CN102815718B - One-step method for preparing 3A type zeolite molecular sieve by kaoline - Google Patents
One-step method for preparing 3A type zeolite molecular sieve by kaoline Download PDFInfo
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- CN102815718B CN102815718B CN201210320721.1A CN201210320721A CN102815718B CN 102815718 B CN102815718 B CN 102815718B CN 201210320721 A CN201210320721 A CN 201210320721A CN 102815718 B CN102815718 B CN 102815718B
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- molecular sieve
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Abstract
The invention relates to a one-step method for preparing a 3A type zeolite molecular sieve by kaoline. The method includes steps of, step one, performing kaoline calcination: uniformly mixing the kaoline with KCl according to a mass ratio of 1: (0.2-0.6), and calcining the mixture at the temperature between 550 DEG C and 700 DEG C for 3-5 hours to obtain a precursor mixture; and step two, preparing the 3A molecular sieve: uniformly mixing the precursor mixture with a NaOH aqueous solution according to the ratio of (15-30g):100mL, heating the precursor mixture and the NaOH aqueous solution to the temperature of 60-80 DEG C, and performing aging for 4-6 hours under strong stirring actions; then heating the precursor mixture and the NaOH aqueous solution to the temperature of 90-100 DEG C, and stirring the precursor mixture and the NaOH aqueous solution at an intermediate speed for 3-5 hours to obtain a mixture; and filtering and drying solid products obtained from the solution to obtain the 3A type zeolite molecular sieve. The one-step method for preparing the 3A type zeolite molecular sieve by the kaoline is simple in process and low in calcination temperatures, and the prepared 3A type zeolite molecular sieve is high in potassium exchange rate.
Description
technical field
The present invention relates to kaolin single stage method and prepare the method for 3A type zeolite molecular sieve, belong to Zeolite synthesis field.
background technology
Molecular sieve is the silico-aluminate of crystal type, has uniform pore texture, and its spacial framework is by silicon-oxy tetrahedron unit [SiO
4] and aluminum-oxygen tetrahedron unit [AlO
4] being staggered forms.In molecular sieve structure, contain a large amount of crystal water, in the process of heating, owing to losing crystal water, form many cavitys that vary in size, between cavity, have again the micropore that many diameters are identical to communicate, form the duct that uniform diameter is molecular size.Therefore, can be by diameter than the large molecular repulsion in hole outside, thus realize the effect of screening molecule, molecular sieve is just gained the name thus.This construction features make molecular sieve have absorption, catalysis and the large characteristic of ion-exchange three of selection.Therefore it is widely used in the industries such as oil, chemistry, metallurgy.
The kind of zeolite is a lot, different according to its source, is divided into natural zeolite and the large class of artificial zeolite two.After natural zeolite is carried out to systematic study, for obtaining pure zeolite, people start to be devoted to artificial synthetic zeolite.By 1954, the just industrialization of the synthetic of zeolite.1948, Barrer synthesized first the zeolite of small-bore, the new era of having started zeolite synthesis under High Temperature High Pressure.Nineteen fifty, Milton and Breck have synthesized important commercial A, X and y-type zeolite under low-temp low-pressure.Nineteen fifty-three, the synthetic zeolite that A type zeolite is produced as the first large-scale commercial applications, is used to the oxygen in separated impure argon.The employing of low-temperature hydrothermal synthetic technology, for large-scale commercial production zeolite provides favourable condition.
At present the zeolite of synthetic surpasses 100 kinds, and conventional have A type, X-type, Y type, M type and a ZSM type etc.In recent years develop again the synthetic zeolite of non-sial element, and be applied in catalytic field.Many important Industrial Catalysis reactions have be unable to do without molecular sieve catalyst, for example, and the reactions such as catalytic cracking, hydrocracking, isomerization, reformation, disproportionation and transalkylation.In eco-friendly fine chemicals production process, molecular sieve is also more widely used.Molecular sieve has become most important gang catalyzer.3A molecular sieve bore diameter is minimum, and adsorbed water molecule only, to N in air
2and O
2adsorptive capacity very low (< 0. 5 %), therefore can be used as the dry of air in double glazing interlayer.
According to the difference of using raw material, the synthetic method of molecular sieve mainly can be divided into two kinds: hydrothermal synthesis method and alkaline purification method.Patent 200910021112.4 is that utilization of fly ash alkali melts the method that steaming process is prepared zeolite molecular sieve, and it take flyash as raw material and at high temperature melting of solid sodium hydroxide, and melts reacts 12 hours and obtains with a small amount of steam generation in reactor.The method of patent 200810138410.7 isothermal One-step production 4A molecular sieves, it is to add industrial chemicals through overaging, crystallization, filtration, washing, oven dry, to obtain through violent stirring by the stoichiometric of molecular sieve again.China most of molecular sieve manufacturer is all a kind of method before utilizing at present, with water glass, silica gel, white carbon black, aluminum oxide, sodium metaaluminate, sodium hydroxide etc., synthesizes.But this method need to be used a large amount of pharmaceutical chemicalss, and production cost is higher.Therefore, many researchers and manufacturer are explored one after another with inorganic non-metallic ore deposit raw material (as kaolin, wilkinite, coal gangue etc.) synthesis of molecular sieve.
Kaolin refers to the aggregate of multiple hydrous alumino silicates mineral composition, is mainly kaolinite.Kaolinic chemical constitution is Al
4(Si
4o
10) (OH)
8or 2SiO
2al
2o
32H
2o, crystal belongs to the silicate minerals of triclinic(crystalline)system laminate structure.Kaolinite has 1:1 type layered silicate structure.Basic structural unit layer is by SiO
4tetrahedron and Al (O, OH) octahedral layer are formed by connecting.Kaolin is a kind of important non-metallic minerals, can increase the volume of material, insulation strength, the resistance of raising plastics, enhancing is to infrared rays barriering effect etc., and is widely used in the fields such as paint, coating, papermaking, rubber, plastics, cable, pottery, enamel, refractory materials, weaving, cement, automobile, chemistry, environmental protection, agricultural.
At present the patent documentation that kaolin prepares A type molecular sieve as raw material be take in China also a lot of reports, if patent 98113363.0 is a kind of secondary perforated molecular siever adsorbents and preparation method thereof.4A molecular sieve is as binding agent moulding.Through alkaline solution, processing, is A type molecular sieve by binding agent Partial Conversion, makes secondary pore-forming 4A adsorbent of molecular sieve; Through secondary pore-forming, then through calcium ion or sodium ion exchange, can make secondary pore-forming 5A or 3A adsorbent of molecular sieve.Patent 200310111435.5 is preparation methods of a kind of nano type A molecular sieve.The He Lv source, silicon source that is 2:1 by ratio adds in sodium hydroxide solution, refilters last processing of washing obtain nano type A molecular sieve through ultrasonic and microwave combined processing.These patents propose respectively diverse ways take kaolin and prepares A type molecular sieve as raw material, but has some problems: the preparation of (1) 3A molecular sieve is all to be obtained by ion-exchange by 4A molecular sieve, and this has just caused the production cycle long, and production cost is large.(2) prepare the calcining temperature higher (generally needing 700～1000 ℃) of metakaolin; (3) need to regulate silica alumina ratio.
summary of the invention
Technical problem to be solved by this invention is for above-mentioned the problems of the prior art, provides a kind of kaolin single stage method to prepare the method for 3A type zeolite molecular sieve, and the method technique is simple, calcining temperature is low, and the potassium exchange rate of the 3A type zeolite molecular sieve of preparation is high.
The present invention is in order to solve the problems of the technologies described above, and the technical scheme adopting is:
Kaolin single stage method is prepared the method for 3A type zeolite molecular sieve, and it comprises the steps:
1), after ratio kaolinic calcining: be 1:(0.2～0.6 in mass ratio with KCl by kaolin) mixes, 550～700 ℃ of calcinings 3～5 hours, obtain precursor mixture;
2) preparation of 3A molecular sieve: according to the ratio of precursor mixture and the NaOH aqueous solution, be (15～30g): 100mL, precursor mixture and NaOH aqueous solution is even, be warming up to 60～80 ℃, under strong stirring effect, ageing is 4～6 hours; Being warmed up to 90～100 ℃, middling speed stirs 3～5 hours again; After gained solid product in solution is filtered, is dried, obtain 3A zeolite molecular sieve.
Press such scheme, described kaolin is the kaolin of taking from when sun area, Al in this kaolin composition
2o
3quality percentage composition be 34.73%, SiO
2quality percentage composition be 37.57%, Fe
2o
3quality percentage composition be 3.22%, TiO
2quality percentage composition be 2.99%, whiteness=41, median size=10 micron.
Press such scheme, the concentration of the described NaOH aqueous solution is 2～5mol/L.
Press such scheme, described strong stirring is for being greater than 600 revs/min, and it is 300～600 revs/min that middling speed stirs.
Press such scheme, described being dried as being dried 2～4 hours at 90～100 ℃.
After calcined kaolin and potassium chloride mixture, kaolin changes active very high metakaolin, the K in Repone K into
+also be doped in the lattice of metakaolin, be accompanied by metakaolin and react the initial amorphous gel that generates water glass and sodium metaaluminate with sodium hydroxide, continue reaction for the secondary gel in crystallization process, the K in metakaolin lattice
+in zeolite crystallization reaction process, also transfer in the lattice of zeolite, and then obtain 3A type zeolite molecular sieve.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention by kaolin, Repone K, mixed after calcining, through ageing, after crystallization, by ion-exchange, generate 3A molecular sieve after need not first synthesize 4A molecular sieve, but directly synthesize 3A type zeolite molecular sieve;
2) the synthetic 3A type zeolite molecular sieve of the present invention is functional, and potassium exchange rate can reach 60%, much larger than 3A molecular screen primary powder country acceptable end product standard potassium exchange rate 45%, is also greater than the potassium exchange rate 50% that the ion-exchange of 4A molecular sieve generates 3A molecular sieve;
3) in building-up process of the present invention, calcining temperature is low, in calcination process, only need, by kaolin calcined to metakaolin, not need to improve the activity that calcining temperature increases raw material again; And in synthetic 3A molecular sieve process, required silicon and aluminium are by kaolin (Al
2o
32SiO
22H
2o) raw ore provides, Al in raw ore
2o
3and SiO
2quality percentage composition be respectively 34.73%, 37.57 %, do not need to carry out again the compensation of silicon and aluminium;
4) preparation technology of the present invention simple, shortened the production time, preparation process is easy to control, production efficiency is high, environmental pollution is little, cost is low.
Accompanying drawing explanation
Fig. 1 is X ray powder crystal diffraction (XRD) figure of kaolin former state.
Fig. 2 is scanning electron microscope (SEM) figure of kaolin former state.
Fig. 3 is X ray powder crystal diffraction (XRD) figure of precursor mixture.
Fig. 4 is X ray powder crystal diffraction (XRD) figure of 3A molecular sieve.
Fig. 5 is scanning electron microscope (SEM) figure of 3A molecular sieve.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further set forth, but within therefore not limiting the present invention to described scope of embodiments.
In following embodiment, all adopt when positive regional kaolin be raw material, described when positive kaolin be the kaolin of taking from when sun area, Al in this kaolin composition
2o
3quality percentage composition be 34.73%, SiO
2quality percentage composition be 37.57%, Fe
2o
3quality percentage composition be 3.22%, TiO
2quality percentage composition be 2.99%, whiteness=41, median size=10 micron.Characterization result is shown in Fig. 1, Fig. 2.
embodiment 1:
Kaolin single stage method is prepared 3A type zeolite molecular sieve, and it comprises the steps:
1) kaolinic calcining: kaolin and KCl for after 1:0.2 mixes, make precursor mixture for 4 hours 550 ℃ of calcinings in mass ratio;
2) preparation of 3A molecular sieve: take 20g precursor mixture, measure the NaOH aqueous solution 100ml of 4mol/L, evenly mix, at 80 ℃ of water-baths, adjusting rotating speed is 610 revs/min of strong stirring 5h, then is warmed up to 100 ℃, and adjusting rotating speed is that 400 revs/min of middling speeds stir 4h; Solid product in solution is filtered out, and filter cake again filters after distilled water wash, again filters gained filter cake and is dried 2 hours, acquisition 3A type zeolite molecular sieve in 100 ℃.
The potassium exchange rate of the 3A type molecular sieve of embodiment 1 preparation can reach 60%, has illustrated that the potassium exchange rate of the 3A type zeolite molecular sieve preparing is high, 3A type zeolite molecular sieve functional.
embodiment 2:
Kaolin single stage method is prepared the method for 3A type zeolite molecular sieve, and it comprises the steps:
1) kaolinic calcining: kaolin and KCl for after 1:0.6 mixes, make precursor mixture for 3 hours 700 ℃ of calcinings in mass ratio;
2) preparation of 3A molecular sieve: take 15g precursor mixture, measure the NaOH aqueous solution 100ml of 2mol/L, evenly mix, at 70 ℃ of water-baths, adjusting rotating speed is 800 revs/min of strong stirring 4h, then is warmed up to 90 ℃, and adjusting rotating speed is that 600 revs/min of middling speeds stir 5h; Solid product in solution is filtered out, and filter cake again filters after distilled water wash, again filters gained filter cake and is dried 4 hours, 3A type zeolite molecular sieve in 90 ℃.
X ray powder crystal diffraction (XRD) figure of the 3A molecular sieve of embodiment 2 preparations as shown in Figure 4, scanning electron microscope (SEM) figure as shown in Figure 5, Fig. 4 shows that the 3A molecular sieve crystallinity of preparation is higher, and Fig. 5 shows the 3A sieve sample even particle size of preparation, smooth surface.The potassium exchange rate of the 3A type molecular sieve of embodiment 2 preparations can reach 56%.The potassium exchange rate that the 3A type zeolite molecular sieve preparing has been described is high, 3A type zeolite molecular sieve functional.
embodiment 3:
Kaolin single stage method is prepared the method for 3A type zeolite molecular sieve, and it comprises the steps:
1) kaolinic calcining: kaolin and KCl for after 1:0.3 mixes, make precursor mixture for 3 hours 650 ℃ of calcinings in mass ratio;
2) preparation of 3A molecular sieve: take 25g precursor mixture, measure the NaOH aqueous solution 100ml of 3mol/L, evenly mix, at 75 ℃ of water-baths, adjusting rotating speed is 700 revs/min of strong stirring 4h, then is warmed up to 95 ℃, and adjusting rotating speed is that 300 revs/min of middling speeds stir 4h; Solid product in solution is filtered out, and filter cake again filters after distilled water wash, again filters gained filter cake and is dried 4 hours, 3A type zeolite molecular sieve in 90 ℃.
The potassium exchange rate of the 3A type molecular sieve of embodiment 3 preparation can reach 50%, has illustrated that the potassium exchange rate of 3A type zeolite molecular sieve of preparation is high, 3A type zeolite molecular sieve functional.
embodiment 4:
Kaolin single stage method is prepared the method for 3A type zeolite molecular sieve, and it comprises the steps:
1), kaolinic calcining: kaolin and KCl are in mass ratio for after 1:0.5 mixes, and 600 ℃ of calcinings make precursor mixture for 5 hours;
2), the preparation of 3A molecular sieve: take 30g precursor mixture, measure the NaOH aqueous solution 100ml of 5mol/L, evenly mix, at 60 ℃ of water-baths, adjusting rotating speed is 900 revs/min of strong stirring 6h, then is warmed up to 95 ℃, and adjusting rotating speed is that 500 revs/min of middling speeds stir 3h; Solid product in solution is filtered out, and filter cake again filters after distilled water wash, again filters gained filter cake and is dried 3 hours, 3A type zeolite molecular sieve in 95 ℃.
The potassium exchange rate of the 3A type molecular sieve of embodiment 4 preparation can reach 54%, has illustrated that the potassium exchange rate of 3A type zeolite molecular sieve of preparation is high, 3A type zeolite molecular sieve functional.
Each cited raw material of the present invention can be realized the present invention, the bound value of each raw material with and interval value can realize the present invention, at this, do not enumerate embodiment.
Claims (4)
1. kaolin single stage method is prepared the method for 3A type zeolite molecular sieve, it is characterized in that it comprises the steps:
1), after ratio kaolinic calcining: be 1:(0.2～0.6 in mass ratio with KCl by kaolin) mixes, 550～700 ℃ of calcinings 3～5 hours, obtain precursor mixture;
2) preparation of 3A molecular sieve: according to the ratio of precursor mixture and the NaOH aqueous solution, be (15～30g): 100mL, precursor mixture and NaOH aqueous solution is even, be warming up to 60～80 ℃, under strong stirring effect, ageing is 4～6 hours; Be warmed up to again 90～100 ℃, middling speed and stir 3～5 hours, by gained solid product in solution filter, dry after, obtain 3A zeolite molecular sieve;
Described kaolin is the kaolin of taking from when sun area, Al in this kaolin composition
2o
3quality percentage composition be 34.73%, SiO
2quality percentage composition be 37.57%, Fe
2o
3quality percentage composition be 3.22%, TiO
2quality percentage composition be 2.99%, whiteness=41, median size=10 micron.
2. kaolin single stage method according to claim 1 is prepared the method for 3A type zeolite molecular sieve, and the concentration that it is characterized in that the described NaOH aqueous solution is 2～5mol/L.
3. kaolin single stage method according to claim 1 is prepared the method for 3A type zeolite molecular sieve, it is characterized in that described strong stirring is for being greater than 600 revs/min, and it is 300～600 revs/min that middling speed stirs.
4. kaolin single stage method according to claim 1 is prepared the method for 3A type zeolite molecular sieve, it is characterized in that described be dried be 90～100 ℃ dry 2～4 hours.
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| CN104437556B (en) * | 2014-11-03 | 2016-09-07 | 湖南理工学院 | A kind of preparation method of synthesizing n-butyl acetate catalyst |
| CN107055566A (en) * | 2017-05-04 | 2017-08-18 | 明光市飞洲新材料有限公司 | A kind of 3A molecular sieves and its processing technology |
| CN108298554A (en) * | 2018-04-20 | 2018-07-20 | 贵州杰傲建材有限责任公司 | A kind of preparation method of hollow glass zeolite molecular sieve |
| CN109534357A (en) * | 2018-12-27 | 2019-03-29 | 中国神华能源股份有限公司 | A kind of Y type molecular sieve prepared using white clay as raw material and its method |
| CN111248223A (en) * | 2020-03-16 | 2020-06-09 | 王鹏 | Nano disinfectant and preparation method thereof |
| CN115432678B (en) * | 2021-04-21 | 2023-12-29 | 上海联风能源科技有限公司 | Preparation method of high-purity argon |
| CN113184873B (en) * | 2021-04-23 | 2022-12-02 | 内蒙古超牌新材料股份有限公司 | Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof |
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