CN102173435B - Preparation method for USX molecular sieve rich in mesopores - Google Patents
Preparation method for USX molecular sieve rich in mesopores Download PDFInfo
- Publication number
- CN102173435B CN102173435B CN201110045612A CN201110045612A CN102173435B CN 102173435 B CN102173435 B CN 102173435B CN 201110045612 A CN201110045612 A CN 201110045612A CN 201110045612 A CN201110045612 A CN 201110045612A CN 102173435 B CN102173435 B CN 102173435B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ammoniacal liquor
- deionized water
- add
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method for a USX molecular sieve rich in mesopores. The preparation method is characterized in that an X-type molecular sieve with the silica alumina ratio between 2.2 and 3.0 is subjected to exchange with a rare earth saline solution, the exchanged ReNaX molecular sieve is filtered, washed and dried, and then water vapour containing an alkaline medium is fed for being carried out 350-550 DEG C high-temperature hydro-thermal treatment so as to obtain the ReUSX molecular sieve.
Description
Technical field
The present invention relates to catalysis technical field; Be a kind of preparation method who is rich in mesoporous ReUSX molecular sieve; More particularly; The present invention relates to the sorbent material preparation method of micro-polar impurity in a kind of suitable degree of depth absorption mixture, said mixture refers to boiling point less than 200 ℃ clean cargo, like sulfur-bearing FCC gasoline, contain oil at the bottom of the alkene reformation tower, coking benzene etc.
Background technology
In recent years, in the evolution of chemical separation technology, adsorption separation technology occupies an important position, adsorption separation technology from a kind of be that the small-sized cleansing operation that removes small amount of impurities develops into a kind of large-scale sepn process basically.The characteristics of this separation method are: separation efficiency is good, product purity is high, especially developed the good molecular sieve of absorption property as sorbent material after, the range of application of adsorption separation process broadens more day by day.
Fractionation by adsorption develops into now, and the emphasis of research is placed on the Dynamic Selection property of absorption/desorption mostly.In general, the polar molecule of absorption is not easy desorption easily, and the polar molecule ratio that is not easy to adsorb is easier to desorption, and this just brings bigger trouble for the selection of sorbing material.Such as having obtained better effects aspect the adsorption desulfurize through metal-modified Y zeolite, but adsorb desorption process after the saturated comparatively difficulty that but seems.
US 5,843,300 with US 5; 935; 422 have reported that respectively X type and Y zeolite are suitable for from FCC gasoline, adsorbing sulfide, and the X type and the Y zeolite that exchanged of basic metal or alkaline earth metal ion particularly demonstrated good adsorption property to the heterocycle sulfide of aromatic nucleus.Though this adsorbent of molecular sieve has absorption property preferably to aromatic nucleus heterocycle sulfide, they can not regenerate with hydrogen, therefore can not be used for commercial run.
US 5,807, and 475 have reported that use NiY, NiX, MoX adsorbent of molecular sieve can effectively remove sulfocompound from gasoline, and desulfurization degree reaches more than 40%.They find, though montmorillonite clay itself is not good sulfur absorbent, through the talcum powder after layer postization or the leafing, hectorite, smectite etc.Its specific surface area is bigger, can reach 150m
2/ g is good sorbent material, its absorption property even surpassed the absorption property of X, Y zeolite.This has just given the investigator bigger inspiration, and the bigger sorbing material in aperture possibly play bigger effect in adsorption process.
CN 1393511A has been through having obtained ReX and ReY adsorbent of molecular sieve with rare earth exchanged, and carries out adsorption desulfurize with them, and adsorption effect is better, but does not also make referrals to the modulation of molecular sieve bore diameter.
About the modulation of molecular sieve bore diameter, comparative maturity be that hydrothermal aging is produced super-stable Y molecular sieves.But the molecular sieve super stabilizing needs earlier molecular sieve to be exchanged into Hydrogen, and for X type molecular sieve, this is the skeleton of saboteur's sieve significantly, causes the decline of loading capacity.The rare report of ultra steady hydrogen type molecular sieve is used for fractionation by adsorption.
Summary of the invention
The present invention provides a kind of method of under the prerequisite that does not change X type molecular sieve cationic property, the pore structure of molecular sieve being carried out modulation.
The present invention provides a kind of preparation method who is rich in mesoporous USX molecular sieve, it is characterized in that:
Silica alumina ratio is exchanged at 2.2～3.0 X type molecular sieve and rare earths salt, and the ReNaX molecular sieve filtration after the exchange, washing, dry back feed the water vapour that contains alkaline medium and carry out high-temperature water thermal treatment, obtain the ReUSX molecular sieve;
Process step comprises:
(1) with silica alumina ratio be 2.2～3.0 X type molecular sieve and deionized water according to certain ratio making beating evenly, deionized water add-on and molecular sieve butt mass ratio are 2.5～25: 1;
(2) in the uniform molecular sieve pulp of making beating, add solid rare earth chloride or nitrated rare earth one or more mixture wherein; To account for the total rare earth mass percent be 75～95% for lanthanum and Ce elements in the rare-earth salts; Add-on counts 0.40～0.80 with exchanging equivalent; Regulate pH value 4～9 with ammoniacal liquor, be warming up to 65～110 ℃, be 1～4h swap time;
(3) molecular sieve that finishes of exchange through filter, behind the deionized water wash, at 110 ℃ of drying 1～4h, temperature programming to 350～550 ℃ feed ammoniacal liquor and carry out hydrothermal treatment consists 3～6h, the mass space velocity of ammoniacal liquor is 0.5～5h
-1, the mass percent concentration of ammoniacal liquor is 3～18%.Cooling obtains the ReUSX molecular sieve of super stabilizing.
According to preparation method of the present invention, its preferred version is characterised in that:
Silica alumina ratio is exchanged at 2.2～3.0 X type molecular sieve and rare earths salt, and the ReNaX molecular sieve filtration after the exchange, washing, dry back feed the water vapour that contains ammonia and carry out high-temperature water thermal treatment, obtain the ReUSX molecular sieve.
Process step comprises:
(1) with silica alumina ratio be 2.6～3.0 X type molecular sieve and deionized water according to certain ratio making beating evenly, deionized water add-on and molecular sieve butt mass ratio are 5～15: 1;
(2) in the uniform molecular sieve pulp of making beating, add the solid rare earth chloride; To account for the total rare earth mass percent be 90～95% for lanthanum and Ce elements in the rare earth chloride; Add-on counts 0.60～0.70 with exchanging equivalent; Regulate pH value 6～8 with ammoniacal liquor, be warming up to 85～100 ℃, be 1～2h swap time;
(3) molecular sieve that finishes of exchange through filter, behind the deionized water wash, at 110 ℃ of drying 3～4h, temperature programming to 400～500 ℃ feed ammoniacal liquor and carry out hydrothermal treatment consists 3～4h, the mass space velocity of ammoniacal liquor is 0.5～3h
-1, the mass percent concentration of ammoniacal liquor is 5～8%.Cooling obtains the ReUSX molecular sieve of super stabilizing.
ReUSX molecular sieve provided by the invention possesses more mesoporous, the reservation of maximum amplitude simultaneously the micropore of molecular sieve.Reasonably pore distribution makes molecular sieve have stronger adsorptive power, and desorption temperature will be lower than and do not contain mesoporous conventional ReX molecular sieve when desorption.
Embodiment:
Further describe characteristic of the present invention through instance below, but the present invention is not limited to following instance.
In each embodiment and Comparative Examples, the content of silicon, aluminium, rare earth, sodium etc. is measured (used instrument is Japanese ZSXPrimus II type Xray fluorescence spectrometer of science) with x ray fluorescence spectrometry (XRF) in the combination of molecular sieve; X-ray diffraction (XRD) data are identified by Japan's D/MAX-2500 type of science X-ray diffractometer; Surface tissue is measured by the ASAP2020 type physical adsorption appearance of U.S. Merck & Co., Inc development.
Comparative Examples 1
30 gram NaX molecular sieves (commercially available, silica alumina ratio is 2.8, down together) are dispersed in the 300ml deionized water, and making beating 20min drops into solid RECl
3.6H
2O 22g (to account for the total rare earth mass percent be 90% for lanthanum and Ce elements in the rare earth chloride, down with) 90 ℃ of exchanges 1 hour down, filters, and filter cake is through water wash, oven dry, 550 ℃ of following roastings 2 hours.Al (the NO of preparation 500ml 0.5mol/L
3)
3The aqueous solution mixes the ReX type molecular sieve that obtains with above-mentioned aluminum salt solution, reacted 1 hour down at 90 ℃, filters, and filter cake is through water wash, and oven dry 550 ℃ of following roastings 2 hours, obtains molecular sieve D1.
Embodiment 1
30 gram NaX molecular sieves (commercially available, silica alumina ratio is 2.8, down together) are dispersed in the 300ml deionized water, and making beating 20min drops into solid RECl
3.6H
2O 22g 90 ℃ of down exchanges 1 hour, filters, and filter cake is through water wash, and at 110 ℃ of dry 3h, temperature programming to 450 ℃ feeds deionized water and carries out hydrothermal treatment consists 3h, and mass space velocity is 3h
-1, cooling obtains the ReUSX molecular sieve Z1 of super stabilizing.
Embodiment 2
With embodiment 1, just the hydrothermal treatment consists medium is an ammoniacal liquor, and the mass space velocity of ammoniacal liquor is 3h
-1, mass percent concentration is 5%.Obtain molecular sieve Z2
Embodiment 3
With embodiment 1, just the hydrothermal treatment consists medium is an ammoniacal liquor, and the mass space velocity of ammoniacal liquor is 3h
-1, mass percent concentration is 8%.Obtain molecular sieve Z3
Table 1 super stabilizing is to the influence of pore structure
Visible by table 1, water vapour modification X molecular sieve effect is also bad, and the micropore loss is bigger, and this explanation framework of molecular sieve caves in more, and behind the ammoniacal liquor in hydrothermal aging framework of molecular sieve obtained better protecting, micropore and specific surface loss are less.
Application examples 1
Comparative Examples 1 and molecular sieve compressing tablet, pulverizing, sieve that embodiment 1～3 makes are got 20～40 orders; Drying is 4 hours under 120 ℃; Place moisture eliminator then, reduce to room temperature after, accurately take by weighing a certain amount of sorbent material; Pour into and be equipped with in advance in the Erlenmeyer flask of FCC gasoline that sulphur content is 315ppm (agent-oil ratio is 1: 10), whip attachment 8 hours ceaselessly under 40 ℃.Measure the variation of adsorbing front and back sulfur in gasoline content with ANTEK 9000 sulphur blood urea/nitrogen analyzers, calculate the adsorptive capacity and the desulfurization degree of sorbent material respectively.The sorbent material that absorption finishes is used the B filtered and recycled, dries 1 hour for 80 ℃, repeats absorption.
Table 2 has provided the desulfurization performance of modified molecular screen to FCC gasoline.Can find out from table 2 data, compare, be significantly increased through the absorption property of the molecular sieve after the ammoniacal liquor hydrothermal treatment consists, and owing to there is more secondary pore, it be more or less freely to regenerate sulfur in gasoline with Comparative Examples 1.
The adsorption desulfurize ability of table 2 modified molecular screen
Application examples 2
Comparative Examples 1 and molecular sieve compressing tablet, pulverizing, sieve that embodiment 1～3 makes are got 20～40 orders; Drying is 4 hours under 120 ℃; Place moisture eliminator then, reduce to room temperature after, accurately take by weighing a certain amount of sorbent material; Pour in the Erlenmeyer flask that oil at the bottom of the reformation tower that the alkene bromine index is 863mgBr/100g is housed in advance (agent-oil ratio is 1: 10) whip attachment 8 hours ceaselessly under 40 ℃ into.Variation with oil bromine index at the bottom of the tower before and after the absorption of LC-6 bromine valency bromine index determinator mensuration calculates the adsorptive capacity of sorbent material respectively and takes off the alkene rate.The sorbent material that absorption finishes is used the B filtered and recycled, dries 1 hour for 80 ℃, repeats absorption.
Table 3 provided modified molecular screen to the reformation tower at the bottom of oil take off the alkene performance.Can find out from table 3 data, compare with Comparative Examples 1, through the molecular sieve after the ammoniacal liquor hydrothermal treatment consists to the reformation tower at the bottom of in the oil absorption property of alkene be significantly increased, and owing to there is more secondary pore, it is more or less freely to regenerate.
The alkene ability is taken off in the absorption of table 3 modified molecular screen
Claims (2)
1. preparation method who is rich in mesoporous USX molecular sieve is characterized in that:
Silica alumina ratio is exchanged at 2.2～3.0 X type molecular sieve and rare earths salt, and the ReNaX molecular sieve filtration after the exchange, washing, dry back feed the water vapour that contains alkaline medium and carry out high-temperature water thermal treatment, obtain the ReUSX molecular sieve;
Process step comprises:
1) with silica alumina ratio be 2.2～3.0 X type molecular sieve and deionized water according to certain ratio making beating evenly, deionized water add-on and molecular sieve butt mass ratio are 2.5～25: 1;
2) in the uniform molecular sieve pulp of making beating, add the solid rare earth chloride; To account for the total rare earth mass percent be 75～95% for lanthanum and Ce elements in the rare-earth salts, and add-on counts 0.40～0.80 with exchanging equivalent, regulates pH value 4～9 with ammoniacal liquor; Be warming up to 65～110 ℃, be 1～4h swap time;
3) molecular sieve that finishes of exchange through filter, behind the deionized water wash, at 110 ℃ of drying 1～4h, temperature programming to 350～550 ℃ feed ammoniacal liquor and carry out hydrothermal treatment consists 3～6h, the mass space velocity of ammoniacal liquor is 0.5～5h
-1, the mass percent concentration of ammoniacal liquor is 3～18%; Cooling obtains the ReUSX molecular sieve of super stabilizing.
2. according to the described preparation method of claim 1, it is characterized in that:
Silica alumina ratio is exchanged at 2.2～3.0 X type molecular sieve and rare earths salt, and the ReNaX molecular sieve filtration after the exchange, washing, dry back feed the water vapour that contains ammonia and carry out high-temperature water thermal treatment, obtain the ReUSX molecular sieve;
Process step comprises:
1) with silica alumina ratio be 2.6～3.0 X type molecular sieve and deionized water according to certain ratio making beating evenly, deionized water add-on and molecular sieve butt mass ratio are 5～15: 1;
2) in the uniform molecular sieve pulp of making beating, add the solid rare earth chloride; To account for the total rare earth mass percent be 90～95% for lanthanum and Ce elements in the rare earth chloride, and add-on counts 0.60～0.70 with exchanging equivalent, regulates pH value 6～8 with ammoniacal liquor; Be warming up to 85～100 ℃, be 1～2h swap time;
3) molecular sieve that finishes of exchange through filter, behind the deionized water wash, at 110 ℃ of drying 3～4h, temperature programming to 400～500 ℃ feed ammoniacal liquor and carry out hydrothermal treatment consists 3～4h, the mass space velocity of ammoniacal liquor is 0.5～3h
-1, the mass percent concentration of ammoniacal liquor is 5～8%; Cooling obtains the ReUSX molecular sieve of super stabilizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045612A CN102173435B (en) | 2011-02-25 | 2011-02-25 | Preparation method for USX molecular sieve rich in mesopores |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110045612A CN102173435B (en) | 2011-02-25 | 2011-02-25 | Preparation method for USX molecular sieve rich in mesopores |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102173435A CN102173435A (en) | 2011-09-07 |
| CN102173435B true CN102173435B (en) | 2012-09-26 |
Family
ID=44516741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110045612A Active CN102173435B (en) | 2011-02-25 | 2011-02-25 | Preparation method for USX molecular sieve rich in mesopores |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102173435B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353086A (en) * | 2000-11-13 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing Y-type molecular sieve |
-
2011
- 2011-02-25 CN CN201110045612A patent/CN102173435B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353086A (en) * | 2000-11-13 | 2002-06-12 | 中国石油化工股份有限公司 | Process for preparing Y-type molecular sieve |
Non-Patent Citations (2)
| Title |
|---|
| 孙书红等.稀土超稳Y 型分子筛催化裂化催化剂的研究.《石油炼制与化工》.2001,第32卷(第6期),25-28. * |
| 庞新梅.化学超稳分子筛孔结构的研究.《石油炼制与化工》.1998,第29卷(第7期),52-55. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102173435A (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8791039B2 (en) | Agglomerated zeolite adsorbents and process for producing the same | |
| Ng et al. | Nanoporous materials with enhanced hydrophilicity and high water sorption capacity | |
| ES2804448T3 (en) | Zeolitic adsorbents in the form of aggregates, their method of preparation and their uses | |
| US20100204043A1 (en) | Adsorbent for selective adsorption of carbon monoxide and process for preparation thereof | |
| Guo et al. | Rational synthesis of chabazite (CHA) zeolites with controlled Si/Al ratio and their CO2/CH4/N2 adsorptive separation performances | |
| US10927016B2 (en) | Low temperature synthesis of aluminum hydr(oxide) inside porous media | |
| CN107971003B (en) | Catalytic cracking auxiliary agent containing phosphorus-containing and metal-loaded Beta molecular sieve and preparation method thereof | |
| JP2001526109A (en) | Barium-exchanged ETS-4 and its use in a method for separating nitrogen from a mixture of methane and nitrogen | |
| CN113548674B (en) | Modified ZSM-5 molecular sieve and preparation method and application thereof | |
| CN104667861B (en) | A kind of sulfur method of the desulfuration adsorbent for gasoline and gasoline | |
| Meng et al. | Durable and regenerable mesoporous adsorbent for deep desulfurization of model jet fuel | |
| Han et al. | Effect of olefin and aromatics on thiophene adsorption desulfurization over modified NiY zeolites by metal Pd | |
| CA2148893A1 (en) | Li-exchanged low silica emt-containing metallosilicates | |
| Alver et al. | Hydrogen (H2) adsorption on natural and cation-exchanged clinoptilolite, mordenite and chabazite | |
| US5573745A (en) | High micropore volume low silica EMT-containing metallosilicates | |
| US6780806B1 (en) | Lithium-based zeolites containing silver and copper and use thereof for selective absorption | |
| Xue et al. | High and fast carbon dioxide capture of hydroxypyridine-based ionogel depending on pore structure of mesoporous silica vesicle in the simulated flue gas | |
| Tatlier et al. | Impact of ion exchange on zeolite hydrophilicity/hydrophobicity monitored by water capacity using thermal analysis | |
| CN102173435B (en) | Preparation method for USX molecular sieve rich in mesopores | |
| Touloumet et al. | Investigation of the impact of zeolite shaping and salt deposition on the characteristics and performance of composite thermochemical heat storage systems | |
| CN109692658B (en) | Binder-free spherical 5A molecular sieve adsorbent and preparation method thereof | |
| Sakizci | Study of thermal and CH 4 adsorption properties | |
| CN107971008A (en) | A kind of catalytic cracking catalyst and preparation method thereof and petroleum hydrocarbon catalytic pyrolysis method | |
| Sakizci | Effect of salt modification and acid activation on ethylene adsorption properties of sepiolite | |
| US20220219997A1 (en) | Rho-type zeolite, precursors thereof, methods for making the same and use of the zeolite as sorbent for co2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |