CN1301790C - Acid resistant zeolite adsorbent and preparation thereof - Google Patents
Acid resistant zeolite adsorbent and preparation thereof Download PDFInfo
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- CN1301790C CN1301790C CNB2004100890315A CN200410089031A CN1301790C CN 1301790 C CN1301790 C CN 1301790C CN B2004100890315 A CNB2004100890315 A CN B2004100890315A CN 200410089031 A CN200410089031 A CN 200410089031A CN 1301790 C CN1301790 C CN 1301790C
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- zeolite
- adsorbent
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- sio
- ion exchanged
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Abstract
The present invention provides an acid resistant zeolite adsorbent and a preparation method thereof. The adsorbent of the present invention is synthesized by water-heating zeolite in a Na2O-SiO2-Al2O3-H2O colloid reaction object system and has X-ray characteristic diffraction spectrum. Sodium is removed via cation exchange; an adhesive is added to form; the adsorbent is prepared after aging in steam. The adsorbent of the present invention has the advantages of good acid resistance, high intensity and uniform pore structure, and is especially suitable for eliminating trace amount of inorganic and organic iodides and molecule iodine from acidic media after loaded with silver via ion exchange.
Description
Technical field
The present invention relates to a kind of acid resistant zeolite adsorbent and preparation method thereof.
Technical background
Need in acid medium, stablize and have the adsorbent of higher ion exchange capacity in the chemical industry production.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 strong 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 the gross porosity pore-size distribution between zeolite grain inhomogeneous, when adsorbent uses, both influenced the diffusion to zeolite grain in adsorbent of absorbate molecule, also reduce the adsorbent service efficiency, influence the intensity of adsorbent again.
China national Department of Intellectual Property has announced that application number is 03141604.7 patent of invention, 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 for 10 oxygen membered ring's openings.In addition application number be 031416055 Chinese patent to have introduced the low silicon H-ZSM-5 zeolite of a kind of usefulness be raw material, after the adding additives moulding, through changeing the brilliant acidproof substrate adsorbent of making binder free of handling.
Summary of the invention
The object of the present invention is to provide that a kind of acid resistance is good, intensity is high, the gross porosity between zeolite grain is evenly distributed and acidproof zeolite adsorbents and preparation method thereof.After this adsorbent carries silver with ion-exchange, be particularly suitable for from acid medium, removing inorganic and the organic iodide and the molecular iodine of trace.
Acid resistant zeolite adsorbent provided by the invention, its zeolitic frameworks silica alumina ratio is 15～25, and cation is a hydrogen, contains 10 oxygen membered rings and 12 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 (°) | Interplanar distance (nm) | Intensity * |
| 1 | 7.9 | 1.11 | Vs |
| 2 | 8.8 | 1.00 | S |
| 3 | 9.8 | 0.906 | Vs |
| 4 | 13.5 | 0.656 | S |
| 5 | 19.7 | 0.451 | S |
| 6 | 22.3 | 0.398 | S |
| 7 | 23.2 | 0.383 | Vvs |
| 8 | 23.8 | 0.373 | S |
| 9 | 25.7 | 0.346 | Vvs |
| 10 | 25.4 | 0338 | S |
| 11 | 27.7 | 0.321 | S |
*Vs-is very strong; S-is strong; Vvs-is the strongest.
The preparation method of acid resistant zeolite adsorbent provided by the 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, carrying out ion-exchange in ion exchanged soln takes off sodium and makes h-type zeolite, after h-type zeolite and the binding agent mixed-forming drying, make acid resistant zeolite adsorbent through burin-in process.
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=15～25, Na
2O/SiO
2=0.10～0.35, H
2O/SiO
2=15～25.
Hydrothermal temperature of the present invention is 140～180 ℃, and the reaction time is 12～40 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 of ion exchanged soln is 0.1～1.0mol/L.Liquid-solid ratio in the ion exchanged soln is by weight: ion exchanged soln/sodalite is 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.
Burin-in process can increase the compressive resistance of adsorbent, improves coarse texture and optimizes its pore-size distribution.The atmosphere of burin-in process of the present invention is steam, and the burin-in process temperature is 150～200 ℃, and ageing time is 24～48 hours.
With the acidproof adsorbent of the present invention's preparation, acid resistance is good, the intensity height, and the gross porosity between zeolite grain is evenly distributed, and helps the diffusion of ion and absorbate.Because opening existing 10 oxygen membered rings in sorbent structure of the present invention duct have 12 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.
Description of drawings
Fig. 1 is an acid resistant zeolite powder x-ray diffraction spectrogram of the present invention.
Fig. 2 is an acid resistant zeolite adsorbent graph of pore diameter distribution of the present invention.
The specific embodiment
Embodiment 1～4: preparation na-pretreated zeolite powder crystal
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, stir 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.With the XRD diffractometer identify this synthetic product zeolite crystalline phase.In the product of example 4, contain a small amount of quartzy stray crystal mutually, other synthetic product is the na-pretreated zeolite pure phase, 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 | 25 | 0.10 | 15 | 180 | 40 |
| 2 | 22 | 0.20 | 20 | 160 | 32 |
| 3 | 22 | 0.25 | 20 | 160 | 24 |
| 4 | 15 | 0.35 | 25 | 140 | 12 |
Embodiment 5～7: sodium type ion zeolite exchange hydrogen manufacturing type zeolite
Take by weighing embodiment 2 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-FJ-1 zeolite ion-exchange system H-FJ-1 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 times | |||
| 5 | HNO 3 | 0.1 | 10 | 25 | 0.5 | 3 | 0.25 |
| 6 | HAC | 0.5 | 5 | 50 | 1.0 | 5 | 0.10 |
| 7 | NH 4NO 3 | 1.0 | 20 | 100 | 2.0 | 1 | 0.20 |
Embodiment 8:
Preparation condition with embodiment 5 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 22.8.Measure the bead adsorbent crushing strength of 2.0 millimeters of 50 diameters respectively, the mean value of acquisition is 40 newton/grains.
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.150 ℃ of static burin-in process are 48 hours in constant temperature oven, are cooled to room temperature, make acid resistant zeolite adsorbent of the present invention, and its X-ray powder diffraction spectrum is as Fig. 1.The crushing strength mean value through the bead adsorbent of burin-in process of measuring 2.0 millimeters of 50 diameters is 48 newton/grains.
Embodiment 10
Get adsorbent 500 grams of embodiment 8 preparations, carry out burin-in process by the method for embodiment 9.200 ℃ of aging temperatures, make acid resistant zeolite adsorbent of the present invention at 24 hours time.The mean value of product crushing strength is 58 newton/grains.
BET surface area and the Langmuir surface area of measuring this substrate adsorbent after aging with automatic cryogenic nitrogen absorption aperture distribution instrument are respectively 391m
2/ g and 494m
2/ g.Its graph of pore diameter distribution is seen Fig. 2, shows that the acid resistant zeolite adsorbent gross porosity that makes is evenly distributed, and pore-size distribution is in about 4nm.
Claims (3)
1, a kind of acid resistant zeolite adsorbent is characterized in that the zeolitic frameworks silica alumina ratio is 15～25, and cation is a hydrogen, contains 10 oxygen membered rings and 12 oxygen membered rings' structure pore opening, and X-ray powder diffraction principal character spectral line is:
The feature diffracted ray The 2 θ angles of diffraction (°) Interplanar distance (nm) Intensity
1 7.9 1.11 Very strong
2 8.8 1.00 By force
3 9.8 0.906 Very strong
4 13.5 0.656 By force
5 19.7 0.451 By force
6 22.3 0.398 By force
7 23.2 0.383 The strongest
8 23.8 0.373 By force
9 25.7 0.346 The strongest
10 25.4 0338 By force
11 27.7 0.321 By force
2, a kind of preparation method of acid resistant zeolite adsorbent as claimed in claim 1 is characterized in 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 powder crystal in reactor, spend deionised water, filtration, dry back and carry out ion-exchange take off sodium and make h-type zeolite in ion exchanged soln, h-type zeolite is made acid resistant zeolite adsorbent through burin-in process after drying with the binding agent mixed-forming; Wherein:
Described Na
2O-SiO
2-Al
2O
3-H
2The chemical composition mol ratio of O colloid is: SiO
2/ Al
2O
3=15～25, Na
2O/SiO
2=0.10～0.35, H
2O/SiO
2=15～25;
Described hydrothermal temperature is 140～180 ℃, and the reaction time is 12～40 hours;
It is HNO that described 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 described na-pretreated zeolite in ion exchanged soln is by weight: ion exchanged soln/sodalite is 5～20;
The exchange temperature is 25～100 ℃ in the described ion exchanged soln, and be 0.5～2.0 hour swap time, and the exchange number of times is 1～5 time;
Described moulding binding agent is amorphous silica or amorphous silicon aluminium glue, and in butt weight, binding agent/h-type zeolite is 0.10～0.30, and wherein, amorphous silica is a kind of or its mixture in Ludox, the white carbon;
The atmosphere of described burin-in process is steam, and the burin-in process temperature is 150～200 ℃, and ageing time is 24～48 hours.
3, acid resistant zeolite adsorbent preparation method according to claim 2 is characterized in that described silicon raw material is waterglass, Ludox, and aluminum feedstock is aluminum sulfate, aluminium chloride, aluminum nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100890315A CN1301790C (en) | 2004-12-02 | 2004-12-02 | Acid resistant zeolite adsorbent and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100890315A CN1301790C (en) | 2004-12-02 | 2004-12-02 | Acid resistant zeolite adsorbent and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1644238A CN1644238A (en) | 2005-07-27 |
| CN1301790C true CN1301790C (en) | 2007-02-28 |
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|---|---|---|---|
| CNB2004100890315A Expired - Fee Related CN1301790C (en) | 2004-12-02 | 2004-12-02 | Acid resistant zeolite adsorbent and preparation thereof |
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| CN102795636B (en) * | 2011-05-26 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of exchange method of modifying reducing sodium oxide content in Y zeolite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4735786A (en) * | 1984-04-25 | 1988-04-05 | Toray Industries, Inc. | Adsorbent for and method of removing iodine compounds |
| CN1277885A (en) * | 1998-03-06 | 2000-12-27 | 环球油品公司 | Method for treatment of organic liquid contaminated by iodides |
| US6506935B1 (en) * | 1998-03-06 | 2003-01-14 | Uop Llc | Combination pretreatment/adsorption for treating a liquid stream contaminated with an iodine-containing compound |
| CN1478595A (en) * | 2003-07-10 | 2004-03-03 | 上海吴泾化工有限公司 | Preparation method of high silver carrying ZSM-5 zeolite deiodine adsorbing agent |
| CN1486784A (en) * | 2003-07-10 | 2004-04-07 | 复旦大学 | Zeolite deiodination adsorbent with high silver carrying amount and its prepn process |
-
2004
- 2004-12-02 CN CNB2004100890315A patent/CN1301790C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4735786A (en) * | 1984-04-25 | 1988-04-05 | Toray Industries, Inc. | Adsorbent for and method of removing iodine compounds |
| CN1277885A (en) * | 1998-03-06 | 2000-12-27 | 环球油品公司 | Method for treatment of organic liquid contaminated by iodides |
| US6380428B1 (en) * | 1998-03-06 | 2002-04-30 | Uop Llc | Method for treating a liquid stream contaminated with an iodine-containing compound using a cation-exchanged zeolite |
| US6506935B1 (en) * | 1998-03-06 | 2003-01-14 | Uop Llc | Combination pretreatment/adsorption for treating a liquid stream contaminated with an iodine-containing compound |
| CN1478595A (en) * | 2003-07-10 | 2004-03-03 | 上海吴泾化工有限公司 | Preparation method of high silver carrying ZSM-5 zeolite deiodine adsorbing agent |
| CN1486784A (en) * | 2003-07-10 | 2004-04-07 | 复旦大学 | Zeolite deiodination adsorbent with high silver carrying amount and its prepn process |
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| CN1644238A (en) | 2005-07-27 |
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