPO-34 molecular sieve.
Embodiment 2
In embodiment 1, only change the 8.34g activated alumina into the 24.5g aluminum isopropylate, amount of deionized water changes 1.0g into, and all the other components and crystallization condition are constant.Crystallization product is done the XRD diffraction analysis, and result shows that synthetic sample is the RHO-SAPO molecular sieve.
Comparative Examples 3
In embodiment 1, only change the 8.34g activated alumina into the 24.5g aluminum isopropylate, amount of deionized water changes 10g into, and all the other components and crystallization condition are constant.Crystallization product is done the XRD diffraction analysis, and result shows that synthetic sample is the SAPO-34 molecular sieve.
Embodiment 3 (FDZ-38-5)
By 11.52g ortho-phosphoric acid (H
3pO
4quality percentage composition 85%) join under the condition of ice-water bath in the mixing solutions of 60ml diethylamine and 15ml triethylamine, and add wherein successively 7.03g activated alumina (Al under whipped state
2o
3quality percentage composition 72.5%), 4.55g silicon sol (SiO
2quality percentage composition 28.2%), and the 0.1g deionized water, after vigorous stirring mixes it, gel is transferred in stainless steel cauldron, under the crystallization temperature of 190 ℃, dynamically synthesize 48 hours.After crystallization finishes, solid product is centrifugal, washing, after drying in 100 ℃ of air, sample is done XRD analysis.The XRD data are in Table 2, and result shows that synthetic product is for having the RHO structure.The gained sample is done scanning electron microscope and is characterized, and the electromicroscopic photograph obtained is shown in Fig. 2.
Embodiment 4
In embodiment 1, only change the 8.34g activated alumina into the 24.5g aluminum isopropylate, 5.69g silicon sol (SiO
2quality percentage composition 28.2%) change the 1.6g fumed silica into, amount of deionized water changes 1.2g into, and all the other components and crystallization condition are constant.Crystallization product is done the XRD diffraction analysis, and result shows that synthetic sample is the RHO-SAPO molecular sieve.
Embodiment 5
In embodiment 1, only change the 8.34g activated alumina into the 6.1g gama-alumina, 5.69g silicon sol (SiO
2quality percentage composition 28.2%) change the 1.6g fumed silica into, all the other components and crystallization condition are constant.Crystallization product is done the XRD diffraction analysis, and result shows that synthetic sample is the RHO-SAPO molecular sieve.
Embodiment 6 (FDZ-31-2)
In embodiment 1, the 60ml diethylamine is changed into to the mixing solutions of 60ml diethylamine and 18ml morpholine, the consumption of phosphoric acid (85wt%) changes 12.35g into, and amount of deionized water changes 0.5g into, keep other components and crystallization condition constant, products therefrom is designated as FDZ-31-2.The XRD diffraction analysis the results are shown in Table 3, and result shows that synthetic product is the RHO-SAPO molecular sieve.
The XRD result of table 1:FDZ-39-6 sample
The XRD result of table 2:FDZ-38-5 sample
The XRD result of table 3:FDZ-31-2 sample
Claims (11)
1. the synthetic method of a RHO-SAPO molecular sieve, is characterized in that, adopts solvent process for thermosynthesizing, and key step is as follows:
A) by organic amine, ,Gui source, ,Lin source, aluminium source and water according to 6～30: 1: 0.5～5: 0.01～1.0: 0.1～10 mixed in molar ratio, obtain preparing the original mixture of RHO-SAPO molecular sieve, wherein the molar ratio of water and described organic amine is less than 2;
B) 160～210 ℃ of lower crystallization of the original mixture described step a) obtained 0.5～15 day,
The molar ratio of wherein said organic amine and water is 1.5～300.
2. the synthetic method of RHO-SAPO molecular sieve according to claim 1 is characterized in that: described aluminium source is any one or several mixture arbitrarily in aluminum isopropylate, aluminum oxide, aluminium hydroxide, aluminum chloride, Tai-Ace S 150.
3. the synthetic method of RHO-SAPO molecular sieve according to claim 1 is characterized in that: described phosphorus source is any one or several mixture arbitrarily in ortho-phosphoric acid, metaphosphoric acid, phosphoric acid salt, phosphite.
4. the synthetic method of RHO-SAPO molecular sieve according to claim 1 is characterized in that: described silicon source is any one or several mixture arbitrarily in silicon sol, tetraethoxy, silicon-dioxide.
5. the synthetic method of RHO-SAPO molecular sieve according to claim 1, it is characterized in that: described organic amine is diethylamine, the mixture of diethylamine and triethylamine, or the mixture of diethylamine and morpholine.
6. the synthetic method of RHO-SAPO molecular sieve according to claim 5, it is characterized in that: in described organic amine, the molar ratio of triethylamine or morpholine and diethylamine is less than 0.5.
7. the synthetic method of RHO-SAPO molecular sieve according to claim 1 is characterized in that: described step b), crystallization temperature is 180～200 ℃.
8. the synthetic method of RHO-SAPO molecular sieve according to claim 1 is characterized in that: described step b), crystallization time is 1～3 day.
9. the synthetic method of RHO-SAPO molecular sieve according to claim 1 is characterized in that: described step prepares the process of original mixture in a), and its material addition sequence is for first mixing phosphorus source and organic amine, then adds ,Gui source, aluminium source and water.
10. the synthetic method of RHO-SAPO molecular sieve according to claim 1, it is characterized in that: described method also comprises step c): until described step b) after crystallization completes, solid product is separated, washing, drying, to obtain the RHO-SAPO molecular screen primary powder.
11. the catalyzer of an acid catalyzed reaction, its according to claim 1 the synthetic RHO-SAPO molecular sieve roasting in 400～700 ℃ of air of method obtain.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010610682.XA CN102557060B (en) | 2010-12-29 | 2010-12-29 | Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010610682.XA CN102557060B (en) | 2010-12-29 | 2010-12-29 | Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102557060A CN102557060A (en) | 2012-07-11 |
| CN102557060B true CN102557060B (en) | 2014-01-08 |
Family
ID=46403885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010610682.XA Active CN102557060B (en) | 2010-12-29 | 2010-12-29 | Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102557060B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106276945B (en) * | 2015-06-10 | 2018-05-18 | 中国科学院大连化学物理研究所 | It is a kind of have in, the RHO-SAPO molecular sieves of micropore compound pore passage structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925586A (en) * | 1996-12-31 | 1999-07-20 | Exxon Chemical Patents, Inc. | Phosphorus modified small pore molecular sieve catalysts, and their use in the production of light olefins |
| CN1299775A (en) * | 1999-12-15 | 2001-06-20 | 中国科学院大连化学物理研究所 | Preparation of SAPO-17 and SAOP-44 molecular sieve |
| CN1485272A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
| CN101121529A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Fast synthetic method for phosphorus-silicon-aluminum molecular sieve |
-
2010
- 2010-12-29 CN CN201010610682.XA patent/CN102557060B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925586A (en) * | 1996-12-31 | 1999-07-20 | Exxon Chemical Patents, Inc. | Phosphorus modified small pore molecular sieve catalysts, and their use in the production of light olefins |
| CN1299775A (en) * | 1999-12-15 | 2001-06-20 | 中国科学院大连化学物理研究所 | Preparation of SAPO-17 and SAOP-44 molecular sieve |
| CN1485272A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
| CN101121529A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | Fast synthetic method for phosphorus-silicon-aluminum molecular sieve |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102557060A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5667311B2 (en) | Method for solvent thermal synthesis of SAPO molecular sieve and catalyst prepared thereby | |
| CN102627296B (en) | Preparation method of ZSM-35 molecular sieve | |
| CN103495436B (en) | Method for manufacturing ALPO-5/SAPO-34 composite molecular sieve for preparing catalyst of low carbon olefin made of organic oxygenated chemicals | |
| CN101993093A (en) | SAPO (silicoaluminophosphate) molecular sieve with RHO skeleton structure and preparation method thereof | |
| CN110182823A (en) | A method of reducing aluminium phosphate molecular sieve size of microcrystal | |
| CN102992346A (en) | Seed crystal synthesis method for preparing ZSM-23 molecular sieve | |
| CN101993095B (en) | Method for preparing SAPO-5 molecular sieve and product obtained through same | |
| CN105682795A (en) | Method for synthesizing silicoaluminophosphate-34 molecular sieves | |
| CN108298550A (en) | A method of it is mixed using tetrahydrofuran as template with organic amine and prepares multi-stage porous SAPO-34 molecular sieves | |
| CN102557072B (en) | Solvothermal synthesis method of silicoaluminophosphate (SAPO)-34 molecular sieve and catalytic agent prepared by using solvothermal synthesis method | |
| CN103011196A (en) | Method for synthesizing SAPO-41 (Phosphoric Acid Silicon-Aluminum-41) molecular sieve by adopting novel template agent | |
| CN103058208A (en) | Preparation method of SAPO-56 molecular sieve | |
| CN102557060B (en) | Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same | |
| CN104671256B (en) | Preparation method of SAPO-5/SAPO-34 composite molecular sieve for preparing catalyst for preparing low-carbon olefin from organic oxygen-containing compound | |
| CN103145145B (en) | Method for synthesizing SAPO-34 molecular sieve by taking A type zeolite as silicon source | |
| CN102530989A (en) | Method for preparing large-crystal SAPO-34 molecular sieve, product obtained by the method and application of the product | |
| CN109574035A (en) | A method of SAPO-34 molecular sieve is synthesized using the mother liquor of recyclable recycling | |
| CN106276967A (en) | A kind of synthetic method of mesoporous zeolite | |
| CN107074571A (en) | Use the method for the molecular sieve of monoisopropanolamine synthesized silicon-aluminum phosphate 34 | |
| CN114031092A (en) | Preparation method of SAPO-20 molecular sieve | |
| CN112777607A (en) | Method for hydrothermally synthesizing SSZ-13 molecular sieve by recycling mother liquor | |
| CN104556142B (en) | A kind of preparation method of low silicon SAPO-34 molecular sieve | |
| CN106276946A (en) | The synthetic method of a kind of RHO-SAPO molecular sieve and application thereof | |
| CN102627288A (en) | Preparation method for FER topological structure molecular sieve | |
| CN107500306A (en) | A kind of molecular sieve catalysts of SAPO 11 and preparation method 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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180511 Address after: 116318 Xingang village, Changxing Island Economic Zone, Dalian, Liaoning Patentee after: China Limited by Share Ltd new technology (Dalian) Limited by Share Ltd Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Synthesizing method for RHO-SAPO molecular sieve and catalyst prepared with same Effective date of registration: 20190201 Granted publication date: 20140108 Pledgee: Dalian Branch of Shanghai Pudong Development Bank Co., Ltd. Pledgor: China Limited by Share Ltd new technology (Dalian) Limited by Share Ltd Registration number: 2019210000001 |
|
| 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: 20200928 Granted publication date: 20140108 Pledgee: Dalian Branch of Shanghai Pudong Development Bank Co.,Ltd. Pledgor: Zhongke New Catalytic Technology (Dalian) Co.,Ltd. Registration number: 2019210000001 |