CN104030313A - Method of synthesizing submicron T-type molecular sieve - Google Patents

Method of synthesizing submicron T-type molecular sieve Download PDF

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CN104030313A
CN104030313A CN201410224944.7A CN201410224944A CN104030313A CN 104030313 A CN104030313 A CN 104030313A CN 201410224944 A CN201410224944 A CN 201410224944A CN 104030313 A CN104030313 A CN 104030313A
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molecular sieve
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submicron
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CN104030313B (en
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臧毅华
郑秋红
盛春光
刘宗园
徐国雄
田初明
姜雨省
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CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a method of synthesizing a submicron T-type molecular sieve. The method comprises the following steps: sequentially putting NaOH and KOH in deionized water, stirring till the solution is clarified, and adding a template TMAOH to stir till the solution is clarified after being cooled to room temperature to obtain a solution A; adding an aluminum source into the solution A to be stirred till the solution is clarified to obtain a solution B; slowly adding a silicon source into the solution B, severely stirring for 2-6 hours to obtain a solution C, wherein the molar ratio of matters in the solution C is as follows: SiO2:Al2O3:Na2O:K2O:H2O:TMAOH=1:(0.05-0.2):(0.2-0.3):(0.08-0.15):(10-30):(0.1-0.3), and putting the solution C in a reaction kettle to be sealed; putting the reaction kettle in a water bath at 60-90 DEG C, crystallizing for 12-14 hours by an ultrasonic wave with the power of 1500-3000W, washing, centrifuging, drying and calcining to finally obtain the submicron T-type molecular sieve. The method provided by the invention shortens the aging time and the crystallizing time of a synthesized liquid to a great extent and is simple in equipment, simple to operate and suitable for industrialized production on a large scale.

Description

A kind of method of synthesizing submicron type T molecular sieve
Technical field
The present invention relates to molecular sieve field, relate in particular to a kind of method of the fast synthetic uniform submicron type T molecular sieve of particle diameter.
Background technology
T-shaped zeolite molecular sieve belongs to symbiosis crystal, and it is by erionite (ERI) and offretite (OFF) intergrowth and form, and both structures are quite similar, and skeleton is all made up of Can-crinite cage and six prisms.Erionite has the duct perpendicular to one dimension 8 rings of c-axis, and it is of a size of 0.36nm × 0.51nm.Offretite has two-dimentional regular pore canal, and the main pore size that is parallel to c-axis direction is 0.67nm × 0.68nm; Another secondary port is perpendicular to c-axis direction, and pore size is 0.36nm × 0.49nm.T-shaped zeolite molecular sieve belongs to pore zeolite, and molecule is had to the very strong type of selecting selectivity.Be C in the reaction of shape selective catalysis dewaxing pour point depression, methanol conversion 2-5in the reaction of alkene, all present high selectivity and catalytic activity.In addition, T-shaped zeolite molecular sieve also has good acid acceptance, selectively some sour gas of fractionation by adsorption; The silica alumina ratio of T-shaped zeolite molecular sieve is 3～4, and wetting ability is only second to NaA type molecular sieve, and absorption aperture is in 0.5nm left and right, so the favourable absorption separating agent of the processes such as the gas drying of can be used as and purification, oil product dewaxing.
Existing document investigate emphatically the crystallizing range of type T molecular sieve and synthesis condition as added template or crystal seed, synthesis temperature, colloidal sol forms the impact on crystallization rate.Donald (US2950952,1960) adopts 0.49Na 2o:0.71K 2o:Al 2o 3: 6.6SiO 2: 6.3H 2o colloidal sol proportioning, at 100～150 DEG C, crystallization 1～5d synthesizes type T molecular sieve.The people such as Wang Xingqiao (SCI, 1984,5 (1): 83) at lower silica alumina ratio Na 2o+K 2o/SiO 2under=0.3～0.33 condition, synthesize the type T molecular sieve that offretite occupies the majority.Konado (Process for producing a T-type zeolite membrane on a porous support for separating a mixture[P] .2000.) etc. is at high silica alumina ratio SiO 2/ Al2O 3=112 and the condition of lower basicity under synthesize the type T molecular sieve of offretite/erionite=0.3/0.7 ratio.Zhang Zhi states etc. (modern chemical industry, 2007,27,269～273) select industrial raw material, synthesize the type T molecular sieve that degree of crystallinity is high in silica alumina ratio is 16～32 scopes.Zhourong flies to wait (Chinese Journal of Inorganic Chemistry, 2009,25 (1): 104-111) to study the crystallisation process of type T molecular sieve in microwave field, and the generated time that uses microwave to synthesize type T molecular sieve is compared ortho-water thermal synthesis and reduced 80%.
In above-mentioned existing report, prepare type T molecular sieve by traditional Hydrothermal Synthesis, digestion time (16～24h) that need to be longer and crystallization time (2～7d), the uniform crystal of more difficult acquisition particle diameter below 1 μ m; The synthetic T molecular sieve of microwave can shorten crystallization time greatly, heats too fast meeting and causes thermal runaway, and specimen temperature is difficult to accurate control, is difficult to maintain definite temperature, and equipment is comparatively expensive, is unfavorable for suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is to overcome the existing deficiency of existing type T molecular sieve synthetic method, a kind of method of ultrasonic crystallization method synthesizing submicron type T molecular sieve is provided, the method is utilized hyperacoustic cavatition and machinery concussion, the second-order effects such as emulsification diffusion, increase the speed of reaction of synthetic lyosol system, with shorter digestion time be (2～6h), and (12～24h) prepares the meter T-shaped zeolite molecular sieve of the uniform sub-micro of particle diameter in the short period of time, have simple to operate, generated time is short, it is even that the type T molecular sieve of preparation has particle diameter, degree of crystallinity high.
The present invention is achieved by the following technical programs:
A method for synthesizing submicron type T molecular sieve, is characterized in that, comprises the steps:
1) NaOH, KOH are put into deionized water for stirring to solution successively and clarify, to be cooledly add template Tetramethylammonium hydroxide to be stirred to solution clarification to room temperature, obtain solution A;
2) aluminium source is added in solution A and stirred to clarify, obtain solution B;
3) silicon source is slowly added in solution B, vigorous stirring 2～6h, obtains solution C, and in described solution C, the mol ratio of material is SiO 2: Al 2o 3: Na 2o:K 2o:H 2o:TMAOH=1:0.05～0.2:0.2～0.3:0.08～0.15:10～30:0.1～0.3, puts into reactor by the solution C preparing, sealing;
4) reactor after sealing is put into 60～90 DEG C of water-baths, ultrasonic crystallization 12～24h, the product obtaining through washing, centrifugal, dryly obtain the former powder of type T molecular sieve, wherein ultrasonic power is 1500w～3000W;
5) former type T molecular sieve powder is put into retort furnace calcining and removed template, obtain submicron type T molecular sieve after cooling.
Described submicron type T molecular sieve particle diameter is 600nm～900nm.
Described silicon source is one or more in silicon sol, white carbon black, powder silica gel, water glass.
Described aluminium source is one or more in aluminum isopropylate, sodium metaaluminate, sodium aluminate, aluminum oxide.
The inventive method is compared with existing T Zeolite synthesis method, and its beneficial effect is; The inventive method adopts ultrasonic wave to carry out the synthetic of T-shaped zeolite molecular sieve, promotes hydrothermal crystallizing reaction by cavatition, has shortened the reaction times; The synthetic liquid water content of type T molecular sieve is very low simultaneously, very thickness, in preparation process, relatively high power ultrasonic wave also has many second-order effects, as the digestion time of colloidal sol the one side such as is spread, smashes and shortened in machinery concussion, emulsification, make on the other hand stock liquid can not reunite, lump, disperseed fully, be more conducive to the synthetic uniform submicron type T molecular sieve of particle diameter under sol system; In addition, by the inventive method synthesizing submicron T molecular sieve, also have equipment simple, operate simple and easyly, be applicable to the advantage of large-scale industrial production.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the synthetic submicron type T molecular sieve of the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the synthetic submicron type T molecular sieve of the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of the synthetic submicron type T molecular sieve of the embodiment of the present invention 2.
Embodiment
Embodiment 1
Weighing sodium hydroxide 10.3g, potassium hydroxide 8.96g, adds in 105.5g deionized water, dissolves after cooling and adds 36.5g Tetramethylammonium hydroxide (content 25wt%), 10.2g sodium metaaluminate.Treat that colloidal sol stirs clarification and drips 196.6g silicon sol (30wt%) again, vigorous stirring 4h, put into water-bath ultrasonic wave (power is 2000W) the crystallization 24h of 85 DEG C, obtain crystallization product through washing, centrifugal, dry after, putting into retort furnace rises at 550 DEG C and calcines after 6h with 1 DEG C/min speed, obtain molecular sieve, turn out to be type T molecular sieve (as shown in Figure 1) through X-ray diffraction, show through electron-microscope scanning result, obtain the uniform submicron type T molecular sieve of particle diameter (as shown in Figure 2), particle size range is 750nm～800nm.
Embodiment 2
Weighing sodium hydroxide 12.1g, potassium hydroxide 11.2g, adds in 217.2g deionized water, dissolves after cooling and adds 54.7g Tetramethylammonium hydroxide (content 25wt%), 16.3g sodium metaaluminate.Treat that colloidal sol stirs clarification and drips 196.6g silicon sol (30wt%) again, vigorous stirring 4h, put into water-bath ultrasonic wave (power is 3000W) the crystallization 16h of 75 DEG C, obtain crystallization product through washing, centrifugal, dry, calcine and obtain object product, turn out to be type T molecular sieve through X-ray diffraction, show through electron-microscope scanning result, obtain the uniform submicron type T molecular sieve of particle diameter (as shown in Figure 3), particle size range is 650nm～750nm.
Embodiment 3
Weighing sodium hydroxide 3.8g, potassium hydroxide 10.1g, adds in 237.8g deionized water, dissolves after cooling and adds 72.9g Tetramethylammonium hydroxide (content 30wt%), 32.6g sodium metaaluminate.Treat that colloidal sol stirs clarification and drips 196.6g silicon sol (30wt%) again, vigorous stirring 6h, put into water-bath ultrasonic wave (power is 2400W) the crystallization 12h of 80 DEG C, obtain product through washing, centrifugal, dry, calcine that to obtain particle diameter be 700nm～850nm, the uniform submicron type T molecular sieve of particle diameter.
Embodiment 4
Weighing sodium hydroxide 13.2g, potassium hydroxide 11.2g, adds in 333.4g deionized water, dissolves after cooling and adds 91.2g Tetramethylammonium hydroxide (content 30wt%), 20.4g sodium metaaluminate.Treat that colloidal sol stirs clarification and drips 196.6g silicon sol (30wt%) again, vigorous stirring 6h, put into water-bath ultrasonic wave (power is 1800W) the crystallization 12h of 60 DEG C, obtain product through washing, centrifugal, dry, calcine that to obtain particle diameter be 800nm～900nm, the uniform submicron type T molecular sieve of particle diameter.
Embodiment 5
Synthesis condition is as embodiment 1, and change ultrasonic power is 1700W, and obtaining type T molecular sieve particle diameter is 800m～900nm.
Embodiment 6
Synthesis condition is as embodiment 1, and change ultrasonic power is 1500W, and obtaining type T molecular sieve particle diameter is 800nm～1000nm.

Claims (4)

1. a method for synthesizing submicron type T molecular sieve, its preparation method is as follows:
1) NaOH, KOH are put into deionized water for stirring to solution successively and clarify, to be cooledly add template Tetramethylammonium hydroxide to be stirred to solution clarification to room temperature, obtain solution A;
2) aluminium source is added in solution A and stirred to clarify, obtain solution B;
3) silicon source is slowly added in solution B, vigorous stirring 2～6h, obtains solution C, and in described solution C, the mol ratio of material is SiO 2: Al 2o 3: Na 2o:K 2o:H 2o:TMAOH=1:0.05～0.2:0.2～0.3:0.08～0.15:10～30:0.1～0.3, puts into reactor by the solution C preparing subsequently, sealing;
4) reactor after sealing is put into 60～90 DEG C of water-baths, ultrasonic crystallization 12～24h, the product obtaining is through washing, centrifugal, the dry former powder of type T molecular sieve that obtains; Wherein said ultrasonic power is 1500w～3000W;
5) former type T molecular sieve powder is put into retort furnace calcining and removed template, obtain submicron type T molecular sieve after cooling.
2. method according to claim 1, is characterized in that, wherein said submicron type T molecular sieve particle diameter is 600nm～900nm.
3. method according to claim 1, is characterized in that step 2) described in aluminium source be one or more in aluminum isopropylate, sodium metaaluminate, sodium aluminate, aluminum oxide.
4. method according to claim 1, is characterized in that step 3) described in silicon source be one or more in silicon sol, white carbon black, powder silica gel, water glass.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN109133089A (en) * 2018-10-10 2019-01-04 江西师范大学 A kind of synthetic method of nanoscale type T molecular sieve
CN109574034A (en) * 2019-01-15 2019-04-05 江西师范大学 A kind of method of the ultra-fine ERI type molecular sieve of ultrasonic wave added rapid synthesis
CN115974098A (en) * 2023-02-15 2023-04-18 大连理工大学 Preparation method of ultra-small nano T-type zeolite molecular sieve

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CN101177280A (en) * 2007-11-06 2008-05-14 广东工业大学 Method for quickly synthesizing nano X-type molecular sieve by low-temperature ultrasonic crystallization process

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109133089A (en) * 2018-10-10 2019-01-04 江西师范大学 A kind of synthetic method of nanoscale type T molecular sieve
CN109574034A (en) * 2019-01-15 2019-04-05 江西师范大学 A kind of method of the ultra-fine ERI type molecular sieve of ultrasonic wave added rapid synthesis
CN115974098A (en) * 2023-02-15 2023-04-18 大连理工大学 Preparation method of ultra-small nano T-type zeolite molecular sieve

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