CN1295150C - Nanometer A type molecular sieve preparation method - Google Patents
Nanometer A type molecular sieve preparation method Download PDFInfo
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- CN1295150C CN1295150C CNB2003101114355A CN200310111435A CN1295150C CN 1295150 C CN1295150 C CN 1295150C CN B2003101114355 A CNB2003101114355 A CN B2003101114355A CN 200310111435 A CN200310111435 A CN 200310111435A CN 1295150 C CN1295150 C CN 1295150C
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Abstract
The present invention relates to a method for preparing a nano A type molecular sieve which includes a 3A molecular sieve, a 4A molecular sieve and a 5A molecular sieve. In the method of the present invention, a silicon source and an aluminum source with the molar ratio of silicon to aluminum of 2 to 1 are used, according to the ratio of the total solid weights of the silicon source and the aluminum source to a NaOH solution of 1:5 to 12, 3 to 7 mol/L of NaOH solution is added into the silicon source and the aluminum source. The method comprises the following steps: the silicon source and the aluminum source added with the NaOH solution are processed by the combined treatment of ultrasonic waves and microwaves for 10 to 150 minutes at a temperature of 90 to 100 DEG C, and then the processed mixture is cooled, filtered, washed to be with a pH value of 7 to 10 and post-processed so that the nano A type molecular sieve is obtained. The combined treatment of the ultrasonic waves and the microwaves are introduced to mainly control the growth of crystals so that the crystals stay in a nano stage and do not grow. Compared with common 4A molecular sieves synthesized with a conventional hydrothermal method, the nano A molecular sieves synthesized with the method of the present invention has the advantages of low energy consumption, high speed, low cost, excellent performance and obvious economic benefit.
Description
Technical field
The present invention relates to a kind of preparation method of A type molecular sieve, especially a kind of preparation method of nano type A molecular sieve.
Background technology
Common 4A zeolite molecular sieve has the surface of good adsorptive power, its calcium exchange capacity is 5 times of tripoly phosphate sodium STPP (STPP), and the antiredeposition performance arranged, can provide deposition surface for grease, dyestuff, can avoid the again deposition of spot on fabric, also have good thermostability and dispersing property simultaneously, free from environmental pollution, to the human body toxicological harmless, non-stimulated.Be to replace the first-selected reagent that STPP makes Ethylene Diaminetetra Acetic Acid in the synthetic detergent.Making detergent builder with the 4A zeolite molecular sieve, is that various countries produce low-phosphorous or non-phosphide detergent, solves phosphorous the exceeding standard of washing composition waste water, causes the effective ways of waters problem of environmental pollutions such as " eutrophication ".In addition, the 4A molecular sieve also can be made chromatogram reagent, selective adsorbent, and siccative, catalyzer and support of the catalyst are widely used in ethene separation in methane, ethane, propane and the coking gas etc.Pass through Ca respectively
2+K
+Ion-exchange again can be by directly synthetic 5A of 4A molecular sieve and 3A molecular sieve.
And nanometer 4A molecular sieve is except that physical and chemical performance that possesses above-mentioned common 4A molecular sieve and purposes, also have small-size effect, quantum size effect, many peculiar, excellent properties such as surface effects and macro quanta tunnel effect, have wider potential application foreground.
Traditional hydrothermal synthesis method can only obtain the A type molecular sieve of micron, submicron usually, and for example particle diameter is the A type molecular sieve of 500nm, can't obtain the zeolite product that particle diameter is 0.1-100nm.
Zhou Zhou, Pan Weixiong etc. relate to the synthetic method of nanometer 4A type molecular sieve in " study on the synthesis of nanometer 4A type molecular sieve " article that " gas chemical industry " 2001-6-4 delivers, this method is the silicon source with the ethyl silicate, aluminum isopropylate is the aluminium source, adopt the collosol and gel supercritical drying to prepare the superfine oxide powder, add appropriate amount of NaOH solution, synthesis of nano 4A type molecular sieve in autoclave, the reaction synthesis process complexity, the required equipment costliness, severe reaction conditions, the industrialization difficulty is big; Long reaction time, energy consumption is big, the cost height.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of simple nano type A molecular sieve, mainly be to utilize ultrasonic wave and the synthetic A type molecular sieve of microwave combined processing, and control crystalline and grow up, can under the condition of gentleness, obtain the nano type A molecular sieve product.
Technical scheme of the present invention is:
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: the ratio of NaOH solution=1: 5-12 adds the NaOH solution of 3-7mol/L, comprise the following steps: the silicon source, the aluminium source adds NaOH solution, and through ultrasonic wave and microwave combined processing 10-150 minute, controlled temperature carried out crystallization at 90-100 ℃, cool off afterwards, filter, wash to PH=7-10, obtain nano type A molecular sieve through aftertreatment.
Can only produce the technology of A type molecular sieve of micron, submicron with the traditional water thermal precipitator method and compare, mainly introduce ultrasonic wave and microwave combined processing controls crystal is grown up.
Utilize chemical precipitation prepared in reaction nano material, key is by the control reaction conditions, makes the easy formation of target product crystal but be difficult to grow up.Liquid phase micro-wave dielectric heating method has been widely used in chemical field, comprise the molecular sieve preparation, radiopharmaceutic synthetic, synthetic and the insertion reaction of inorganic complexes, organic reaction under the drying conditions, the sample pretreatment in plasma chemistry and the analytical chemistry etc., but micro-wave dielectric heating is few at the research report of nano material aspect synthetic, and lack systematic research, find only to adopt microwave technology can only obtain the common A type molecular sieve of submicron order through the experiment contrast.
Do not find that both at home and abroad ultrasonic technology is used for nano type A molecular sieve synthetic report yet.Our experiments show that simple use ultrasonic wave still can't obtain nano type A molecular sieve.
The present invention's data contrasts and screening by experiment finds that ultrasonic wave and microwave combined processing just can obtain nano level A type molecular sieve.
The present invention introduces ultrasonic technology, by getting over sound wave, the method that microwave combines, successful nanometer 4A, 5A, the 3A molecular sieve of having synthesized fast.
More excellent technical scheme has following:
In ultrasonic wave and microwave combined treating processes, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, and power 300-1500 watt, the time of combination treatment is 10-150 minute.The time of preferred combination treatment is 30-60 minute.
The frequency that studies show that ultrasonic wave and microwave is in very wide scope, as long as unite use, no matter sequencing can obtain nano level A type molecular sieve." the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt but exceed; Microwave technology parameter frequency is 880-2500MHz " scope, the nano-scale product yield descends.In preferred parameter area, the nano-scale product yield is up to more than 90%.
Silicon source, aluminium source are natural kaolin, and for example Jiangxi kaolin that produce in Jing Dezhen gets through pulverizing 600-900 ℃ of calcining 2-6 hour.
Silicon source, aluminium source are that sodium silicate, aluminic acid are received.
Other silicon source, aluminium source can obtain nano level A type molecular sieve equally through the inventive method.
NaOH mother liquor in the washing procedure is recyclable, returns former technology.
Postprocessing working procedures difference of the present invention can obtain dissimilar A type molecular sieves:
Postprocessing working procedures is dry under 100-120 ℃ of condition, time 30-240 minute, gets the 4A product.
Postprocessing working procedures is: the solid behind the washing and filtering is added K
+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt; The time of combination treatment is 10-60 minute, carries out K under 30-60 ℃ of temperature
+Ion-exchange refilters afterwards, washing, and drying time 30-240 minute, obtains the 3A product.
Postprocessing working procedures is: the solid behind the washing and filtering is added Ca
2+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt; The time of combination treatment is 10-60 minute, carries out Ca under 30-60 ℃ of temperature
2+Ion-exchange refilters afterwards, washing, and drying time 30-240 minute, obtains the 5A product.
The influence of step before and after ultrasonic wave of the present invention and microwave combined processing are not subjected to, the coupling of ultrasonic wave and microwave can also be used for pre-treatment, be specially and increase ultrasonic wave and microwave combined pre-treatment when the aluminium source adds NaOH solution, uniting the pretreated time is 10-150 minute, and controlled temperature is at 50-70 ℃; The ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt.
Be controlled at the total time of ultrasonic wave and microwave combined processing 10-150 minute, and can segmentation carry out.
The invention has the advantages that: the method for the synthetic nanometer 4A of institute molecular sieve of the present invention is lower than the method energy consumption of the synthetic common 4A molecular sieve of conventional hydrothermal method, speed is fast, with low cost, excellent performance, and remarkable economic efficiency is arranged.
The present invention is with kaolin, also available general chemistry reagent water glass and sodium aluminate are silicon source and aluminium source, with the alkali effect, for traditional hydrothermal method and common microwave synthesis method, synthesize even particle size distribution with the dielectric heating technology generation of ultrasonic-microwave, particle diameter is about the nanometer 4A molecular sieve of 80nm.This nanometer 4A molecular sieve passes through K respectively under the condition of ultrasonic wave control size
+, Ca
2+Nanometer 3A and nanometer 5A molecular sieve have further been synthesized in ion-exchange.
Embodiment
The granular size of the product of following examples gained gets by the transmission electron microscope measurement; 3A, 4A, definite employing X-ray diffraction crystalline phase of 5A crystal formation molecular sieve is analyzed and is got, and its judgment criteria is seen " zeolite molecular sieve " the 332nd page of Science Press's publication in 1978.
Embodiment 1
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: NaOH solution=ratio of 1: 8 adds the NaOH solution of 5mol/L, comprise the following steps: the silicon source, the aluminium source added NaOH solution, through ultrasonic wave and microwave combined processing 100 minutes, controlled temperature carries out crystallization at 98 ℃, afterwards cold filtration, wash to PH=7-10, NaOH mother liquor in the washing procedure reclaims, and returns former technology and utilizes.
Obtain nano type A molecular sieve through aftertreatment.
In ultrasonic wave and microwave combined treating processes, the ultrasonic technology parameter is frequency 50KHz, 1000 watts of power; Microwave technology parameter frequency is 2000MHz, 1000 watts of power.
Silicon source, aluminium source specifically are chosen as sodium silicate, aluminic acid is received.
Postprocessing working procedures is dry under 110 ℃ of conditions, 40 minutes time, gets the 4A product.All the other are with embodiment 1.
By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 4A product, and granular size is 80nm.
Embodiment 2
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: NaOH solution=ratio of 1: 8 adds the NaOH solution of 10mol/L, comprise the following steps: the silicon source, the aluminium source added NaOH solution, through ultrasonic wave and microwave combined processing 100 minutes, controlled temperature carries out crystallization at 98 ℃, cool off afterwards, filter, wash to PH=7-10, the NaOH mother liquor in the washing procedure reclaims, and returns former technology and utilizes.
All the other are with embodiment 1.By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 4A product, and can only obtain granular size is the 4A product of 140nm.NaOH strength of solution height is unfavorable for forming short grained nanometer 4A product.
Embodiment 3
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is produced kaolin by 2: 1 Jing Dezhen, Jiangxi, gets through pulverizing 800 ℃ of calcinings 5 hours.The silicon source increases ultrasonic wave and microwave combined pre-treatment when the aluminium source adds NaOH solution, uniting the pretreated time is 80 minutes, and controlled temperature is at 60 ℃; The ultrasonic technology parameter is frequency 60KHz, 1500 watts of power; Microwave technology parameter frequency is 1000MHz, 400 watts of power.
Through ultrasonic wave and microwave combined pre-treatment, crystallization temperature does not need too high, and 90 ℃ of states just can obtain nano type A molecular sieve down.All the other are with embodiment 1.
Embodiment 4
Postprocessing working procedures is: the solid behind the washing and filtering is added K
+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 80KHz, 1000 watts of power; Microwave technology parameter frequency is 1500MHz, 500 watts of power; The time of combination treatment is 50 minutes, carries out K under 35 ℃ of temperature
+Ion-exchange refilters afterwards, washing, and drying, 140 minutes time, all the other obtain the 3A product with embodiment 1.By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 3A product, and granular size is 80nm.
Embodiment 5
Postprocessing working procedures is: the solid behind the washing and filtering is added Ca
2+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 70KHz, 1000 watts of power; Microwave technology parameter frequency is 1800MHz, 600 watts of power; The time of combination treatment is 20 minutes, carries out Ca under 45 ℃ of temperature
2+Ion-exchange refilters afterwards, washing, and drying, 120 minutes time, all the other obtain the 5A product with embodiment 1.By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 5A product, and granular size is 80nm.
Embodiment 6
One group of correlation data:
(1) the ultrasonic technology parameter is frequency 10KHz, 100 watts of power; Microwave technology parameter frequency is 1700MHz, 200 watts of power.All the other can only obtain the 4A type molecular sieve of 220-250nm with embodiment 1.
(2) the ultrasonic technology parameter is frequency 40KHz, 90 watts of power; Microwave technology parameter frequency is 2500MHz, 500 watts of power.All the other can only obtain the 4A type molecular sieve of 120-130nm with embodiment 1.
(3) the ultrasonic technology parameter is frequency 60KHz, 200 watts of power; Microwave technology parameter frequency is 700MHz, 1000 watts of power.All the other can only obtain the 4A type molecular sieve of 180-230nm with embodiment 1.
(4) the ultrasonic technology parameter is frequency 80KHz, 200 watts of power; Microwave technology parameter frequency is 1700MHz, 200 watts of power.All the other can only obtain the 3A type molecular sieve of 185-235nm with embodiment 4.
(5) the ultrasonic technology parameter is frequency 300KHz, 200 watts of power; Microwave technology parameter frequency is 2200MHz, 600 watts of power.All the other can only obtain the 3A type molecular sieve of 160-190nm with embodiment 4.
(6) the ultrasonic technology parameter is frequency 35KHz, 2200 watts of power; Microwave technology parameter frequency is 1700MHz, 600 watts of power.All the other can only obtain the 5A type molecular sieve of 180-230nm with embodiment 5.
(7) the ultrasonic technology parameter is frequency 60KHz, 300 watts of power; Microwave technology parameter frequency is 2600MHz, 700 watts of power.All the other can only obtain the 5A type molecular sieve of 150-170nm with embodiment 5.
(8) the ultrasonic technology parameter is frequency 20KHz, 90 watts of power; Microwave technology parameter frequency is 1700MHz, 1600 watts of power.All the other can only obtain the 4A type molecular sieve of 320-350nm with embodiment 1.
(9) the ultrasonic technology parameter is frequency 30KHz, 50 watts of power; Microwave technology parameter frequency is 600MHz, 1000 watts of power.All the other can only obtain the 4A type molecular sieve of 420-450nm with embodiment 1.
(10) the ultrasonic technology parameter is frequency 10KHz, 80 watts of power; Microwave technology parameter frequency is 1700MHz, 800 watts of power.All the other can only obtain the 4A type molecular sieve of 310-330nm with embodiment 1.
(11) the ultrasonic technology parameter is frequency 20KHz, 100 watts of power; Microwave technology parameter frequency is 880MHz, 300 watts of power.All the other obtain the 4A type molecular sieve of 80nm with embodiment 1.
(12) the ultrasonic technology parameter is frequency 100KHz, 2000 watts of power; Microwave technology parameter frequency is 2500MHz, 1500 watts of power.All the other obtain the 4A type molecular sieve of 85nm with embodiment 1.
(13) the ultrasonic technology parameter is frequency 20KHz, 100 watts of power; Microwave technology parameter frequency is 880MHz, 300 watts of power.All the other obtain the 3A type molecular sieve of 80nm with embodiment 4.
(14) the ultrasonic technology parameter is frequency 100KHz, 2000 watts of power; Microwave technology parameter frequency is 2500MHz, 1500 watts of power.All the other obtain the 3A type molecular sieve of 85nm with embodiment 4.
(15) the ultrasonic technology parameter is frequency 60KHz, 600 watts of power; Microwave technology parameter frequency is 1200MHz, 1200 watts of power.All the other obtain the 3A type molecular sieve of 75nm with embodiment 4.
(16) the ultrasonic technology parameter is frequency 20KHz, 100 watts of power; Microwave technology parameter frequency is 880MHz, 300 watts of power.All the other obtain the 5A type molecular sieve of 80nm with embodiment 5.
(17) the ultrasonic technology parameter is frequency 100KHz, 2000 watts of power; Microwave technology parameter frequency is 2500MHz, 1500 watts of power.All the other obtain the 5A type molecular sieve of 85nm with embodiment 5.
(18) the ultrasonic technology parameter is frequency 90KHz, 1800 watts of power; Microwave technology parameter frequency is 900MHz, 600 watts of power.All the other obtain the 5A type molecular sieve of 78nm with embodiment 5.
Embodiment 7
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: the ratio of NaOH solution=1: 5-12 adds the NaOH solution of 3-7mol/L, comprise the following steps: the silicon source, the aluminium source added NaOH solution, through ultrasonic wave and microwave combined processing 10-150 minute, controlled temperature carries out crystallization at 90-100 ℃, cooling afterwards refilters, and washs to PH=7-10, obtains nano type A molecular sieve through aftertreatment.
In ultrasonic wave and microwave combined treating processes, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz.Power 300-1500 watt.All the other are with embodiment 1.
Embodiment 8
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is produced kaolin by 2: 1 Jing Dezhen, Jiangxi, gets through pulverizing 600-900 ℃ of calcining 2-6 hour.The silicon source increases ultrasonic wave and microwave combined pre-treatment when the aluminium source adds NaOH solution, uniting the pretreated time is 10-150 minute, and controlled temperature is at 50-70 ℃; The ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt.Through ultrasonic wave and microwave combined pre-treatment, crystallization temperature does not need too high, and 90 ℃ of states just can obtain nano type A molecular sieve down.
All the other are with embodiment 1.
Embodiment 9
A kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is produced kaolin by 2: 1 Jing Dezhen, Jiangxi, gets through pulverizing 750 ℃ of calcinings 5 hours.The silicon source increases ultrasonic wave and microwave combined pre-treatment when the aluminium source adds NaOH solution, uniting the pretreated time is 10-150 minute; Controlled temperature is at 60 ℃; The ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt.Through ultrasonic wave and microwave combined pre-treatment, can obtain nano type A molecular sieve.All the other are with embodiment 1.
Embodiment 10
Postprocessing working procedures is: the solid behind the washing and filtering is added K
+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt; The time of combination treatment is 10-60 minute, carries out K under 30-60 ℃ of temperature
+Ion-exchange refilters afterwards, washing, and drying, time 30-240 minute, all the other obtained the 3A product with embodiment 1.
By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 3A product, and granular size is 70-85nm.
Embodiment 11
Postprocessing working procedures is: the solid behind the washing and filtering is added Ca
2+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt; The time of combination treatment is 10-60 minute, carries out Ca under 30-60 ℃ of temperature
2+Ion-exchange refilters afterwards, washing, and drying, time 30-240 minute, all the other obtained the 5A product with embodiment 1.By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 5A product, and granular size is 70-85nm.
The preparation method of 12 1 kinds of nano type A molecular sieves of embodiment, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: NaOH solution=ratio of 1: 5 adds the NaOH solution of 3-7mol/L, comprise the following steps: the silicon source, the aluminium source added NaOH solution, through ultrasonic wave and microwave combined processing 150 minutes, controlled temperature is at 90 ℃, cooling afterwards refilters, and washs to PH=7, obtains the 70nm nano type A molecular sieve through aftertreatment.
In ultrasonic wave and microwave combined treating processes, the ultrasonic technology parameter is frequency 70KHz, 1070 watts of power; Microwave technology parameter frequency is 900MHz.300 watts of power.All the other are with embodiment 1.
The preparation method of 13 1 kinds of nano type A molecular sieves of embodiment, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: NaOH solution=ratio of 1: 12 adds the NaOH solution of 3-7mol/L, comprise the following steps: the silicon source, the aluminium source added NaOH solution, through ultrasonic wave and microwave combined processing 10 minutes, controlled temperature is at 100 ℃, cooling afterwards refilters, and washs to PH=10, obtains the 85nm nano type A molecular sieve through aftertreatment.In ultrasonic wave and microwave combined treating processes, the ultrasonic technology parameter is frequency 80KHz, 1300 watts of power; Microwave technology parameter frequency is 1500MHz.800 watts of power.All the other are with embodiment 1.
Combination treatment has only the yield of 10 minutes gained 85nm nano type A molecular sieves not high, has only the particle of 63% A type molecular sieve to reach 85nm.
Prolonging the combination treatment time can improve yield, and for example 100 minutes yield is that 92%, 120 minute yield is that 95%, 150 minute yield is 99.45%.
The preparation method of 14 1 kinds of nano type A molecular sieves of embodiment, select silicon: al mole ratio is produced kaolin by 2: 1 Jing Dezhen, Jiangxi, gets through pulverizing 600 ℃ of calcinings 6 hours.The silicon source increases ultrasonic wave and microwave combined pre-treatment when the aluminium source adds NaOH solution, uniting the pretreated time is 10 minutes; All the other are with embodiment 1.
The preparation method of 15 1 kinds of nano type A molecular sieves of embodiment, select silicon: al mole ratio is produced kaolin by 2: 1 Jing Dezhen, Jiangxi, gets through pulverizing 900 ℃ of calcinings 2 hours.The silicon source increases ultrasonic wave and microwave combined pre-treatment when the aluminium source adds NaOH solution, uniting the pretreated time is 150 minutes; All the other are with embodiment 1.
Embodiment 16 postprocessing working procedures are: the solid behind the washing and filtering is added K
+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20KHz, 100 watts of power; Microwave technology parameter frequency is 880MHz, 300 watts of power; The time of combination treatment is 60 minutes, carries out K under 3 ℃ of temperature
+Ion-exchange refilters afterwards, washing, and drying, 30 minutes time, all the other obtain the 3A product with embodiment 1.
By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 3A product, and granular size is 80nm.
Embodiment 17 postprocessing working procedures are: the solid behind the washing and filtering is added K
+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 100KHz, 2000 watts of power; Microwave technology parameter frequency is 2500MHz, 1500 watts of power; The time of combination treatment is 10 minutes, carries out K under 60 ℃ of temperature
+Ion-exchange refilters afterwards, washing, and drying, 240 minutes time, all the other obtain the 3A product with embodiment 1.
By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 3A product, and granular size is 80nm.
Embodiment 18 postprocessing working procedures are: the solid behind the washing and filtering is added Ca
2+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20KHz, 100 watts of power; Microwave technology parameter frequency is 880MHz, 300 watts of power; The time of combination treatment is 10 minutes, carries out Ca under 30 ℃ of temperature
2+Ion-exchange refilters afterwards, washing, and drying, 30 minutes time, all the other obtain the 5A product with embodiment 1.By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 5A product, and granular size is 80nm.
Embodiment 19 postprocessing working procedures are: the solid behind the washing and filtering is added Ca
2+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 100KHz, 2000 watts of power; Microwave technology parameter frequency is 2500MHz, 1500 watts of power; The time of combination treatment is 60 minutes, carries out Ca under 60 ℃ of temperature
2+Ion-exchange refilters afterwards, washing, and drying, 240 minutes time, all the other obtain the 5A product with embodiment 1.By infrared spectra detection and X-ray diffraction crystalline phase analytical proof is the 5A product, and granular size is 80nm.
Claims (10)
1, a kind of preparation method of nano type A molecular sieve, select silicon: al mole ratio is 2: 1 silicon source and aluminium source, and in the total solid weight in aluminium source, silicon source: the ratio of NaOH solution=1: 5-12 adds the NaOH solution of 3-7mol/L, it is characterized in that comprising the following steps: the silicon source, the aluminium source adds NaOH solution, through ultrasonic wave and microwave combined processing 10-150 minute, controlled temperature carries out crystallization at 90-100 ℃, cool off afterwards, filter, wash to PH=7-10, obtain nano type A molecular sieve through aftertreatment.
2, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: in ultrasonic wave and microwave combined treating processes, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt.
3, the preparation method of a kind of nano type A molecular sieve according to claim 1, it is characterized in that: the silicon source, when adding NaOH solution, the aluminium source increases ultrasonic wave and microwave combined pre-treatment, uniting the pretreated time is 10-150 minute, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt.
4, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: the time of combination treatment is 30-60 minute.
5, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: silicon source, aluminium source are natural kaolin, get through pulverizing 600-900 ℃ of calcining 2-6 hour.
6, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: silicon source, aluminium source are that sodium silicate, aluminic acid are received.
7, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: the mother liquor in the washing procedure reclaims.
8, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: postprocessing working procedures is dry under 100-120 ℃ of condition, time 30-240 minute, gets the 4A product.
9, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: postprocessing working procedures is: the solid behind the washing and filtering is added K
+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt; The time of combination treatment is 10-60 minute, carries out K under 30-60 ℃ of temperature
+Ion-exchange refilters afterwards, washing, and drying time 30-240 minute, obtains the 3A product.
10, the preparation method of a kind of nano type A molecular sieve according to claim 1 is characterized in that: postprocessing working procedures is: the solid behind the washing and filtering is added Ca
2+, through ultrasonic wave and microwave combined processing, the ultrasonic technology parameter is frequency 20-100KHz, power 100-2000 watt; Microwave technology parameter frequency is 880-2500MHz, power 300-1500 watt; The time of combination treatment is 10-60 minute, carries out Ca under 30-60 ℃ of temperature
2+Ion-exchange refilters afterwards, washing, and drying time 30-240 minute, obtains the 5A product.
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| CN100443616C (en) * | 2007-03-23 | 2008-12-17 | 中南大学 | Fast microwave crystallizing process for preparing nanometer crystalline iron-base soft magnetic alloy |
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