CN1806908A - Macroporous zeolite absorbent and preparation method thereof - Google Patents
Macroporous zeolite absorbent and preparation method thereof Download PDFInfo
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- CN1806908A CN1806908A CN 200510030775 CN200510030775A CN1806908A CN 1806908 A CN1806908 A CN 1806908A CN 200510030775 CN200510030775 CN 200510030775 CN 200510030775 A CN200510030775 A CN 200510030775A CN 1806908 A CN1806908 A CN 1806908A
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Abstract
The invention provides the large aperture zeolitic adsorbent and preparing method. The method comprises the following steps: hydrothermal synthesizing the zeolitic in Na2O-SiO2-Al2O3-H2O colloidal system, possessing the X-ray spectrum, removing the sodium with positive ion exchange, forming with binding agent and modifying with aqueous vapor. The average pore size of adsorbent is 11 nanometers, and the adsorbent is used to remove micro inorganic or organic iodide and iodine from acid medium.
Description
Technical field
The present invention relates to a kind of macroporous zeolite absorbent and preparation method thereof
Technical background
Need higher cation exchange capacity in the chemical industry production and stable macropore footpath adsorbent in acid medium.For example micro-iodide (derivative) and the molecular iodine of remnants in the acetic acid of being produced by the low-pressure methanol oxo synthesis and the aceticanhydride product need be removed.
U.S. Pat 5,692,735 have reported the silver-colored type zeolite molecular sieve that modenite is made by exchange the earliest, can be used for removing the iodide in the acetic acid.U.S. Pat 6,380,428 propose to make silver-colored type zeolite adsorbents with LZ-210 zeolite (a kind of sealumination modified Y zeolite) by exchange, are used for removing iodide from acid medium.The opening in above-mentioned two kinds of zeolite structured ducts be 12 oxygen membered rings (0.65～0.70nm), higher to the removal efficiency of bigger iodide of molecular dimension and derivative, and for iodine molecule and undersized iodide, its removal efficiency is relatively low.In addition, this sealumination modified Y zeolite of LZ-210, because of the primary structure base person in its crystal structure is 4 oxygen membered rings, acid resistance is relatively poor, influences the service life in acid.
The ZSM-5 zeolite that Taiwan patent 393464 has proposed silver-colored exchange can be used for the removing of iodide in the acetic acid.Primary structure base person in the ZSM-5 zeolite crystal structure is 5 oxygen membered rings, and acid resistance is better.Its structure hole is 10 oxygen membered ring's openings, and (0.55nm) is less in the aperture, is fit to remove the iodide of iodine molecule and reduced size.
The adsorbent preparation process of above-mentioned patent is all earlier made zeolite with carrying silver with the zeolite powder crystal with ion-exchange, makes adsorbent with amorphous binding agent bonding again.Because of skewness between the zeolite powder Jingjing grain of amorphous binding agent in absorbent particles, cause that average pore size between zeolite grain is little, the gross porosity pore-size distribution is inhomogeneous, when adsorbent uses, influence the absorbate molecule from the diffusion of liquid phase, reduce the adsorbent service efficiency to adsorbent mesolite crystal grain.
Chinese invention patent 03141604.7 has proposed zeolite deioidining adsorbent of a kind of high silver carrying with the preparation of STI type natural minerals zeolite and preparation method thereof.The primary structure base person of STI type zeolite is 5 oxygen membered rings, and its structure hole is that (0.49 * 0.62nm), the aperture is less, structure silica alumina ratio 6-8 for 10 oxygen membered ring's openings.It is raw material that Chinese patent ZL03141605.5 has introduced a kind of low silicon H-ZSM-5 zeolite with structure silica alumina ratio 15-30, after the adding additives moulding, through change brilliant handle the acetic acid of making binder free to take off iodo at the bottom of adsorbent.This adsorbent promptly has higher cation exchange capacity, again tool acid resistance preferably.
Summary of the invention
The object of the present invention is to provide zeolite adsorbents that gross porosity is evenly distributed and average pore size is big between a kind of zeolite grain and preparation method thereof.After this adsorbent carries silver with ion-exchange, be particularly suitable for from weak acidic medium, removing inorganic and the organic iodide and the molecular iodine of trace.
The macroporous zeolite absorbent that the present invention proposes has following feature: zeolitic frameworks silica alumina ratio 12～20, and cation is a hydrogen, contains 12 oxygen membered rings and 10 oxygen membered rings' structure pore opening, the X-ray powder diffraction characteristic spectral line is:
| The feature diffracted ray | The 2 θ angles of diffraction (°) | D-interplanar distance (nm) | |
| 1 | 6.4 | 1.39 | Vvs |
| 2 | 8.0 | 1.10 | |
| 3 | 8.9 | 0.991 | S |
| 4 | 10.3 | 0.859 | |
| 5 | 12.0 | 0.735 | |
| 6 | 15.8 | 0.558 | Vs |
| 7 | 18.9 | 0.469 | |
| 8 | 20.6 | 0.430 | |
| 9 | 23.0 | 0.384 | |
| 10 | 23.7 | 0371 | Vvs |
| 11 | 24.5 | 0.363 | S |
| 12 | 27,4 | 0.325 | S |
| 13 | 30.0 | 0.297 | S |
| 14 | 31.8 | 0.282 | S |
Wherein, Vvs represents the strongest, and Vs represents very strong, and S represents by force.
The preparation method of macroporous zeolite absorbent of the present invention is that silicon raw material, aluminum feedstock, sulfuric acid and water are mixed into Na
2O-SiO
2-Al
2O
3-H
2The O colloid, hydro-thermal reaction is made the na-pretreated zeolite mealy crystal in reactor, its X-ray powder diffraction figure such as Fig. 1.After this zeolite crystal spends deionised water, filtration, drying, carry out ion-exchange and take off sodium in ion exchanged soln, make h-type zeolite, h-type zeolite and binding agent mixed-forming, drying are made macroporous zeolite absorbent through the modification processing.
It is waterglass, Ludox that the present invention prepares used silicon raw material, and aluminum feedstock is aluminum sulfate, aluminium chloride, aluminum nitrate.Na
2O-SiO
2-Al
2O
3-H
2The chemical composition mol ratio of O colloid: SiO
2/ Al
2O
3=10～30, Na
2O/SiO
2=0.10～0.40, H
2O/SiO
2=15～40.
Hydrothermal temperature of the present invention is 105～130 ℃, and the reaction time is 24～100 hours.It is HNO that na-pretreated zeolite takes off the ion exchanged soln that sodium uses
3, HAC, NH
4NO
3, NH
4Any or its mixture among the AC, the concentration 0.1～1.0mol/L of ion exchanged soln.The liquid-solid ratio of ion exchanged soln and sodalite is by weight: ion exchanged soln/sodalite=5～20.The exchange temperature is 25～100 ℃ in ion exchanged soln, and be 0.5～2.0 hour swap time, and the exchange number of times is 1～5 time.
The be shaped binding agent of usefulness of the present invention is amorphous silica or amorphous silicon aluminium glue, in butt weight, and binding agent/h-type zeolite=0.10～0.30.Amorphous silica is a kind of or its mixture in Ludox, the white carbon, and the shape of adsorbent was both coccoid, also column.
Modification is handled and can be improved coarse texture and optimize its pore-size distribution, improves surface area.The atmosphere that modification of the present invention is handled is steam, and treatment temperature is 150～200 ℃, and the time is 24～48 hours.
Be evenly distributed with the gross porosity between the macroporous adsorbent zeolite grain of the present invention's preparation, average pore size is big, helps the diffusion of ion and absorbate.Because opening existing 12 oxygen membered rings in sorbent structure of the present invention duct have 10 oxygen membered rings again, so, after adsorbent of the present invention carries silver, can remove bigger iodide of molecular dimension and derivative, and be applicable to the iodide that remove iodine molecule and reduced size.
The liquor argenti nitratis ophthalmicus of macroporous zeolite absorbent of the present invention with 0.5mol/L exchanged 1 time, exchange liquid (gram)/adsorbent (gram)=10/1,80 ℃ of exchange temperature, 2 hours time, product after the exchange is the silver-carried big-hole zeolite deiodination adsorbent, is 7.9% through its silver carrying amount of chemical analysis.The aceticanhydride that contains iodine 1000ppb is at 60 ℃ of temperature, air speed 4.0h
-1Condition under, feed the adsorbent bed of filling silver-carried big-hole zeolite adsorbent, from adsorbent bed outlet sample analysis, its content of iodine is reduced to 8ppb, as seen removes the respond well of micro iodine from weak acidic medium.
Description of drawings
Fig. 1 is a large pore zeolite powder x-ray diffraction spectrogram of the present invention.
Fig. 2 is cryogenic nitrogen adsorption isotherm (a) and a graph of pore diameter distribution (b) before the macroporous zeolite absorbent steam of the present invention modification.
Fig. 3 is cryogenic nitrogen adsorption isotherm (a) and a graph of pore diameter distribution (b) after the macroporous zeolite absorbent steam of the present invention modification.
The specific embodiment
Reactant mole proportioning by table 1 takes by weighing waterglass (its quality chemical composition (%): SiO respectively
2=25.33; Na
2O=7.28), solid sulphuric acid aluminium Al
2SO
418H
2O, sulfuric acid and water, after the mixing, brute force stirs 1～2 hour to generating uniform Na
2O-SiO
2-Al
2O
3-H
2O reactant colloid.This colloid places the stainless steel autoclave, and sealing is warming up to the temperature that sets in constant temperature oven, leave standstill isothermal reaction to preset time, takes out this reactor and be cooled to room temperature from baking oven.Product spends deionised water, filtration, oven dry.Identify the crystalline phase of this synthetic product zeolite with the XRD diffractometer.Contain in the product of example 2 a small amount of stray crystal, other synthetic product is the na-pretreated zeolite pure phase, and its X-ray powder diffraction spectrum is as Fig. 1.
Table 1
| Embodiment | Reactant molar ratio | Hydrothermal reaction condition | |||
| SiO 2/Al 2O 3 | Na 2O/SiO 2 | H 2O/SiO 2 | Temperature (℃) | Time (hour) | |
| 1 | 12 | 0.35 | 35 | 130 | 35 |
| 2 | 30 | 0.20 | 15 | 120 | 90 |
| 3 | 22 | 0.40 | 40 | 105 | 50 |
| 4 | 10 | 0.35 | 40 | 125 | 45 |
Take by weighing embodiment 3 synthetic na-pretreated zeolites 500 and restrain, in rustless steel container, use the cited acid of table 2 (or ammonium salt) solution to carry out ion-exchange respectively, make h-type zeolite.The exchange product spends deionised water to PH=6, filters oven dry.Analyze the Na of the h-type zeolite that obtains
2O content, data are listed in table 2, and are respond well with the proof exchange.
Table 2 Na type zeolite ion-exchange system H type zeolite embodiment
| Embodiment | Exchange liquid kind | Give-and-take conditions | Product Na 2O content (%) | ||||
| Concentration (mol/L) | Liquid-solid ratio (gram/gram) | Temperature (℃) | Time (hour) | Number of | |||
| 5 | HNO 3 | 0.1 | 10 | 25 | 0.5 | 3 | 0.50 |
| 6 | HAC | 0.5 | 5 | 50 | 1.0 | 5 | 0.05 |
| 7 | NH 4NO 3 | 1.0 | 20 | 100 | 2.0 | 1 | 0.15 |
Embodiment 8:
Preparation condition with embodiment 6 amplifies, prepares 10 kilograms h-type zeolite powder crystal.In the spin forming machine, progressively add powder crystal and silica sol binder (contains 30%SiO
2), make the adsorbent bead of 1.5～2.2 millimeters of diameters.Consumption according to binding agent calculates, in the adsorbent bead that makes, and by butt weight, its amorphous silica binding agent/h-type zeolite=0.2.After oven for drying, measure the content of its silica and aluminium oxide, the mol ratio that calculates its silica and aluminium oxide is 15.5.This adsorbent is measured its cryogenic nitrogen adsorption isotherm and graph of pore diameter distribution with adsorbing instrument automatically, and is calculated its surface area, pore volume and average pore size after 550 ℃ of activation.
Embodiment 9:
Get adsorbent bead 500 grams of embodiment 8 preparations, place the stainless steel wire basket, this basket is in the middle part of the stainless steel autoclave of 1.5L capacity, and the bottom of autoclave is placed with deionized water 350mL, and water does not directly contact with adsorbent.Seal this autoclave.200 ℃ of stationary water steam treated are 48 hours in constant temperature oven, are cooled to room temperature, make macroporous zeolite absorbent of the present invention, and its X-ray powder diffraction spectrum is as Fig. 1.This adsorbent is measured its cryogenic nitrogen adsorption isotherm and graph of pore diameter distribution with adsorbing instrument automatically, and is calculated its surface area, pore volume and average pore size after 550 ℃ of activation.Test data sees Table 3.After the steam modification is handled, the surface area of adsorbent, pore volume and average pore size are significantly increased.
Adsorbent porous before and after the modification of table 3. steam
| Sample | BET (m 2/g) | Langmuir (m 2/g) | Micro pore volume (cm 3/g) | Average pore size (nm) |
| | 402 | 508 | 0.132 | 8.07 |
| | 461 | 583 | 0.173 | 11.5 |
Claims (10)
1, a kind of macroporous zeolite absorbent is characterized in that the zeolitic frameworks silica alumina ratio is 12～20, and cation is a hydrogen, contains 12 oxygen membered rings and 10 oxygen membered rings' structure pore opening, and the X-ray powder diffraction characteristic spectral line is:
The feature diffracted ray The 2 θ angles of diffraction (°) D-interplanar distance (nm) Intensity
*
1 6.4 1.39 Vvs
2 8.0 1.10 Vs
3 8.9 0.991 S
4 10.3 0.859 S
5 12.0 0.735 S
6 15.8 0.558 Vs
7 18.9 0.469 S
8 20.6 0.430 S
9 23.0 0.384 Vvs
10 23.7 0371 Vvs
11 24.5 0.363 S
12 27,4 0.325 S
13 30.0 0.297 S
14 31.8 0.282 S
Wherein, Vvs represents the strongest, and Vs represents very strong, and S represents by force.
2, a kind of preparation method of macroporous zeolite absorbent as claimed in claim 1 is characterized in that concrete steps are as follows: with the silicon raw material, and aluminum feedstock, sulfuric acid and water are mixed into Na
2O-SiO
2-Al
2O
3-H
2The O colloid; Hydro-thermal reaction is made the na-pretreated zeolite powder crystal in reactor, spends deionised water, filtration, drying; In ion exchanged soln, carry out ion-exchange then and take off sodium, make h-type zeolite; H-type zeolite and binding agent mixed-forming, oven dry are handled through modification again, make macroporous zeolite absorbent.
3, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that described silicon raw material is waterglass or Ludox, and aluminum feedstock is aluminum sulfate, aluminium chloride or aluminum nitrate.
4, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that Na
2O-SiO
2-Al
2O
3-H
2The chemical composition mol ratio of O colloid is:
SiO
2/Al
2O
3＝10～30，Na
2O/SiO
2＝0.10～0.40，H
2O/SiO
2＝15～40。
5, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that described hydrothermal temperature is 105～130 ℃, and the reaction time is 24～100 hours.
6, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that, it is HNO that na-pretreated zeolite takes off the ion exchanged soln that sodium uses
3, HAC, NH
4NO
3, NH
4Any or its mixture among the AC, the concentration 0.1～1.0mol/L of ion exchanged soln; The liquid-solid ratio of na-pretreated zeolite in ion exchanged soln is by weight: ion exchanged soln/sodalite=5～20.
7, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that the exchange temperature is 25～100 ℃ in ion exchanged soln, and be 0.5～2.0 hour swap time, and the exchange number of times is 1～5 time.
8, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that described moulding binding agent is amorphous silica or amorphous silicon aluminium glue, in butt weight, and binding agent/h-type zeolite=0.10～0.30.
9, macroporous zeolite absorbent preparation method according to claim 8 is characterized in that amorphous silica is a kind of or its mixture in Ludox, the white carbon.
10, macroporous zeolite absorbent preparation method according to claim 2 is characterized in that the atmosphere that described modification is handled is steam, and treatment temperature is 150～200 ℃, and the time is 24～48 hours.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811023A (en) * | 2010-03-11 | 2010-08-25 | 上海复旭分子筛有限公司 | Preparation method, product and applications thereof of acetate deep deiodination adsorbent |
| CN102557061A (en) * | 2010-12-16 | 2012-07-11 | 华东理工大学 | Sodium type zeolite molecular sieve hydrogen ion exchange method |
| CN102795634A (en) * | 2011-05-26 | 2012-11-28 | 中国石油化工股份有限公司 | Exchange modification method for reducing content of sodium oxide in beta-type molecular sieve |
| WO2013072808A1 (en) * | 2011-11-18 | 2013-05-23 | Basf Se | Process for ion exchange on zeolites |
| WO2013072809A1 (en) * | 2011-11-18 | 2013-05-23 | Basf Se | Process for ion exchange on zeolites |
| CN107670644A (en) * | 2017-11-03 | 2018-02-09 | 江西鑫陶科技股份有限公司 | A kind of preparation method of pyridine adsorption agent |
| CN111482158A (en) * | 2020-03-19 | 2020-08-04 | 复榆(张家港)新材料科技有限公司 | Preparation system of pure silicon zeolite-3 adsorbent without adhesive |
-
2005
- 2005-10-27 CN CN 200510030775 patent/CN1806908A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811023A (en) * | 2010-03-11 | 2010-08-25 | 上海复旭分子筛有限公司 | Preparation method, product and applications thereof of acetate deep deiodination adsorbent |
| CN102557061A (en) * | 2010-12-16 | 2012-07-11 | 华东理工大学 | Sodium type zeolite molecular sieve hydrogen ion exchange method |
| CN102795634A (en) * | 2011-05-26 | 2012-11-28 | 中国石油化工股份有限公司 | Exchange modification method for reducing content of sodium oxide in beta-type molecular sieve |
| CN102795634B (en) * | 2011-05-26 | 2014-12-31 | 中国石油化工股份有限公司 | Exchange modification method for reducing content of sodium oxide in beta-type molecular sieve |
| WO2013072808A1 (en) * | 2011-11-18 | 2013-05-23 | Basf Se | Process for ion exchange on zeolites |
| WO2013072809A1 (en) * | 2011-11-18 | 2013-05-23 | Basf Se | Process for ion exchange on zeolites |
| CN103946160A (en) * | 2011-11-18 | 2014-07-23 | 巴斯夫欧洲公司 | Process for ion exchange on zeolites |
| CN103946160B (en) * | 2011-11-18 | 2016-07-13 | 巴斯夫欧洲公司 | The method of ion exchange on zeolite |
| US9446960B2 (en) | 2011-11-18 | 2016-09-20 | Basf Se | Process for ion exchange on zeolites |
| CN107670644A (en) * | 2017-11-03 | 2018-02-09 | 江西鑫陶科技股份有限公司 | A kind of preparation method of pyridine adsorption agent |
| CN111482158A (en) * | 2020-03-19 | 2020-08-04 | 复榆(张家港)新材料科技有限公司 | Preparation system of pure silicon zeolite-3 adsorbent without adhesive |
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