CN101318667A - Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof - Google Patents
Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof Download PDFInfo
- Publication number
- CN101318667A CN101318667A CNA2008100407614A CN200810040761A CN101318667A CN 101318667 A CN101318667 A CN 101318667A CN A2008100407614 A CNA2008100407614 A CN A2008100407614A CN 200810040761 A CN200810040761 A CN 200810040761A CN 101318667 A CN101318667 A CN 101318667A
- Authority
- CN
- China
- Prior art keywords
- metal
- molecular sieve
- preparation
- hours
- remodeling
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a metal modified silicoaluminophosphate molecular sieve with the structural formula of (0.2-5.0) R:(Si0.01-0.3 Al0.01-1 P0.01-.0.9):10-400H2O:(0.01-0.5)Me, wherein, Me is one of Co, Ni, Mn and La or is a plurality of kinds of Co, Ni, Mn and La. Compared with the prior art, the invention provides a Me-SAPO-34 molecular sieve which is applied as a catalyst to the reaction for the preparation of low-carbon olefin by using methanol, the transformation ratio of raw material methanol reaches 100%, the highest yield of (ethane plus propylene) reaches 93.40%, the longest service life of the catalyst can reach 566 minutes, the metal modified silicoaluminophosphate molecular sieve is characterized by high selectivity and high yield (ethane plus propylene), and long service life of the catalyst.
Description
Technical field
The present invention relates to modified SAPO-34 molecular sieve.Especially relate to a kind of metal remodeling silicoaluminophosphamolecular molecular sieves and preparation method thereof and the catalytic applications in MTO.
Background technology
Low-carbon alkene, especially ethene and propylene as basic Organic Chemicals, play a part very important in modern oil and chemical industry.The traditional mode of production route of alkene mainly is a petroleum path.Because the long-term continuous rise of oil price, supply is unstable, and resource reserves are limited, and it is not enough that increase ethene, propone output only depend on traditional petroleum path.By preparing light olefins from methanol (Methanol-to-Olefins, be called for short MTO) is to be the technological process of raw material via low-carbon alkenes such as methyl alcohol system ethene, propylene with coal or Sweet natural gas, is the novel process of most promising non-petroleum path.The gordian technique of MTO technology is a catalyzer, and the MTO catalysts need have high reactivity, highly selective and good regenerability.1984, the silicon phosphorus aluminium zeolite molecular sieve (be called for short SAPO molecular sieve) of aperture about 0.4nm invented by U.S. combinating carbide company (UCC), in the SAPO catalyst series, behaving most, what attract attention is the SAPO-34 molecular sieve, the MTO catalytic performance excellence of this kind molecular sieve: methanol conversion is close to 100%, the selectivity about 60% of ethene and propylene does not almost have C
4Above product.
USP5912393, USP4554143, all proposing on the AlPO basis to add metallic element among the USP4853197 carries out modification and obtains the MeAPO molecular sieve, wherein Me refers to Si, Mg, Zn, Fe etc., and being applied to the reaction of methanol-to-olefins, the result shows that the molecular sieve catalyst performance in reaction for preparing light olefins from methanol after metal ion-modified is improved.
Exxon company proposes to introduce alkaline-earth metal Sr, Ca or Ba in the SAPO-34 molecule in USP6040264, the performance of catalyzer is further improved, after wherein introducing Sr, the total recovery of ethene and propylene is up to 89.5%, and the mol ratio of ethene and propylene is up to 2.3.
CN1704390 obtains the Zn-SAPO-34 molecular sieve by adopting metallic element Zn that SAPO-34 is carried out modification, and with its catalyzer as methanol-to-olefins, reaction generates low-carbon alkene under suitable reaction conditions.Because the adding of metallic element Zn has improved the selectivity of molecular sieve to low-carbon alkene to the influence that skeleton and the pore structure of SAPO-34 causes, the selectivity of (ethene+propylene) reaches 91.34%, and the reaction times reaches 6 hours.
But these catalyzer are to being applied to the reaction of preparing light olefins from methanol, and conversion of raw material is not high, and are lower to the selectivity and the life-span of low-carbon alkene.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of ethene, propylene selectivity height, metal remodeling silicoaluminophosphamolecular molecular sieves that catalyst life is long and preparation method thereof and the catalytic applications in MTO for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions: a kind of metal remodeling silicoaluminophosphamolecular molecular sieves is characterized in that the structural formula of this molecular sieve is (0.2-5.0) R: (Si
0.01-0.3Al
0.01-1P
0.01-0.9): 10-400H
2O: (0.01-0.5) Me, wherein Me is one or more among Co, Ni, Mn, the La.
A kind of preparation method of metal remodeling silicoaluminophosphamolecular molecular sieves is characterized in that this method may further comprise the steps:
(2) preparation of raw mix
Form mole proportioning (0.2-5.0) R according to reactant: (Si
0.01-0.3Al
0.01-1P
0.01-0.9): 10-400H
2O: (0.01-0.5) Me, take by weighing a certain amount of aluminium source, phosphorus source, metal-salt, silicon source, water, R is a template;
(2) earlier above-mentioned aluminium source, phosphorus source, metal-salt and water are mixed, be stirred well to evenly;
(3) in the mixture of step (2), add silicon source and template, fully stir 1～5h to gel;
(4) gained gel in the step (3) is transferred in the crystallizing kettle, 150-250 ℃ of following crystallization 24～96 hours;
(5) solid product that takes out in the crystallizing kettle is washed to neutrality repeatedly, and drying is 4～8 hours in 50-150 ℃ of airflow, obtains the Me-SAPO-34 molecular screen primary powder.
Described template is a kind of in tetraethyl ammonium hydroxide, triethylamine, diethylamine, the morpholine or or their mixture.
Described silicon source comprises silicon sol, active silica or tetraethoxy, and described aluminium source comprises aluminum isopropylate, pseudo-boehmite or activated alumina, and described phosphorus source comprises ortho-phosphoric acid, aluminum phosphate, described metal-salt is a soluble salt, comprise vitriol, nitrate, chlorate.
The catalytic applications of a kind of metal remodeling silicoaluminophosphamolecular molecular sieves in MTO is characterized in that 300 ℃～600 ℃ roastings 2～6 hours, the back was applied to the reaction of preparing light olefins from methanol as catalyzer with described molecular sieve.
Compared with prior art, the present invention has good catalytic performance in methanol conversion by the Me-SAPO-34 molecular sieve catalyst that the metallic element modification obtains to the low-carbon alkene reaction, improved the selectivity of catalytic activity, low-carbon alkene greatly than the SAPO-34 of modifications such as other metallicss such as chromium, anti-coking performance and thermal stability, and prolonged the activity of such catalysts time greatly.In the MTO reaction, conversion of methanol is 100%, and the yield of (ethene+propylene) can reach 93.40%, and the yield of ethene can reach 70.88%, and the yield of propylene is 22.52%, and the mol ratio of ethene and propylene is 3.14, and life of catalyst can reach 566min.It is applied to the reaction of preparing light olefins from methanol (MTO) as catalyzer, can improve conversion of raw material, to the selectivity and the life-span of low-carbon alkene, has ethene, propylene selectivity height, the characteristics that catalyst life is long.
Embodiment
Below in conjunction with specific embodiment the present invention is specifically described in detail.
Embodiment 1
Synthetic 1 of molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.8H
3PO
4: 0.10Co (NO
3)
2: 60H
2O takes by weighing raw material.Behind a certain amount of pseudo-boehmite and certain water gaging thorough mixing, add H again
3PO
4, Co (NO
3)
2, silicon sol, TEA, fully stir certain hour after evenly.The gel that makes is moved in the 200ml crystallizing kettle, 190 ℃ of lower seal crystallization 72 hours.Take out solid product, to neutral, place 110 ℃ of dry 6h of loft drier airflow promptly to get SAPO-34 zeolite product 1 with the deionized water repetitive scrubbing.
Embodiment 2
The Synthetic 2 of molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.8H
3PO
4: 0.05Ni (NO
3)
2: 60H
2O takes by weighing raw material.Behind a certain amount of pseudo-boehmite and certain water gaging thorough mixing, add H again
3PO
4, Ni (NO
3)
2, silicon sol, TEA, fully stir certain hour after evenly.The gel that makes is moved in the 200ml crystallizing kettle, 190 ℃ of lower seal crystallization 72 hours.Take out solid product, to neutral, place 110 ℃ of dry 6h of loft drier airflow promptly to get SAPO-34 zeolite product 2 with the deionized water repetitive scrubbing.
Embodiment 3
Synthetic 3 of molecular sieve
According to proportioning: 2.5TEA: 0.5TEAOH: 0.75SiO
2: Al
2O
3: 2.8H
3PO
4: 0.05Ni (NO
3)
2: 60H
2O takes by weighing raw material.Behind a certain amount of pseudo-boehmite and certain water gaging thorough mixing, add H again
3PO
4, silicon sol, Ni (NO
3)
2, TEA, TEAOH, fully stir certain hour after evenly.The gel that makes is moved in the 200ml crystallizing kettle, 190 ℃ of lower seal crystallization 72 hours.Take out solid product, to neutral, place 110 ℃ of dry 6h of loft drier airflow promptly to get SAPO-34 zeolite product 3 with the deionized water repetitive scrubbing.
Embodiment 4
Synthetic 4 of molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.8H
3PO
4: 0.05Ni (NO
3)
2: 0.05Co (NO
3)
2: 60H
2O takes by weighing raw material.Behind a certain amount of pseudo-boehmite and certain water gaging thorough mixing, add H again
3PO
4, Co (NO
3)
2, Ni (NO
3)
2, silicon sol, TEA, fully stir certain hour after evenly.The gel that makes is moved in the 200ml crystallizing kettle, 190 ℃ of lower seal crystallization 72 hours.Take out solid product, to neutral, place 110 ℃ of dry 8h of loft drier airflow promptly to get SAPO-34 zeolite product 4 with the deionized water repetitive scrubbing.
Embodiment 5
Synthetic 5 of molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.8H
3PO
4: 0.05MnCl
2: 60H
2O takes by weighing raw material.Behind a certain amount of pseudo-boehmite and certain water gaging thorough mixing, add H again
3PO
4, MnCl
2, silicon sol, TEA, fully stir certain hour after evenly.The gel that makes is moved in the 200ml crystallizing kettle, 190 ℃ of lower seal crystallization 72 hours.Take out solid product, to neutral, place 110 ℃ of dry 8h of loft drier airflow promptly to get SAPO-34 zeolite product 5 with the deionized water repetitive scrubbing.
Embodiment 6
Synthetic 6 of molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.8H
3PO
4: 0.05La (NO
3)
3: 60H
2O takes by weighing raw material.Behind a certain amount of pseudo-boehmite and certain water gaging thorough mixing, add H again
3PO
4, La (NO
3)
3, silicon sol, TEA, fully stir certain hour after evenly.The gel that makes is moved in the 200ml crystallizing kettle, 190 ℃ of lower seal crystallization 72 hours.Take out solid product, to neutral, place 110 ℃ of dry 8h of loft drier airflow promptly to get SAPO-34 zeolite product 6 with the deionized water repetitive scrubbing.
Embodiment 7
SAPO-34 molecular sieve catalyst preparation 1
The synthetic SAPO-34 molecular screen primary powder that obtains of example 1 was removed template in 4.0 hours 550 ℃ of following roastings, is cooled to room temperature, carry out compressing tablet, fragmentation respectively after, the sieve particle that sieves out 20-40 order granularity is a catalyzer 1.
Embodiment 8
SAPO-34 molecular sieve catalyst preparation 2
The synthetic SAPO-34 molecular screen primary powders that obtain of example 2 were removed template in 4.0 hours 550 ℃ of following roastings, are cooled to room temperature, carry out compressing tablet, fragmentation respectively after, the sieve particle that sieves out 20-40 order granularity is a catalyzer 2.
Embodiment 9
SAPO-34 molecular sieve catalyst preparation 3
The synthetic SAPO-34 molecular screen primary powders that obtain of example 3 were removed template in 4.0 hours 550 ℃ of following roastings, are cooled to room temperature, carry out compressing tablet, fragmentation respectively after, the sieve particle that sieves out 20-40 order granularity is a catalyzer 3.
Embodiment 10
SAPO-34 molecular sieve catalyst preparation 4
The synthetic SAPO-34 molecular screen primary powders that obtain of example 4 were removed template in 4.0 hours 550 ℃ of following roastings, are cooled to room temperature, carry out compressing tablet, fragmentation respectively after, the sieve particle that sieves out 20-40 order granularity is a catalyzer 4.
Embodiment 11
SAPO-34 molecular sieve catalyst preparation 5
The synthetic SAPO-34 molecular screen primary powders that obtain of example 5 were removed template in 4.0 hours 550 ℃ of following roastings, are cooled to room temperature, carry out compressing tablet, fragmentation respectively after, the sieve particle that sieves out 20-40 order granularity is a catalyzer 5.
Embodiment 12
SAPO-34 molecular sieve catalyst preparation 6
The synthetic SAPO-34 molecular screen primary powders that obtain of example 6 were removed template in 4.0 hours 550 ℃ of following roastings, are cooled to room temperature, carry out compressing tablet, fragmentation respectively after, the sieve particle that sieves out 20-40 order granularity is a catalyzer 6.
Embodiment 13
Molecular sieve catalyst examination reaction 1
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer 1 to embodiment 7 preparations carries out the examination of MTO reactive behavior, checking and rating used processing condition is: loaded catalyst 4.6ml, temperature of reaction is 450 ℃, reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, and mass space velocity is 1.0 hours
-1, use nitrogen to be carrier gas, the mol ratio of nitrogen and methyl alcohol is 3: 1.Full product on-line analysis.Appraisal result is as shown in table 4.
The result of table 1 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dme occurred
Embodiment 14
Molecular sieve catalyst examination reaction 2
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer 2 to embodiment 8 preparations carries out the examination of MTO reactive behavior, checking and rating used processing condition is: loaded catalyst 4.6ml, temperature of reaction is 450 ℃, reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, and mass space velocity is 1.0 hours
-1, use nitrogen to be carrier gas, the mol ratio of nitrogen and methyl alcohol is 3: 1.Full product on-line analysis.Appraisal result is as shown in table 4.
The result of table 2 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dme occurred
Embodiment 15
Molecular sieve catalyst examination reaction 3
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer 3 to embodiment 9 preparations carries out the examination of MTO reactive behavior, checking and rating used processing condition is: loaded catalyst 4.6ml, temperature of reaction is 450 ℃, reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, and mass space velocity is 1.0 hours
-1, use nitrogen to be carrier gas, the mol ratio of nitrogen and methyl alcohol is 3: 1.Full product on-line analysis.Appraisal result is as shown in table 4.
The result of table 3 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dme occurred
Embodiment 16
Molecular sieve catalyst examination reaction 4
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer 4 to embodiment 10 preparations carries out the examination of MTO reactive behavior, checking and rating used processing condition is: loaded catalyst 4.6ml, temperature of reaction is 450 ℃, reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, and mass space velocity is 1.0 hours
-1, use nitrogen to be carrier gas, the mol ratio of nitrogen and methyl alcohol is 3: 1.Full product on-line analysis.Appraisal result is as shown in table 4.
The result of table 4 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dme occurred
Embodiment 17
Molecular sieve catalyst examination reaction 5
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer 5 to embodiment 11 preparations carries out the examination of MTO reactive behavior, checking and rating used processing condition is: loaded catalyst 4.6ml, temperature of reaction is 450 ℃, reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, and mass space velocity is 1.0 hours
-1, use nitrogen to be carrier gas, the mol ratio of nitrogen and methyl alcohol is 3: 1.Full product on-line analysis.Appraisal result is as shown in table 4.
The result of table 5 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dme occurred
Embodiment 18
Molecular sieve catalyst examination reaction 6
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyzer 6 to embodiment 11 preparations carries out the examination of MTO reactive behavior, checking and rating used processing condition is: loaded catalyst 4.6ml, temperature of reaction is 450 ℃, reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, and mass space velocity is 1.0 hours
-1, use nitrogen to be carrier gas, the mol ratio of nitrogen and methyl alcohol is 3: 1.Full product on-line analysis.Appraisal result is as shown in table 4.
The result of table 6 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dme occurred
Embodiment 19
A kind of metal remodeling silicoaluminophosphamolecular molecular sieves, forming the mole proportioning according to reactant is 0.2 triethylamine: 0.01 active silica: 0.01 aluminum isopropylate: 0.01 ortho-phosphoric acid: 10H
2O: 0.01MnCl
2, take by weighing raw material; Earlier with aluminum isopropylate, water, ortho-phosphoric acid and MnCl
2Be stirred well to evenly, interpolation active silica and triethylamine fully stir 1h to gel in mixture again, the gained gel is transferred in the crystallizing kettle, 150 ℃ of following crystallization 24 hours, the solid product that takes out in the crystallizing kettle is washed to neutrality repeatedly, drying is 4 hours in 50 ℃ of airflows, obtains the Me-SAPO-34 molecular screen primary powder.
300 ℃ of roastings 2 hours, the back was applied to the reaction of preparing light olefins from methanol as catalyzer with described molecular sieve.
Embodiment 20
A kind of metal remodeling silicoaluminophosphamolecular molecular sieves, forming the mole proportioning according to reactant is 5.0 morpholines: 0.3 tetraethoxy: 1 activated alumina: 0.9 ortho-phosphoric acid: 400H
2O: 0.5LaNO
3, take by weighing raw material; Earlier with activated alumina, water, ortho-phosphoric acid and LaNO
3Be stirred well to evenly, interpolation tetraethoxy and morpholine fully stir 5h to gel in mixture again, the gained gel is transferred in the crystallizing kettle, 250 ℃ of following crystallization 96 hours, the solid product that takes out in the crystallizing kettle is washed to neutrality repeatedly, drying is 8 hours in 150 ℃ of airflows, obtains the Me-SAPO-34 molecular screen primary powder.
600 ℃ of roastings 6 hours, the back was applied to the reaction of preparing light olefins from methanol as catalyzer with described molecular sieve.
Claims (5)
1. a metal remodeling silicoaluminophosphamolecular molecular sieves is characterized in that the structural formula of this molecular sieve is (0.2-5.0) R:(Si
0.01-0.3Al
0.01-1P
0.01-0.9): 10-400H
2O:(0.01-0.5) Me, wherein Me is one or more among Co, Ni, Mn, the La.
2. the preparation method of a metal as claimed in claim 1 remodeling silicoaluminophosphamolecular molecular sieves is characterized in that this method may further comprise the steps:
(1) preparation of raw mix
Form mole proportioning (0.2-5.0) R:(Si according to reactant
0.01-0.3Al
0.01-1P
0.01-0.9): 10-400H
2O:(0.01-0.5) Me takes by weighing a certain amount of aluminium source, phosphorus source, metal-salt, silicon source, water, and R is a template;
(2) earlier above-mentioned aluminium source, phosphorus source, metal-salt and water are mixed, be stirred well to evenly;
(3) in the mixture of step (2), add silicon source and template, fully stir 1～5h to gel;
(4) gained gel in the step (3) is transferred in the crystallizing kettle, 150-250 ℃ of following crystallization 24～96 hours;
(5) solid product that takes out in the crystallizing kettle is washed to neutrality repeatedly, and drying is 4～8 hours in 50-150 ℃ of airflow, obtains the Me-SAPO-34 molecular screen primary powder.
3. the preparation method of a kind of metal remodeling silicoaluminophosphamolecular molecular sieves according to claim 2 is characterized in that, described template is a kind of in tetraethyl ammonium hydroxide, triethylamine, diethylamine, the morpholine or their mixture.
4. the preparation method of a kind of metal remodeling silicoaluminophosphamolecular molecular sieves according to claim 2, it is characterized in that, described silicon source comprises silicon sol, active silica or tetraethoxy, described aluminium source comprises aluminum isopropylate, pseudo-boehmite or activated alumina, described phosphorus source comprises ortho-phosphoric acid, aluminum phosphate, and described metal-salt is a soluble salt, comprises vitriol, nitrate, chlorate.
5. the catalytic applications of a metal remodeling silicoaluminophosphamolecular molecular sieves as claimed in claim 1 in MTO is characterized in that 300 ℃～600 ℃ roastings 2～6 hours, the back was applied to the reaction of preparing light olefins from methanol as catalyzer with described molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100407614A CN101318667A (en) | 2008-07-18 | 2008-07-18 | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100407614A CN101318667A (en) | 2008-07-18 | 2008-07-18 | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101318667A true CN101318667A (en) | 2008-12-10 |
Family
ID=40178978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100407614A Pending CN101318667A (en) | 2008-07-18 | 2008-07-18 | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101318667A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857244A (en) * | 2010-06-22 | 2010-10-13 | 上海兖矿能源科技研发有限公司 | Silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN102078822A (en) * | 2010-12-10 | 2011-06-01 | 陕西师范大学 | Method for preparing catalyst for preparing low carbon olefin by using methanol |
| CN108262068A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The method of oxygenate producing light olefins |
| CN114182280A (en) * | 2021-11-08 | 2022-03-15 | 太原理工大学 | MEC hydrogen evolution cathode electrode based on Ni-SAPO-34 composite material |
| CN115672393A (en) * | 2021-07-28 | 2023-02-03 | 国家能源投资集团有限责任公司 | Catalyst for preparing low-carbon olefin through methanol conversion, preparation method of catalyst and method for preparing low-carbon olefin through methanol conversion |
| CN116328829A (en) * | 2023-03-29 | 2023-06-27 | 上海兖矿能源科技研发有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
-
2008
- 2008-07-18 CN CNA2008100407614A patent/CN101318667A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857244A (en) * | 2010-06-22 | 2010-10-13 | 上海兖矿能源科技研发有限公司 | Silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN101857244B (en) * | 2010-06-22 | 2012-02-29 | 上海兖矿能源科技研发有限公司 | Silicoaluminophosphate molecular sieve and preparation method and application thereof |
| CN102078822A (en) * | 2010-12-10 | 2011-06-01 | 陕西师范大学 | Method for preparing catalyst for preparing low carbon olefin by using methanol |
| CN102078822B (en) * | 2010-12-10 | 2012-11-07 | 陕西师范大学 | Method for preparing catalyst for preparing low carbon olefin by using methanol |
| CN108262068A (en) * | 2017-01-04 | 2018-07-10 | 中国石油化工股份有限公司 | The method of oxygenate producing light olefins |
| CN115672393A (en) * | 2021-07-28 | 2023-02-03 | 国家能源投资集团有限责任公司 | Catalyst for preparing low-carbon olefin through methanol conversion, preparation method of catalyst and method for preparing low-carbon olefin through methanol conversion |
| CN114182280A (en) * | 2021-11-08 | 2022-03-15 | 太原理工大学 | MEC hydrogen evolution cathode electrode based on Ni-SAPO-34 composite material |
| CN114182280B (en) * | 2021-11-08 | 2023-08-11 | 太原理工大学 | MEC hydrogen evolution cathode electrode based on Ni-SAPO-34 composite material |
| CN116328829A (en) * | 2023-03-29 | 2023-06-27 | 上海兖矿能源科技研发有限公司 | Catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101259431B (en) | Cobalt modification silicoaluminophosphate molecular sieve and its preparation and catalytic application in MTO | |
| CN101555022A (en) | Preparation method of metal-modified SAPO-34 molecular sieve and catalyst containing the molecular sieve | |
| CN101857244B (en) | Silicoaluminophosphate molecular sieve and preparation method and application thereof | |
| AU2007283967B2 (en) | A microsphere catalyst used for converting oxygen compound to olefine and preparation method thereof | |
| CN101450806A (en) | AEI/CHA eutectic molecular sieve containing triethylamine and synthetic method thereof | |
| CN104056652B (en) | A kind of hud typed ZSM-5 molecular sieve pellet catalyst | |
| CN104556143A (en) | SAPO-34/ZSM-5 composite molecular sieve and synthesis method of composite molecular sieve | |
| CN101318667A (en) | Metal modified silicon aluminum phosphoric molecular sieve, preparation method and catalysis application in MTO thereof | |
| CN101195492B (en) | Method for synthesizing SAPO-11 and SAPO-34 molecular sieve with diethylamine as template agent | |
| CN101778808A (en) | Catalyst composition and process for converting aliphatic oxygenates to aromatics | |
| CN104828842A (en) | Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve | |
| CN102430424A (en) | Catalyst used for methanol-to-olefin reaction and its preparation method | |
| CN101503201B (en) | Preparations of SAPO-11 molecular sieve and SAPO-11 molecular sieve based catalyst | |
| CN104056654A (en) | ZSM-5 molecular sieve composition, preparation method and application thereof | |
| CN102275948B (en) | Synthesis method of small-crystal-grain molecular sieve SAPO-34 | |
| CN103030158B (en) | Synthetic method of SAPO-44 molecular sieve modified by rare earth metals | |
| CN101195093A (en) | Chromium modified silicon aluminum phosphoric acid molecular sieve, preparation method and application thereof | |
| CN100368086C (en) | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve | |
| CN101935049B (en) | Silicoaluminophosphate molecular sieve | |
| CN1683079A (en) | Catalyst for reaction to produce olefine with methanol | |
| CN103663483A (en) | Synthesis method of SAPO-34 molecular sieve and catalyst prepared from SAPO-34 molecular sieve | |
| CN101492169B (en) | Production method of composite mould plate agent synthesized silicon-aluminum phosphate molecular sieve | |
| CN101279281B (en) | High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof | |
| CN106542547B (en) | A kind of preparation method of the SAPO-34 molecular sieve of high activity low silicon content | |
| CN101948120A (en) | SAPO-18 molecular sieve catalyst for producing low-carbon olefin 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 | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20081210 |