CN101259431A - Cobalt modification silicoaluminophosphate molecular sieve and its preparation and catalytic application in MTO - Google Patents
Cobalt modification silicoaluminophosphate molecular sieve and its preparation and catalytic application in MTO Download PDFInfo
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- CN101259431A CN101259431A CNA200810036195XA CN200810036195A CN101259431A CN 101259431 A CN101259431 A CN 101259431A CN A200810036195X A CNA200810036195X A CN A200810036195XA CN 200810036195 A CN200810036195 A CN 200810036195A CN 101259431 A CN101259431 A CN 101259431A
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Abstract
The invention relates to a Co-modified silicoaluminophosphate molecular sieve, a preparation method and catalytic application in MTO thereof. The structural formula of the molecular sieve is (0.2-5.0) R: (Si0.01-1 Al0.5-1 P0.1-3):10- 400H2O: (0.01-0.5) Co. Compared with the prior art, the invention provides a Co-SAPO-34 molecular sieve, which is used as a catalyst and applied to prepare light olefins by using methanol, the transformation ratio of the methanol material achieves 100 percent. Due to the selectivity and service life of the light olefins, the Co-modified silicoaluminophosphate molecular sieve, the preparation method and the catalytic application in MTO of the invention is characterized by high selectivity (ethylene plus propylene), high yield rate and long service life of the catalytic agent.
Description
Technical field
The present invention relates to modified SAPO-34 molecular sieve.Especially relate to a kind of cobalt 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 production method of alkene can be divided into two classes: a class is a petroleum path, and another kind of is non-petroleum path.But for oil, the long-term continuous rise of price, supply is unstable, and resource reserves are limited.Therefore increasing ethene, propone output, to only depend on traditional petroleum path be not enough, by preparing light olefins from methanol (Methanol-to-Olefins, be called for short MTO) be to be the technical process of raw material via low-carbon alkenes such as methyl alcohol system ethene, propylene with coal or natural gas, it is the new technology of most promising non-petroleum path.And methyl alcohol is one of the abundantest chemical products, can be from coal, natural gas and solid waste via synthesis gas (CO+H
2) obtain.The key technology of MTO technical process is a catalyst, and good catalyst is a key point to have high activity, high selectivity and 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).The SAPO molecular sieve has the AlO that is connected by oxygen atom
4, SiO
4And PO
4Tetrahedral network, intracrystalline duct, because of Si
4+Replace P
5+Or Al
3+Produce acid or replace and produce acidity this molecular sieve is played an important role in MTO catalysis with metal.In the SAPO catalyst series, behave most that 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%, and 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 the metallic modification is improved.
Exxon company proposes to introduce alkaline-earth metal Sr, Ca or Ba in the SAPO-34 molecule in USP6040264, the performance of catalyst 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 catalyst as methanol-to-olefins, reaction generates low-carbon alkene under suitable reaction condition.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.
But these catalyst 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, yield height, cobalt 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 cobalt remodeling silicoaluminophosphamolecular molecular sieves is characterized in that the structural formula of this molecular sieve is (0.2-5.0) R:(Si
0.01-1Al
0.5-1P
0.1-3): 10-400H
2O:(0.01-0.5) Co.
A kind of preparation method of cobalt remodeling silicoaluminophosphamolecular molecular sieves is characterized in that this method may further comprise the steps:
(2) preparation of raw mix
According to reactant ratio (0.2-5.0) R: (Si
0.01-1Al
0.5-1P
0.1-3): 10-400H
2O: (0.01-0.5) Co, take by weighing a certain amount of aluminium source, phosphorus source, Cobalt salts, silicon source, water, R is the template agent;
(2) earlier above-mentioned aluminium source, phosphorus source, Cobalt salts and water are mixed, be stirred well to evenly;
(3) in the mixture of step (2), add silicon source and template agent, 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;
(6) solid product that takes out in the crystallizing kettle is washed to neutrality repeatedly, and drying is 4～8 hours in 50-150 ℃ of air stream, obtains the Co-SAPO-34 molecular screen primary powder.
Described template agent comprises tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their mixture.
Described silicon source comprises Ludox, active silica or ethyl orthosilicate, described aluminium source comprises aluminium isopropoxide, boehmite or activated alumina, and described phosphorus source comprises orthophosphoric acid, aluminum phosphate, and described slaine comprises cobalt chloride, cobalt nitrate, the cobaltous sulfate soluble-salt.
The catalytic applications of a kind of cobalt remodeling silicoaluminophosphamolecular molecular sieves in MTO is characterized in that 300 ℃～600 ℃ roastings 2～6 hours, the back was applied to the reaction of MTO (preparing light olefins from methanol) as catalyst with described molecular sieve.
Compared with prior art, the present invention has good catalytic performance in methanol conversion by the Co-SAPO-34 molecular sieve catalyst that metallic element Co 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 metallics such as manganese, chromium, magnesium, 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 92.60%, and the yield of ethene can reach 66.67%, and the mol ratio of ethene and propylene is 2.57.It is applied to the reaction of preparing light olefins from methanol as catalyst, can improve conversion of raw material, to the selectivity and the life-span of low-carbon alkene, has ethene, propylene selectivity height, yield height, the characteristics that catalyst life is long.
Description of drawings
Fig. 1 is the XRD spectra of the catalyst a of the embodiment of the invention 4;
Fig. 2 is the XRD spectra of the catalyst b of the embodiment of the invention 5;
Fig. 3 is the XRD spectra of the catalyst c of the embodiment of the invention 6.
The specific embodiment
Below in conjunction with the drawings and specific embodiments the present invention is specifically described in detail.
Embodiment 1
Synthetic 1 of Co-SAPO-34 molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.0H
3PO
4: 0.02Co (NO
3)
2: 60H
2O takes by weighing raw material.With a certain amount of boehmite with after necessarily water gaging fully mixes, add H again
3PO
4, Co (NO
3)
2, Ludox, TEA (triethylamine), 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 dried overnight of drying box hollow air-flow promptly to get Co-SAPO-34 zeolite product 1 with the deionized water cyclic washing.
The Synthetic 2 of Co-SAPO-34 molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.0H
3PO
4: 0.05Co (NO
3)
2: 60H
2O takes by weighing raw material.With a certain amount of boehmite with after necessarily water gaging fully mixes, add H again
3PO
4, Co (nO
3)
2, Ludox, 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 dried overnight of drying box hollow air-flow promptly to get Co-SAPO-34 zeolite product 2 with the deionized water cyclic washing.
Embodiment 3
Synthetic 3 of Co-SAPO-34 molecular sieve
According to proportioning: 3.0TEA: 0.75SiO
2: Al
2O
3: 2.0H
3PO
4: 0.10Co (NO
3)
2: 60H
2O takes by weighing raw material.With a certain amount of boehmite with after necessarily water gaging fully mixes, add H again
3PO
4, Co (NO
3)
2, Ludox, 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 dried overnight of drying box hollow air-flow promptly to get Co-SAPO-34 zeolite product 3 with the deionized water cyclic washing.
Embodiment 4
Co-SAPO-34 molecular sieve catalyst preparation 1
The synthetic Co-SAPO-34 molecular screen primary powder that obtains of example 1 was removed the template agent 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 catalyst a.Fig. 1 is the XRD spectra of catalyst a, and XRD result shows that product is the SAPO-34 molecular sieve of pure phase, the characteristic diffraction peak of metallic element Co do not occur, and this explanation Co has entered in the skeleton of molecular sieve uniformly.
Embodiment 5
Co-SAPO-34 molecular sieve catalyst preparation 2
The synthetic Co-SAPO-34 molecular screen primary powder that obtains of example 1 was removed the template agent 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 catalyst b.Fig. 2 is the XRD spectra of catalyst b, and XRD result shows that product is the SAPO-34 molecular sieve of pure phase, the characteristic diffraction peak of metallic element Co do not occur, and this explanation Co has entered in the skeleton of molecular sieve uniformly.
Embodiment 6
Co-SAPO-34 molecular sieve catalyst preparation 3
The synthetic Co-SAPO-34 molecular screen primary powder that obtains of example 1 was removed the template agent 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 catalyst c.Fig. 3 is the XRD spectra of catalyst c, and XRD result shows that product is the SAPO-34 molecular sieve of pure phase, the characteristic diffraction peak of metallic element Co do not occur, and this explanation Co has entered in the skeleton of molecular sieve uniformly.
Embodiment 7
Molecular sieve catalyst examination reaction 1
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyst a to embodiment 4 preparations carries out the examination of MTO reactivity, loaded catalyst 4.6ml, reaction temperature is 450 ℃, and reaction pressure is a normal pressure, and raw material is that volume ratio is the mixture of 1: 1 first alcohol and water, mass space velocity is 1.0h-1, and nitrogen and methyl alcohol volume flow ratio are 3.Full product on-line analysis.Appraisal result is as shown in table 2.
The result of table 2 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dimethyl ether occurred
Embodiment 8
Molecular sieve catalyst examination reaction 2
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyst a to embodiment 5 preparations carries out the examination of MTO reactivity, checking and rating used process conditions is: loaded catalyst 4.6ml, reaction temperature 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, nitrogen and methyl alcohol volume flow ratio are 3.Full product on-line analysis.Appraisal result is as shown in table 3.
The result of table 3 methanol-to-olefins reaction
*Active timing definition is that the oxygenate rate was 100% time before dimethyl ether occurred
Embodiment 9
Molecular sieve catalyst examination reaction 3
Adopt fixed-bed catalytic reactor, reactor is a stainless steel tube, catalyst c to embodiment 5 preparations carries out the examination of MTO reactivity, checking and rating used process conditions is: loaded catalyst 4.6ml, reaction temperature 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, nitrogen and methyl alcohol volume flow ratio are 3.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 dimethyl ether occurred
Embodiment 8
Synthetic 4 of Co-SAPO-34 molecular sieve
According to proportioning: 0.2TEA: 0.3SiO
2: 0.01Al
2O
3: 0.1H
3PO
4: 0.01Co (NO
3)
2: 60H
2O takes by weighing raw material.With a certain amount of boehmite with after necessarily water gaging fully mixes, add H again
3PO
4, Co (NO
3)
2, Ludox, TEA, 1 time of fully stirring moved into the gel that makes in the 200ml crystallizing kettle after evenly, 150 ℃ of lower seal crystallization 24 hours.Take out solid product, to neutral, place 110 ℃ of dried overnight of drying box hollow air-flow promptly to get Co-SAPO-34 zeolite product 4 with the deionized water cyclic washing.
300 ℃ of roastings 2 hours, the back was applied to the reaction of preparing light olefins from methanol as catalyst with above-mentioned zeolite product 4.
Embodiment 9
Synthetic 5 of Co-SAPO-34 molecular sieve
According to proportioning: 5TEA: 0.01SiO
2: Al
2O
3: 3H
3PO
4: 0.5Co (NO
3)
2: 60H
2O takes by weighing raw material.With a certain amount of boehmite with after necessarily water gaging fully mixes, add H again
3PO
4, Co (NO
3)
2, Ludox, TEA, 5 times of fully stirring moved into the gel that makes in the 200ml crystallizing kettle after evenly, 250 ℃ of lower seal crystallization 96 hours.Take out solid product, to neutral, place 110 ℃ of dried overnight of drying box hollow air-flow promptly to get Co-SAPO-34 zeolite product 5 with the deionized water cyclic washing.
600 ℃ of roastings 6 hours, the back was applied to the reaction of preparing light olefins from methanol as catalyst with above-mentioned zeolite product 5.
Claims (5)
1. a cobalt remodeling silicoaluminophosphamolecular molecular sieves is characterized in that the structural formula of this molecular sieve is (0.2-5.0) R:(Si
0.01-1Al
0.5-1P
0.1-3): 10-400H
2O:(0.01-0.5) Co.
2. the preparation method of the described cobalt remodeling of a claim 1 silicoaluminophosphamolecular molecular sieves is characterized in that this method may further comprise the steps:
(1) preparation of raw mix
According to reactant ratio (0.2-5.0) R: (Si
0.01-1Al
0.5-1P
0.1-3): 10-400H
2O: (0.01-0.5) Co, take by weighing a certain amount of aluminium source, phosphorus source, Cobalt salts, silicon source, water, R is the template agent;
(2) earlier above-mentioned aluminium source, phosphorus source, Cobalt salts and water are mixed, be stirred well to evenly;
(3) in the mixture of step (2), add silicon source and template agent, 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;
(6) solid product that takes out in the crystallizing kettle is washed to neutrality repeatedly, and drying is 4～8 hours in 50-150 ℃ of air stream, obtains the Co-SAPO-34 molecular screen primary powder.
3. the preparation method of a kind of cobalt remodeling silicoaluminophosphamolecular molecular sieves according to claim 2 is characterized in that described template agent comprises tetraethyl ammonium hydroxide, triethylamine, diethylamine, morpholine or their mixture.
4. the preparation method of a kind of cobalt remodeling silicoaluminophosphamolecular molecular sieves according to claim 1, it is characterized in that, described silicon source comprises Ludox, active silica or ethyl orthosilicate, described aluminium source comprises aluminium isopropoxide, boehmite or activated alumina, described phosphorus source comprises orthophosphoric acid, aluminum phosphate, described slaine comprises cobalt chloride, cobalt nitrate, cobaltous sulfate soluble-salt.
5. the catalytic applications of a cobalt 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 MTO (preparing light olefins from methanol) as catalyst with described molecular sieve.
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| 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 |
| CN101947467A (en) * | 2010-09-14 | 2011-01-19 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN103551184A (en) * | 2013-11-07 | 2014-02-05 | 中国石油大学(北京) | Preparation of zeolite coated oxide catalyst, and application thereof in methanol to propylene reaction |
| CN104817428A (en) * | 2015-03-25 | 2015-08-05 | 华东理工大学 | Method for production of cyclohexanol and cyclohexanone through selective oxidation of cyclohexane |
| CN106732762A (en) * | 2015-11-19 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of metal-modified SAPO-34 molecular sieves and preparation method and application |
| CN109485068A (en) * | 2018-08-30 | 2019-03-19 | 南京大学 | A kind of two-dimensional ultrathin Me-SAPO-34 molecular sieve sheeting and preparation method thereof |
| CN110255579A (en) * | 2019-06-19 | 2019-09-20 | 正大能源材料(大连)有限公司 | Metal-modified hollow SAPO-34 molecular sieve of one kind and its preparation method and application |
| CN110801862A (en) * | 2019-10-24 | 2020-02-18 | 杜成荣 | Catalyst for preparing low-carbon olefin from methanol |
| CN113083358A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Ti-HMS/carbon nanofiber composite catalyst modified by magnesium-containing compound, preparation and application |
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| 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 |
| CN101947467A (en) * | 2010-09-14 | 2011-01-19 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN101947467B (en) * | 2010-09-14 | 2012-09-05 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN103551184B (en) * | 2013-11-07 | 2016-03-09 | 中国石油大学(北京) | The preparation of the oxide coated catalyst of zeolite and the application in preparing propylene from methanol reaction thereof |
| CN103551184A (en) * | 2013-11-07 | 2014-02-05 | 中国石油大学(北京) | Preparation of zeolite coated oxide catalyst, and application thereof in methanol to propylene reaction |
| CN104817428A (en) * | 2015-03-25 | 2015-08-05 | 华东理工大学 | Method for production of cyclohexanol and cyclohexanone through selective oxidation of cyclohexane |
| CN106732762A (en) * | 2015-11-19 | 2017-05-31 | 中国石油天然气股份有限公司 | A kind of metal-modified SAPO-34 molecular sieves and preparation method and application |
| CN106732762B (en) * | 2015-11-19 | 2019-07-05 | 中国石油天然气股份有限公司 | A kind of metal-modified SAPO-34 molecular sieve and the preparation method and application thereof |
| CN109485068A (en) * | 2018-08-30 | 2019-03-19 | 南京大学 | A kind of two-dimensional ultrathin Me-SAPO-34 molecular sieve sheeting and preparation method thereof |
| CN109485068B (en) * | 2018-08-30 | 2020-11-13 | 南京大学 | Two-dimensional ultrathin Me-SAPO-34 molecular sieve sheet material and preparation method thereof |
| CN110255579A (en) * | 2019-06-19 | 2019-09-20 | 正大能源材料(大连)有限公司 | Metal-modified hollow SAPO-34 molecular sieve of one kind and its preparation method and application |
| CN110801862A (en) * | 2019-10-24 | 2020-02-18 | 杜成荣 | Catalyst for preparing low-carbon olefin from methanol |
| CN113083358A (en) * | 2019-12-23 | 2021-07-09 | 中国石油化工股份有限公司 | Ti-HMS/carbon nanofiber composite catalyst modified by magnesium-containing compound, preparation and application |
| CN113083358B (en) * | 2019-12-23 | 2023-07-25 | 中国石油化工股份有限公司 | Magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst, preparation and application |
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