CN103435062A - Rapid preparation method for A-type nano zeolite molecular sieve - Google Patents
Rapid preparation method for A-type nano zeolite molecular sieve Download PDFInfo
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- CN103435062A CN103435062A CN2013103635844A CN201310363584A CN103435062A CN 103435062 A CN103435062 A CN 103435062A CN 2013103635844 A CN2013103635844 A CN 2013103635844A CN 201310363584 A CN201310363584 A CN 201310363584A CN 103435062 A CN103435062 A CN 103435062A
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910021536 Zeolite Inorganic materials 0.000 title abstract description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title abstract description 19
- 239000010457 zeolite Substances 0.000 title abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000004411 aluminium Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 230000001186 cumulative effect Effects 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001679 gibbsite Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 abstract description 44
- 239000002245 particle Substances 0.000 abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 238000005119 centrifugation Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000011049 filling Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- -1 silicate ion Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010198 maturation time Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000005477 standard model Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a rapid preparation method for an A-type nano zeolite molecular sieve. The rapid preparation method comprises the following steps: adding a certain amount of aluminium source into deionized water, and then adding sodium hydroxide and an organic template agent of tetramethyl ammonium hydroxide to the deionized water; adding ethyl orthosilicate being subjected to catalytic hydrolysis of an acid solution with a pH value of 1-5 into the solution; stirring and aging the mixed solution for 1-10 h at the room temperature, then filling the mixed solution into a hydro-thermal synthesis kettle for crystallizing for 3-15 h at the temperature of 70-120 DEG C, and obtaining the A-type nano zeolite molecular sieve after the steps of ultrasonic treatment, centrifugation, drying, calcination, and the like. According to the invention, the preparation method is simple, the reaction time is greatly shortened, the particle diameter of the obtained A-type nano zeolite molecular sieve can reach below 100 nm, and the particle diameter distribution is uniform.
Description
Technical field
The invention belongs to the molecular sieve of Nano zeolite preparation field, be specifically related to the method for synthesizing nano type A zeolite molecular sieve in a kind of short period.
Background technology
With regard to solid state physics, when the yardstick of particle is being decreased to below 100nm, enter to the category of nano material, now will show the not available small-size effect of conventional yardstick particle and surface effects.With respect to the molecular sieve of stock size, the nanoscale molecular sieve has larger outer surface area and more outside surface active centre, thereby has more activated adsorption position to come out, and is conducive to the realization of molecular sieve catalytic and absorption property.Synthetic nanoscale molecular sieve commonly used has two kinds of methods at present: the one, increase the low temperature maturation time; The 2nd, reduce crystallization temperature.These two kinds of approach all unavoidably cause synthesis cycle longer, and practical application is brought to much inconvenience.
For A type zeolite molecular sieve synthetic in strongly basic medium, the polymeric form of silicate ion has very important impact to nucleation process.The sial acid group that the polymerization degree is too high or silicate are difficult to replace positively charged ion water molecules on every side, and this has just caused its nucleation time inductive phase longer, finally causes synthesis cycle longer.Mintova etc. (Science, 1999,283:958-960) take silicon sol (HS-30, PH=10) as the silicon source, the A type zeolite molecular sieve that successfully to have synthesized particle diameter be 200-400nm, but it needs at room temperature ageing 10 days, 80
oc crystallization 1-2 days.Zhu etc. (Chem. Mater, 1998,10:1483-1486) tetraethoxy is added in alkaline mixed solution, by adjusting each material rate, the A type zeolite molecular sieve that to prepare particle diameter be 100-900nm, minimum grain size can reach 100-200nm, and synthesis cycle reaches 11-18 days.Wherein causing the longer principal element of synthesis cycle is that the nucleation induction time of molecular sieve is partially long.
Summary of the invention
The object of the invention is to solve the long problem of nano type A zeolite molecular sieve preparation cycle, and the method for a kind of Simple fast synthesizing nano type A zeolite molecular sieve proposed.
Use the catalyzer of acid as teos hydrolysis in building-up process, reduced the polymerization degree of silicate ion, changed its nucleation and crystallization process power, thereby synthesis cycle is effectively shortened, the A type zeolite molecular sieve particle diameter of gained is less, can reach below 100nm.
The objective of the invention is to be achieved through the following technical solutions, concrete steps are as follows:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 5-15:1-3:0.2-0.8:10-15:500-1000, the corresponding reaction raw materials tetraethoxy of weighing above-mentioned substance, aluminium source, sodium hydroxide, Tetramethylammonium hydroxide, deionized water etc., standby;
(2) deionized water calculated in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, account for toward volume in 2/3 deionized water and slowly add the aluminium source, then add sodium hydroxide, Tetramethylammonium hydroxide, stir, prepare out solution A, in this step, temperature is controlled at 30-40 ℃;
(3) add acid in volume accounts for 1/3 deionized water, add the pH=1-5 of the solution after acid, then add tetraethoxy, be stirred to abundant hydrolysis, prepare out solution B;
(4) solution B is poured in solution A fast, stirring at room is even, obtains initial reaction liquid;
(5) initial reaction liquid is put into to hydrothermal reaction kettle, through stirring ageing, crystallization, ultrasonic, centrifugal, drying, calcining obtains the purpose sample.Utilize X-ray diffraction technology (XRD) to carry out the phase detection to the sample be synthesized, prove that product is A type zeolite molecular sieve.Application scanning electron microscope (SEM) and transmission electron microscope (TEM) etc. carry out pattern and size detection to sample, and detected result proof product meets the distinctive square pattern of A type zeolite molecular sieve, and grain-size is in the 100nm left and right.
A kind of in aluminum isopropylate, aluminium powder, gibbsite of the aluminium source of using in the present invention.
The acid of using in the present invention is hydrochloric acid, nitric acid or sulfuric acid.
Tetraethoxy described in the present invention slowly adds in acid solution with the speed of 0.1-0.5ml/min.
Ageing described in the present invention is stir process 1-10 hour at room temperature.
Crystallization described in the present invention is to process 3-15 hour under 70-120 ℃.
The present invention compared with prior art has following innovative point:
1, the sour catalyzer as teos hydrolysis for the present invention, accelerated the hydrolysis rate of tetraethoxy, suppress its polycondensation speed, thereby the polymeric form of silicate ion is reduced, and then shortened the time that generates the necessary primary unit structure of A type zeolite molecular sieve;
2, the tetraethoxy that the present invention crosses by acid catalysis, as the silicon source, has increased the degree of supersaturation at synthetic system initial stage, is conducive to form more nucleus in the reaction starting stage, thereby causes the final crystal grain formed less.
The present invention compared with prior art has following remarkable advantage:
1, the present invention has obviously shortened the synthesis cycle of nano type A zeolite molecular sieve;
2, the resulting nano type A zeolite molecular sieve of the present invention particle diameter is less and be evenly distributed, and by controlling reaction conditions, can make its particle diameter basic controlling below 100nm.
3, the little and uniform nano type A zeolite of the particle diameter that the present invention prepares can be applied to the preparation of the A type zeolite membrane of densification and even thickness.
The accompanying drawing explanation
Fig. 1 is the A type zeolite molecular sieve XRD figure that Solution on Chemical Reagents in Shanghai company produces;
Fig. 2 is nano type A zeolite molecular sieve XRD figure synthetic in the embodiment of the present invention 1;
Fig. 3 is nano type A zeolite molecular sieve SEM figure synthetic in the embodiment of the present invention 1;
Fig. 4 is that grain-size synthetic in the embodiment of the present invention 1 is 50-80nm nano type A zeolite molecular sieve TEM figure.
Embodiment
Below by specific embodiment and accompanying drawing, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 10.95:1.8:0.45:14:690, the corresponding reaction raw materials tetraethoxy of weighing above-mentioned substance, aluminum isopropylate, sodium hydroxide, Tetramethylammonium hydroxide, deionized water, standby;
(2) the deionized water 27ml in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, in accounting for 2/3 deionized water 18ml, volume slowly adds aluminum isopropylate 2.29g under 40 ℃ of stirrings, within one hour, add, then add sodium hydroxide solution, 15.9g Tetramethylammonium hydroxide (TMAOH5H that 2.8g concentration is 1mol/L
2o), stir, prepare out solution A;
(3) add hydrochloric acid soln in volume accounts for 1/3 deionized water 9ml, add pH value of solution after hydrochloric acid=5, then under the room temperature magnetic agitation, the 7.1g tetraethoxy is slowly added to hydrochloric acid soln with the speed of 0.5ml/min, be mixed with solution B;
(4) B solution is poured in A solution, stirring at room is even, obtains initial soln;
(5) initial soln is put into to the hydrothermal reaction kettle of 100ml, stirring at room ageing 5 hours, 90 ℃ of crystallization 8 hours, the crystallization after product is through ultrasonic (150W, 5min), centrifugation (15000rpm, 30min), 80
othe dry 24h of C, obtain the purpose sample after 550 ℃ of calcining 6h; As shown in Figure 2, the XRD figure by the standard model shown in comparison diagram 1 proves that prepared product is A type zeolite molecular sieve to the XRD figure of purpose sample; Scheme (Fig. 3) by SEM, TEM figure (Fig. 4) can find out that product has the distinctive cube structure of A type zeolite molecular sieve, and TEM figure it can also be seen that the A type zeolite molecular sieve grain-size prepared is 50-80nm.
Embodiment 2:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 12.2:1.89:0.56:15:780, the corresponding reaction raw materials tetraethoxy of weighing above-mentioned substance, aluminium powder, sodium hydroxide, Tetramethylammonium hydroxide, deionized water, standby;
(2) the deionized water 36ml in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, in accounting for 2/3 deionized water 24ml, volume slowly adds the 0.38g aluminium powder under 30 ℃ of stirrings, within one hour, add, then add sodium hydroxide solution, 21.5g Tetramethylammonium hydroxide (TMAOH5H that 4.15g concentration is 1mol/L
2o), stir, prepare out solution A;
(3) add salpeter solution in volume accounts for 1/3 deionized water 12ml, add pH value of solution after nitric acid=1, then under the room temperature magnetic agitation, the 9.3g tetraethoxy is slowly added to hydrochloric acid soln with the speed of 0.2ml/min, be mixed with solution B;
(4) B solution is poured in A solution, stirring at room is even, obtains initial reaction liquid;
(5) initial reaction liquid is put into to the hydrothermal reaction kettle of 100ml, stirring at room ageing 2 hours, 100 ℃ of crystallization 6 hours, the crystallization after product is through ultrasonic (150W, 5min), centrifugation (15000rpm, 30min), 80 ℃ of dry 24h, obtain nano type A zeolite molecular sieve finished product after 550 ℃ of calcining 6h; The nano type A zeolite molecular sieve grain-size prepared is 50-100nm.
Embodiment 3:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 5:1:0.2:10:500, the corresponding reaction raw materials tetraethoxy of weighing above-mentioned substance, gibbsite, sodium hydroxide, Tetramethylammonium hydroxide, deionized water etc., standby;
(2) the deionized water 33ml in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, in accounting for 2/3 deionized water 22ml, volume slowly adds the 0.76g gibbsite under 35 ℃ of stirrings, within one hour, add, then add sodium hydroxide solution, 17.4g Tetramethylammonium hydroxide (TMAOH5H that 1.95g concentration is 1mol/L
2o), stir, prepare out solution A;
(3) add sulphuric acid soln in volume accounts for 1/3 deionized water 11ml, add pH value of solution after sulfuric acid=3, then under the room temperature magnetic agitation, the 4.91g tetraethoxy is slowly added to salpeter solution with the speed of 0.3ml/min, be mixed with solution B;
(4) B solution is poured in A solution, stirring at room is even, obtains initial reaction liquid;
(5) initial reaction liquid is put into to the hydrothermal reaction kettle of 100ml, stirring at room ageing 5 hours, 90 ℃ of crystallization 8 hours, the crystallization after product is through ultrasonic (150W, 5min), centrifugation (15000rpm, 30min), 80
othe dry 24h of C, obtain A type zeolite molecular sieve after 550 ℃ of calcining 6h, and the nano type A zeolite molecular sieve grain-size prepared is 50-80nm.
Embodiment 4:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 15:3:0.8:12:1000, the corresponding reaction raw materials tetraethoxy of weighing above-mentioned substance, aluminum isopropylate, sodium hydroxide, Tetramethylammonium hydroxide, deionized water, standby;
(2) the deionized water 42ml in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, in accounting for 2/3 deionized water 28ml, volume slowly adds aluminum isopropylate 4.16g under 40 ℃ of stirrings, add in one hour, then add sodium hydroxide solution, 14.7g Tetramethylammonium hydroxide (TMAOH5H that 5.33g concentration is 1mol/L
2o), stir, prepare out solution A;
(3) add salpeter solution in volume accounts for 1/3 deionized water 14ml, add pH value of solution after nitric acid=2, then under the room temperature magnetic agitation, the 10.31g tetraethoxy is slowly added to salpeter solution with the speed of 0.1ml/min, be mixed with solution B;
(4) B solution is poured in A solution, stirring at room is even, obtains initial reaction liquid;
(5) initial reaction liquid is put into to the hydrothermal reaction kettle of 100ml, stirring at room ageing 10 hours, 120 ℃ of crystallization 3 hours, the crystallization after product is through ultrasonic (150W, 5min), centrifugal (15000rpm, 30min), 80 ℃ of dry 24h, obtain A type zeolite molecular sieve after 550 ℃ of calcining 6h, the nano type A zeolite molecular sieve grain-size prepared is 60-120nm.
Embodiment 5:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 10:2:0.7:13:800, the corresponding reaction raw materials tetraethoxy of weighing above-mentioned substance, aluminium powder, sodium hydroxide, Tetramethylammonium hydroxide, deionized water, standby;
(2) the deionized water 21ml in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, in accounting for 2/3 deionized water 14ml, volume slowly adds the 0.23g aluminium powder under 30 ℃ of stirrings, add in one hour, then add sodium hydroxide solution, 10.51g Tetramethylammonium hydroxide (TMAOH5H that 2.98g concentration is 1mol/L
2o), stir, prepare out solution A;
(3) add hydrochloric acid soln in volume accounts for 1/3 deionized water 7ml, add pH value of solution after hydrochloric acid=4, then under the room temperature magnetic agitation, the 4.32g tetraethoxy is slowly added to hydrochloric acid soln with the speed of 0.4ml/min, be mixed with solution B;
(4) B solution is poured in A solution, stirring at room is even, obtains initial reaction liquid;
(5) initial reaction liquid is put into to the hydrothermal reaction kettle of 100ml, stirring at room ageing 1 hour, 70 ℃ of crystallization 15 hours, the crystallization after product is through ultrasonic (150W, 5min), centrifugation (15000rpm, 30min), 80 ℃ of dry 24h, obtain the nano type A molecular sieve finished product after 550 ℃ of calcining 6h; The nano type A zeolite molecular sieve grain-size prepared is 60-110nm.
Claims (6)
1. the fast preparation method of a nano type A zeolite molecular sieve, is characterized in that, comprises the steps:
(1) press SiO
2: Al
2o
3: Na
2o:(TMA)
2o:H
2the ratio that the mol ratio of O is 5-15:1-3:0.2-0.8:10-15:500-1000, the corresponding reaction raw materials of weighing above-mentioned substance is tetraethoxy, aluminium source, sodium hydroxide, Tetramethylammonium hydroxide, deionized water, standby;
(2) deionized water taken in step (1) is divided into to two parts, portion accounts for 2/3 of cumulative volume, another part accounts for 1/3 of cumulative volume, in accounting for 2/3 deionized water, volume slowly adds the aluminium source, then add sodium hydroxide, Tetramethylammonium hydroxide, stir, prepare out solution A, in this step, temperature is controlled at 30-40 ℃;
(3) in volume accounts for 1/3 deionized water, add acid to make pH value of solution=1-5, then in acid solution, add tetraethoxy, be stirred to abundant hydrolysis, prepare out solution B;
(4) solution B is poured in solution A fast, stirring at room is even, obtains initial reaction liquid;
(5) initial reaction liquid is put into to reactor, through ageing, crystallization, ultrasonic, centrifugal, drying, calcining obtains nano type A zeolite molecular sieve finished product.
2. the preparation method of nano type A zeolite molecular sieve according to claim 1, is characterized in that the aluminium source is a kind of in aluminum isopropylate, aluminium powder, gibbsite.
3. the preparation method of nano type A zeolite molecular sieve according to claim 1 is characterized in that: a kind of in hydrochloric acid, nitric acid, sulfuric acid etc. of acid.
4. the preparation method of nano type A zeolite molecular sieve according to claim 1, it is characterized in that: tetraethoxy slowly adds in acid solution with the speed of 0.1-0.5ml/min.
5. the preparation method of nano type A zeolite molecular sieve according to claim 1 is characterized in that: ageing is to process 1-10 hour under stirring at room.
6. the preparation method of nano type A zeolite molecular sieve according to claim 1 is characterized in that: crystallization is to process 3-15 hour under 70-120 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862310A (en) * | 2018-07-03 | 2018-11-23 | 洛阳建龙微纳新材料股份有限公司 | A kind of weakly acidic pH zeolite molecular sieve and its preparation method and application |
| CN112642474A (en) * | 2019-10-12 | 2021-04-13 | 中国石油天然气股份有限公司 | Preparation method of SBA-16/MOR composite molecular sieve, catalyst and application in double-branch chain isomerization |
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2013
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| CN1721325A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Process for preparing fine grain zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108862310A (en) * | 2018-07-03 | 2018-11-23 | 洛阳建龙微纳新材料股份有限公司 | A kind of weakly acidic pH zeolite molecular sieve and its preparation method and application |
| CN112642474A (en) * | 2019-10-12 | 2021-04-13 | 中国石油天然气股份有限公司 | Preparation method of SBA-16/MOR composite molecular sieve, catalyst and application in double-branch chain isomerization |
| CN112642474B (en) * | 2019-10-12 | 2023-07-25 | 中国石油天然气股份有限公司 | Preparation method of SBA-16/MOR composite molecular sieve, catalyst and application thereof in double branched chain isomerization |
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