CN87105499A - Production method of binder-free spherical model-a molecular sieves - Google Patents
Production method of binder-free spherical model-a molecular sieves Download PDFInfo
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- CN87105499A CN87105499A CN87105499.XA CN87105499A CN87105499A CN 87105499 A CN87105499 A CN 87105499A CN 87105499 A CN87105499 A CN 87105499A CN 87105499 A CN87105499 A CN 87105499A
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Abstract
With inorganic ammonium salt, inorganic acid, waterglass is raw material, prepares the silica hydrogel bead with the oil column spherical container shaping method, through washing, soaking surfactant, drying, roasting, makes low bulk silica bead.The silica bead is mixed with sodium aluminate solution, and aging at a certain temperature, crystallization make silica change A type molecular sieve substantially into.Its profile and size remain unchanged, and this binder-free spherical model-A molecular sieves has the adsorption capacity height, and selectivity is good, characteristics such as absorption, desorption rate height and excellent mechanical intensity.
Description
The invention relates to a kind of production method of binder-free spherical model-A molecular sieves.Molecular sieve with this law preparation has high-adsorption-capacity, high absorption, desorption rate and excellent mechanical intensity characteristic.It is simple to have technology simultaneously, easy to operate, low cost and other advantages.
Molecular sieve has been used as desirable adsorbent and has been applied in various adsorbing separation and the adsorption refining process owing to its unique crystal structure.NaA(4A) molecular sieve adsorption passage effective aperture be 4 dusts (
).Through with calcium ion-exchanged after be CaA(5A), its absorption aperture increase to 5 dusts (
).The 5A molecular sieve only can adsorb positive structure hydrocarbon and can not adsorb branched-chain hydrocarbons, cycloalkane and aromatic hydrocarbons.Utilize this adsorptive selectivity can from gasoline fraction, isolate positive structure hydrocarbon, thereby improve its octane number.Can from kerosene, fraction of diesel oil, isolate highly purified n-alkane.The latter is important source material such as the biodegradable synthetic detergent of preparation, higher alcohol, aliphatic acid, lube oil additive, plastic plasticizer and alpha-olefin.
A type molecular sieve with the preparation of general synthetic method is Powdered, and size of microcrystal could be used after must adding the binding agent machine-shaping of q.s in 1-5 micron (μ) scope.This molecular sieve that contains binding agent since added do not have the binding agent of molecular sieve performance after, not only adsorption capacity descends, and also makes adsorptive selectivity simultaneously, absorption, desorption rate variation.Because the catalytic activity of binding agent is usually than A type molecular sieve height, when processing contained olefin feedstock, catalytic polymerization may take place in alkene on binding agent, thereby influenced molecular sieve service life.
U.S. associating oil product company (Universal Oil Products Co.) has delivered binder-free spherical model-A molecular sieves and has prepared patent (US3359068, US3348911), and this molecular sieve has overcome the above-mentioned shortcoming that the binding agent molecular sieve is arranged on substantially.Its preparation method is: with preformed silica bead and sodium aluminate solution reaction, make the silica bead be converted into A type molecular sieve basically, and its profile and size remain unchanged.In order to prepare the A type molecular sieve of high absorption, desorption rate, must prepare low bulk silica bead earlier.The method that these patents adopt is, hydrochloric acid, waterglass and hexamethylenetetramine (making gel) mixed at low temperatures form colloidal sol and spray in 95 ℃ the moulding oil, the silica hydrogel bead high temperature ageing in moulding oil that generates is made low bulk silica bead through washing, drying, roasting.The silica hydrogel bead that generates also can be washed soluble-salt earlier, is immersed in then in the isopropanol solvent, and low bulk silica bead is made in drying, roasting.
Said method exists the operating condition harshness, very easily causes to overflow as hydrogel bead high temperature ageing in moulding oil and boils; Contaminated environment generates oil-polluted water and cost height as the oil degradation after washing, and as the isopropyl alcohol infusion method, isopropyl alcohol is difficult to shortcomings such as recovery.
U.S. Mobil Oil Corporation (Mobil Oil Co.) has delivered preparation silica aerosol patent (US3079234), with ammonium salt solution, waterglass is raw material, prepare the silica hydrogel bead with oil column balling-up method, again through washing, dry in the overheated steam atmosphere, roasting makes the extremely low silica aerosol of bulk density in the air.But its mechanical strength extreme difference can not be used for synthetic spherical model-A molecular sieves.
The invention provides preparation low bulk silica bead and improve one's methods, eliminated the shortcoming in the said method substantially, have that technology is simple, easy to operate, low cost and other advantages.By method provided by the invention, earlier with inorganic acid such as sulfuric acid, hydrochloric acid, it is that 5～30%(is heavy that nitric acid (being preferably sulfuric acid) is made into concentration) (best 16～22%(is heavy)) solution A, with inorganic ammonium salt such as ammonium sulfate, ammonium chloride, ammonium fluoride, it is that 5～35%(is heavy that ammonium nitrate (being preferably ammonium sulfate) is made into concentration) (best 20～30%(is heavy)) solution B, and A: B=1～4: 2～10(best 2～3 by volume: 4～5) with A, B two solution mix, be that 8～20%(is heavy with dioxide-containing silica then) (best 10～16%(is heavy)) waterglass carry out forming oil column, colloidal sol PH is controlled at 6.0～8.5(best 7.0～8.0), 25～90 ℃ of oil column temperature (best 40～60 ℃), the gelled pill that generates is immersed in 0.05～10%(after washing heavy) (best 0.1～5%(is heavy)) the nonionic surface active agent aqueous solution in, non-ionic surface active agent is a NPE, fatty alcohol etc., soaking temperature is 10～70 ℃ (best 30～60 ℃), 2～24 hours time, 250～350 ℃ of air dryings 0.5～2 hour, 550～650 ℃ of roastings 0.5～2 hour, can make bulk density is 0.26～0.36 gram per centimeter
3The silica bead.
The present invention also provides the preparation binder-free spherical model-A molecular sieves to improve one's methods: the silica bead with above-mentioned the inventive method preparation mixes with sodium aluminate solution, and the mol ratio of mixture is: Na
2O/Al
2O
3=1.5～2.5(best 1.7～2.1)
SiO
2/ Al
2O
3=1.5～3.5(best 1.8～2.5)
H
2O/Na
2O=15～60(best 20～40)
Mixture wore out 2～24 hours through 20～75 ℃ (best 35～65 ℃) earlier, was warming up to 90～103 ℃ of crystallization then 1～10 hour, promptly made binder-free spherical model-A molecular sieves through washing, dry reaching in 1～3 hour 400～500 ℃ of roastings.Because the present invention in preparation process, has increased aging step, can make the molecular sieve of making have characteristics such as purity height, no stray crystal, adsorption capacity height.
Ion-exchange process with routine can further prepare binder-free spherical model 3A, 5A equimolecular sieve.
Binder-free spherical model-A molecular sieves with the inventive method preparation has the adsorption capacity height, and selectivity is good, characteristics such as absorption, desorption rate height and excellent mechanical intensity.This product is used for positive isohydrocarbon and separates (especially liquid phase separation technology), alcohols, ethene, propylene, liquid hydrocarbon drying, oxygen enriching, rich nitrogen, refinery tail-gas hydrogen upgrading and to be used for aspects such as gas chromatographic analysis all superior than existing commercially available molecular sieve performance of the same type.
Accompanying drawing is commercially available have binding agent 5A molecular sieve and liquid phase adsorption rate curve by the binder-free spherical model 5A molecular sieve of the inventive method preparation.
Implement best mode of the present invention
Example 1
Preparation 30%(is heavy) (NH
4)
2SO
4Solution A, 18%(is heavy) H
2SO
4Solution B and SiO
2Content 14%(is heavy) water glass solution C, A: B=5 by volume: 2 evenly mix A, B two solution, in shower nozzle, mix with certain flow rate and ratio with C then, mixing ratio is so that colloidal sol PH=7.5, it is that the silica hydrogel bead of generation is washed to no SO in 50 ℃ the light diesel fuel that the colloidal sol drop sprays into temperature
= 4After, it is heavy to be immersed in 0.4%() in the NP-11 nonionic surface active agent aqueous solution (NP-11 is that Nanjing plastic molding and processing plant of Nanjing petrochemical corporation (complex) produces), 50 ℃ of soaking temperatures, 4 hours time, then 250 ℃ of dry half an hour, 650 ℃ of roasting half an hour, silica bead bulk density is 0.30 gram per centimeter
3
Example 2
The silica bead 112 of getting example 1 preparation restrains in synthesis tank, adds sodium aluminate solution and (contains Al
2O
31.48 mol, Na
2O 2.77 mol) 812 grams, water 366 gram mixes being placed in the constant temperature oven, 50 ℃ aging 4 hours, 100 ℃ of crystallization 2 hours, product finally makes binder-free spherical model 4A molecular sieve through washing, dry and 400 ℃ of roastings 1 hour.Its methyl alcohol adsorbance is 197 milligrams of methanol/gram molecular sieves, and mechanical strength is 1.7kg/ grain (16～20 order).
Example 3
The 4A molecular sieve 200 of getting example 2 preparations restrains in swap tank, and adding concentration is 1060 milliliters of 0.3 mol calcium chloride solutions, stirs and is warming up to 90～95 ℃, constant temperature 1 hour, after washing, drying,, finally make binder-free spherical model 5A molecular sieve 400 ℃ of roastings 1 hour.The n-hexane adsorbance is 135 milligrams of n-hexanes/gram molecule sieve.
Accompanying drawing is a 5A molecular sieve adsorption rate curve.Assay method is: preparation contains positive nonane (nC
9H
20) the 15%(weight), isooctane (iC
8H
18) the 85%(weight) binary solution, in rub oral examination tube, take by weighing the baked 5A molecular sieve of about 1 gram (accurately to 0.0004 gram), accurately add 2 milliliters of binary solutions with pipette, and start stopwatch simultaneously, under constantly vibrating, from rub oral examination tube, extracted 0.5 microlitre solution every 2 minutes with micro syringe, its composition of chromatograph, the 5A molecular sieve adsorbs nC when calculating sampling by following formula from binary solution
9H
20Amount:
A%(is heavy)=(2(C
0-C
i) d)/(W)
A is i instantaneous time 5A molecular sieve adsorption nC in the formula
9H
20Amount %(heavy)
C
oBe nC in the binary solution before measuring
9H
20Content %(is heavy)
C
iBe nC in the i instantaneous time binary solution
9H
20Content %(is heavy)
D is a binary solution proportion gram per centimeter
3
W heavily restrains for the test molecular sieve
With A% to adsorption time T(branch) make a curve.(a) being binder-free spherical model 5A molecular sieve adsorption rate curve of the present invention, (b) is the commercially available binding agent 5A molecular sieve adsorption rate curve that has.Can find out thus, by its rate of adsorption of 5A molecular sieve of the present invention preparation obviously faster than the 5A molecular sieve that binding agent is arranged.
Claims (7)
1, a kind of production technology of the silica bead for the low bulk used of preparation binder-free spherical model-A molecular sieves is to mix to form colloidal sol and spray into inorganic acid, waterglass and gel to generate the silica hydrogel bead in the oil, makes through aging, washing, drying, roasting.Also can be with the washing earlier of described silica hydrogel bead, be immersed in then in isopropyl alcohol (or methyl alcohol, ethanol, the acetone etc.) solvent, drying, roasting are made.The above-mentioned low bulk silica bead of making is mixed with sodium aluminate solution, make binder-free spherical model-A molecular sieves through crystallization, washing, drying and roasting.The invention is characterized in that the above-mentioned low bulk silica bead of preparation is to carry out forming oil column generation hydrogel bead with solution and water glass solution that inorganic acid, inorganic ammonium salt mix, be immersed in the nonionic surface active agent aqueous solution after washing, making bulk density again after drying, the roasting is 0.26～0.36 gram per centimeter
3The silica bead.This bead is mixed with sodium aluminate solution, make binder-free spherical model-A molecular sieves through aging, crystallization, washing, drying, roasting.
2, according to claim 1, it is ammonium sulfate, ammonium chloride, ammonium fluoride, ammonium nitrate (being preferably ammonium sulfate) that low bulk silica bead prepares used inorganic ammonium salt.Inorganic acid is sulfuric acid, hydrochloric acid, nitric acid (being preferably sulfuric acid).
3, according to claim 2, inorganic ammonium salt concentration is that 5～35%(is heavy) (best 20～30%), inorganic acid concentration is that 5～30%(is heavy) (best 16～22%), it is that 8～20%(is heavy that water glass solution contains silica) (best 10～16%), acid solution and ammonium salt solution volume ratio are 1～4: 2～10(best 2～3: 4～5).
4, according to claim 1, oil column balling-up condition PH is 6.0～8.5(best 7.0～8.0), 25～90 ℃ of temperature (best 40～60 ℃).
5, according to claim 1, nonionic surface active agent is surfactants such as NPE, fatty alcohol, concentration is that 0.05～10%(is heavy) (best 0.1～5%), 10～70 ℃ of soaking temperatures (best 30～60 ℃), soak time 2～24 hours.
6, according to claim 1, silica and sodium aluminate solution mixture constitutive molar ratio are: Na
2O/Al
2O
3=1.5～2.5(best 1.7～2.1)
SiO
2/ Al
2O
3=1.5～3.5(best 1.8～2.5)
H
2O/Na
2O=15～60(best 20～40)
7, according to claim 1, aging temperature is 20～75 ℃ (best 35～65 ℃), ageing time 2～24 hours, 90～103 ℃ of crystallization temperatures, crystallization time 1～10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105499 CN1010301B (en) | 1987-08-03 | 1987-08-03 | Production method of binder-free spherical model-a molecular sieves |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105499 CN1010301B (en) | 1987-08-03 | 1987-08-03 | Production method of binder-free spherical model-a molecular sieves |
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| Publication Number | Publication Date |
|---|---|
| CN87105499A true CN87105499A (en) | 1988-09-21 |
| CN1010301B CN1010301B (en) | 1990-11-07 |
Family
ID=4815346
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105499 Expired CN1010301B (en) | 1987-08-03 | 1987-08-03 | Production method of binder-free spherical model-a molecular sieves |
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|---|---|
| CN (1) | CN1010301B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864096A (en) * | 2010-05-27 | 2010-10-20 | 南京工业大学 | Organic/zeolite hybrid material and preparation method thereof |
| CN103506069A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Molecular sieve dewaxing adsorbent and preparation method thereof |
| CN103508463A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of binderless spherical faujasite particles |
| CN103864090A (en) * | 2014-03-18 | 2014-06-18 | 山东理工大学 | Method for preparing spherical molecular sieve from rice hulls as silicon sources |
| CN106395846A (en) * | 2016-08-30 | 2017-02-15 | 中科合成油技术有限公司 | Spherical non-acidic molecular sieve, and preparation method and application thereof |
| US9656241B2 (en) | 2012-10-29 | 2017-05-23 | China Petroleum & Chemical Corporation | 5A molecular sieve adsorbent and method for preparation of the same |
| CN107961759A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of 5A adsorbent of molecular sieve and its preparation method and application |
| CN108996510A (en) * | 2018-06-25 | 2018-12-14 | 确成硅化学股份有限公司 | The preparation method of dustless easy dispersed silicon dioxide |
| CN109351326A (en) * | 2018-12-19 | 2019-02-19 | 四川省达科特能源科技股份有限公司 | A kind of renewable mercury removal agent and preparation method thereof for natural gas |
| CN110228812A (en) * | 2018-03-06 | 2019-09-13 | 华东理工大学 | A kind of binderless A type sieve particle and preparation method thereof |
-
1987
- 1987-08-03 CN CN 87105499 patent/CN1010301B/en not_active Expired
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864096A (en) * | 2010-05-27 | 2010-10-20 | 南京工业大学 | Organic/zeolite hybrid material and preparation method thereof |
| CN103508463A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of binderless spherical faujasite particles |
| CN103508463B (en) * | 2012-06-15 | 2015-07-01 | 中国石油化工股份有限公司 | Preparation method of binderless spherical faujasite particles |
| CN103506069A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Molecular sieve dewaxing adsorbent and preparation method thereof |
| CN103506069B (en) * | 2012-06-27 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of dewaxing by molecular sieve adsorbent and preparation method thereof |
| US9656241B2 (en) | 2012-10-29 | 2017-05-23 | China Petroleum & Chemical Corporation | 5A molecular sieve adsorbent and method for preparation of the same |
| CN103864090B (en) * | 2014-03-18 | 2017-11-14 | 山东理工大学 | The method that ball-type molecular sieve is prepared using rice husk as silicon source |
| CN103864090A (en) * | 2014-03-18 | 2014-06-18 | 山东理工大学 | Method for preparing spherical molecular sieve from rice hulls as silicon sources |
| CN106395846A (en) * | 2016-08-30 | 2017-02-15 | 中科合成油技术有限公司 | Spherical non-acidic molecular sieve, and preparation method and application thereof |
| CN106395846B (en) * | 2016-08-30 | 2019-02-22 | 中科合成油技术有限公司 | A kind of spherical shape non-acidic molecular sieve and the preparation method and application thereof |
| CN107961759A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | A kind of 5A adsorbent of molecular sieve and its preparation method and application |
| CN107961759B (en) * | 2016-10-19 | 2020-08-11 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method and application thereof |
| CN110228812A (en) * | 2018-03-06 | 2019-09-13 | 华东理工大学 | A kind of binderless A type sieve particle and preparation method thereof |
| CN108996510A (en) * | 2018-06-25 | 2018-12-14 | 确成硅化学股份有限公司 | The preparation method of dustless easy dispersed silicon dioxide |
| CN109351326A (en) * | 2018-12-19 | 2019-02-19 | 四川省达科特能源科技股份有限公司 | A kind of renewable mercury removal agent and preparation method thereof for natural gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1010301B (en) | 1990-11-07 |
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