CN101973563A - Method for synthetizing ZSM-35 molecular sieve by seed crystal process - Google Patents
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Abstract
The invention relates to a molecular sieve preparation method, aiming to provide a method for synthetizing a ZSM-35 molecular sieve by a seed crystal process. After sodium aluminate is dissolved in water, adding NaOH and stirring; after a settled solution is obtained, adding white carbon black, and stirring the mixture at room temperature until forming even sialsphere gel; then adding zeolite seed crystal RUB-37 or ZSM-35 and evenly stirring; transferring the mixture to an agitated reactor and crystallizing at the temperature of 120-150 DEG C for 3-10 days; and filtering and drying to obtain the ZSM-35 molecular sieve. The product of the invention keeps good degree of crystallization and purity and has good catalytic reaction activity. The whole production process does not use organic template agent or potassium ion and can greatly shorten crystallization time by the seed crystal process, thus reducing unnecessary loss in the production process; and meanwhile, the product has larger specific surface area. The adopted inorganic raw materials for production protect environment and have low price.
Description
Technical field
The invention belongs to molecular sieve preparation method, specially refer to the method for the synthetic ZSM-35 molecular sieve of crystal seed method.
Background technology
Micro porous molecular sieve is owing to fields such as its regular pore passage structure is widely used in absorption with uniform pore size distribution, separates, ion-exchange, catalysis.The ZSM-35 molecular sieve is a kind of zeolite with intermediate pore size, has FER type skeleton structure, and it has the two-dimentional channel system of square crossing, and the ten-ring duct size that wherein is parallel to [001] face is 4.2 * 5.4
The octatomic ring duct size that is parallel to [010] face is 3.5 * 4.8
The ZSM-35 molecular sieve can be widely used in the conversion process of hydro carbons, and for example the isomerization of normal olefine, polymerization, aromizing and cracking etc. have a good application prospect industrial.Barrer and Marshall1964 synthesize the molecular sieve with FER structure with strontium first as inorganic cation under hot conditions.Afterwards, Vaughan resolved the FER structure in 1966.Up to the present, many organic formwork agents can be used for synthesizing the FER zeolite, for example, and Tetramethylammonium hydroxide, tetramethyleneimine, quadrol, hexanediamine, tetrahydrofuran (THF) etc.Yet the use of organic formwork agent has not only improved synthetic cost, produces a large amount of obnoxious flavoures simultaneously in the process of calcining template agent removing.For fear of using organic formwork agent, Jens Weitkamp reported the synthetic FER molecular sieve of organic-free template under the condition that potassium ion exists in 2002, and reaction conditions is 180 degree rotation crystallization six days.But the shortcoming of this method long big energy-consuming of high time that is temperature of reaction, the use of potassium ion simultaneously also can increase synthetic cost.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of simpler no template crystal seed method to synthesize the ZSM-35 molecular sieve.This method can synthesize pure phase ZSM-35 molecular sieve at lesser temps in the short period.
Be the technical solution problem, the invention provides the method for the synthetic ZSM-35 molecular sieve of a kind of crystal seed method, the steps include:
With sodium aluminate water-soluble after, to wherein adding NaOH and stirring, wait to add white carbon black obtain settled solution after again, continue under the room temperature to stir up to the uniform silica-alumina gel of formation, stir after adding zeolite seed crystal RUB-37 or ZSM-35 then; Mixture is transferred in the reactor, and crystallization is 3～10 days under 120～150 ℃ of conditions, and product suction filtration, oven dry can obtain the ZSM-35 molecular sieve; The addition of each reaction raw materials should make the mole proportioning of each composition in the silica-alumina gel be: SiO
2: NaAlO
2: NaOH: H
2O is 1: 0.057～0.1: 0.22～0.4: 35, and the usage quantity of zeolite seed crystal is 3～10% of a white carbon black.
Among the present invention, described water is deionized water.
Preparation method of the present invention is with white carbon black (SiO
2) as the silicon source, sodium aluminate is the aluminium source, sodium hydroxide is as alkali source.Wherein, the analog structure revulsion is to have the unitary RUB-37[CDO structure of same structure with ZSM-35] molecular sieve is as " crystal seed ", and directly the crystal seed synthesis method is as crystal seed with ZSM-35 itself.
Beneficial effect of the present invention is:
Compare with background technology, product has not only kept good degree of crystallinity and purity, has good catalytic reaction activity.Whole process of production is not only used organic formwork agent and potassium ion, and can greatly shorten crystallization time by crystal seed method, so just reduced unnecessary in process of production loss, product has bigger specific surface area simultaneously, and product has the potential using value for some important catalyzed reactions.It is all environmentally friendly to produce the inorganic raw material that is adopted, and price is cheaper, thereby the present invention is significant in actual chemical production field.
Description of drawings
Fig. 1: the structural relation figure of RUB-37 crystal seed and ZSM-35.
Fig. 2: with RUB-37 is the XRD spectra of inducing the crystal seed product.
Fig. 3: the nitrogen adsorption isotherm of product.
Fig. 4: with RUB-37 is the SEM photo of inducing the crystal seed product.
Fig. 5: with ZSM-35 is the XRD spectra of inducing the crystal seed product.
Embodiment
Embodiment 1: synthesize the ZSM-35 molecular sieve with RUB-37 for inducing crystal seed
At first, the 0.078g sodium aluminate is water-soluble, again to wherein adding 0.182gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.036g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 3 days under 150 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.08NaAlO
2: 0.38NaOH: 35H
2O: 5%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve.
Accompanying drawing 1 is the structural relation of RUB-37 and ZSM-35, and as can be seen from the figure the two has identical structural unit, and is just different on the mode of connection.
Accompanying drawing 3 is the nitrogen adsorption desorption isotherm of sample, and therefrom sample has typical micro-porous adsorption curve as can be seen, and has higher specific surface area.
Accompanying drawing 4 is scanning electron microscope (SEM) photo of sample.Can see that from stereoscan photograph sample has typical sheet pattern.
Embodiment 2: with RUB-37 for inducing 120 ℃ of synthetic ZSM-35 molecular sieves of crystal seed
At first, the 0.088g sodium aluminate is water-soluble, again to wherein adding 0.192gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.036g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 10 days under 120 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.09NaAlO
2: 0.4NaOH: 35H
2O: 5%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve.
Embodiment 3: synthesize the ZSM-35 molecular sieve with 3%RUB-37 for inducing crystal seed
At first, the 0.088g sodium aluminate is water-soluble, again to wherein adding 0.172gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.022g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 3 days under 150 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.09NaAlO
2: 0.36NaOH: 35H
2O: 3%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve.
Embodiment 4: synthesize the ZSM-35 molecular sieve with 10%RUB-37 for inducing crystal seed
At first, the 0.098g sodium aluminate is water-soluble, again to wherein adding 0.172gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.072g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 4 days under 140 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.1NaAlO
2: 0.36NaOH: 35H
2O: 10%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve.
Embodiment 5: synthesize the ZSM-35 molecular sieve with RUB-37 for inducing crystal seed under low basicity
At first, the 0.088g sodium aluminate is water-soluble, again to wherein adding 0.104NaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue to stir, add 0.036g RUB-37 at last and stir up to forming uniform silica-alumina gel, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron, crystallization is 7 days under 150 ℃ of conditions, and the proportioning of reaction raw materials is as follows, SiO
2: 0.09NaAlO
2: 0.22NaOH: 35H
2O: 5%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve.
Embodiment 6: synthesize the ZSM-35 molecular sieve with RUB-37 for inducing crystal seed under higher alkalisation
At first, the 0.088g sodium aluminate is water-soluble, again to wherein adding 0.193gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.036g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 3 days under 150 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.09NaAlO
2: 0.4NaOH: 35H
2O: 5%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve
Embodiment 7: than synthesizing the ZSM-35 molecular sieve with RUB-37 for inducing crystal seed under the low-aluminum-content
At first, the 0.057g sodium aluminate is water-soluble, again to wherein adding 0.188gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.036g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 4 days under 150 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.057NaAlO
2: 0.39NaOH: 35H
2O: 5%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve
Embodiment 8: synthesize the ZSM-35 molecular sieve with RUB-37 for inducing crystal seed under higher aluminum content
At first, the 0.099g sodium aluminate is water-soluble, again to wherein adding 0.168gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue under the room temperature to stir, add 0.036g RUB-37 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, crystallization is 3 days under 150 ℃ of conditions, and the proportioning of reaction raw materials is as follows; SiO
2: 0.1NaAlO
2: 0.35NaOH: 35H
2O: 5%RUB-37, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve
Embodiment 9: with synthetic ZSM-35 is the synthetic ZSM-35 molecular sieve of crystal seed
At first, the 0.079g sodium aluminate is water-soluble, again to wherein adding 0.139gNaOH, wait to add after obtaining settled solution the 0.72g white carbon black, continue to stir, add 0.036g ZSM-35 at last and stir, reaction raw materials is transferred in the tetrafluoroethylene stainless steel cauldron up to forming uniform silica-alumina gel, under 150 ℃ of conditions crystallization 3-5 days, the proportioning of reaction raw materials was as follows: SiO
2: 0.08NaAlO
2: 0.29NaOH: 35H
2O: 5%ZSM-35, the product suction filtration, oven dry can obtain the ZSM-35 molecular sieve.
Accompanying drawing 3 is the XRD spectra of sample, and as can be seen from Figure, product has typical ZSM-35 zeolite molecules sieve structure, and sample has very high degree of crystallinity.
The above, it only is several case study on implementation of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferable case study on implementation, yet be not in order to limit the present invention, any those skilled in the art are not in breaking away from the technical solution of the present invention scope, when the structure that can utilize above-mentioned announcement and technology contents are made a little change or be modified to the equivalent case study on implementation of equivalent variations.But every content that does not break away from technical solution of the present invention, any simple modification, equivalent variations and modification according to technical spirit of the present invention is done above case study on implementation all still belong in the technical solution of the present invention scope.
Claims (2)
1. the method for the synthetic ZSM-35 molecular sieve of crystal seed method the steps include:
With sodium aluminate water-soluble after, to wherein adding NaOH and stirring, wait to add white carbon black obtain settled solution after again, continue under the room temperature to stir up to the uniform silica-alumina gel of formation, stir after adding zeolite seed crystal RUB-37 or ZSM-35 then; Mixture is transferred in the reactor, and crystallization is 3～10 days under 120～150 ℃ of conditions, and product suction filtration, oven dry can obtain the ZSM-35 molecular sieve;
The addition of each reaction raw materials should make the mole proportioning of each composition in the silica-alumina gel be: SiO
2: NaAlO
2: NaOH: H
2O is 1: 0.057～0.1: 0.22～0.4: 35, and the usage quantity of zeolite seed crystal is 3～10% of a white carbon black.
2. the method for the synthetic ZSM-35 molecular sieve of crystal seed method according to claim 1 is characterized in that described water is deionized water.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058222A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-35 molecular sieve |
| CN103101924A (en) * | 2013-02-01 | 2013-05-15 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
| WO2015021610A1 (en) * | 2013-08-14 | 2015-02-19 | 中国科学院大连化学物理研究所 | Zsm-35 molecular sieve and synthesis method for me-zsm-35 |
| CN104370295A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve and Me-ZSM-35 synthesis methods |
| CN104495869A (en) * | 2014-12-17 | 2015-04-08 | 中国石油天然气股份有限公司 | Preparation method of small grain ZSM-35 molecular sieve |
| CN104649705A (en) * | 2015-02-28 | 2015-05-27 | 中国地质大学（武汉） | Zeolite molecular sieve composite rectorite water purification ceramic and preparation method thereof |
| CN105314647A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | Silicon-aluminum and silicon-iron Beta molecular sieves, and preparation methods and applications thereof |
| CN106542537A (en) * | 2016-10-25 | 2017-03-29 | 浙江大学 | In the method for omnipotent gel synthesizing high-silicon zeolite molecular sieve |
| CN106698465A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Method used for preparing nano ZSM-12 molecular sieve |
| CN107138176A (en) * | 2017-06-23 | 2017-09-08 | 广东工业大学 | A kind of preparation method of middle micro-diplopore lamella MFI molecular sieve catalysts |
| CN108910910A (en) * | 2018-08-02 | 2018-11-30 | 中国石油大学(北京) | A kind of ZSM-35 molecular sieve and preparation method thereof |
| CN110877912A (en) * | 2018-09-06 | 2020-03-13 | 中国科学院大连化学物理研究所 | Rapid synthesis method of FER molecular sieve with controllable size |
| CN112744827A (en) * | 2021-01-05 | 2021-05-04 | 江南大学 | Method for synthesizing ferrierite molecular sieve by seed crystal method |
| CN113979448A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Fluorine-containing ZSM-35 molecular sieve and preparation method thereof |
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| CN103058222A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-35 molecular sieve |
| CN103058222B (en) * | 2011-10-24 | 2015-02-18 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-35 molecular sieve |
| CN103101924A (en) * | 2013-02-01 | 2013-05-15 | 浙江大学 | Method for preparing ZSM-22 molecular sieve by using seed crystal synthesis method |
| WO2015021610A1 (en) * | 2013-08-14 | 2015-02-19 | 中国科学院大连化学物理研究所 | Zsm-35 molecular sieve and synthesis method for me-zsm-35 |
| CN104370295A (en) * | 2013-08-14 | 2015-02-25 | 中国科学院大连化学物理研究所 | ZSM-35 molecular sieve and Me-ZSM-35 synthesis methods |
| CN104370295B (en) * | 2013-08-14 | 2016-06-08 | 中国科学院大连化学物理研究所 | A kind of synthetic method of ZSM-35 molecular sieve and Me-ZSM-35 |
| CN105314647B (en) * | 2014-07-29 | 2017-12-26 | 孙红 | Sial and ferrosilicon Beta molecular sieves and its preparation method and application |
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| CN104495869A (en) * | 2014-12-17 | 2015-04-08 | 中国石油天然气股份有限公司 | Preparation method of small grain ZSM-35 molecular sieve |
| CN104649705A (en) * | 2015-02-28 | 2015-05-27 | 中国地质大学（武汉） | Zeolite molecular sieve composite rectorite water purification ceramic and preparation method thereof |
| CN104649705B (en) * | 2015-02-28 | 2016-08-31 | 中国地质大学（武汉） | A kind of zeolite molecular sieve composite rectorite water purification pottery and preparation method thereof |
| CN106698465A (en) * | 2015-11-12 | 2017-05-24 | 中国石油化工股份有限公司 | Method used for preparing nano ZSM-12 molecular sieve |
| CN106698465B (en) * | 2015-11-12 | 2018-08-14 | 中国石油化工股份有限公司 | A method of preparing a nanometer ZSM-12 molecular sieves |
| CN106542537A (en) * | 2016-10-25 | 2017-03-29 | 浙江大学 | In the method for omnipotent gel synthesizing high-silicon zeolite molecular sieve |
| CN107138176A (en) * | 2017-06-23 | 2017-09-08 | 广东工业大学 | A kind of preparation method of middle micro-diplopore lamella MFI molecular sieve catalysts |
| CN107138176B (en) * | 2017-06-23 | 2020-02-07 | 广东工业大学 | Preparation method of medium-micro double-pore lamellar MFI molecular sieve catalyst |
| CN108910910A (en) * | 2018-08-02 | 2018-11-30 | 中国石油大学(北京) | A kind of ZSM-35 molecular sieve and preparation method thereof |
| US10822242B2 (en) | 2018-08-02 | 2020-11-03 | China University of Petroleum—Beijing | ZSM-35 molecular sieve and preparation method thereof |
| CN110877912A (en) * | 2018-09-06 | 2020-03-13 | 中国科学院大连化学物理研究所 | Rapid synthesis method of FER molecular sieve with controllable size |
| CN110877912B (en) * | 2018-09-06 | 2023-01-13 | 中国科学院大连化学物理研究所 | Rapid synthesis method of FER molecular sieve with controllable size |
| CN113979448A (en) * | 2020-07-27 | 2022-01-28 | 中国石油化工股份有限公司 | Fluorine-containing ZSM-35 molecular sieve and preparation method thereof |
| CN112744827A (en) * | 2021-01-05 | 2021-05-04 | 江南大学 | Method for synthesizing ferrierite molecular sieve by seed crystal method |
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