CN103816936A - Modified aluminium phosphate molecular sieve and preparation method thereof - Google Patents
Modified aluminium phosphate molecular sieve and preparation method thereof Download PDFInfo
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- CN103816936A CN103816936A CN201410069280.1A CN201410069280A CN103816936A CN 103816936 A CN103816936 A CN 103816936A CN 201410069280 A CN201410069280 A CN 201410069280A CN 103816936 A CN103816936 A CN 103816936A
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Abstract
The invention provides a modified aluminium phosphate molecular sieve, which is prepared by a ZSM-5 molecular sieve, diammonium phosphate and zinc nitrate, wherein ratio of silica to alumina is 25-40. The preparation method comprises the following steps: adding 0.5-1.5 parts of ZSM-5 molecular sieve in 3-5 parts of purified water according to weight, adding 0.48-0.52 parts of diammonium phosphate and 0.006-0.010 parts of zinc nitrate solution in purified water, stirring for 30-40 minutes, then heating to the temperature of 120-150 DEG C, controlling the pressure at 0.18-0.40MPa, stirring for 120-150 minutes for completing an exchange reaction, then filtering and drying, and finally roasting for 2 hours under the temperature of 530-590 DEG C to obtain the modified ZSM-5 molecular sieve. The modified aluminium phosphate molecular sieve has strong B acid site, crystal phase conversion is not generated through high temperature and hydro-thermal treatment, and the modified aluminium phosphate molecular sieve has good heat and hydro-thermal stability, excellent adsorption performance and cracking performance. The invention also provides a preparation method of the modified aluminium phosphate molecular sieve.
Description
Technical field
The present invention relates to a kind of molecular sieve, be specifically related to a kind of aluminium phosphate molecular sieve of modification, and preparation method thereof.
Background technology
ZSM-5 molecular sieve silica alumina ratio is higher, and acidity is stronger, and hydrogen transfer activity is very low, is to be applied at present producing more propylene FCC catalyst and the most extensive and important component of auxiliary agent.But due to hydrothermal stability and the activity influence of ZSM-5, be directly used in catalytic cracking catalyst and conventionally can make the reduction such as conversion ratio and gasoline yield, the productive rate of heavy oil can increase.Therefore, in the time of the application of ZSM-5 molecular sieve, need to first carry out modification, improve its hydrothermal stability and activity, the study on the modification of ZSM-5 molecular sieve becomes one of core technology in propylene catalyst with yield increase exploitation.
In prior art, mostly use phosphorus and metallic element to realize by exchange process, infusion process or coprecipitation method to the modification of ZSM-5 molecular sieve.For example, a kind of method that uses zinc nitrate, zirconium nitrate and ammonium dihydrogen phosphate (ADP) ZSM-5 molecular sieve to be carried out to modification is disclosed in CN1323755C, the method joins ZSM-5 molecular sieve in one or both the aqueous solution being dissolved with in zinc nitrate, zirconium nitrate and ammonium dihydrogen phosphate (ADP) in certain proportion, after stirring, room temperature leaves standstill 2-15 hour, then dry completing for 3-10 hour at 90-150 ℃.The modified zsm-5 zeolite obtaining is thus and then the catalytic activity of hydrogenation aromatized catalyst of preparation has been brought certain lifting.But the modified zsm-5 zeolite that the method obtains is still not ideal enough aspect hydrothermal stability, absorption property and cracking performance.
Therefore, be necessary to provide a kind of more excellent modified phosphate aluminum molecular screen of Gao Re and hydrothermal stability, absorption property and cracking performance that has.
Summary of the invention
The object of the invention is to: a kind of aluminium phosphate molecular sieve with the modification that more Gao Re and hydrothermal stability, absorption property and cracking performance are more excellent is provided, and preparation method thereof.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of aluminium phosphate molecular sieve of modification is provided, and it is prepared from by ZSM-5 molecular sieve, diammonium hydrogen phosphate and zinc nitrate, and silica alumina ratio is 25-40;
Its preparation method is as follows:
By weight, the ZSM-5 molecular sieve of 0.5～1.5 part is added in 3-5 part pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.006-0.010 part zinc nitrate solution, stir 30min-40min, then be warming up to 120-150 ℃, pressure is controlled at 0.18-0.40MPa, stirs 120-150min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 530 ℃-590 ℃, the aluminium phosphate molecular sieve of the modification described in obtaining.
In preferred embodiments of the present invention, described ZSM-5 molecular sieve Na
2o weight percentage is not more than 0.1, and degree of crystallinity is not less than 90, SiO
2/ Al
2o is 30-40; Described diammonium hydrogen phosphate purity is not less than 98%; Zinc nitrate purity is not less than 95%.
In preferred embodiments of the present invention, the preparation method of the aluminium phosphate molecular sieve of described modification is as follows:
By weight, the ZSM-5 molecular sieve of 1 part is added in 4 parts of pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.008 part of zinc nitrate solution, stir 35min-40min, then be warming up to 130～140 ℃, pressure is controlled at 0.28-0.32MPa, stirs 140min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 560 ℃, obtains the aluminium phosphate molecular sieve of the preferred modification of the present invention.
The aluminium phosphate molecular sieve degree of crystallinity of modification of the present invention is not less than 80, Na
2the weight percent content of O is not more than the weight percent content that the weight percent content of 0.1, P element is 1.0～3.0, ZnO and is greater than 0.15.
The present invention also provides a kind of method of the aluminium phosphate molecular sieve of preparing modification, comprises the following steps:
By weight, the ZSM-5 molecular sieve of 0.5～1.5 part is added in 3-5 part pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.006-0.010 part zinc nitrate solution, stir 30min-40min, then be warming up to 120-150 ℃, pressure is controlled at 0.18-0.40MPa, stirs 120-150min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 530 ℃-590 ℃, obtains a kind of aluminium phosphate molecular sieve of modification.
The method that the present invention preferably prepares the aluminium phosphate molecular sieve of modification comprises the steps:
By weight, the ZSM-5 molecular sieve of 1 part is added in 4 parts of pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.008 part of zinc nitrate solution, stir 35min-40min, then be warming up to 130～140 ℃, pressure is controlled at 0.28-0.32MPa, stirs 140min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 560 ℃, obtains the aluminium phosphate molecular sieve of modification.
The aluminium phosphate molecular sieve product of modification of the present invention is a kind of new product between ZSM-5 and ZSM-8, compared with prior art, its perfect crystalline, granularity be little, it is not obvious to reunite, have stronger B acid site, there is not crystal transition through high temperature, hydrothermal treatment consists, there are good heat and hydrothermal stability, show comparatively excellent absorption property and cracking performance.The aluminium phosphate molecular sieve of modification of the present invention is applied to petrochemical industry, while being particularly applied in catalytic cracking catalyst, can significantly improving octane number and increase the productive rate of propylene and selective.
In the method for the aluminium phosphate molecular sieve of preparation modification of the present invention, the exchange procedure of diammonium hydrogen phosphate and zinc nitrate and ZSM-5 molecular sieve is placed under specific pressure and temperature condition, with the synthetic chemical reaction that waits, modifying element is combined by exchange with the ZSM-5 molecular sieve degree of depth, reach molecular sieve modified object, the modified molecular screen obtaining is with compared with the modified molecular screen the disclosed molecular sieve of CN1323775C, no matter be the variation that microstructure or performance have all produced matter, particularly catalytic reaction activity and stability, all obtain significant lifting.
In petroleum catalytic cracking reaction, compared with the catalyst that the catalyst that modified molecular screen of the present invention is produced is prepared with the common ZSM-5 molecular sieve of application, productivity of propylene at least improves 1 percentage point, and octane number at least improves 1 unit.In continuous catalysis cracking reaction process, the catalyst that produce the service life of the catalyst of producing with the molecular sieve of modification of the present invention than common ZSM-5 molecular sieve has extended 1 times service life.
Accompanying drawing explanation
Fig. 1 is that molecular sieve prepared by the embodiment of the present invention 1 amplifies the electron-microscope scanning picture of 20,000 times.
Fig. 2 is the crystalline phase figure of the molecular sieve prepared of the embodiment of the present invention 1.
The specific embodiment
Embodiment 1
By weight, the ZSM-5 molecular sieve of 1 part is added in 4 parts of pure water, in pure water, add after 0.50 part of diammonium hydrogen phosphate and 0.008 part of zinc nitrate solution, stir 35min-40min, then be warming up to 140 ℃, pressure is controlled at 0.30MPa, stirs 140min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 560 ℃, obtains the aluminium phosphate molecular sieve of a kind of modification of the present invention, and its structure is as shown in the crystalline phase figure of the electron-microscope scanning figure of Fig. 1 and Fig. 2.
Embodiment 2
By weight, the ZSM-5 molecular sieve of 1.5 parts is added in 5 parts of pure water, in pure water, add after 0.48 part of diammonium hydrogen phosphate and 0.010 part of zinc nitrate solution, stir 30min-35min, then be warming up to 130 ℃, pressure is controlled at 0.38MPa, stirs 150min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 590 ℃, obtains the aluminium phosphate molecular sieve of a kind of modification of the present invention, and its structure is with reference to the electron-microscope scanning figure of figure 1 and the crystalline phase figure of Fig. 2.
Embodiment 3
By weight, the ZSM-5 molecular sieve of 0.5 part is added in 3 parts of pure water, in pure water, add after 0.52 part of diammonium hydrogen phosphate and 0.010 part of zinc nitrate solution, stir 30min-35min, then be warming up to 150 ℃, pressure is controlled at 0.18MPa, stirs 130min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 590 ℃, obtains the aluminium phosphate molecular sieve of a kind of modification of the present invention, and its structure is with reference to the electron-microscope scanning figure of figure 1 and the crystalline phase figure of Fig. 2.
Effect example
Getting the modified molecular screen that 6 parts of embodiment 1-3 make adds ball mill ball milling to become coccoid, intermittently spray into the mixed liquor of 5 parts of aluminium sol solutions and 1 part of deionized water, then under 140 ℃ of conditions, more than dry 5h, at 400-600 ℃ of roasting temperature 2-8h, obtain catalyst.
Be 600-700 ℃ in reaction temperature, reaction velocity 4h
-1, water oil volume is than being 0.6-0.8, and pressure, under the condition of 0.18-0.2MPa, is investigated its catalytic cracking reaction performance in certain petro-chemical corporation with the catalyst making, and result shows that productivity of propylene and octane number all significantly improve.Wherein, productivity of propylene at least improves 1 percentage point, and octane number at least improves 1 unit.
Claims (8)
1. an aluminium phosphate molecular sieve for modification, is characterized in that, it is prepared from by ZSM-5 molecular sieve, diammonium hydrogen phosphate and zinc nitrate, and silica alumina ratio is 25-40;
And its preparation method is as follows:
By weight, the ZSM-5 molecular sieve of 0.5～1.5 part is added in 3-5 part pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.006-0.010 part zinc nitrate solution, stir 30min-40min, then be warming up to 120-150 ℃, pressure is controlled at 0.18-0.40MPa, stirs 120-150min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 530 ℃-590 ℃, the aluminium phosphate molecular sieve of the modification described in obtaining.
2. the aluminium phosphate molecular sieve of modification claimed in claim 1, is characterized in that: described preparation method is as follows:
By weight, the ZSM-5 molecular sieve of 1 part is added in 4 parts of pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.008 part of zinc nitrate solution, stir 35min-40min, then be warming up to 130～140 ℃, pressure is controlled at 0.28-0.32MPa, stirs 140min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 560 ℃, obtains the aluminium phosphate molecular sieve of the preferred modification of the present invention.
3. the aluminium phosphate molecular sieve of any one modification described in claim 1 or 2, is characterized in that: described ZSM-5 molecular sieve Na
2o weight percentage is not more than 0.1, and degree of crystallinity is not less than 90, SiO
2/ Al
2o is 30-40.
4. the aluminium phosphate molecular sieve of any one modification described in claim 1 or 2, is characterized in that: described diammonium hydrogen phosphate purity is not less than 98%.
5. the aluminium phosphate molecular sieve of any one modification described in claim 1 or 2, is characterized in that: described zinc nitrate purity is not less than 95%.
6. the aluminium phosphate molecular sieve of modification claimed in claim 1, is characterized in that: the aluminium phosphate molecular sieve degree of crystallinity of described modification is not less than 80, Na
2the weight percent content of O is not more than the weight percent content that the weight percent content of 0.1, P element is 1.0～3.0, ZnO and is greater than 0.15.
7. the method for the aluminium phosphate molecular sieve of a kind of modification of preparation, comprises the following steps:
By weight, the ZSM-5 molecular sieve of 0.5～1.5 part is added in 3-5 part pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.006-0.010 part zinc nitrate solution, stir 30min-40min, then be warming up to 120-150 ℃, pressure is controlled at 0.18-0.40MPa, stirs 120-150min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 530 ℃-590 ℃, obtains the aluminium phosphate molecular sieve of modification.
8. method claimed in claim 7, comprises the steps:
By weight, the ZSM-5 molecular sieve of 1 part is added in 4 parts of pure water, in pure water, add after 0.48-0.52 part diammonium hydrogen phosphate and 0.008 part of zinc nitrate solution, stir 35min-40min, then be warming up to 130～140 ℃, pressure is controlled at 0.28-0.32MPa, stirs 140min and completes exchange reaction, then filters, is dried; Finally roasting 2h at 560 ℃, obtains the aluminium phosphate molecular sieve of modification.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899606A (en) * | 2017-11-30 | 2018-04-13 | 鹤壁博文科峰催化技术有限公司 | A kind of ferrophosphorus modified molecular screen and preparation method thereof |
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| CN1651141A (en) * | 2004-12-01 | 2005-08-10 | 中国石油化工集团公司 | Aromatization catalyst, its preparation method and application |
| US20070082809A1 (en) * | 2005-10-07 | 2007-04-12 | Sk Corporation | Hydrothermally stable microporous molecular sieve catalyst and preparation method thereof |
| CN101440302A (en) * | 2008-12-22 | 2009-05-27 | 洛阳瑞泽石化工程有限公司 | Method for lowering benzene content in gasoline and catalyst thereof |
| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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Patent Citations (5)
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| CN1590296A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Synthesis method of AEL structured aluminium silicon phosphate molecular sieve |
| CN1651141A (en) * | 2004-12-01 | 2005-08-10 | 中国石油化工集团公司 | Aromatization catalyst, its preparation method and application |
| US20070082809A1 (en) * | 2005-10-07 | 2007-04-12 | Sk Corporation | Hydrothermally stable microporous molecular sieve catalyst and preparation method thereof |
| CN101440302A (en) * | 2008-12-22 | 2009-05-27 | 洛阳瑞泽石化工程有限公司 | Method for lowering benzene content in gasoline and catalyst thereof |
| CN103357430A (en) * | 2012-03-30 | 2013-10-23 | 中国科学院大连化学物理研究所 | Cocrystallization molecular sieve catalyst for aromatization, as well as preparation method and application thereof |
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| CN107899606A (en) * | 2017-11-30 | 2018-04-13 | 鹤壁博文科峰催化技术有限公司 | A kind of ferrophosphorus modified molecular screen and preparation method thereof |
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Effective date of registration: 20161028 Address after: 458006 Baoshan circular economy industrial agglomeration area, Henan, Hebi Patentee after: Hebi Bowen peak Catalytic Technology Co., Ltd. Address before: 100190, Beijing, Zhongguancun, Haidian District, north two, No. 1, building 516, room 13 Patentee before: Zhao Liantang |