CN100572274C - A kind of preparation method of large-grain 4 A-type molecular screen primary powder - Google Patents
A kind of preparation method of large-grain 4 A-type molecular screen primary powder Download PDFInfo
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- CN100572274C CN100572274C CNB2008100941264A CN200810094126A CN100572274C CN 100572274 C CN100572274 C CN 100572274C CN B2008100941264 A CNB2008100941264 A CN B2008100941264A CN 200810094126 A CN200810094126 A CN 200810094126A CN 100572274 C CN100572274 C CN 100572274C
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- temperature
- primary powder
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- 239000000843 powder Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000012452 mother liquor Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 238000013019 agitation Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims abstract description 4
- 239000000084 colloidal system Substances 0.000 claims abstract description 3
- 230000029087 digestion Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000003483 aging Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 4
- 239000003513 alkali Substances 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- 230000000274 adsorptive effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
A kind of preparation method of large-grain 4 A-type molecular screen primary powder is by molecular ratio SiO
2/ Al
2O
3=1.9～2.1, Na
2O/SiO
2=1.2～1.6, H
2O/Na
2O=50～80 take by weighing a certain amount of silicon-containing material, aluminium-containing substance, burning alkali and water respectively; Under agitation add successively in the synthetic axe, stirred 45 minutes, become the glue temperature to be controlled at 15～35 ℃; Colloid carries out ageing after becoming glue, 15～35 ℃ of temperature, and digestion time started stirring after 1～24 hour, fed the high pressure steam crystallization temperature that is rapidly heated and stopped to stir; 85～100 ℃ of crystallization temperatures, crystallization time 6～16 hours; After crystallization is finished, utilize plate-and-frame filter press that solidliquid mixture is separated, mother liquor is recycled, and solid product is for further processing; Mother liquor is in the enterprising washing of pressure filter, and is dry on flash dryer when washing pH and being 10-11, promptly gets large-grain 4 A-type molecular screen primary powder.
Description
Technical field
The invention belongs to chemical technology field, refer more particularly to a kind of preparation method of large-grain 4 A-type molecular screen primary powder.
Background technology
Zeolite molecular sieve has absorption, shape selective catalysis and the ion-exchange three big characteristics of selection, thereby is widely used as sorbent material, catalyzer and ion-exchanger.The 4A molecular sieve is a kind of product of sorbent material consumption maximum, is widely used in the depth drying of gas and liquid, the pure system of Sweet natural gas and hydrogen, the purification of making oxygen by air separation and nitrogen, oil dewaxing, double glazing and industrial chemicals etc.The 4A molecular sieve is through K
+And Ca
++The ionic exchange can be prepared into 3A and 5A, and its range of application and field are more extensive.
Prior art is produced the mean diameter (D of 4A type sieve particle
50) at 3-5um, bulk specific gravity is about 0.70g/ml, water regain often can not satisfy the requirement of equipment to 4A sorbent material loadings at 26.5-27.0% in industrial application, thereby reduces plant factor.
Summary of the invention
For addressing the above problem, the invention provides a kind of preparation method of large-grain 4 A-type molecular screen primary powder, the prepared 4A type molecular screen primary powder of this method has the advantages that crystal grain is big, bulk density is high, loading capacity is big, can load abundant molecular sieve as much as possible in limited volumetric spaces, increase economic efficiency and usage ratio of equipment.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of described large-grain 4 A-type molecular screen primary powder, its preparation method is divided into gets the raw materials ready, becomes glue, ageing, crystallization, isolation of crystalline, washing and drying, wherein
I, get the raw materials ready
By molecular ratio SiO
2/ Al
2O
3=1.9～2.1, Na
2O/SiO
2=1.2～1.6, H
2O/Na
2O=50～80 take by weighing a certain amount of silicon-containing material, aluminium-containing substance, caustic soda and water respectively;
II, one-tenth glue
Under agitation successively with silicon-containing material, caustic soda in water and the aluminium-containing substance adding synthesis reactor, stirred 45 minutes, became the glue temperature to be controlled at 15～35 ℃;
III, ageing
After becoming glue, colloid carries out ageing, and temperature is 15～35 ℃, and digestion time started stirring after 1～24 hour, feeds the high pressure steam crystallization temperature that is rapidly heated, and stops to stir;
IV, crystallization
Crystallization temperature is 85～100 ℃, crystallization time 6～16 hours;
V, isolation of crystalline
After crystallization is finished, utilize plate-and-frame filter press that solidliquid mixture is separated, mother liquor is recycled, and solid product is for further processing;
VI, washing and drying
After isolating mother liquor, dry on flash dryer when washing pH and being 10-11 in the enterprising washing of pressure filter, promptly get particle diameter D
50At 8.0～9.0 microns and bulk density large-grain 4 A-type molecular screen primary powder at 0.76-0.78g/ml.
Owing to adopt technical scheme as mentioned above, the present invention has following superiority:
One, the present invention has adopted the method that ageing combines with crystallization, the 4A molecular screen primary powder D for preparing
50At 8.0～9.0 microns, bulk density is 0.76-0.78g/ml, and the D of general 4A molecular sieve
50At 3～5 microns, bulk density is about 0.70.Aspect water absorption, with the 4A molecular sieve of the inventive method preparation, under 25 ℃ and 50% relative humidity, saturated water adsorptive value is 27.5-28.5%, and also the 4A molecular sieve than prior art for preparing is a height.
Two, the present invention has realized that raw material recycles, and is suitable for industrialization, and cost is reduced greatly.
Embodiment
Embodiment 1
By molecular ratio SiO
2/ Al
2O
3=2.0, Na
2O/SiO
2=1.5, H
2O/Na
2O=68 takes by weighing silicon-containing material (water glass solution), under agitation is added in the stainless steel synthesis reactor, adds caustic soda NaOH solution and water again, stirred 3 minutes, adding aluminium-containing substance then is sodium aluminate solution, and restir stopped to stir in 45 minutes, at this moment the silica-alumina gel temperature is 30 ℃, still aging 1 hour, start stirring, feed high pressure steam and be rapidly heated 95 ℃, thermostatic crystallization 10 hours, through separating, wash and drying, obtain large-grain 4 A-type molecular screen primary powder, record D with laser particle size analyzer
50=8.03 microns, at 25 ℃, recording saturated water adsorptive value under 50% the relative humidity is 28.50%, and bulk density is 0.76g/ml.
Embodiment 2
By molecular ratio SiO
2/ Al
2O
3=1.9, Na
2O/SiO
2=1.4, H
2O/Na
2O=50 takes by weighing silicon-containing material (water glass solution), under agitation is added in the stainless steel synthesis reactor, add caustic soda NaOH solution and water again, stirred 3 minutes, adding aluminium-containing substance then is sodium aluminate solution, restir stopped to stir in 45 minutes, and at this moment the silica-alumina gel temperature is 15 ℃, still aging 10 hours, start stirring, feed high pressure steam and be rapidly heated 90 ℃, thermostatic crystallization 15 hours is through separating, wash and drying, obtain large-grain 4 A-type molecular screen primary powder, record D with laser particle size analyzer
50=8.53 microns, at 25 ℃, recording saturated water adsorptive value under 50% the relative humidity is 28.0%, and bulk density is 0.77g/ml.
Embodiment 3
By molecular ratio SiO
2/ Al
2O
3=2.1, Na
2O/SiO
2=1.6, H
2O/Na
2O=78 takes by weighing silicon-containing material (water glass solution), under agitation is added in the stainless steel synthesis reactor, add caustic soda NaOH solution and water again, stirred 3 minutes, adding aluminium-containing substance then is sodium aluminate solution, restir stopped to stir in 45 minutes, and at this moment the silica-alumina gel temperature is 22 ℃, still aging 4 hours, start stirring, feed high pressure steam and be rapidly heated 98 ℃, thermostatic crystallization 12 hours is through separating, wash and drying, obtain large-grain 4 A-type molecular screen primary powder, record D with laser particle size analyzer
50=7.62 microns, at 25 ℃, recording saturated water adsorptive value under 50% the relative humidity is 27.80%, and bulk density is 0.76g/ml.
Above-mentioned three described separation of embodiment are after crystallization is finished, and utilize plate-and-frame filter press that solidliquid mixture is separated, and mother liquor is recycled, and solid product is for further processing.Described washing and drying are after isolating mother liquor, and be in the enterprising washing of pressure filter, dry on flash dryer when washing PH and being 10-11.
Claims (1)
1, a kind of preparation method of large-grain 4 A-type molecular screen primary powder is characterized in that: its preparation method is divided into gets the raw materials ready, becomes glue, ageing, crystallization, isolation of crystalline, washing and drying, wherein
I, get the raw materials ready
By molecular ratio SiO
2/ Al
2O
3=1.9～2.1, Na
2O/SiO
2=1.2～1.6, H
2O/Na
2O=50～80 take by weighing a certain amount of silicon-containing material, aluminium-containing substance, caustic soda and water respectively;
II, one-tenth glue
Under agitation successively with silicon-containing material, caustic soda in water and the aluminium-containing substance adding synthesis reactor, stirred 45 minutes, became the glue temperature to be controlled at 15～35 ℃;
III, ageing
After becoming glue, colloid carries out ageing, and temperature is 15～35 ℃, and digestion time started stirring after 1～24 hour, feeds the high pressure steam crystallization temperature that is rapidly heated, and stops to stir;
IV, crystallization
Crystallization temperature is 85～100 ℃, crystallization time 6～16 hours;
V, isolation of crystalline
After crystallization is finished, utilize plate-and-frame filter press that solidliquid mixture is separated, mother liquor is recycled, and solid product is for further processing;
VI, washing and drying
After isolating mother liquor, dry on flash dryer when washing pH and being 10-11 in the enterprising washing of pressure filter, promptly get particle diameter D
50At 8.0～9.0 microns and bulk density large-grain 4 A-type molecular screen primary powder at 0.76-0.78g/ml.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100941264A CN100572274C (en) | 2008-05-05 | 2008-05-05 | A kind of preparation method of large-grain 4 A-type molecular screen primary powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100941264A CN100572274C (en) | 2008-05-05 | 2008-05-05 | A kind of preparation method of large-grain 4 A-type molecular screen primary powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101264900A CN101264900A (en) | 2008-09-17 |
| CN100572274C true CN100572274C (en) | 2009-12-23 |
Family
ID=39987625
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502693A (en) * | 2011-10-27 | 2012-06-20 | 江苏奥石科技有限公司 | Method for synthesizing large-grain and highly-dispersed 4A zeolite |
| CN103553066A (en) * | 2013-10-14 | 2014-02-05 | 中国石油化工股份有限公司 | Molecular sieve drying and crushing combined continuous method |
| CN103723742A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Post-treatment method for washing, drying and calcining SAPO (silicoaluminophosphate) molecular sieve |
| BR112020001724A2 (en) * | 2017-07-31 | 2020-07-21 | Katholieke Universiteit Leuven | post-treatment method of zeolites |
| CN109678173A (en) * | 2019-02-26 | 2019-04-26 | 郑州雪山实业股份有限公司 | With the process of the sodium metaaluminate waste liquid synthesis 4A molecular sieve containing potassium |
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2008
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