CN103318913B - Preparation method for small-grain A-type molecular sieve primary powder - Google Patents
Preparation method for small-grain A-type molecular sieve primary powder Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 47
- 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 47
- 239000000843 powder Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- 230000032683 aging Effects 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011734 sodium Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 25
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 11
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 11
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 3
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract description 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052682 stishovite Inorganic materials 0.000 abstract description 2
- 229910052905 tridymite Inorganic materials 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 238000000034 method Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012169 petroleum derived wax Substances 0.000 description 2
- 235000019381 petroleum wax Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
Abstract
A preparation method for a small-grain A-type molecular sieve primary powder comprises preparing a directing agent, stocking, gelating, aging, crystallizing, solid-liquid separating, washing and drying, when feeding, the mol ratio of SiO2/Al2O3 is 1.7-2.1, the mol ratio of Na2O/Al2O3 is 2.3-4.2, and the mol ratio of H2O/Na2O is 20.0-40.0, the directing agent accounts for 0.01-0.1% by total volume of the raw materials, the gelating temperature is controlled at 15-40 DEG C, aging at 45-75 DEG C for 1-10 h, then standing and crystallizing at 85-100 DEG C for 1-10 h, separating the crystal, washing and drying, and then getting the product. The A-type molecular sieve primary powder has water-absorbing capacity of 26.5% or more, granularity of 500 nm-1000 nm in a uniform particle size distribution, is good in repeatability, and helps to realize cycle usage of the raw materials.
Description
Technical field
The present invention relates to technical field of molecular sieve preparation, be specifically related to the preparation method that a kind of particle is less than the former powder of A type molecular sieve of 1 μm.
Background technology
Type A zeolite is the artificial zeolite synthesized the earliest, is commonly used for drying, fractionation by adsorption, ion modification.Be applied to detergent builder in recent years, replacement tri-polyphosphate meets the environmental requirement without phosphatization, and annual production is more than 1,000,000 tons.As detergent builder, require to reduce product particle granularity, small-particle exchange velocity is very fast, and in hard water, calcium ions and magnesium ions is easy to make water demineralization with sodium ion exchange.And A type molecular sieve is as conventional sorbent material, its higher loading capacity does not embody in nano particle molecular sieve, and major cause is: after one, reducing product granularity, molecular sieve active adsorption volume declines; Two, reduce product granularity, often to sacrifice product degree of crystallinity for means, particle is less, occurs that unbodied possibility is larger.
Along with the fast development of sieve technology, its Application Areas is day by day expanded, molecular sieve petrochemical field application widely, such as, in the cut institute hydrocarbon-containifirst such as gasoline, kerosene and diesel oil, the octane value of normal paraffin is minimum and freezing point is the highest, and its molecular diameter is 4.9, less than component diameters such as isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons, therefore adopt 5 molecular sieves, optionally from hydrocarbon mixture, adsorb normal paraffin, thus realize the object of separation.The process removing normal paraffin is dewaxing process, it is the important means of refinery refining of petroleum products, also be the important production method of liquid petroleum wax, molecular sieve dewaxing unit is in early days for improving the octane value of gasoline, develop into later for reducing rocket engine fuel freezing point and produce liquid petroleum wax, and produce low freezing point diesel fuel.
For the adsorbent of molecular sieve dewaxed, mainly consider two indices, one is molecular sieve adsorption ability, and two is sieve particle sizes.Dewaxing by molecular sieve is mainly by molecular sieve adsorption normal paraffin, so the molecular sieve that synthetic crystallization degree is high, reducing inner skeleton defect is improve the main path of molecular sieve adsorption ability; Complete the molecular sieve after absorption by heat hot steam or other gas purging to remove the normal paraffin of absorption, reduce sieve particle and can improve desorption rate, prevent organic alkane from removing comparatively slow and being present in molecular sieve pore passage and causing carbon distribution or coking, cause zeolite product aftertreatment to bother or lost efficacy.
Summary of the invention
The present invention, in order to overcome above-mentioned the deficiencies in the prior art, provides a kind of preparation method of small-grain A-type molecular sieve primary powder, and the method is raw materials used to be generally easy to get, raw material reusable edible, and production cost is lower, and technique is simple, reproducible, is convenient to suitability for industrialized production.
The present invention is the deficiency solved the problems of the technologies described above, and the technical scheme adopted is: a kind of preparation method of small-grain A-type molecular sieve primary powder, specifically comprises the following steps:
1), directed agents is prepared
SiO in molar ratio
2/ A1
2o
3=15 ~ 20, Na
2o/A1
2o
3=15 ~ 20, H
2o/Na
2the ratio of O=10 ~ 30 feeds intake, and takes a certain amount of silicon source, aluminium source, alkali source and water respectively, first alkali source and aluminium source is added to the water and obtains high alkalinity sodium aluminate, then silicon source is added in high alkalinity sodium aluminate fast, after stirred at ambient temperature, 2 ~ 10 DEG C of aging 1 ~ 7d, namely obtain required directed agents;
2), the former powder of synthesizing small-grain A-type molecular sieve
A, to get the raw materials ready
Be Na in molar ratio
2o:A1
2o
3: SiO
2: H
2o=2 ~ 3.5: 1:2 ~ 3: the ratio of 80 ~ 150 feeds intake, take a certain amount of silicon source, aluminium source, alkali source and water respectively as raw material, and measure the directed agents that a certain amount of step 1) is obtained in addition, the consumption of directed agents is 0.01% ~ 0.1% of raw material cumulative volume;
B, plastic
Under agitation, add in reactor successively by water, alkali lye and silicon source, after stirring 2 ~ 5min, evenly add aluminium source solution, finally add directed agents, controlling gelling temperature is 15 ~ 40 DEG C, stirs 15 ~ 70 min, carries out plastic;
C, aging, crystallization
After plastic completes, room temperature leaves standstill 1 ~ 5h, then passes into high-pressure steam, makes system temperature rise to 50 ~ 75 DEG C, stops stirring, aging 1 ~ 10h; After aging end, open and stir, then pass into high-pressure steam, make system temperature rise to 85 ~ 100 DEG C, leave standstill crystallization 1 ~ 10h;
D, filtration, washing, drying
After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to PH=10 ~ 11, namely obtains product after drying.
Water in described step 1) is deionized water.
Described step 2) in the concentration > 55g/L of sodium oxide in alkali source.
Described step 1), 2) in silicon source comprise sodium silicate or silicon sol.
Described step 1), 2) in aluminium source comprise sodium aluminate or aluminium hydroxide.
Described step 1), 2) in alkali source comprise sodium hydroxide solution.
beneficial effect:
1, the present invention is in described ratio range, uses directed agents, and adopt the aging mode combined of dynamic, prepare the former powder of A type molecular sieve that granularity is 500 ~ 1000nm, product consists of: Na
2o: A1
2o
3: SiO
2=1: 1: 1,25 DEG C, under 50% relative humidity, saturated water adsorptive value is greater than 26.5%;
2, the present invention adopts directing agent method to control product granularity, and product repeatability better;
3, the present invention uses directed agents to prepare and adopts low temperature aging method, and directed agents is activity stabilized, is easy to control;
4, present invention uses mother liquor to originate as highly basic, achieve feedstock circulation and use, be suitable for suitability for industrialized production, cost is lower, avoids environmental pollution simultaneously.
Accompanying drawing explanation
Fig. 1 is the SEM photo of product prepared by the embodiment of the present invention 1;
Fig. 2 is the test data of product prepared by embodiment of the present invention 1-6.
Embodiment
A preparation method for small-grain A-type molecular sieve primary powder, specifically comprises the following steps:
1), directed agents is prepared
SiO in molar ratio
2/ A1
2o
3=15 ~ 20, Na
2o/A1
2o
3=15 ~ 20, H
2o/Na
2the ratio of O=10 ~ 30 feeds intake, take a certain amount of silicon source, aluminium source, alkali source and water respectively, first alkali source and aluminium source are added to the water and obtain high alkalinity sodium aluminate, then silicon source quick (complete in 2 ~ 3min and feed intake) is added in high alkalinity sodium aluminate, after stirred at ambient temperature, 2 ~ 10 DEG C of aging 1 ~ 7d, namely obtain required directed agents;
2), the former powder of synthesizing small-grain A-type molecular sieve
A, to get the raw materials ready
Be Na in molar ratio
2o:A1
2o
3: SiO
2: H
2o=2 ~ 3.5: 1:2 ~ 3: the ratio of 80 ~ 150 feeds intake, take a certain amount of silicon source, aluminium source, alkali source and water respectively as raw material, and measure the directed agents that a certain amount of step 1) is obtained in addition, the consumption of directed agents is 0.01% ~ 0.1% of raw material cumulative volume;
B, plastic
Under agitation, add in reactor successively by water, alkali lye and silicon source, after stirring 2 ~ 5min, evenly add aluminium source solution, finally add directed agents, controlling gelling temperature is 15 ~ 40 DEG C, stirs 15 ~ 70 min, carries out plastic;
C, aging, crystallization
After plastic completes, room temperature leaves standstill 1 ~ 5h, then passes into high-pressure steam, makes system temperature rise to 50 ~ 75 DEG C, stops stirring, aging 1 ~ 10h; After aging end, open and stir, then pass into high-pressure steam, make system temperature rise to 85 ~ 100 DEG C, leave standstill crystallization 1 ~ 10h;
D, filtration, washing, drying
After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to PH=10 ~ 11, namely obtains product after drying.
Water in described step 1) is deionized water.
Described step 2) in the concentration > 55g/L of sodium oxide in alkali source.
Described step 1), 2) in silicon source comprise sodium silicate or silicon sol.
Described step 1), 2) in aluminium source comprise sodium aluminate or aluminium hydroxide.
Described step 1), 2) in alkali source comprise sodium hydroxide solution.
Below in conjunction with drawings and Examples, the present invention is described in further detail.
embodiment 1
A preparation method for small-grain A-type molecular sieve primary powder, specifically comprises the following steps:
1), directed agents is prepared
Add 185ml sodium hydroxide solution (Na under agitation successively
2o content is 345g/L), 80ml sodium aluminate solution (Na
2o content is 155g/L, Al
2o
3content is 130g/L) in, obtain high alkalinity sodium aluminate, then by 280ml sodium silicate solution (Na
2o content is 110g/L, SiO
2content is 335g/L) add fast in high alkalinity sodium aluminate solution, and add 65ml water, at room temperature stir 45min, after leaving standstill aging 40h under 5 DEG C of conditions, be directed agents.
2), the former powder of synthesizing small-grain A-type molecular sieve
Add 213ml water, 120ml sodium silicate (Na under agitation successively
2o content is 110g/L, SiO
2content is 335g/L), 132ml sodium hydroxide solution (Na
2o content is 44g/L), 285ml sodium aluminate solution (Na
2o content is 145g/L, Al
2o
3content is 115g/L) and directed agents 0.35%, stir 45min under room temperature condition, room temperature leaves standstill 1h, is warming up to 75 DEG C, aging 5h, is warming up to 85 DEG C of crystallization 3h; After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to PH=10 ~ 11, namely obtains product after drying.SEM photo is done to product, as shown in Figure 1.
embodiment 2
A preparation method for small-grain A-type molecular sieve primary powder, specifically comprises the following steps:
1), directed agents is prepared
Add 160ml sodium hydroxide solution (Na under agitation successively
2o content is 345g/L), 60ml sodium aluminate solution (Na
2o content is 155g/L, Al
2o
3content is 130g/L) in, obtain high alkalinity sodium aluminate, then by 270ml sodium silicate solution (Na
2o content is 110g/L, SiO
2content is 335g/L) add fast in high alkalinity sodium aluminate solution, and add 180ml water, at room temperature stir 45min, after leaving standstill aging 2d under 10 DEG C of conditions, be directed agents.
2), the former powder of synthesizing small-grain A-type molecular sieve
Add 145ml water, 115ml sodium silicate (Na under agitation successively
2o content is 110g/L, SiO
2content is 335g/L), 30ml sodium hydroxide solution (Na
2o content is 125g/L), 281ml sodium aluminate solution (Na
2o content is 145g/L, Al
2o
3content is 115g/L) and directed agents 1%, stir 45min under room temperature condition, room temperature leaves standstill 1h, is warming up to 75 DEG C, aging 5h, is warming up to 85 DEG C of crystallization 3h; After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to PH=10 ~ 11, namely obtains product after drying.
embodiment 3
A preparation method for small-grain A-type molecular sieve primary powder, specifically comprises the following steps:
1), directed agents is prepared
Add 160ml sodium hydroxide solution (Na under agitation successively
2o content is 345g/L), 70ml sodium aluminate solution (Na
2o content is 155g/L, Al
2o
3content is 130g/L) in, obtain high alkalinity sodium aluminate, then by 270ml sodium silicate solution (Na
2o content is 110g/L, SiO
2content is 335g/L) add fast in high alkalinity sodium aluminate solution, and add 180ml water, at room temperature stir 45min, after leaving standstill aging 40h under 5 DEG C of conditions, be directed agents.
2), the former powder of synthesizing small-grain A-type molecular sieve
Add 145ml water, 115ml sodium silicate (Na under agitation successively
2o content is 110g/L, SiO
2content is 335g/L), 30ml sodium hydroxide solution (Na
2o content is 125g/L), 281ml sodium aluminate solution (Na
2o content is 145g/L, Al
2o
3content is 115g/L) and directed agents 0.25%, stir 45min under room temperature condition, room temperature leaves standstill 1h, is warming up to 75 DEG C, aging 5h, is warming up to 85 DEG C of crystallization 3h; After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to PH=10 ~ 11, namely obtains product after drying.
embodiment 4
A preparation method for small-grain A-type molecular sieve primary powder, specifically comprises the following steps:
1), directed agents is prepared
Add 185ml sodium hydroxide solution (Na under agitation successively
2o content is 345g/L), 80ml sodium aluminate solution (Na
2o content is 155g/L, Al
2o
3content is 130g/L) in, obtain high alkalinity sodium aluminate, then by 280ml sodium silicate solution (Na
2o content is 110g/L, SiO
2content is 335g/L) add fast in high alkalinity sodium aluminate solution, and add 65ml water, at room temperature stir 45min, after leaving standstill aging 40h under 5 DEG C of conditions, be directed agents.
2), the former powder of synthesizing small-grain A-type molecular sieve
Add 255ml water, 82ml sodium silicate (Na under agitation successively
2o content is 110g/L, SiO
2content is 335g/L), 57ml sodium hydroxide solution (Na
2o content is 125g/L), 177ml sodium aluminate solution (Na
2o content is 145g/L, Al
2o
3content is 125g/L) and directed agents 0.35%, stir 45min under room temperature condition, room temperature leaves standstill 1h, is warming up to 75 DEG C, aging 5h, is warming up to 85 DEG C of crystallization 3h; After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to PH=10 ~ 11, namely obtains product after drying.
embodiment 5
According to the preparation of embodiment 1 method, difference is recovery mother liquor at use alkali source.
embodiment 6
According to the preparation of embodiment 1 method, difference is that directed agents aging temperature is 30 DEG C.
Carry out granularity, XRD, degree of crystallinity, Static Water absorption, specific surface area test by ordinary method to the product of embodiment 1-6 gained, test result as shown in Figure 2.The present invention is in described ratio range, use directed agents, adopt the aging mode combined of dynamic, prepare the former powder of A type molecular sieve that granularity is 500-1000nm, product consists of Na2O: A12O3: SiO2=1: 1: 1,25 DEG C, under 50% relative humidity, saturated water adsorptive value is greater than 26.5%, and the present invention adopts directing agent method to control product granularity, and product repeatability better.
Claims (4)
1. a preparation method for small-grain A-type molecular sieve primary powder, is characterized in that: specifically comprise the following steps:
1), directed agents is prepared
SiO in molar ratio
2/ A1
2o
3=15 ~ 20, Na
2o/A1
2o
3=15 ~ 20, H
2o/Na
2the ratio of O=10 ~ 30 feeds intake, take a certain amount of silicon source, aluminium source, alkali source and deionized water respectively, first alkali source and aluminium source are added in deionized water and obtain high alkalinity sodium aluminate, then silicon source is added in high alkalinity sodium aluminate fast, after stirred at ambient temperature, 2 ~ 10 DEG C of aging 1 ~ 4d, namely obtain required directed agents;
2), the former powder of synthesizing small-grain A-type molecular sieve
A, to get the raw materials ready
Be Na in molar ratio
2o:A1
2o
3: SiO
2: H
2o=2 ~ 3.5: 1:2 ~ 3: the ratio of 80 ~ 150 feeds intake, take a certain amount of silicon source, aluminium source, alkali source and water respectively as raw material, measure the directed agents that a certain amount of step 1) is obtained in addition, the consumption of directed agents is 0.01% ~ 1% of raw material cumulative volume, the concentration > 55g/L of sodium oxide in described alkali source;
B, plastic
Under agitation, add in reactor successively by water, alkali lye and silicon source, after stirring 2 ~ 5min, evenly add aluminium source solution, finally add directed agents, controlling gelling temperature is 15 ~ 40 DEG C, stirs 15 ~ 70 min, carries out plastic;
C, aging, crystallization
After plastic completes, room temperature leaves standstill 1 ~ 5h, then passes into high-pressure steam, makes system temperature rise to 50 ~ 75 DEG C, stops stirring, aging 1 ~ 10h; After aging end, open and stir, then pass into high-pressure steam, make system temperature rise to 85 ~ 100 DEG C, leave standstill crystallization 1 ~ 10h;
D, filtration, washing, drying
After crystallization completes, start stirring, slip is separated into solid molecular sieves crystal and mother liquor, solid product washes with water to pH=10 ~ 11, namely obtains product after drying.
2. the preparation method of a kind of small-grain A-type molecular sieve primary powder as claimed in claim 1, is characterized in that: described step 1), 2) in silicon source comprise sodium silicate or silicon sol.
3. the preparation method of a kind of small-grain A-type molecular sieve primary powder as claimed in claim 1, is characterized in that: described step 1), 2) in aluminium source comprise sodium aluminate or aluminium hydroxide.
4. the preparation method of a kind of small-grain A-type molecular sieve primary powder as claimed in claim 1, is characterized in that: described step 1), 2) in alkali source comprise sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310121082.0A CN103318913B (en) | 2013-04-09 | 2013-04-09 | Preparation method for small-grain A-type molecular sieve primary powder |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4173622A (en) * | 1978-01-03 | 1979-11-06 | Fmc Corporation | Zeolite A crystals of uniformly small particle size and the manufacture thereof |
| CN1160600A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Process of producing fine-grain Model. A zeolite |
| CN101323455A (en) * | 2008-07-16 | 2008-12-17 | 山东南山铝业股份有限公司 | Method for producing 4A zeolite molecular sieve by isothermal one-step method |
| CN101337680A (en) * | 2008-08-07 | 2009-01-07 | 中国科学院新疆理化技术研究所 | Method for synthesizing 4A zeolite molecular sieve by adding guiding agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS593019A (en) * | 1982-06-25 | 1984-01-09 | Kanto Kagaku Kk | Manufacture of fine-grained a-type zeolite |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4173622A (en) * | 1978-01-03 | 1979-11-06 | Fmc Corporation | Zeolite A crystals of uniformly small particle size and the manufacture thereof |
| CN1160600A (en) * | 1996-03-21 | 1997-10-01 | 中国石油化工总公司石油化工科学研究院 | Process of producing fine-grain Model. A zeolite |
| CN101323455A (en) * | 2008-07-16 | 2008-12-17 | 山东南山铝业股份有限公司 | Method for producing 4A zeolite molecular sieve by isothermal one-step method |
| CN101337680A (en) * | 2008-08-07 | 2009-01-07 | 中国科学院新疆理化技术研究所 | Method for synthesizing 4A zeolite molecular sieve by adding guiding agent |
Non-Patent Citations (1)
| Title |
|---|
| "用高效NaY沸石导向剂快速合成A型沸石";熊晓云 等;《高等学校化学学报》;20070131;第28卷(第1期);第21－25页 * |
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