CN103506069B - A kind of dewaxing by molecular sieve adsorbent and preparation method thereof - Google Patents
A kind of dewaxing by molecular sieve adsorbent and preparation method thereof Download PDFInfo
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Abstract
A kind of dewaxing by molecular sieve adsorbent, comprise the A molecular sieve of 90 ~ 99 quality % and the binding agent of 1 ~ 10 quality %, the grain size of described A molecular sieve is 0.1 ~ 1.0 micron, and its cation is Ca
2+or Mg
2+.This adsorbent has higher hydrothermal stability and absorption property, adsorbing separation can go out the n-alkane that carbon number is greater than 14 from raw material.
Description
Technical field
The present invention is dewaxing by molecular sieve adsorbent and preparation method thereof, specifically, is a kind of from C
9~ C
30the adsorbent of separating-purifying n-alkane and preparation method in hydrocarbon mixture material.
Background technology
Usual virgin kerosene, by dewaxing by molecular sieve and cut cutting, can obtain aviation kerosine and atoleine.Normal paraffin content is the important quality index of atoleine, all vital for the understanding of atoleine and aviation kerosine character and Instructing manufacture, grasp normal paraffin content and distribution situation in atoleine and raw material, on purpose can carry out the production of aviation kerosine.
Linear paraffin can be used as the alkyl component of sulfolane aryl and alkylsulfonate synthetic detergent.Linear paraffin is preferentially selected in the production of washing agent, because the product obtained can be made like this to have excellent scourability, and compared with the washing agent produced with branched paraffin, also has excellent biodegradability.Other important use of pure linear paraffin also comprises as flame retardant compositions, as reaction diluent; As solvent; As the intermediate of aromatization; As plasticizer; Also can be applied in the preparation of protein/vitamin liquid contracting thing.
But, pure linear paraffin is very difficult to obtain, the linear paraffin be intended to for industry and business is not produce by synthetic method, but from native hydrocarbon source, typically emanate out from the kerosene boiling fraction coming from natural hydrocarbon raw material, the boiling point of the kerosene boiling range of indication is approximately 182 ~ 277 DEG C here.This boiling range material is made up of hydrocarbons component, also comprises the pollutant such as aromatic compounds and heteroatomic compound (as sulfur-containing compound, nitrogen-containing compound and oxygenatedchemicals) except alkane.
The dewaxing by molecular sieve technique of Uop Inc. adopts Molex method, take virgin kerosene as raw material, by moving-bed adsorption by n-alkane and isoparaffin, aromatics seperation.N-alkane is adsorbed, and desorbing agent is the mixture of pentane and isooctane, finally from desorption product, reclaims desorbing agent with rectification method and recycles.The maximum feature of Molex technique carries out liquid phase adsorption, Desorption separation at a lower temperature, and which dictates that the adsorbent for this technique must have lower diffusional resistance, its adsorbent is 5A molecular sieve, separable go out C
10~ C
14n-alkane.
CN1087030A proposes a kind of preparation method of binder free 5A wax molecular sieve adsorbent, this method is in synthesis 4A molecular sieve process or after crystal washing, add by the kaolin families clay of crystal weight 15 ~ 35% and 0.2 ~ 2% sesbania powder, sodium cellulosate or other plant amylum shaping, then in 450 ~ 600 DEG C of roastings.Process with in 0.5 ~ 3.0mol/L sodium hydrate aqueous solution, after washing, product 0.05 ~ 2.0mol/L calcium chloride water exchanges, obtained product after washing, drying.But adopt sorbent treatment not heavy wax (n-alkanes of carbon number>=14) raw material, the 5A adsorbent of molecular sieve that this binder free legal system is standby in addition uses (NH in process of production
4)
2sO
4, cause environment NH
3, N contaminated wastewater, if need not (NH
4)
2sO
4in forming process, so will carry out modification to Si bead, the situation of unstable properties may be occurred.
CN1305767C discloses a kind of method preparing ultra-fine 4A zeolite, adds surfactant and fully stir in sodium aluminate solution, and then adds sodium silicate solution and fully stir, and obtains so-called ultra-fine 4A zeolite product by crystallization after alkali lye adjust ph.Although surfactant plays the effect of dispersion soln ion to a certain extent, grain size can not be controlled completely, and in this patent, not provide the data of ultra-fine 4A zeolite grain size.
CN1103635C discloses a kind of method of synthesis of 4 A zeolite by sei-synthesis, with kaolin group's clay for raw material, add NaOH and water, then add Complexing Iron screening agent, stir, be warming up to 90 ~ 100 DEG C of crystallization, after completing, obtain the 4A molecular sieve that average grain diameter is 2.0 ~ 3.5 μm.
Adopt water heat transfer for separating of the powdery 5A molecular sieve of n-alkane in naphtha in article " being separated the preparation of the novel 5A adsorbent of molecular sieve of naphtha n-alkane " (" petrochemical technology and application " vol24No.6Nov.2006), through extrusion molding, drying, activation, obtain bar shaped 5A molecular sieve, its n-C
6 0, n-C
7 0, n-C
8 0static saturated adsorption capacity is respectively 115,108,112mg/g.
Summary of the invention
The object of this invention is to provide a kind of dewaxing by molecular sieve adsorbent and preparation method thereof, this adsorbent has higher hydrothermal stability and absorption property, adsorbing separation can go out the n-alkane that carbon number is greater than 14 from raw material.
Dewaxing by molecular sieve adsorbent provided by the invention, comprises the A molecular sieve of 90 ~ 99 quality % and the binding agent of 1 ~ 10 quality %, and the grain size of described A molecular sieve is 0.1 ~ 1.0 micron, and its cation is Ca
2+or Mg
2+.
The present invention uses a kind of ultra micro A molecular sieve as the adsorbent of adsorbing separation n-alkane, from C
9~ C
30isolate n-alkane in hydrocarbon mixture material, particularly can isolate the n-alkane that carbon number is greater than 14, thus the yield of n-alkane can be significantly improved.
Accompanying drawing explanation
Fig. 1 is NaA(4A prepared by the present invention) XRD of molecular sieve figure.
Detailed description of the invention
Fig. 2 is breakthrough curve schematic diagram.
The present invention uses grain size to be ultra micro A molecular sieve and the binding agent mixed-forming of 0.1 ~ 1.0 micron (100nm ~ 1.0 μm), then uses Ca
2+or Mg
2+carry out ion-exchange to obtain aperture and be
the adsorbent of molecular sieve of left and right, can from C
9~ C
30isolate n-alkane in hydrocarbon mixture material, and there is high adsorption capacity and n-alkane yield, particularly have the higher rate of recovery to hexadecane.In addition, adsorbent of molecular sieve provided by the invention can adsorb the n-alkane that carbon number is more than 20, has good adsorptive selectivity.
The preferred adsorbent of the present invention is the ultra micro A molecular sieve the present invention prepared and aperture
modified zeolite compound make adsorbent, preferred adsorbent comprises the binding agent of the A molecular sieve of 70 ~ 98 quality %, the modified molecular screen of 1 ~ 25 quality % and 1 ~ 8 quality %, more preferably comprises the binding agent of the A molecular sieve of 75 ~ 95 quality %, the modified molecular screen of 4 ~ 20 quality % and 1 ~ 5 quality %.Described modified molecular screen is selected from MCM-22, ZSM-11, Silicalite-1, ZSM-57, EU-1, NU-87, Theta-1 or ZSM-5, and the grain size of described A type molecular sieve is 0.1 ~ 1.0 micron.
The preferred kaolin of binding agent of the present invention, rectorite, Yun Mengshi, bentonite or imvite.In described binding agent, the content of aluminium oxide is greater than 40 quality %, can also contain other component, as SiO
2, K
2o, CaO, MgO, Fe
2o
3and TiO
2in one or more.
Provided by the invention not containing the preparation method of the adsorbent of modified molecular screen, comprise the steps:
(1) by silicon source, aluminium source, alkali compounds and water mixing, mol ratio is mixed with for (15 ~ 17) Na
2o:Al
2o
3: (14.0 ~ 16.0) SiO
2: (270 ~ 374) H
2the mixed material of O, 10 ~ 30 DEG C are aging 20 ~ 48 hours, obtain directed agents; Again by by silicon source, aluminium source, alkali compounds, water and directed agents mixing, make the mol ratio of each material in mixture for (3.0 ~ 4.2) Na
2o:Al
2o
3: (1.8 ~ 2.0) SiO
2: (150 ~ 200) H
2o, and make directed agents account for 1.0 ~ 15 quality % of amount of the mixture, 95 ~ 100 DEG C of crystallization 3.0 ~ 6.0 hours, obtain NaA molecular sieve,
(2) by NaA molecular sieve and binding agent mixing roller forming, with alkaline solution treatment after 450 ~ 600 DEG C of roastings, then ion-exchange is carried out with calcium salt or magnesium salt solution, dry.
The preparation method of the preferred adsorbent containing modified molecular screen provided by the invention, comprises the steps:
(1) by silicon source, aluminium source, alkali compounds and water mixing, mol ratio is mixed with for (15 ~ 17) Na
2o:Al
2o
3: (14.0 ~ 16.0) SiO
2: (270 ~ 374) H
2the mixed material of O, 10 ~ 30 DEG C are aging 20 ~ 48 hours, obtain directed agents; Again by by silicon source, aluminium source, alkali compounds, water and directed agents mixing, make the mol ratio of each material in mixture for (3.0 ~ 4.2) Na
2o:Al
2o
3: (1.8 ~ 2.0) SiO
2: (150 ~ 200) H
2o, and make directed agents account for 1.0 ~ 15 quality % of total material, 95 ~ 100 DEG C of crystallization 3.0 ~ 6.0 hours, obtain NaA molecular sieve,
(2) by NaA molecular sieve, modified molecular screen and binding agent mixing roller forming, with alkaline solution treatment after 450 ~ 600 DEG C of roastings, then ion-exchange is carried out with calcium salt or magnesium salt solution, dry.
In said method, (1) step is prepare the ultra micro A type molecular sieve that grain size of the present invention is 0.1 ~ 1.0 micron, first prepares directed agents, then synthesize A type molecular sieve under the existence of directed agents.
The present invention introduces directed agents in the solution of synthesis A type molecular sieve, size distribution and the reunion degree of product can be improved well, and the crystallization time of zeolite can be made to shorten more than 90%, and obtain the A molecular sieve that grain size of the present invention is 100nm ~ 1.0 μm.The addition of directed agents preferably accounts for 1.0 ~ 10 quality % of the total material of synthesis A type molecular sieve.
Preparation directed agents charging sequence is preferably: by alkali compounds, preferred NaOH is dissolved in the water, and is heated to boiling, then is cooled to 20 ~ 50 DEG C, add aluminium source and make solution.This solution is added silicon source while stirring under the condition of azeotropic.
The present invention (1) step synthesis of molecular sieve and the directed agents preferred sodium metasilicate in silicon source, silica or Ludox used, the preferred sodium aluminate in aluminium source, sodium metaaluminate or aluminium isopropoxide, the preferred NaOH of alkali compounds.
Above-mentioned preparation method (2) step is for preparing adsorbent.For the adsorbent not containing modified molecular screen, its preparation method is that wherein molecular sieve content is 90 ~ 97 quality % first by NaA molecular sieve and kaolin mixing roller forming, and shaping bead particle diameter is 0.3 ~ 0.8mm.Shaping bead is preferable over 500 ~ 600 DEG C of roastings, alkali treatment is carried out with the sodium hydrate aqueous solution of 0.5 ~ 3.0mol/L, preferably 1.45 ~ 1.55mol/L, its alkali purification temp preferably 90 ~ 100 DEG C, preferably 3 ~ 4 hours processing time, after process, solid carries out ion-exchange with calcium salt or magnesium salt solution after washing, washing, drying obtain adsorbent, the chloride of described calcium salt or the preferred calcium of magnesium salts or magnesium or nitrate.Ion-exchange can be carried out repeatedly, and the exchange degree of calcium or magnesium ion reaches more than 70 % by mole, and described exchange degree is the amount that calcium or magnesium ion and exchange occupy the sodium ion of cation-bit.
Adsorbent containing modified molecular screen is substantially identical with the preparation method not containing the adsorbent of modified molecular screen, during unlike adsorbent roller forming, in NaA molecular sieve, adds modified molecular screen.Described modified molecular screen is selected from MCM-22, ZSM-11, Silicalite-1, ZSM-57, EU-1, NU-87, Theta-1 or ZSM-5.
Adsorbent provided by the invention is applicable to adsorbing separation n-alkane from hydrocarbon mixture, is specially adapted to from containing C
16~ C
30hydrocarbon mixture in adsorbing separation C
9~ C
30n-alkane.
Below by example in detail the present invention, but the present invention is not limited to this.
Preparing molecular sieve silicon source used in example is waterglass (sodium metasilicate, Shandong water glass plant produces), its SiO
2content is 28.30 quality %, modulus (silica equivalent in waterglass and the mol ratio of alkali metal oxide: SiO
2/ Na
2o) be 3.32.
Aluminium source is sodium metaaluminate (production of Shandong catalyst plant), its Al
2o
3content is 12.62 quality %, Crater corrosion (sodium oxide molybdena of equivalence in sodium aluminate solution and alumina molar ratio: Na
2o/Al
2o
3) be 2.45.
Example 1
Prepare adsorbent of the present invention.
(1) directed agents is prepared
By 16Na
2o:Al
2o
3: 15SiO
2: 320H
2the molar ratio of O prepares directed agents.First be dissolved in 79g deionized water by 18.79gNaOH solid particle, be uniformly mixed, add sodium metaaluminate 21.02g successively, waterglass 82.86g, fully stir 60 minutes, aging 25 hours of 30 DEG C of constant temperature, obtaining milky colloidal solution was directed agents.
(2) NaA molecular sieve is prepared
Be dissolved in 85.4g deionized water by 1.74g NaOH solid particle, be uniformly mixed, add 7.42g waterglass successively, 12.92g directed agents, 25.56g sodium metaaluminate, stir 30 minutes, obtain thick shape silica-alumina gel, wherein molar ratio of material is 4.1Na
2o:Al
2o
3: 1.8SiO
2: 200H
2o, added directed agents accounts for 1.2 quality % of total inventory.Being sealed in by above-mentioned silica-alumina gel in polypropylene vial and being placed in water bath with thermostatic control, 99 DEG C of crystallization 4 hours, are then cooled to 25 DEG C, filter, gained solid spends deionized water to cleaning solution pH<9.0, and after washing, solid was in 100 DEG C of dryings 12 hours, obtained NaA(4A) molecular sieve, its grain size is 0.1 ~ 1.0 μm, XRD spectra is shown in Fig. 1, XRD highest peak d=4.107,3.714,3.293 aperture is
naA molecular sieve mole consists of: Na
2oAl
2o
32SiO
2.
(3) adsorbent is prepared
By NaA molecular sieve powder and kaolin, (Linfen, Shanxi produces, containing 90 quality % kaolinites) mix by the mass ratio of 92:8, put into rolling limit, rotating disk limit and spray into appropriate deionized water, so that solid powder agglomerates into the bead that particle diameter is 0.3 ~ 0.8mm, the water yield sprayed into during spin is 12 quality % of solid powder.By bead in 540 DEG C of roastings 2 hours, be then the sodium hydroxide solution process 3 hours of 1.5mol/L by concentration, 100 DEG C of dryings 10 hours, 540 DEG C of roastings, 2 hours obtained matrix pellet.
Get above-mentioned matrix pellet, carry out Ca with the calcium chloride water that concentration is 0.25mol/L
2+exchange.Ion-exchange CaCl used
2the amount of solution should make Ca
2+/ Na
+equivalent proportion is 1.5.Matrix pellet is put into the CaCl of amount of calculation
2in solution, be heated to boil, keep boiling temperature to carry out ion-exchange 4 hours, divided by solution and exchange better several times, final calcium ion-exchanged degree is 75 % by mole, and after ion-exchange, solid obtains adsorbent A in 10 hours in 100 DEG C of dryings, wherein containing CaA(5A) molecular sieve 95 quality %, kaolin 5 quality %.
Example 2
Preparing adsorbent by the method for example 1, is 64.60g unlike directed agents addition in (2) step, accounts for 5.96 quality % of total synthesis material, in (3) step, the matrix pellet of roller forming is carried out Mg
2+exchange, the MgCl of exchange liquid used to be concentration be 0.25mol/L
2solution, Mg
2+exchange degree is 75 % by mole, obtains adsorbent E, wherein containing MgA molecular sieve 94 quality %, kaolin 6 quality %.
Example 3
Prepare adsorbent by the method for example 1, unlike after NaA molecular sieve powder being mixed with MCM-22 molecular sieve in (3) step again with kaolin roller forming, NaA molecular sieve: MCM-22 molecular sieve: kaolinic mass ratio is 90:6:4.Adsorbent B is obtained, wherein containing CaA molecular sieve 92 quality %, MCM-22 molecular sieve 5 quality %, kaolin 3 quality % after obtained matrix pellet calcium ion-exchanged.
Example 4
Adsorbent is prepared by the method for example 1, unlike after NaA molecular sieve powder being mixed with Silicalite-1 molecular sieve (total silicon ZSM-5) in (3) step again with kaolin roller forming, NaA molecular sieve: Silicalite-1 molecular sieve: kaolinic mass ratio is 84:11:5.Adsorbent C is obtained, wherein containing CaA molecular sieve 86 quality %, Silicalite-1 molecular sieve 10 quality %, kaolin 4 quality % after obtained matrix pellet calcium ion-exchanged.
Example 5
Prepare adsorbent by the method for example 1, unlike after NaA molecular sieve powder being mixed with EU-1 molecular sieve in (3) step again with kaolin roller forming, NaA molecular sieve: EU-1 molecular sieve: kaolinic mass ratio is 83:14:3.Adsorbent D is obtained, wherein containing CaA molecular sieve 85 quality %, EU-1 molecular sieve 13 quality %, kaolin 2 quality % after obtained matrix pellet calcium ion-exchanged.
Comparative example 1
Ultra-fine NaA molecular sieve is prepared by the method for CN 1305767C.
Sodium silicate solution is configured to, wherein Na by soluble in water for waterglass
2o content is 45g/L, SiO
2content is 120g/L, and sodium aluminate solution is configured to sodium aluminate solution in NaOH solution, wherein Na
2o content is 90g/L, A1
2o
3content is 60g/L.1g APG is added the above-mentioned sodium aluminate solution of 140m1 fully to stir, then press A1
2o
3/ SiO
2the amount of=1.8 adds above-mentioned sodium silicate solution, regulates material pH value to be 10 rear strong stirring 10 minutes, obtain colloid with sodium hydroxide solution.
Above-mentioned colloid is loaded crystallization device, is warming up to 75 DEG C, static crystallization 30 minutes.Filter, gained solids washed with water to cleaning solution pH value is 8,200 DEG C of dryings 5 hours, obtains ultra-fine NaA molecular sieve, and its grain size is 1.2 ~ 2.0 μm.
Above-mentioned ultra-fine NaA molecular sieve powder is mixed with kaolin, by example 1(3) the method roller forming of step, then carry out Ca
2+exchange, exchange degree reaches 75 quality %, obtains adsorbent F, wherein containing CaA molecular sieve 95 quality %, kaolin 5 quality %.
Comparative example 2
Conventional NaA molecular sieve is prepared by the method for CN1087030A.
With sodium aluminate (Na
2oAl
2o
33H
2o) with sodium metasilicate (Na
2siO
35H
2o) and sodium hydroxide solution be raw material, by 3.165Na
2o:Al
2o
3: 1.926SiO
2: 128H
2o mol ratio prepares synthesized gel rubber as follows:
(1) 7.23g NaOH is dissolved in 800ml deionized water, solution is divided equally, be positioned over respectively in two polypropylene vial.
(2) in one bottle of NaOH solution, add 82.58g sodium aluminate, stir 20 minutes all mixed, cap seal place until clarification.
(3) in another bottle of NaOH solution, add 154.80g sodium metasilicate, stir 20 minutes all mixed, cap seal place until clarification.
(4) solution that (3) step is obtained is poured in the obtained solution of (2) step fast, until thick shape homogeneous gel generates.
Kaolin and sesbania powder is added in the gel that (4) step obtains, kaolinic addition is 20 quality % of total inventory, the addition of sesbania powder is 0.5 quality % of total inventory, after adding kaolin and sesbania powder, under agitation heat to 105 DEG C of reactions and generate NaA molecular sieve in 3 hours, drain after filtration, shaping, dry in 500 DEG C of roastings 3 hours, with 1.0mol/L sodium hydroxide solution process 2 hours, treatment temperature is 96 DEG C, obtains 4A molecular sieve, and its particle diameter is 2 ~ 4 μm.
Above-mentioned 4A molecular sieve 1.0mol/L calcium chloride solution is carried out ion-exchange 6 hours in 80 DEG C, obtains 5A dewaxing by molecular sieve adsorbent H, wherein containing CaA molecular sieve 95 quality %, kaolin 5 quality %.
Example 6
The adsorbent that this example is prepared the present invention and contrast adsorbent carry out performance evaluation.
Load the adsorption column of absorber in 500 DEG C of activation after 2 hours by adsorbent, adjustment temperature is 177 DEG C, and pressure is 1.6MPa, and testing raw material one used is 16.0 quality % hexadecane (nC
16) and 84.0 quality % isooctane (iC
8) mixture, raw material two is 16.0 quality % n-decane (nC
10) and 84.0 quality % isooctane (iC
8) mixture.Use measuring pump (2PB80C type, Beijing Satellite Manufacturing Factory) with 1.0h raw material one
-1air speed inject adsorbent bed, after making its complete saturated adsorption, then switch to raw material two, with 1.0h by entering adsorbent bed raw material
-1air speed replaces the nC adsorbed
16, along with nC
10continuous inflow, flows out nC in adsorbent bed material
16content raises gradually, and in final and raw material one, content is completely close, then switches to raw material one by entering adsorbent bed charging again, the nC in displacement sorption agent bed
10, detect and flow out nC in adsorbent bed material
10and nC
16the relation that content is changed in time, enters the time of adsorption column for abscissa, with c/c with raw material
0for ordinate curve plotting (breakthrough curve), c flows out by the content of absorbed component in the logistics of adsorption column in a certain moment, c
0for in raw material by the content of absorbed component, Fig. 2 is shown in by breakthrough curve schematic diagram.By nC
10and nC
16the each adsorbent that calculates of breakthrough curve be separated nC
10and nC
16correlation performance parameters in table 1, use the same method and obtain positive octacosane (nC
28) adsorption breakthrough curve, each adsorbent calculated by breakthrough curve is separated nC
28correlation performance parameters in table 1.
Table 1
As known from Table 1, the performance of adsorbent (A ~ E) prepared by the present invention is all obviously better than the adsorbent of comparative example 1 ~ 2 preparation, static saturated adsorption capacity (q
0) be all greater than 150mg/g, particularly for nC
16absorption property on more obvious, in table 1, mass-transfer zone length shorter expression adsorbent performance is better.
In table 1, each evaluation index presses formula (1) ~ (6) calculating.
1, saturated extent of adsorption q
0
2, the proportionality coefficient f of adsorbent is not utilized in mass-transfer zone
3, mass-transfer zone length Z
a
4, dynamic adsorbance q
5, bed utilization rate β
6, overall mass transfer coefficient K
f
In above-mentioned computing formula, each symbol implication is as follows:
Q
0: saturated extent of adsorption, mg/g
Q: dynamic adsorbance, mg/g
V: the flow entering adsorbent bed raw material, ml/min;
ρ: by the density of absorbed component, g/ml;
C: a certain moment flows out by the content of absorbed component in the logistics of adsorption column, wt%;
C
0: by the content of absorbed component in raw material, wt%;
C
b: go out by the content of absorbed component in absorber logistics when breakthrough point, wt%;
M: the butt amount of adsorbent filling, g;
T
b: adsorption penetration time (c/c
0adsorption time when being 0.1), min;
T
e: adsorption saturation time (c/c
0adsorption time when being 0.9), min;
T: raw material enters the time of adsorption column, min;
N
1: by the amount of absorbed component in bed space, mg
N
2: by the amount of absorbed component in the dead volume of entry/exit absorber pipeline, mg;
Z
a: absorption mass-transfer zone length, mm;
Z: adsorption bed length, mm;
F: the proportionality coefficient not utilizing adsorbent in mass-transfer zone;
β: bed utilization rate (bed saturation degree);
U: fluid line speed, mm/min, K
f: overall mass transfer coefficient.
Claims (6)
1. a dewaxing by molecular sieve adsorbent, comprise the binding agent of the A molecular sieve of 70 ~ 98 quality %, the modified molecular screen of 1 ~ 25 quality % and 1 ~ 8 quality %, described modified molecular screen is selected from MCM-22, ZSM-11, Silicalite-1, ZSM-57, EU-1, NU-87, Theta-1 or ZSM-5, the grain size of described A molecular sieve is 0.1 ~ 1.0 micron, and its cation is Ca
2+or Mg
2+, described binding agent is selected from kaolin, rectorite, Yun Mengshi, bentonite or imvite.
2., according to adsorbent according to claim 1, it is characterized in that described adsorbent comprises the binding agent of the A molecular sieve of 75 ~ 95 quality %, the modified molecular screen of 4 ~ 20 quality % and 1 ~ 5 quality %.
3. a preparation method for adsorbent described in claim 1, comprises the steps:
(1) by silicon source, aluminium source, alkali compounds and water mixing, mol ratio is mixed with for (15 ~ 17) Na
2o:Al
2o
3: (14.0 ~ 16.0) SiO
2: (270 ~ 374) H
2the mixed material of O, 10 ~ 30 DEG C are aging 20 ~ 48 hours, obtain directed agents; Again by by silicon source, aluminium source, alkali compounds, water and directed agents mixing, make the mol ratio of each material in mixture for (3.0 ~ 4.2) Na
2o:Al
2o
3: (1.8 ~ 2.0) SiO
2: (150 ~ 200) H
2o, and make directed agents account for 1.0 ~ 15 quality % of total material, 95 ~ 100 DEG C of crystallization 3.0 ~ 6.0 hours, obtain NaA molecular sieve,
(2) by NaA molecular sieve, modified molecular screen and binding agent mixing roller forming, with alkaline solution treatment after 450 ~ 600 DEG C of roastings, then ion-exchange is carried out with calcium salt or magnesium salt solution, dry.
4. in accordance with the method for claim 3, it is characterized in that described silicon source is sodium metasilicate, silica, Ludox, aluminium source is sodium aluminate, sodium metaaluminate or aluminium isopropoxide, and alkali compounds is NaOH.
5. in accordance with the method for claim 3, it is characterized in that described modified molecular screen is selected from MCM-22, ZSM-11, Silicalite-1, ZSM-57, EU-1, NU-87, Theta-1 or ZSM-5.
6. in accordance with the method for claim 3, it is characterized in that the aqueous slkali described in (2) step is NaOH solution, its concentration is 0.5 ~ 3.0mol/L, and its alkali purification temp is 90 ~ 100 DEG C.
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| CN109012225B (en) * | 2018-07-27 | 2021-03-16 | 西安建筑科技大学 | Application of self-supporting Li-ABW molecular sieve membrane in separation of calcium ions in hard water |
| CN111111609B (en) * | 2018-10-30 | 2022-02-22 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method and application thereof |
| WO2020225911A1 (en) * | 2019-05-09 | 2020-11-12 | 日新電機株式会社 | Insulating gas adsorbent and gas-insulated power equipment |
| CN111672458A (en) * | 2020-06-23 | 2020-09-18 | 江苏华邑环境科技有限公司 | Flame-retardant honeycomb adsorbent and preparation method and application thereof |
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| CN87105499A (en) * | 1987-08-03 | 1988-09-21 | 金凌石油化工公司南京炼油厂 | Production method of binder-free spherical model-a molecular sieves |
| US4818508A (en) * | 1985-08-20 | 1989-04-04 | Uop | Process for preparing molecular sieve bodies |
| CN102451664A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of adsorbent used for whole naphtha adsorption separation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818508A (en) * | 1985-08-20 | 1989-04-04 | Uop | Process for preparing molecular sieve bodies |
| CN87105499A (en) * | 1987-08-03 | 1988-09-21 | 金凌石油化工公司南京炼油厂 | Production method of binder-free spherical model-a molecular sieves |
| CN102451664A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of adsorbent used for whole naphtha adsorption separation process |
Non-Patent Citations (1)
| Title |
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| 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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