CN110117017A - A kind of method that oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve - Google Patents
A kind of method that oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve Download PDFInfo
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- CN110117017A CN110117017A CN201910378272.8A CN201910378272A CN110117017A CN 110117017 A CN110117017 A CN 110117017A CN 201910378272 A CN201910378272 A CN 201910378272A CN 110117017 A CN110117017 A CN 110117017A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention discloses the method that a kind of oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, includes the following steps: that (1) oxalic acid solution acid is handled: taking NaY molecular sieve and H2C2O4Solution is uniformly mixed, and is placed in oil bath pan, is stirred；By above-mentioned oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral, is put it into baking oven and is dried overnight, obtains oxalic acid treatment sample；(2) NH3·H2O solution alkali process: by oxalic acid treatment sample obtained by step (1) and NH3·H2O solution is uniformly mixed, and is placed in oil bath pan and is handled；By oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral；Filter cake is taken out, dries in an oven, and roasted with Muffle furnace, obtains multi-stage porous Y molecular sieve.The present invention prepares multi-stage porous Y molecular sieve using oxalic acid-ammonium hydroxide coprocessing, and the external surface area ratio NaY of gained multi-stage porous Y molecular sieve increases by 3 times or more, and the mesopore volume ratio NaY of gained multi-stage porous Y molecular sieve increases 4 times or more.
Description
Technical field
The present invention relates to technical field of molecular sieve, specifically, being related to a kind of technology of preparing of multi-stage porous Y molecular sieve.
Background technique
Micro-pore zeolite pore size is smaller, is distributed wide, open deficiency, drastically influence biggish heavy oil molecules and its
The diffusion of intermediate product, the mass transfer for causing catalysis reaction is difficult, this just needs to develop novel catalysis material.1992 orderly
Mesoporous material attract attention, it has biggish aperture, Kong Rong, higher specific surface area and cellular structure height
Orderly, this makes it highlight excellent catalytic performance in the catalysis reaction for having macromolecular to participate in, but in practical applications, mesoporous
Material hydrothermal stability is poor and lower than micro-pore zeolite with catalytic activity, this seriously constrains its application in catalysis reaction.
The advantages of in order to make up the deficiency in single duct, integrate micropore canals and mesopore orbit, people are in micro-pore zeolite point
It introduces mesoporous in son sieve, is prepared for having both intrinsic micropore and secondary intergranular/transgranular meso-hole structure multistage porous molecular sieve.Research hair
Existing multi-stage pore zeolite molecular sieve duct is more flourishing, unobstructed, shortens diffusion path, improves diffusion rate, fills active sites
Divide exposure, acidity stronger, while can inhibit catalyst surface coking, improves catalyst life.In addition, having to adsorption molecule
There is the understanding of the absorption and mass transfer behavior in the molecular sieve of different pore distributions, often develops the thought of high-performance catalysis material
Source.The acid of Y type molecular sieve makes its body in more catalysis reaction compared with strong, shape selective catalysis and the easy modulation of catalytic performance
Reveal fabulous catalytic activity.As the main active component of heavy oil conversion catalyst, be largely applied to petroleum refining with
Catalytic process and adsorption separation process in processing.
However the external surface area and mesopore volume of multi-stage porous Y molecular sieve obtained by prior art preparation are smaller.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of external surface areas and mesopore volume to be significantly increased
Multi-stage porous Y molecular sieve preparation method.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of method that oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, includes the following steps:
(1) oxalic acid solution acid is handled: taking NaY molecular sieve and H2C2O4Solution is uniformly mixed in flask, is placed on oil bath
In pot, it is sufficiently stirred；By above-mentioned oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral, puts it into baking
It is dried overnight in case, obtains oxalic acid treatment sample；
(2)NH3·H2O solution alkali process: by oxalic acid treatment sample obtained by step (1) and NH3·H2O solution is in flask
It is uniformly mixed, is placed in oil bath pan, stir process；By oil bath treated mixed liquor, decompression is filtered to filtrate close to neutrality
Until；Filter cake is taken out, dries in an oven, and roasted with Muffle furnace, obtains multi-stage porous Y molecular sieve.
Preferably, step (1) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The temperature of oil bath pan is constant temperature 363K.
Preferably, step (1) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The temperature of baking oven is 337K.
Preferably, step (2) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The temperature of oil bath pan is 328K.
Preferably, step (2) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The stir process time is 4h~8h.
Preferably, step (2) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The temperature of baking oven is 373K.
Preferably, step (2) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The temperature of Muffle furnace roasting is 500 DEG C.
Preferably, step (1) is described in the method that above-mentioned oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
H2C2O4The concentration of solution is 0.12mol/L.
Compared with prior art, it is more using oxalic acid-ammonium hydroxide coprocessing preparation that the invention has the following beneficial effects: the present invention
Grade hole Y molecular sieve, the external surface area ratio NaY of gained multi-stage porous Y molecular sieve increase by 3 times or more, Jie of gained multi-stage porous Y molecular sieve
Pore volume ratio NaY increases 4 times or more.
Detailed description of the invention
Fig. 1 is the XRD spectra of NaY, NaY-AT-E2 molecular sieve；
Fig. 2 is the low temperature nitrogen adsorption/desorption isotherms of NaY, NaY-AT-E1 and NaY-AT-E2 molecular sieve；
Fig. 3 is the SEM picture of NaY (A) and NaY-AT-E2 (B).
Specific embodiment
Embodiment 1: the method that oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The processing of oxalic acid solution acid: the NaY molecular sieve of 6g, the H that configuration 100ml concentration is 0.12mol/L are weighed2C2O4Solution
It is spare.According to the H of every 1g sample addition 15ml2C2O4The ratio of solution, by above-mentioned sample and the H measured out2C2O4Solution is being burnt
It is uniformly mixed, is placed in the oil bath pan of constant temperature 363K, stir process 60min in bottle.By above-mentioned oil bath treated mixed liquor,
Decompression filters until filtrate is close to neutrality, puts it into the baking oven of 337K and is dried overnight.By H2C2O4The sample of solution processing
Product are denoted as AT.
NH3·H2O solution alkali process: according to the NH of the sample addition 20ml of every 1g3·H2The ratio of O solution, by above-mentioned sample
Product and the NH measured out3·H2O solution is uniformly mixed in flask, is placed in the oil bath pan of constant temperature 328K, stir process 4h.
By above-mentioned oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral.Filter cake is taken out, is done in the baking oven of 373K
Dry 6h.And with Muffle furnace at 500 DEG C, 5h is roasted.E1 will be denoted as by the sample of ammonia spirit processing.
Embodiment 2: the method that oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve
The processing of oxalic acid solution acid: the NaY molecular sieve of 6g, the H that configuration 100ml concentration is 0.12mol/L are weighed2C2O4Solution
It is spare.According to the H of every 1g sample addition 15ml2C2O4The ratio of solution, by above-mentioned sample and the H measured out2C2O4Solution is being burnt
It is uniformly mixed, is placed in the oil bath pan of constant temperature 363K, stir process 60min in bottle.By above-mentioned oil bath treated mixed liquor,
Decompression filters until filtrate is close to neutrality, puts it into the baking oven of 337K and is dried overnight.By H2C2O4The sample of solution processing
Product are denoted as AT.
NH3·H2O solution alkali process: according to the NH of the sample addition 20ml of every 1g3·H2The ratio of O solution, by above-mentioned sample
Product and the NH measured out3·H2O solution is uniformly mixed in flask, is placed in the oil bath pan of constant temperature 328K, stir process 8h.
By above-mentioned oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral.Filter cake is taken out, is done in the baking oven of 373K
Dry 6h.And with Muffle furnace at 500 DEG C, 5h is roasted.E2 will be denoted as by the sample of ammonia spirit processing.
Embodiment 3:
Oxalic acid-ammonium hydroxide coprocessing method is selected to prepare multi-stage porous NaY molecular sieve, the concentration for selecting oxalic acid is 0.12mol/
L, treatment temperature is 90 DEG C, and the reaction time of modulation ammonium hydroxide, which sees, generates mesoporous situation under the different reaction time.Specific experiment
Condition such as table 1.
Table 1, the label of sample and treatment conditions
| Sample model | Reagent | pH | T(K) | t(h) |
| AT | H2C2O4 | 1 | 363 | 1 |
| E1 | NH3·H2O | 11 | 328 | 4 |
| E2 | NH3·H2O | 11 | 328 | 8 |
(1) XRD of molecular sieve
Fig. 1 gives the XRD spectrum of NaY and NaY-AT-E2 molecular sieve.Pass through Y molecule after observing oxalic acid-ammonium hydroxide before modified
Known to the crystalline structure of sieve: NaY-AT-E2 molecular sieve remains as the structure of Y type molecular sieve, does not occur other any stray crystals；It is logical
The intensity of observation NaY and NaY-AT-E2 molecular sieve diffraction maximum is crossed it is found that the modified crystallinity decline that will lead to molecular sieve of Acid-Base.
(2) porous of molecular sieve
Fig. 2 is the low temperature nitrogen adsorption/desorption isotherms of NaY, NaY-AT-E1 and NaY-AT-E2 molecular sieve.As seen from the figure:
Low than pressure area, the adsorbance of NaY, NaY-AT-E1 and NaY-AT-E2 rise rapidly, this is caused by micropore hole filling effect
's；Under medium to relatively high pressure, it is in level that the adsorbance of NaY, which goes up slowly rear, and NaY-AT-E1 and NaY-AT-
E2 is 0.7 or so jumping occur in relative pressure, hysteresis loop but unobvious occurs.Illustrate that be jointly processed by can by oxalic acid-ammonium hydroxide
Mesoporous to introduce, mesoporous content increases with the increase of alkali process time.
Table 2 lists NaY, NaY-AT-E1 and NaY-AT-E2 Molecular Sieve Pore physical data.As can be seen from Table 2:
Compared with NaY, the external surface area of NaY-AT-E1 and NaY-AT-E2 increase it is obvious, but mesoporous Kong Rong and average pore size amplification compared with
It is small.The external surface area of NaY-AT-E1 is by 44m2/ g increases to 131m2/ g increases 3 times, the outer surface of NaY-AT-E2 molecular sieve
Product is by 44m2/ g increases to 165m2/ g increases 4 times；The mesopore volume of NaY-AT-E1 is by 0.03cm3/ g increases to 0.12cm3/
G, and NaY-AT-E2 then increases to 0.16cm3/ g has increased separately 4 times and 5 times.Mesoporous Kong Rong and aperture increase there is no obvious
Add, it may be possible to because ammonium hydroxide is volatile and is not form the roughening of transgranular mesoporous only Extra specific surface area caused by weak base,
It can be confirmed by SEM picture.
The texture property data of table 2, NaY, NaY-AT-E1 and NaY-AT-E2 molecular sieve
(3) the modified influence to molecular sieve appearance of oxalic acid-ammonium hydroxide
Using scanning electron-microscopy it can be seen that the variation on the molecular sieve crystal surface after oxalic acid-AMMONIA TREATMENT NaY, Fig. 3
Give the electromicroscopic photograph of NaY and NaY-AT-E2 molecular sieve.As shown in Figure 3: NaY molecular sieve shape is more regular, boils for octahedral
Stone shape and surface is smooth (Fig. 3 A)；And the crystallite dimension of NaY-AT-E2 molecular sieve reduces, thick good fortune (figure is presented in outer surface
3B), there is no cracked or duck eyes for molecular sieve surface.
Claims (8)
1. the method that a kind of oxalic acid-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, it is characterised in that include the following steps:
(1) oxalic acid solution acid is handled: taking NaY molecular sieve and H2C2O4Solution is uniformly mixed in flask, is placed in oil bath pan,
It is sufficiently stirred；By above-mentioned oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral, puts it into mistake in baking oven
Night is dry, obtains oxalic acid treatment sample；
(2) NH3·H2O solution alkali process: by oxalic acid treatment sample obtained by step (1) and NH3·H2O solution mixes in flask
It is even, it is placed in oil bath pan, stir process；By oil bath treated mixed liquor, decompression is filtered to filtrate close to until neutral；It takes
Filter cake out is dried in an oven, and is roasted with Muffle furnace, and multi-stage porous Y molecular sieve is obtained.
2. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(1) temperature of the oil bath pan is 363 K of constant temperature.
3. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(1) temperature of the baking oven is 337 K.
4. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(2) temperature of the oil bath pan is 328 K.
5. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(2) the stir process time is the h of 4 h ~ 8.
6. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(2) temperature of the baking oven is 373 K.
7. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(2) temperature of the Muffle furnace roasting is 500 DEG C.
8. the method that oxalic acid as described in claim 1-ammonium hydroxide coprocessing prepares multi-stage porous Y molecular sieve, which is characterized in that step
(1) H2C2O4The concentration of solution is 0.12 mol/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320185A (en) * | 2019-12-11 | 2020-06-23 | 中国石油大学(华东) | Molecular sieve pore-enlarging treatment method |
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| CN109368655A (en) * | 2018-10-15 | 2019-02-22 | 沈阳化工大学 | A kind of multi-stage porous molecular sieve preparation method of high-crystallinity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368655A (en) * | 2018-10-15 | 2019-02-22 | 沈阳化工大学 | A kind of multi-stage porous molecular sieve preparation method of high-crystallinity |
Non-Patent Citations (3)
| Title |
|---|
| MARIUSZ GACKOWSKI ET AL.: "IR and NMR studies of hierarchical material obtained by the treatment of zeolite Y by ammonia solution", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 * |
| 万晓蕊等: "苯在酸碱处理多级孔Y分子筛上的吸附及传质行为", 《燃料化学学报》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320185A (en) * | 2019-12-11 | 2020-06-23 | 中国石油大学(华东) | Molecular sieve pore-enlarging treatment method |
| CN111320185B (en) * | 2019-12-11 | 2023-06-16 | 中国石油大学(华东) | Molecular sieve reaming treatment method |
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