CN106552582B - From C8The adsorbent and preparation method of ethylbenzene are separated in aromatic hydrocarbons - Google Patents
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Abstract
One kind is from C8The adsorbent of ethylbenzene is separated in aromatic hydrocarbons, the kaolin matrix of Cs-Na-X zeolite and 0.5~5 mass % including 95~99.5 mass %, it is 0.1~0.5 micron that Cs ion, which at least accounts for the size of microcrystal of 67%, the X zeolite of X zeolite exchangeable cations position, in the Cs-Na-X zeolite.Adsorbent ethylbenzene selectivity with higher and mass transfer rate.
Description
Technical field
The present invention is a kind of ethylbenzene adsorbent and preparation method, specifically, being a kind of from mixing C8It is inhaled in aromatic component
Adsorbent and preparation method of the Fufen from ethylbenzene.
Background technique
Ethylbenzene is important basic organic chemical raw material, mainly for the production of styrene, and then produces polystyrene and ABS
Resin etc..Ethylbenzene is mainly synthesized by benzene alkylation with ethylene method at present.Mix C8Aromatic hydrocarbons includes ethylbenzene, paraxylene, diformazan
Four kinds of isomers of benzene and ortho-xylene are difficult to separate in ethylbenzene since boiling point is close using conventional rectification method, industrial universal
The separation between isomer is realized using the method for selective absorption.
The principle of adsorbing separation is not adsorb purpose product using its Preferential adsorption or preferentially using specific adsorbent
Characteristic cooperates process form appropriate to separate from mixed raw material, purifies purpose product.Adsorbent is the base of adsorption separation technology
Plinth and core, in the prior art, from mixing C8The adsorbent of aromatics absorption separation ethylbenzene is broadly divided into two classes, one kind be it is preferential not
Ethylbenzene, the i.e. non-ethylbenzene component of Preferential adsorption are adsorbed, obtains ethylbenzene product from inhaling in excess.Such as USP3917734, USP4079094
And USP4108915 uses Ca-X/Y, Sr-K-X or Sr-X zeolite, Preferential adsorption C respectively8Xylene isomer in aromatic hydrocarbons, from
It inhales in excess and obtains ethylbenzene product.It is more difficult to obtain high purity ethylbenzene product using such adsorbent, and its purity vulnerable to
The influence formed to raw material.
Another kind of adsorbent Preferential adsorption ethylbenzene, in raw material ethylbenzene be adsorbed agent Preferential adsorption to its excess-three kind isomery
Body separation reuses strippant desorption ethylbenzene and obtains Extract, recycles strippant by rectifying and obtain ethylbenzene product.
USP5453560 discloses a kind of Cs-X zeolite adsorbents, the adsorbent Preferential adsorption ethylbenzene, wherein X zeolite silicon
Aluminium is than preferably smaller than 2.1, and cesium ion exchange degree is preferably greater than 40%, and strippant selects the mixing of toluene or toluene and p-Diethylbenzene
Object.This method does not limit X zeolite grain size.
X zeolite exchangeable cations is one of Cs and Sr, K or Na in USP3867470, it is required that the exchange degree of Cs
Reach 0.0119A-0.5, wherein atomicity of the A for aluminium in faujasite structure cell, the exchange degree of Cs minimum 0.15, either
0.0119A-0.7.Cs ion-exchange degree is about 58% in USP4593149, the preferred n-nonyl benzene of strippant.
Summary of the invention
The object of the present invention is to provide one kind from C8The adsorbent and preparation method of ethylbenzene, the adsorbent are separated in aromatic hydrocarbons
Ethylbenzene selectivity with higher and mass transfer rate.
It is provided by the invention from C8The adsorbent that ethylbenzene is separated in aromatic hydrocarbons, the Cs-Na-X boiling including 95~99.5 mass %
The kaolin matrix of stone and 0.5~5 mass %, Cs ion at least accounts for X zeolite exchangeable cations in the Cs-Na-X zeolite
The size of microcrystal of 67%, the X zeolite of position is 0.1~0.5 micron.
Adsorbent of the present invention uses fine-grain X zeolite for active component, and the cation-bit of zeolite is by more
Cs ion occupies.The adsorbent is used for from C8Adsorbing separation ethylbenzene in aromatic hydrocarbons, ethylbenzene selectivity with higher.
Detailed description of the invention
Fig. 1 is the flow diagram that moving-bed adsorption separation ethylbenzene process is carried out using adsorbent of the present invention.
Specific embodiment
The present invention rolls molding after mixing little crystal grain NaX zeolite powder with kaolin, at aqueous slkali after dry, roasting
Reason, so that the part kaolin in-situ in shaped granule is turned brilliant is X zeolite；By the aqueous solution of the shaped granule cesium salt after turning brilliant into
Row ion exchange occupies exchangeable cations position in part in adsorbent largely by cesium ion, is made after drying, activation
Adsorbent.It the use of the high fine-grain X zeolite of cesium ion exchange degree is active component in adsorbent of the present invention, adsorbent not only holds
Amount is big, mass transfer rate is high, but also ethylbenzene selectivity with higher.
In Cs-Na-X zeolite of the present invention, Cs ion preferably accounts for the 73~85% of X zeolite exchangeable cations position,
Remaining is Na ion.
The silica/alumina molar ratio preferably 2.0~2.4, more preferable 2.0~2.3 of the X zeolite.
Adsorbent is reduced after there is adsorbent of the present invention less water content, adsorbent to roast 2 hours in 600 DEG C
Quality and the ratio for roasting preceding quality, i.e., 600 DEG C of igloss amount is preferably 0.1~1.0 mass %, more preferable 0.1~0.5 matter
Measure %.
The kaolin matrix is the residue after kaolin turns brilliant, and the crystallization object in the kaolin is selected from kaolinite
One of stone, galapectite, dickite, nacrite and ovenstone are a variety of.Crystallization content of material is at least 90 matter in kaolin
Measure %.
The preparation method of adsorbent provided by the invention, includes the following steps:
(1) sodium form X zeolite powder and kaolin are mixed by the mass ratio of 88~96:4~12, rolling balling, after dry
It is roasted in 500~700 DEG C,
(2) by the mixed solution of bead sodium hydroxide solution or sodium hydroxide and sodium metasilicate after roasting in 90~100
DEG C carry out alkali process, make the kaolin in-situ crystallization X zeolite in bead,
(3) aqueous solution of the bead cesium salt after (2) step alkali process is subjected to ion exchange, the ion-exchange temperature
It is 90~150 DEG C, the bead after ion exchange is washed, dries post activation.
In the above method, (1) step is by NaX zeolite and kaolin roller forming, when roller forming, by na-pretreated zeolite and high
Ridge soil is mixed and made into mixed powder by scheduled mass ratio, mixed powder is put into roll turntable, coating pan or roller etc. at
In type equipment, suitable water is sprayed into mixed material when rolling, the additional amount of water is the 10~40 of mixed powder gross mass
Quality %, preferably 20~30 mass %；Mixed powder under the action of aqueous solution gradually at bead and grow up by cohesive mass, rolls
It is taken out after molding to certain particle size bead, screening, takes 0.2~1.5 millimeter of diameter, preferably 0.35~0.80 millimeter of bead is done
Molding bead is made in dry, roasting.Preferably 80~120 DEG C of the drying temperature, the time preferably 4~12 hours；Maturing temperature is excellent
500~650 DEG C, the time preferably 2~6 hours are selected, the crystallization substance that kaolin contains in bead can be made to activate by roasting, with
Just in-situ crystallization is carried out.
Shaping assistant can be added by rolling in forming process, such as sesbania powder, starch, carboxymethyl cellulose or active carbon, be helped
Agent additional amount is 1~8 mass %, preferably 2~5 mass % of zeolite and kaolin gross mass.
The method (2) step by after (1) one-step baking molding bead carry out alkali process, make wherein can zeolitization kaolin
In-situ crystallization is X zeolite, and to further increase the adsorption capacity of bead after roasting, and alkali process turns brilliant process and also makes in bead
Closer combination is formed between the zeolite grain in portion.
(2) liquid/solid volume ratio when step alkali process in-situ crystallization is 1.2~2.0:1.In-situ crystallization handles lye used
The mixed solution of sodium hydroxide or sodium hydroxide and sodium metasilicate, the purpose that sodium metasilicate is added in sodium hydroxide solution is to improve
Silicone content in lye, to be easy to kaolin in-situ crystallization as X zeolite.
When the lye used in the alkali process is sodium hydroxide solution, concentration preferably 1.0~4.0 mol/Ls；When lye is hydrogen
When the mixed solution of sodium oxide molybdena and sodium metasilicate, the content of sodium oxide molybdena preferably 3.0~8.0 mass %, titanium dioxide in the mixed solution
The content of silicon preferably 1.0~7.0 mass %.The temperature that alkali process carries out in-situ crystallization is 90~100 DEG C, the time preferably 3~10
Hour.It is after in-situ crystallization that gained bead is ion-exchangeable after washing.
The method (3) step is that the bead by (2) step after alkali process carries out ion exchange and activation, makes to hand in zeolite
The major part for changing cation-bit is occupied by Cs ion.
(3) step prepares the preferred cesium chloride of cesium salt, cesium nitrate or cesium sulfate used in exchange liquid.Ion exchange preferably uses will
Exchange liquid continues through the method progress of bead after alkali process, it is preferred to use the continuous exchange process of pillar, exchange temperature preferably 90~
130 DEG C, pressure preferably 0.1~0.8MPa, exchanging liquid product air speed preferably 1~8h-1.It exchanges in the Cs ion and adsorbent in liquid
The molar ratio of Na ion, i.e. ion exchange ratio are 3~8.
(3) step is that the bead after ion exchange is washed and activated, and the bead is washed to remove
It is activated after free metal ion, to remove the moisture in adsorbent, reaches suitable water content.Activation is preferably in nitrogen
It is carried out in stream or air stream, preferably 200~400 DEG C of activation temperature, the time preferably 2~8 hours.
(3) bead after step ion exchange is washed, it is dry after activation carried out in nitrogen stream or air stream, activation temperature
Preferably 300~400 DEG C of degree.Activation time preferably 2~8 hours.
Adsorbent provided by the invention is suitable for the adsorption separation process of arene isomer, especially from mixing C8In aromatic hydrocarbons
Adsorbing separation ethylbenzene.Liquid phase can be used in the adsorbing separation or the multicolumn series system of gas phase is operated, and can also be used and borrows
The Simulation moving bed mode for helping rotary valve or sequencing valve to realize is operated.Adsorbing separation operation temperature is 100-190 DEG C, operation
Pressure is 0.5-2.0MPa.
The important indicator for measuring performance of the adsorbent is adsorbent to the adsorption capacity of aromatic hydrocarbons, adsorptive selectivity and to ethylbenzene
Adsorption and desorption rate.
Adsorptive selectivity refers to when reaching adsorption equilibrium, adsorbs in phase in the quality of two components or volume ratio and fluid phase
The ratio between quality or volume ratio of two component.The adsorption equilibrium refers to C8After aromatic hydrocarbons is contacted with adsorbent, Xiang Yufei is adsorbed
The state when transfer of net component does not occur between absorption phase.The calculation formula of adsorptive selectivity are as follows:
E and R respectively indicates absorption mutually and inhales remaining phase in above formula, and Ea, Eb respectively indicate two constituent mass or body in absorption phase
Product ratio, Ra, Rb respectively indicate two constituent mass or volume ratio in the remaining phase of suction.When two component selection β are about 1.0, they that
This is adsorbed or unadsorbed degree is almost the same, and there is no the Preferential adsorptions of one of component.When β is more than or less than
When 1.0, that is, a kind of separation process that component is preferentially adsorbed is occurred in which, specifically, adsorbent is to A group when β is greater than 1.0
Divide Preferential adsorption, adsorbent is to B component Preferential adsorption when β is less than 1.0.Consider from the complexity of adsorption separation process, mentions
Take component for remaining component, β value is bigger, the easier progress of adsorbing separation, and then can reduce adsorbent amount
With the circulation dosage of strippant, the operating cost of adsorption separation device is reduced, improves purpose product yield and purity.
The present invention measures the rate of adsorptive selectivity and Adsorption and desorption ethylbenzene using dynamic pulse experimental provision.The device
It is made of feed system, adsorption column, heating furnace and pressure-control valve etc..The stainless steel that adsorption column is 8 × 1 × 1800 millimeters of Φ
Coil pipe, adsorbent inventory are 50 milliliters, are placed in temperature automatically controlled vertical heater and heat.Adsorption column lower inlet and charging
It is connected with nitrogen system, upper end outlet connects voltage-controlled valve and connect with effluent collector.
The continuous mode of dynamic pulse experiment are as follows: load weighted adsorbent is packed into adsorption column concussion and is tamped, nitrogen is passed through
With the air in displacement sorption column, the gas in strippant removal system is then passed to, pressure is risen into 0.8MPa, temperature rises to
130 DEG C, stopping is passed through strippant, when by 1.0-1Volume space velocity be passed through 8 milliliters of pulsed feeds, then change general solution vapor and with
Same air speed is desorbed, and is taken within every 2 minutes a drop desorption liquid sample, is formed with gas chromatographic analysis.With desorption strippant
Feed volume is abscissa, and n -nonane, ethylbenzene, paraxylene, meta-xylene and ortho-xylene each component concentration are ordinate, can
To draw out the peak-shaped curve that above-mentioned each component content increases with strippant dosage and changed.N -nonane as tracer not by
Absorption, first appearance, it gives the dead volume of adsorption system.Using the midpoint of tracer half-peak breadth as zero point, measure ethylbenzene,
The strippant feed volume of paraxylene, meta-xylene and ortho-xylene each component half-peak breadth midpoint to zero point, i.e., net retention body
Product VR.The net retention volume of any component is directly proportional to distribution coefficient when adsorption equilibrium, and it is flat that it reflects Isomers absorption
The case where weighing apparatus.The ratio between two component net retention volumes are adsorptive selectivity β value, also referred to as separation.
It is selectively also one important in order to realize the circulation continuous use of adsorbent, between extraction components and strippant
Performance indicator.The present invention is by determining the further parsing of pulse test extraction components peak-shaped curve.By the pulse of ethylbenzene
Required strippant volume is defined as when ethylbenzene concentration rises to 90 mass % from 10 mass % in the efflux of peak-shaped curve forward position
The rate of adsorption [SA]10-90, strippant volume required when dropping to 10 mass % from 90 mass % along ethylbenzene concentration after curve is determined
Justice is desorption rate [SD]90-10, the ratio [S of the twoD]90-10/[SA]10-90It can indicate ethylbenzene (EB) and strippant toluene (T)
Between adsorptive selectivity βEB/T.If βEB/TLess than 1.0, indicate that adsorbent is strong to the selectivity of strippant, this is to adsorption process
Unfavorable, if βEB/TMuch larger than 1.0, then it represents that strippant adsorption capacity is too weak, it will become difficult desorption process, preferably
Situation is ratio betaEB/TEqual or slightly larger than 1.0.
The present invention is further illustrated below by example, but the present invention is not limited thereto.
In example and comparative example, the aromatics absorption capacity of adsorbent is by sample under certain condition to the absorption meter of toluene
It calculates, determination condition is to carry toluene vapor by adsorbent with the nitrogen of atmospheric flow until adsorption saturation, first under 35 DEG C of constant temperature
The relative pressure of benzene vapor is 0.5 (ratio that relative pressure is toluene partial pressure and test temperature Toluene saturated vapour pressure)；It surveys
Toluene amount when adsorbent reaches adsorption saturation is determined to get the toluene adsorption capacity of adsorbent.Set the toluene adsorbance of X zeolite
It is 234 milligrams per grams, the toluene adsorbance of adsorbent is directly proportional to the zeolite content in adsorbent, bead after measurement alkali process
Toluene adsorbance can calculate the content of X zeolite in adsorbent.
Example 1
Prepare adsorbent of the present invention.
(1) roller forming: average by 94 kilograms (butt quality, similarly hereinafter, Sinopec catalyst Chang Ling branch company produce)
The NaX zeolite powder and 6 kilograms of kaolin (crystallization objects that size of microcrystal is 0.3 micron, silica/alumina molar ratio is 2.17
Matter content is 92 mass %, and Linfen, Shanxi produces) and 3.4 kilograms of sesbania powders are uniformly mixed forms mixed powder, are put into side in turntable
It rolls side and sprays into suitable water, solid mixed powder is made to be agglomerated into bead, the water that when rolling sprays into is solid mixed powder
25 mass %.It is 0.35~0.80 millimeter of bead that sieve, which takes diameter, 80 DEG C drying 10 hours, in air stream 540 DEG C to roast 4 small
When.
(2) in-situ crystallization: by the matrix pellet after above-mentioned roasting in liquid/solid volume ratio be 1.6:1 ratio, be with concentration
The sodium hydroxide solution of 1.5 mol/Ls, in 96 DEG C stewing process 4.0 hours, so that kaolin in-situ crystallization therein is converted into X
Zeolite, then being washed with deionized to cleaning solution pH value is 9.0.
(3) ion exchange: washed bead after 100 milliliters of (2) step in-situ crystallization processing is taken, ion exchange column is put into
In, it is passed through exchange liquid and is carried out continuously ion exchange, exchange liquid uses concentration for the CsCl aqueous solution of 0.5 mol/L, exchange temperature
It is 95 DEG C, pressure 0.1MPa, exchanging liquid product air speed is 5.0 hours-1, exchange Cs in liquid and exchange to compare and be with Na in adsorbent
4.0.After the completion of ion exchange, being washed with 700 ml deionized waters can't detect Cl into cleaning solution-Ion.
(4) it activates: the bead after ion exchange is activated 5 hours in 350 DEG C of nitrogen streams, adsorbent A, composition is made
Transitivity data are shown in Table 1.
Example 2
Adsorbent is prepared by the method for example 1, the difference is that (1) step roller forming is 0.2 micro- using average crystal grain partial size
Mixed powder is made in rice, NaX zeolite powder, kaolin and the sesbania powder that silica/alumina molar ratio is 2.05.Suction obtained
The composition transitivity data of attached dose of B are shown in Table 1.
Example 3
Adsorbent is prepared by the method for example 1, the difference is that the lye of addition is that concentration 1.5 is rubbed when (2) step in-situ crystallization
You/liter sodium hydroxide and modulus be 3.66 waterglass mixed liquor, wherein contain 4.4 mass % of sodium oxide molybdena, silica
1.32 quality %.The composition transitivity data of adsorbent C obtained are shown in Table 1.
Example 4
Adsorbent is prepared by the method for example 1, the difference is that the concentration of CsCl solution used in (3) step ion exchange is 0.3
Mol/L, exchange temperature are 130 DEG C, pressure 0.5MPa, and air speed is 5.0 hours-1, ion exchange ratio is 4.0.Absorption obtained
The composition transitivity data of agent D are shown in Table 1.
Example 5
Adsorbent is prepared by the method for example 1, the difference is that bead is placed in 300 DEG C of nitrogen streams living when the activation of (4) step
Change 4 hours, the composition transitivity data of adsorbent E-1 obtained are shown in Table 1.
Example 6
Adsorbent is prepared by the method for example 1, the difference is that bead is placed in 250 DEG C of nitrogen streams living when the activation of (4) step
Change 3 hours, the composition transitivity data of adsorbent E-2 obtained are shown in Table 1.
Example 7
Adsorbent is prepared by the method for example 1, the difference is that when (1) step roller forming, by 92 kilograms of silica/aluminas
NaX zeolite, 8 kilograms of kaolin and the 4 kilograms of carboxymethyl celluloses that molar ratio is 2.30, average crystal grain partial size is 0.4 micron are mixed
It closes uniformly, the water that when spin sprays into is 30 mass % of solid mixed powder.
(2) when step carries out in-situ crystallization, the ratio for being 1.5:1 in liquid/solid volume ratio is molten with 1.7 mol/L sodium hydroxides
The mixed solution for the waterglass that liquid and modulus are 3.66, wherein containing 4.2 mass % of sodium oxide molybdena, silica 1 .45 mass %.
(3) when step carries out ion exchange, CsCl solution concentration used is 0.7 mol/L, and exchange temperature is 120 DEG C, pressure
Power is 0.5MPa, and exchanging liquid product air speed is 4.0 hours-1, ion exchange ratio is 5.0.By the bead after ion exchange in 320 DEG C
It is activated 5 hours in nitrogen stream, adsorbent F is made, composition transitivity data are shown in Table 1.
Comparative example 1
Adsorbent is prepared by the method for example 1, the difference is that using average grain diameter when (1) step roller forming is 3 microns, oxygen
The NaX zeolite powder that SiClx/alumina molar ratio is 2.18, the composition transitivity data of adsorbent G-1 obtained are shown in Table 1.
Comparative example 2
Adsorbent is prepared by the method for example 1, the difference is that using average grain diameter when (1) step roller forming is 3 microns, oxygen
The NaX zeolite powder that SiClx/alumina molar ratio is 2.18；(3) autoclave ion exchange is used when step ion exchange, i.e., with exchange
Liquid stands bead of the dipping after in-situ crystallization, and CsCl solution concentration used is 0.3 mol/L, the liquid/solid volume of ion exchange
Than for 1.5:1, temperature is 95 DEG C, pressure 0.1MPa, ion exchange number is 4 times.The composition of adsorbent G-2 obtained and
Physical data is shown in Table 1.
Comparative example 3
Adsorbent is prepared by the method for example 1, the difference is that using autoclave ion exchange when (3) step ion exchange, that is, is used
It exchanges liquid and stands bead of the dipping after in-situ crystallization, CsCl solution concentration used is 0.4 mol/L, the liquid/solid of ion exchange
Volume ratio is 1.5:1, and temperature is 95 DEG C, pressure 0.1MPa, and ion exchange number is 3 times, the composition of adsorbent H obtained and
Physical data is shown in Table 1.
Example 8
50 milliliters of adsorbents are loaded in the adsorption column of dynamic pulse experimental provision of the present invention carries out dynamic pulse reality
It tests.Pulsed feeds liquid group becomes ethylbenzene, paraxylene, meta-xylene, ortho-xylene, n -nonane and 75 matter for respectively accounting for 5 mass %
The strippant of % is measured, for strippant group used as the toluene of 30 volume % and the normal heptane of 70 volume %, each adsorbent pulse is real
It tests and the results are shown in Table 2.
Example 9
The test of adsorbing separation ethylbenzene is carried out using adsorbent A on the Small-Scale Simulated Moving Bed of continuous flow upstream.
The Small-Scale Simulated Moving Bed device includes 24 concatenated adsorption columns, and every 195 millimeters of column length, internal diameter 30 is in the least
Rice, the total filling amount of adsorbent A are 3300 milliliters.One is connected and composed with circulating pump between the 1st pillar and the 24th pillar
A closed loop.24 adsorption columns are divided into four areas by four strands of absorption raw material, strippant, Extract, raffinate disengaging materials
Section, i.e. 7 adsorption columns between absorption raw material and raffinate are adsorption zone, 9 adsorption columns between Extract and absorption charging
For purification section, 5 adsorption columns between strippant and Extract are desorption zone, 3 adsorption columns between raffinate and strippant
For buffer area, Fig. 1 is seen.Entire absorption system temperature control is 130 DEG C, pressure 0.8MPa.
In operating process, it is used absorption raw material group become 15.17 mass % of ethylbenzene, 22.20 mass % of paraxylene,
The non-aromatics of 40.75 mass 5% of dimethylbenzene, ortho-xylene 19.70 mass % and 2.18 mass %.Respectively by 2019 milliliters/it is small
When and 1462 mls/hour of flow toluene and absorption raw material are continuously injected into above-mentioned Simulation moving bed device, and with 631
Ml/hour flow by Extract withdrawing device, the flows of 2850 millis l/h is by raffinate withdrawing device.Set circulating pump
Flow is 4560 mls/hour, according to Simulated Moving Bed Chromatography principle, flows to phase by with liquid every 80 seconds four bursts of material positions
Anti- 1 adsorption column of direction Forward, position as shown in phantom in Figure 1.
The ethylbenzene purity obtained under stable mode of operation is 99.98 mass %, and the rate of recovery is 98.5 mass %, thus
The ethylbenzene productivity of calculating is every cubic metre of adsorbent 0.066 cubic metre of adsorbing separation ethylbenzene per hour.
Comparative example 4
The test of Small-Scale Simulated Moving Bed adsorbing separation ethylbenzene is carried out by method described in example 9, the difference is that absorption used
Agent is comparison adsorbent G-2, and the ethylbenzene purity obtained under steady state operation is 99.72 mass %, and the rate of recovery is 89.38 matter
% is measured, the ethylbenzene productivity thus calculated is every cubic metre of adsorbent 0.060 cubic metre of adsorbing separation ethylbenzene per hour.
Table 1
* 600 DEG C roasting 2 hours after adsorbent reduction quality and roast before quality ratio
Table 2
Claims (10)
1. a kind of from C8The adsorbent of ethylbenzene, Cs-Na-X zeolite and 0.5 ~ 5 mass % including 95 ~ 99.5 mass % are separated in aromatic hydrocarbons
Kaolin matrix, Cs ion accounts for the 73 ~ 85% of X zeolite exchangeable cations position in the Cs-Na-X zeolite, remaining is Na
Ion, the size of microcrystal of X zeolite are 0.1 ~ 0.5 micron.
2. adsorbent described in accordance with the claim 1, it is characterised in that the silica/alumina molar ratio of the X zeolite is
2.0~2.4。
3. adsorbent described in accordance with the claim 1, it is characterised in that the adsorbent is 0.1 ~ 1.0 in 600 DEG C of igloss amount
Quality %.
4. adsorbent described in accordance with the claim 1, it is characterised in that the kaolin matrix is surplus after kaolin turns brilliant
Excess, the crystallization object in the kaolin are selected from one of kaolinite, galapectite, dickite, nacrite and ovenstone or more
Kind.
5. a kind of preparation method of adsorbent described in claim 1, includes the following steps:
(1) sodium form X zeolite powder and kaolin are mixed by the mass ratio of 88 ~ 96:4 ~ 12, rolling balling, it is dry after in 500 ~
700 DEG C of roastings,
(2) mixed solution of the sodium hydroxide solution of the bead after roasting or sodium hydroxide and sodium metasilicate is carried out in 90 ~ 100 DEG C
Alkali process makes the kaolin in-situ crystallization X zeolite in bead,
(3) aqueous solution of the bead cesium salt after (2) step alkali process is subjected to ion exchange, the ion-exchange temperature is 90
~ 150 DEG C, bead after ion exchange is washed, dry post activation.
6. according to the method for claim 5, it is characterised in that (2) liquid/solid volume ratio when step alkali process is 1.2 ~ 2.0:
1。
7. according to the method for claim 5, it is characterised in that (2) concentration of sodium hydroxide solution used in step alkali process is
The content of sodium oxide molybdena in 1.0 ~ 4.0 mol/Ls, sodium hydroxide and sodium metasilicate mixed solution is 3.0 ~ 8.0 mass %, titanium dioxide
The content of silicon is 1.0 ~ 7.0 mass %.
8. according to the method for claim 5, it is characterised in that (3) cesium salt described in step is cesium chloride, cesium nitrate or sulfuric acid
Caesium.
9. according to the method for claim 5, it is characterised in that (3) the ion exchange use of step will exchange liquid and continue through alkali
The method of treated bead carries out.
10. according to the method for claim 5, it is characterised in that (3) bead step ion exchange after is washed, it is dry after
Activation carries out in nitrogen stream or air stream, and activation temperature is 200 ~ 400 DEG C.
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| CN112169373B (en) * | 2019-07-05 | 2022-03-11 | 中国石油化工股份有限公司 | Method for adsorbing and separating target product by simulated moving bed |
| CN112573987B (en) * | 2019-09-29 | 2024-02-09 | 中国石油化工股份有限公司 | From C containing ethylbenzene 8 Method for producing paraxylene and ethylbenzene from aromatic hydrocarbon |
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