CN104477937A - Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof - Google Patents
Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof Download PDFInfo
- Publication number
- CN104477937A CN104477937A CN201410737917.XA CN201410737917A CN104477937A CN 104477937 A CN104477937 A CN 104477937A CN 201410737917 A CN201410737917 A CN 201410737917A CN 104477937 A CN104477937 A CN 104477937A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mesoporous
- type molecular
- sorbent material
- particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a preparation method of a mesoporous X-type molecular sieve and a method for preparing an adsorbent by using the molecular sieve as an active component. The prepared adsorbent based on the mesoporous X-type molecular sieve is used as a paraxylene adsorptive separation adsorbent. The method for preparing the mesoporous X-type molecular sieve comprises the following steps: by using water glass as a silicon source and aluminum hydroxide as an aluminum source, adding a template, and carrying out hydrothermal synthesis to obtain the mesoporous X-type molecular sieve. The mesoporous molecular sieve and kaolin are proportionally molded to obtain 0.3-0.8mm granules, and the granules are subjected to barium ion or (and) potassium ion exchange until the exchange degree is greater than 99%, thereby obtaining the adsorbent which has excellent adsorptive separation capacity for paraxylene in C8 aromatic hydrocarbons. Compared with the prior art, the active component mesoporous X-type molecular sieve of the adsorbent, which is prepared by using the template, has the crystal form structure of the X-type molecular sieve and the pore distribution of the mesoporous and microporous dual models; the mesoporous pore size distribution is 2nm or so; and thus, the problem of overlow mass transfer rate in the adsorbent can be solved.
Description
Technical field
The invention belongs to molecular sieve and Application Areas, especially relate to a kind of mesoporous X-type molecular sieve, based on the sorbent material of this molecular sieve and preparation and application thereof.
Background technology
P-Xylol is a kind of important Organic Chemicals, and highly purified p-Xylol is the basic raw material of trevira industry, and along with the develop rapidly of global polyester industrial, the market demand of p-Xylol significantly increases.Industrial production p-Xylol generally adopts simulated moving bed adsorption separating technology to produce, and p-Xylol adsorptive separation technology coordinates simulation moving-bed continuous countercurrent isolation technique to form by sorbent material, and its core is the development and application of high-efficiency adsorbent.
The U.S. global oil product (UOP) company points out that in initial patent Introduction FAU type molecular sieve is after potassium or (barium) exchange, adsorbable separating paraxylene, point out in patent US 3663638, after X-type molecular sieve or Y molecular sieve exchange certain density K, Ba ion, adsorption stripping dimethyl benzene respond well.Patent US 7638677B2 reports, in the technique of adsorption stripping dimethyl benzene, use worked in coordination with by BaX molecular sieve and KY molecular sieve can reach good fractionation by adsorption effect, BaX molecular sieve obtains by exchanging K, Ba ion on NaX molecular sieve, wherein kalium ion and natrium ion content is lower than 3wet%, KY molecular sieve is in NaY molecular sieve, exchange K ion, and the add-on of this molecular sieve is 6 ~ 10% of BaX molecular sieve volume.Patent US 7812208B2 has described the preparation process of BaX adsorbent of molecular sieve in detail, crystal grain is selected to be less than 1.8 μm, the X-type molecular sieve of Si/Al=1.15 ~ 1.5, by itself and kaolin and water mixing moulding, roasting is carried out to the particle after shaping, maturing temperature is greater than 600 DEG C, then particle being placed in sodium hydroxide solution makes it be converted into binder free particle, finally barium ion or the exchange of potassium barium ion are carried out to this particle, wherein exchange degree is greater than 99%, the adsorbable separating paraxylene of the sorbent material prepared.After US 7812208B2, issue patent US8283274 B2 again, the preparation process of report is similar to above-mentioned patent, select the X-type molecular sieve of Si/Al=1.15 ~ 1.35, W-Gum is auxiliary agent, and wherein the content of W-Gum is not more than 5wet%, with kaolin mixing moulding granulation by a certain percentage, dry it afterwards, activate, turn brilliant and ion-exchange, in the sorbent material obtained after exchange, the massfraction of potassium ion is 0.25 ~ 0.9%, and barium ion content is higher than 31.6%.
The US 7452840B2 of IFP (IFP) reports, select the X-type molecular sieve of Si/Al=1.15 ~ 1.5, with kaolin, CMC and water mixing granulation, obtaining particle diameter is 0.7mm particulate state X-type molecular sieve, its reactivation process selects roasting under nitrogen gas stream environment, then NaOH alkaline system crystallization is placed in, after crystallization, ion-exchange is carried out to particle, its give-and-take conditions difference is after each barium (barium and potassium) ion-exchange, calcination activation need be carried out to it, then ion-exchange is continued, at least exchange and prepare sorbent material 4 times, wherein barium ion or barium potassium ion exchange degree are greater than 90%.
The preparation method of the separating paraxylene sorbent material that French CE CA company US 6410815B1 reports is similar to IFP, namely the X-type molecular sieve of low silica-alumina ratio (Si/Al=1.15-1.25) is selected, mix with kaolin, CMC and water, granulation, 100 DEG C of oven dry, granularity is about 0.7mm; Particle activation after shaping, activation temperature is 550-600 DEG C; Particle after activation is placed in the mixing solutions of sodium hydroxide or sodium hydroxide and potassium hydroxide, makes particle Middle molecule sieve content more than 95%; Finally carry out barium ion to this particle or potassium barium ion changes, obtain barium ion or barium potassium ion exchange degree in sorbent material and be greater than 90% after repeatedly exchanging, when obtaining sorbent material requirement 900 DEG C, loss on ignition scope is 4.0%-7.7%.Toray company delivers patent JP 05163015 and reports, use X molecular sieve for silica alumina ratio lower than 1.25 X-type molecular sieve and low silica-alumina ratio X-type (LSX) molecular sieve, with kaolin and water mixing moulding, dry, after calcination activation, be immersed in the mixing solutions of sodium hydroxide and potassium hydroxide, then carry out barium ion exchange to it, exchange process is the same with above-mentioned.
The preparation method of the separating paraxylene sorbent material that company limited of Sinopec patent CN 1448213A reports is different from above-mentioned, its X-type molecular sieve is the small crystal grain molecular sieve of directing agent method synthesis, silica alumina ratio is about 2.4-2.5, it is mixed with kaolin, silicon sol and water, roll and shapingly obtain the bead that particle diameter is 0.3 ~ 0.8mm, dry, roasting, turn brilliant, turning activeconstituents in the particle after crystalline substance is more than 85%, then carry out ion-exchange to it, in the sorbent material obtained after repeatedly exchanging, the ratio range of Ba/K is 20 ~ 30.
In sum; preparation method about separating paraxylene sorbent material is roughly divided into four steps; namely former powder is shaping, shaped granule activates, turn brilliant, ion-exchange; the selection of former powder, binding agent and auxiliary agent and proportioning condition of molding, calcination activation condition, turn crystal bar part, ion exchange conditions is but not quite similar, the sorbent material therefore obtained is also different in adsorption stripping dimethyl benzene.Up to now, in the patent report announced both at home and abroad, prepare molecular sieve that sorbent material adopts and be micro porous molecular sieve prepared by traditional method.We know, loading capacity and adsorption selectivity are the important indicators weighing performance of the adsorbent quality, but be also a very important index to the Adsorption and desorption speed of extraction components p-Xylol, if only there is microvoid structure in molecular sieve pore passage, sorbent material adsorption rate in use and desorption rate are all declined, and loading capacity also decline, and can increase the circulation consumption of sorbent material and strippant like this, reduce product yield, add the process cost of adsorption separation device.Therefore, seek a kind of micropore-mesopore material, both can adsorption stripping dimethyl benzene, the rate of mass transfer of adsorption process can be increased again, be this area in the urgent need to.
Therefore, this area in the urgent need to developing a kind of novel p-Xylol sorbent material, for solving loading capacity, speed and desorption rate problem on the low side.
Summary of the invention
Object of the present invention is exactly provide a kind of mesoporous X-type molecular sieve, based on the sorbent material of this molecular sieve and preparation and application thereof to overcome defect that above-mentioned prior art exists, the obtained sorbent material based on mesoporous X-type molecular sieve is used as adsorption stripping dimethyl benzene sorbent material, under ensureing the prerequisite of higher p-Xylol adsorption selectivity, improve the loading capacity of sorbent material in adsorption process, sorption and desorption speed.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for mesoporous X-type molecular sieve, comprises the following steps:
A. template is dropwise dropped in the aqueous solution of silicon source, stir;
B. the solution that step a obtains is dropped in the aqueous solution of aluminium source, add a certain amount of sodium hydroxide solution, make mol ratio wherein be SiO
2: Al
2o
3: Na
2o: H
2o=(2.5 ~ 5): 1: (3 ~ 7.5): (180 ~ 300), continue to stir, obtain white gels;
C. the white gels that step b obtains is transferred to crystallization in reactor, taking out washing after crystallization is 7 ~ 8, after drying to pH, and roasting, roasting object is to remove the template in former powder, obtains the former powder of mesoporous X-type molecular sieve.
Described template is selected from the combination of one or more in sodium stearate, cetyl trimethylammonium bromide (CTAB) or silane coupling agent;
The add-on of described template is 0.0001 ~ 5% of reaction total mixture total mass;
Described silicon source is selected from the combination of one or more in water glass, water glass, silicon sol, white carbon black or active silica;
Described aluminium source is selected from the combination of one or more in aluminium hydroxide, pseudo-boehmite or sodium metaaluminate;
Described silane coupling agent is selected from the combination of one or more in commercially available KH550, KH560, KH570 or KH792.
The temperature stirred in step a or b and 25 ~ 35 DEG C;
In step c, crystallization temperature is 80 ~ 180 DEG C, preferably 100 ~ 150 DEG C, and crystallization time is 24 ~ 120 hours, preferably 36 ~ 90 hours;
In step c, maturing temperature is 350 ~ 850 DEG C, preferably 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour, preferably 4 ~ 7 hours.
A kind of mesoporous X-type molecular sieve be made up of above-mentioned preparation method.
Based on a preparation method for the sorbent material of mesoporous X-type molecular sieve, comprise the following steps:
A. shaping: using mesoporous X-type molecular sieve as adsorption activity component, be binding agent with kaolin, add auxiliary agent, mixing moulding, obtaining particle size range is the particle of 0.3 ~ 0.8mm;
B. calcination activation: activate the particle that step a obtains, make the kaolin in particle be converted into metakaolin, activation temperature is 400 ~ 800 DEG C, preferably 500 ~ 700 DEG C, and soak time is 1 ~ 9 hour, preferably 3 ~ 5 hours;
C. turn brilliant: the particle that step b obtains added sodium hydroxide solution, drip water glass, make mol ratio be SiO
2: Al
2o
3: Na
2o: H
2o=(3 ~ 5): 1: (3 ~ 7.5): (180 ~ 250), carry out crystallization after stirring;
D. ion-exchange: adopt separately barium ion or adopt barium ion and potassium ion to carry out ion-exchange to the particle that step c obtains simultaneously, obtain the sorbent material of ion-exchange degree > 99%, namely based on the sorbent material of mesoporous X-type molecular sieve.
In step a, the content of mesoporous X-type molecular sieve is 80 ~ 94.5wt%, and kaolinic content is 5 ~ 19.5wt%, and the content of auxiliary agent is 0.5 ~ 5%;
Described auxiliary agent is selected from one or more in W-Gum, sesbania powder or Xylo-Mucine.
The size distribution obtaining particle in step a is: particle diameter is the particle percentage composition of 0.5 ~ 0.71mm is 60 ~ 70wt%, and particle diameter is the particle percentage composition of 0.28 ~ 0.5mm is 20 ~ 30wt%.
In steps d, ion-exchange temperature is 20 ~ 150 DEG C, preferably 60 ~ 110 DEG C, and swap time is 0.5 ~ 30 hour, preferably 10 ~ 20 hours.
A kind of sorbent material based on mesoporous X-type molecular sieve be made up of aforesaid method.
The described sorbent material based on mesoporous X-type molecular sieve is used as adsorption stripping dimethyl benzene sorbent material.
Compared with prior art, the mesoporous X-type molecular sieve of active ingredient of sorbent material provided by the invention adopts template agent method to prepare, molecular template agent instructs zeolite to carry out crystallization on mesoporous wall, meso-hole structure is formed while microvoid structure is formed, select template can effectively by mesoporous pore size distributed controll at about 2nm, compared with the molecular sieve of the microvoid structure prepared with traditional method, obstacle has been cleared away in the mesoporous transmission for medium in duct, thus can increase the transfer rate of medium.Therefore, sorbent material of the present invention has good adsorption selectivity and higher loading capacity, adsorption rate and desorption rate.
Accompanying drawing explanation
Fig. 1 is the N of molecular sieve obtained in embodiment 4 and comparative example 1
2adsorption-desorption sorption isotherm;
Fig. 2 is the graph of pore diameter distribution of molecular sieve obtained in embodiment 4 and comparative example 1.
Embodiment
A preparation method for mesoporous X-type molecular sieve, comprises the following steps:
A. template is dropwise dropped in the aqueous solution of silicon source, stir at 25 ~ 35 DEG C;
B. the solution that step a obtains is dropped in the aqueous solution of aluminium source, add a certain amount of sodium hydroxide solution, make mol ratio wherein be SiO
2: Al
2o
3: Na
2o: H
2o=(2.5 ~ 5): 1: (3 ~ 7.5): (180 ~ 300), the add-on of template is 0.0001 ~ 5%, 25 ~ 35 DEG C of continuation stirrings of reaction total mixture total mass, obtains white gels;
C. the white gels that step b obtains is transferred to crystallization in reactor, crystallization temperature is 80 ~ 180 DEG C, preferably 100 ~ 150 DEG C, crystallization time is 24 ~ 120 hours, preferably 36 ~ 90 hours, and taking out washing after crystallization to pH is 7 ~ 8, after drying, roasting, maturing temperature is 350 ~ 850 DEG C, preferably 450 ~ 700 DEG C, roasting time is 1 ~ 10 hour, preferably 4 ~ 7 hours, roasting object was to remove the template in former powder, obtained the former powder of mesoporous X-type molecular sieve.
Template is selected from the combination of one or more in sodium stearate, cetyl trimethylammonium bromide (CTAB) or silane coupling agent; Silane coupling agent is selected from the combination of one or more in commercially available KH550, KH560, KH570 or KH792;
Silicon source is selected from the combination of one or more in water glass, water glass, silicon sol, white carbon black or active silica;
Aluminium source is selected from the combination of one or more in aluminium hydroxide, pseudo-boehmite or sodium metaaluminate;
The mesoporous X-type molecular sieve that above-mentioned preparation method makes, pore size distribution is at about 2nm, and silica alumina ratio is 2 ~ 3, and preferably 2.4 ~ 2.8.
Based on a preparation method for the sorbent material of mesoporous X-type molecular sieve, comprise the following steps:
A. shaping: using mesoporous X-type molecular sieve as adsorption activity component, take kaolin as binding agent, add auxiliary agent, mixing moulding, obtaining particle size range is the particle of 0.3 ~ 0.8mm, the size distribution of particle is: particle diameter is the particle percentage composition of 0.5 ~ 0.71mm is 60 ~ 70wt%, and particle diameter is the particle percentage composition of 0.28 ~ 0.5mm is 20 ~ 30wt%; Wherein, the content of mesoporous X-type molecular sieve is 80 ~ 94.5wt%, and kaolinic content is 5 ~ 19.5wt%, and the content of auxiliary agent is 0.5 ~ 5%; Auxiliary agent is selected from one or more in W-Gum, sesbania powder or Xylo-Mucine.
B. calcination activation: activate the particle that step a obtains, make the kaolin in particle be converted into metakaolin, activation temperature is 400 ~ 800 DEG C, preferably 500 ~ 700 DEG C, and soak time is 1 ~ 9 hour, preferably 3 ~ 5 hours;
C. turn brilliant: added by the particle that step b obtains in sodium hydroxide solution, drip water glass, make mol ratio be SiO
2: Al
2o
3: Na
2o: H
2o=(3 ~ 5): 1: (3 ~ 7.5): (180 ~ 250), carry out crystallization after stirring;
D. ion-exchange: adopt separately barium ion or adopt barium ion and potassium ion to carry out ion-exchange to the particle that step c obtains simultaneously, ion-exchange temperature is 20 ~ 150 DEG C, preferably 60 ~ 110 DEG C, swap time is 0.5 ~ 30 hour, preferably 10 ~ 20 hours, obtain the sorbent material of ion-exchange degree > 99%, namely based on the sorbent material of mesoporous X-type molecular sieve.
The sorbent material based on mesoporous X-type molecular sieve be made up of aforesaid method, be specially adapted to BTX aromatics adsorption stripping dimethyl benzene, there is higher adsorption selectivity, loading capacity, adsorption rate and desorption rate in adsorption stripping dimethyl benzene, its loading capacity adopts Gas Phase Adsorption balance test to measure sorbent material to the loading capacity of BTX aromatics, and adsorption selectivity, adsorption rate and desorption rate adopt dynamic pulse test device to measure.
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
In following examples, mesopore molecular sieve crystalline phase is with XRD determining; The content of sorbent material is with X-ray fluorescence spectra quantitative analysis; Pore distribution adopts N
2adsorption-desorption method is analyzed; Loading capacity adopts Gas Phase Adsorption balance test to measure, and adsorption selectivity, adsorption rate and desorption rate adopt dynamic pulse test device to measure.
Embodiment 1
The aqueous solution of 15 grams of silane coupling agents (KH550) is added in the water glass of 400 grams, add water 150 grams, solution clarification is stirred at 30 DEG C, this clear liquor is slowly added drop-wise in the sodium aluminate solution (aluminium hydroxide is dissolved in sodium hydroxide solution and obtains) of 250 grams, stir at 30 DEG C and obtain white gels in 1 hour, this gel is moved in the stainless steel cauldron of tetrafluoroethylene lining, 120 DEG C of crystallization 72 hours, take out product, to be cooledly to filter to room temperature, getting solid matter with deionized water washing is about 8 to pH, drying is carried out at 100 DEG C, the roasting 4 hours at 550 DEG C of dried solid, namely the former powder ZA of mesoporous X-type molecular sieve is obtained, particle diameter is 0.9 ~ 1.1 μm.
Embodiment 2
The aqueous solution of 20 grams of silane coupling agents (KH560) is added in the silicon sol solution of 350 grams, add water 150 grams, solution clarification is stirred at 35 DEG C, it is slowly added drop-wise to (pseudo-boehmite is dissolved in sodium hydroxide solution and obtains) in the sodium aluminate solution of 200 grams, stir at 30 DEG C and obtain white gels in 1 hour, this gel is moved in the stainless steel cauldron of tetrafluoroethylene lining, 150 DEG C of crystallization 48 hours, take out product, to be cooledly to filter to room temperature, get solid matter with deionized water washing to washings in neutral, drying is carried out at 100 DEG C, the roasting 4 hours at 550 DEG C of dried solid, namely the former powder ZB of mesoporous X-type molecular sieve is obtained, particle diameter is 0.9 ~ 1.1 μm.
Embodiment 3
Prepare mesoporous X-type molecular sieve according to the method for example 1, unlike selecting the methanol solution (KH 560: KH 660=1: 1) of silane coupling agent to be template, obtain the former powder ZC of mesoporous X molecular sieve, particle diameter is 0.9 ~ 1.1 μm.
Embodiment 4
Prepare mesoporous X-type molecular sieve according to the method for example 2, unlike selecting white carbon black to be silicon source, silane coupling agent (KH792) is template, and obtain the former powder ZD of mesoporous X molecular sieve, particle diameter is 0.9 ~ 1.1 μm.
Embodiment 5
Prepare mesoporous X-type molecular sieve according to the method for example 1, unlike selecting sodium stearate to be template, obtain the former powder ZE of mesoporous X molecular sieve, particle diameter is 0.9 ~ 1.1 μm.
Embodiment 6
Prepare mesoporous X-type molecular sieve according to the method for example 2, unlike selecting cetyl trimethylammonium bromide (CTAB) to be template, obtain the former powder ZF of mesoporous X molecular sieve, particle diameter is 0.9 ~ 1.1 μm.
Comparative example 1
Ordinary method prepares NaX type molecular sieve.
The high alkali deflection aluminium acid sodium solution of 150 grams, 150 ml waters are added in 300 grams of water glass, after stirring at 30 DEG C, still aging 8 hours at 30 DEG C, be warming up to 110 DEG C of static crystallization 10 hours, take out product, to be cooledly to filter to room temperature, getting solid matter with deionized water washing is about 8 to pH, carry out drying 10 hours at 100 DEG C, obtain molecular screen primary powder ZG, particle diameter is 1.8 ~ 2.0 μm.
The N of the molecular sieve adopting template method to be synthesized
2obvious hysteresis loop is there is in adsorption-desorption sorption isotherm, see Fig. 1, the distribution of its mesoporous pore size concentrates on 2nm, the crystalline structure both remaining X-type molecular sieve that the method is synthesized, overcome again the restriction of conventional molecular sieve pore passage structure narrow and small (< 1.0nm), this provides larger space, duct when adsorption stripping dimethyl benzene for the sorbent material based on this molecular sieve, can significantly improve the loading capacity of sorbent material, adsorption rate and desorption rate.
Embodiment 7 ~ embodiment 12, comparative example 2 are adopt the former powder in above embodiment or comparative example 1 to carry out shaping, ion-exchange, prepare p-Xylol sorbent material.
Embodiment 7
Prepare sorbent material of the present invention and evaluate the performance of its adsorption stripping dimethyl benzene.
1) shaping: 17 kilograms, the former powder of mesoporous X-type molecular sieve ZA getting preparation in above-described embodiment 1, add the kaolin of 3 kilograms, 400 grams of W-Gums and 400 grams of sesbania powder, in rotation limit, coater inner rotary table top glue spraying water after mixing, after shaping end, sieve out the particle that particle diameter is 0.3-0.8mm, drying 20 hours at 80 DEG C.
2) calcination activation: to 1) in particle activate, kaolin is wherein made to be converted into metakaolin, active silica-alumina is converted into by the amorphous aluminum silicide in kaolin, adopt the mode of temperature programming to carry out roasting, keep constant temperature 4 hours when reaching 200 DEG C, be warming up to 400 DEG C, keep constant temperature 1 hour, continue to be warming up to 600 DEG C, be incubated 1 hour, take out, be cooled to room temperature.
3) turn brilliant: get 2) in the active particle 50 grams that obtains in beaker, add the sodium hydroxide solution (C of 600ml
naOH=50g/L), the water glass of dropping 2ml, after stirring, add a cover, be positioned in the baking oven of 90 DEG C, within 6 hours, crystallization terminates, cooling, and washing is extremely neutral, drying 10 hours at 120 DEG C.
4) ion-exchange: get 3) in the particle 50 grams that obtains in exchange column, adopt the method exchanged continuously to carry out ion-exchange, exchanging liquid is the bariumchloride of 0.18M and the mixing solutions of 0.02M Repone K, and exchange temperature is 90 DEG C, when volume space velocity is 8
-1, exchange 13 hours in atmospheric conditions, exchanged rear deionized water wash to not containing barium ion in washings, drying 8 hours at 150 DEG C, namely obtain adsorbent A, its chemical constitution and physico-chemical property are in table 1.
5) evaluation of adsorbent separating paraxylene performance
The Small-Scale Simulated Moving Bed of continuous countercurrent is undertaken by adsorbent A the experiment of separating paraxylene, gets 45 grams of adsorbent A in the adsorption column of this device, vibration makes it tamp.In absorption BTX aromatics composition, the massfraction of ethylbenzene, p-Xylol, m-xylene and o-Xylol is 5%, with toluene be strippant, nonane is that tracer agent is tested, the performance measurement of sorbent material the results are shown in Table 2.In table 2, the loading capacity of sorbent material represents with C, and selectivity β represents, the desorption rate strippant reached in the p-Xylol peak width at half height time sucks volume W
drepresent.
Embodiment 8
Prepare sorbent material, unlike 1 according to the method for embodiment 7) in shaping raw material be the former powder of ZB of embodiment 2, get 18 kilograms of former powder of ZB, 2 kilograms of kaolin, 300 grams of sesbania powder and 300 grams of Xylo-Mucines mix, shaping.4) exchanging liquid in is the barium chloride solution of 0.2M, and other steps are the same with embodiment 4 method, obtain adsorbent B, and its chemical group prejudice table 1, absorption property is in table 2.
Embodiment 9
Prepare sorbent material, unlike 1 according to the method for embodiment 7) in shaping raw material be the former powder of ZC of embodiment 3, get 19 kilograms of former powder of ZC, 1 kilogram of kaolin, 500 grams of W-Gums and 500 grams of Xylo-Mucines mix, shaping.Other steps are the same with embodiment 4 method, obtain sorbent material C, and its chemical group prejudice table 1, absorption property is in table 2.
Embodiment 10
Sorbent material is prepared according to the method for embodiment 7, unlike 1) in shaping raw material be the former powder of ZD of embodiment 4, get 16 kilograms of former powder of ZD, 4 kilograms of kaolin, 200 grams of sesbania powder, 200 grams of W-Gums and 200 grams of Xylo-Mucines mix, shaping.4) exchanging liquid in is the barium chloride solution of 0.3M, and other steps are the same with embodiment 4 method, obtain sorbent material D, and its chemical group prejudice table 1, absorption property is in table 2.
Embodiment 11
Prepare sorbent material, unlike 1 according to the method for embodiment 7) in shaping raw material be the former powder of ZE of embodiment 5, get 18 kilograms of former powder of ZE, 2 kilograms of kaolin, 1000 grams of W-Gums mix, shaping.4) exchanging liquid in is the barium chloride solution of 0.4M, and other steps are the same with embodiment 4 method, obtain sorbent material E, and its chemical group prejudice table 1, absorption property is in table 2.
Embodiment 12
Prepare sorbent material, unlike 1 according to the method for embodiment 7) in shaping raw material be the former powder of ZF of embodiment 6, get 17 kilograms of former powder of ZF, 3 kilograms of kaolin, 1000 grams of sesbania powder mix, shaping.4) exchanging liquid in is the barium chloride solution of 0.5M, and other steps are the same with embodiment 4 method, obtain sorbent material F, and its chemical group prejudice table 1, absorption property is in table 2.
Comparative example 2
Prepare sorbent material, unlike 1 according to the method for embodiment 7) in shaping raw material be the molecular screen primary powder ZG of comparative example 1, other steps are the same with embodiment 7 method, obtain sorbent material G, and its chemical group prejudice table 1, absorption property is in table 2.
Table 1
Table 2
Loading capacity, gram/100 grams
Selectivity
Adsorption rate, milliliter
Desorption rate, milliliter
Observe table 1 data known, the sorbent material G obtained after the X molecular sieve prepared based on ordinary method is shaping, the sorbent material that its chemical constitution, silica alumina ratio and template agent method obtain is close, but its tap density is starkly lower than the sorbent material that template agent method obtains, this is because X-type molecular sieve prepared by template agent method, not only have micro-meso-hole structure, and its crystal grain is significantly less than molecular sieve G, this just significantly improves its tap density when shaping.
Observe table 2 data known, the sorbent material G obtained after the X molecular sieve prepared based on ordinary method is shaping, the sorbent material that the selectivity of its adsorption stripping dimethyl benzene obtains a little less than template agent method, but the loading capacity of its adsorption stripping dimethyl benzene, rate of mass transfer are starkly lower than the sorbent material that template agent method obtains, this is because the existence of X-type molecular sieve intermediary hole, not only increase the useful volume of sorbent material, make the increase of its loading capacity, and increase the rate of mass transfer of dimethylbenzene.
In industrial application, the selectivity of adsorbent separating paraxylene does not change substantially, but the raising of the increase of its loading capacity, rate of mass transfer obviously can shorten adsorption cycle, thus reduces production cost, therefore has good industrial application value.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a preparation method for mesoporous X-type molecular sieve, is characterized in that, comprises the following steps:
A. template is dropwise dropped in the aqueous solution of silicon source, stir;
B. the solution that step a obtains is dropped in the aqueous solution of aluminium source, add a certain amount of sodium hydroxide solution, make mol ratio wherein be SiO
2: Al
2o
3: Na
2o: H
2o=(2.5 ~ 5): 1: (3 ~ 7.5): (180 ~ 300), continue to stir, obtain white gels;
C. the white gels that step b obtains is transferred to crystallization in reactor, taking out washing after crystallization is 7 ~ 8, after drying to pH, and roasting, obtains the former powder of mesoporous X-type molecular sieve.
2. the preparation method of a kind of mesoporous X-type molecular sieve according to claim 1, is characterized in that, described template is selected from the combination of one or more in sodium stearate, cetyl trimethylammonium bromide or silane coupling agent;
The add-on of described template is 0.0001 ~ 5% of reaction total mixture total mass;
Described silicon source is selected from the combination of one or more in water glass, water glass, silicon sol, white carbon black or active silica;
Described aluminium source is selected from the combination of one or more in aluminium hydroxide, pseudo-boehmite or sodium metaaluminate;
Described silane coupling agent is selected from the combination of one or more in commercially available KH550, KH560, KH570 or KH792.
3. the preparation method of a kind of mesoporous X-type molecular sieve according to claim 1, is characterized in that, the temperature stirred in step a or b is 25 ~ 35 DEG C;
In step c, crystallization temperature is 80 ~ 180 DEG C, and crystallization time is 24 ~ 120 hours;
In step c, maturing temperature is 350 ~ 850 DEG C, and roasting time is 1 ~ 10 hour.
4. the mesoporous X-type molecular sieve be made up of method described in any one of claims 1 to 3.
5., based on a preparation method for the sorbent material of mesoporous X-type molecular sieve according to claim 4, it is characterized in that, comprise the following steps:
A. shaping: using mesoporous X-type molecular sieve as adsorption activity component, be binding agent with kaolin, add auxiliary agent, mixing moulding, obtaining particle size range is the particle of 0.3 ~ 0.8mm;
B. calcination activation: activate the particle that step a obtains, activation temperature is 500 ~ 700 DEG C, and soak time is 1 ~ 5 hour;
C. turn brilliant: the particle that step b obtains added sodium hydroxide solution, drip water glass, make the mol ratio of total mixture be SiO
2: Al
2o
3: Na
2o: H
2o=(3 ~ 5): 1: (3 ~ 7.5): (180 ~ 250), carry out crystallization after stirring;
D. ion-exchange: adopt separately barium ion or adopt barium ion and potassium ion to carry out ion-exchange to the particle that step c obtains simultaneously, obtain the sorbent material of ion-exchange degree > 99%, namely based on the sorbent material of mesoporous X-type molecular sieve.
6. the preparation method of a kind of sorbent material based on mesoporous X-type molecular sieve according to claim 5, it is characterized in that, in step a, the content of mesoporous X-type molecular sieve is 80 ~ 94.5wt%, kaolinic content is 5 ~ 19.5wt%, and the content of auxiliary agent is 0.5 ~ 5%;
Described auxiliary agent is selected from one or more in W-Gum, sesbania powder or Xylo-Mucine.
7. the preparation method of a kind of sorbent material based on mesoporous X-type molecular sieve according to claim 5, it is characterized in that, the size distribution obtaining particle in step a is: particle diameter is the particle percentage composition of 0.5 ~ 0.71mm is 60 ~ 70wt%, and particle diameter is the particle percentage composition of 0.28 ~ 0.5mm is 20 ~ 30wt%.
8. the preparation method of a kind of sorbent material based on mesoporous X-type molecular sieve according to claim 5, is characterized in that, in step c, crystallization temperature selects 80 ~ 100 DEG C, and crystallization time is 4 ~ 10 hours; In steps d, ion-exchange temperature is 20 ~ 150 DEG C, and swap time is 0.5 ~ 30 hour.
9. the sorbent material based on mesoporous X-type molecular sieve be made up of method described in any one of claim 5 ~ 8.
10. as claimed in claim 9 based on an application for the sorbent material of mesoporous X-type molecular sieve, it is characterized in that, the described sorbent material based on mesoporous X-type molecular sieve is used as adsorption stripping dimethyl benzene sorbent material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410737917.XA CN104477937A (en) | 2014-12-05 | 2014-12-05 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410737917.XA CN104477937A (en) | 2014-12-05 | 2014-12-05 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104477937A true CN104477937A (en) | 2015-04-01 |
Family
ID=52752581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410737917.XA Pending CN104477937A (en) | 2014-12-05 | 2014-12-05 | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104477937A (en) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214605A (en) * | 2015-11-03 | 2016-01-06 | 浙江海洋学院 | Based on the preparation method of adsorbent revealing PX in water body |
| CN105251441A (en) * | 2015-11-12 | 2016-01-20 | 环境保护部华南环境科学研究所 | High-performance mesoporous-micro double hole controllable molecular sieve adsorbent and preparation and application thereof |
| CN106315613A (en) * | 2016-08-19 | 2017-01-11 | 西南化工研究设计院有限公司 | Novel 13X-type molecular sieve for CO adsorption as well as preparation method and application thereof |
| CN106554029A (en) * | 2016-11-14 | 2017-04-05 | 南开大学 | The compound FAU types molecular sieve of package metals chromic compound and its synthetic method |
| CN106622115A (en) * | 2016-12-30 | 2017-05-10 | 华南农业大学 | Potassium type heavy metal mesoporous adsorption material with molybdenum ore tailings as raw material, and preparation method and application thereof |
| CN106946271A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of X-type molecular sieve and its synthetic method |
| CN109123775A (en) * | 2018-08-06 | 2019-01-04 | 江西中烟工业有限责任公司 | A kind of heating of the perfume (or spice) of solid-state containing herbal odor type pearl is not burnt cigarette and preparation method thereof |
| CN109692657A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of mesoporous X zeolite and adsorbent and sorbent preparation method |
| CN109748292A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve bar shaped agent and its extruded moulding methods and applications |
| KR20190126096A (en) * | 2017-03-17 | 2019-11-08 | 아르끄마 프랑스 | How to Synthesize Zeolite Crystals with Seeding Agent |
| CN110564005A (en) * | 2019-08-28 | 2019-12-13 | 中国第一汽车股份有限公司 | Anion additive |
| CN110804204A (en) * | 2018-08-06 | 2020-02-18 | 南京理工大学 | Bacterial cellulose/X-type molecular sieve composite aerogel and preparation method thereof |
| CN111378300A (en) * | 2020-03-20 | 2020-07-07 | 上海安费诺永亿通讯电子有限公司 | Laser-enhanced chemical plating filler and preparation method thereof, laser-enhanced chemical plating material and method for carrying out selective metallization on surface of laser-enhanced chemical plating material |
| CN111960430A (en) * | 2020-09-01 | 2020-11-20 | 常州工学院 | Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve |
| CN112191280A (en) * | 2020-12-10 | 2021-01-08 | 苏州立昂新材料有限公司 | Continuous crystal transformation and ion exchange device and process |
| CN112246217A (en) * | 2020-10-30 | 2021-01-22 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for purifying VOCs (volatile organic compounds) in zeolite adsorption rotating wheel and preparation method thereof |
| CN112588258A (en) * | 2021-03-03 | 2021-04-02 | 苏州立昂新材料有限公司 | Composite A-type molecular sieve raw powder containing wave absorbing material and full-zeolite molecular sieve, and preparation method and application thereof |
| CN112958144A (en) * | 2021-02-07 | 2021-06-15 | 内蒙古师范大学 | Preparation method and application of X-type zeolite molecular sieve catalyst |
| CN113083222A (en) * | 2021-03-30 | 2021-07-09 | 中触媒新材料股份有限公司 | Modified adsorbent for adsorption separation and preparation method and application thereof |
| CN113441111A (en) * | 2021-05-11 | 2021-09-28 | 常州大学 | Preparation method of modified metal organic framework material for adsorbing and separating BTEX in C8 aromatic hydrocarbon |
| CN114160096A (en) * | 2022-02-08 | 2022-03-11 | 中海油天津化工研究设计院有限公司 | Adsorbent for separating ethylbenzene in carbon octaaromatic hydrocarbon and preparation method thereof |
| CN114425297A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Para-disubstituted benzene adsorbent and preparation method thereof |
| CN114433017A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-strength molecular sieve adsorbent and preparation method thereof |
| CN115970637A (en) * | 2022-07-29 | 2023-04-18 | 正大能源材料(大连)有限公司 | Adsorbent and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347339A (en) * | 1999-02-22 | 2002-05-01 | 策卡有限公司 | Agglomerated zeolitic adsorbents, method for obtaining same and uses thereof |
| US6410815B1 (en) * | 1997-08-21 | 2002-06-25 | Elf Atochem S.A. | Agglomerated zeolite adsorbents, process for their preparation, and their use for adsorbing paraxylene from aromatic C8 fractions |
| CN1448213A (en) * | 2002-03-29 | 2003-10-15 | 中国石油化工股份有限公司 | Adsorbent for adsorption stripping dimethyl benzene and its preparing process |
| CN101772377A (en) * | 2007-06-04 | 2010-07-07 | 塞卡股份公司 | Based on the spherical agglomerates of zeolite, its method for making, with and purposes in adsorption process or catalysis |
| CN102159674A (en) * | 2008-09-22 | 2011-08-17 | 环球油品公司 | Binderless adsorbents with improved mass transfer properties and their use in adsorptive separation of para-xylene |
| CN103028372A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Binderless zeolite adsorbent and preparation method thereof |
| CN103073020A (en) * | 2012-11-08 | 2013-05-01 | 大连理工大学 | Preparation method and application of hierarchical zeolite molecular sieve |
| CN103214003A (en) * | 2013-04-09 | 2013-07-24 | 华南理工大学 | Mesoporous Y-type zeolite molecular sieve and preparation method thereof |
| CN103442800A (en) * | 2011-03-31 | 2013-12-11 | 环球油品公司 | Binderless zeolitic adsorbents, methods for producing binderless zeolitic adsorbents, and adsorptive separation processes using the binderless zeolitic adsorbents |
| CN105050954A (en) * | 2013-08-05 | 2015-11-11 | 塞卡股份公司 | Zeolites with hierarchical porosity |
| CN105121345A (en) * | 2013-08-05 | 2015-12-02 | 塞卡股份公司 | Zeolite material made from mesoporous zeolite |
| CN105263616A (en) * | 2013-09-09 | 2016-01-20 | 塞卡股份公司 | Zeolitic adsorbents with large external surface area, process for preparing same and uses thereof |
-
2014
- 2014-12-05 CN CN201410737917.XA patent/CN104477937A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6410815B1 (en) * | 1997-08-21 | 2002-06-25 | Elf Atochem S.A. | Agglomerated zeolite adsorbents, process for their preparation, and their use for adsorbing paraxylene from aromatic C8 fractions |
| CN1347339A (en) * | 1999-02-22 | 2002-05-01 | 策卡有限公司 | Agglomerated zeolitic adsorbents, method for obtaining same and uses thereof |
| CN1448213A (en) * | 2002-03-29 | 2003-10-15 | 中国石油化工股份有限公司 | Adsorbent for adsorption stripping dimethyl benzene and its preparing process |
| CN101772377A (en) * | 2007-06-04 | 2010-07-07 | 塞卡股份公司 | Based on the spherical agglomerates of zeolite, its method for making, with and purposes in adsorption process or catalysis |
| CN102159674A (en) * | 2008-09-22 | 2011-08-17 | 环球油品公司 | Binderless adsorbents with improved mass transfer properties and their use in adsorptive separation of para-xylene |
| CN103442800A (en) * | 2011-03-31 | 2013-12-11 | 环球油品公司 | Binderless zeolitic adsorbents, methods for producing binderless zeolitic adsorbents, and adsorptive separation processes using the binderless zeolitic adsorbents |
| CN103028372A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Binderless zeolite adsorbent and preparation method thereof |
| CN103073020A (en) * | 2012-11-08 | 2013-05-01 | 大连理工大学 | Preparation method and application of hierarchical zeolite molecular sieve |
| CN103214003A (en) * | 2013-04-09 | 2013-07-24 | 华南理工大学 | Mesoporous Y-type zeolite molecular sieve and preparation method thereof |
| CN105050954A (en) * | 2013-08-05 | 2015-11-11 | 塞卡股份公司 | Zeolites with hierarchical porosity |
| CN105121345A (en) * | 2013-08-05 | 2015-12-02 | 塞卡股份公司 | Zeolite material made from mesoporous zeolite |
| CN105263616A (en) * | 2013-09-09 | 2016-01-20 | 塞卡股份公司 | Zeolitic adsorbents with large external surface area, process for preparing same and uses thereof |
Non-Patent Citations (3)
| Title |
|---|
| ALEXANDRA INAYAT ET AL.: ""Assemblies of Mesoporous FAU-Type Zeolite Nanosheets"", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| DANNY VERBOEKEND ET AL.: ""Hierarchical FAU- and LTA-Type Zeolites by Post-Synthetic Design: A New Generation of Highly Effi cient Base Catalysts"", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| YAN CHAO FENG ET AL.: ""Synthesis of mesoporous LTA zeolites with large BET areas"", 《J POROUS MATER》 * |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214605A (en) * | 2015-11-03 | 2016-01-06 | 浙江海洋学院 | Based on the preparation method of adsorbent revealing PX in water body |
| CN105251441A (en) * | 2015-11-12 | 2016-01-20 | 环境保护部华南环境科学研究所 | High-performance mesoporous-micro double hole controllable molecular sieve adsorbent and preparation and application thereof |
| CN106946271A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of X-type molecular sieve and its synthetic method |
| CN106946271B (en) * | 2016-01-07 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of X-type molecular sieve and its synthetic method |
| CN106315613A (en) * | 2016-08-19 | 2017-01-11 | 西南化工研究设计院有限公司 | Novel 13X-type molecular sieve for CO adsorption as well as preparation method and application thereof |
| CN106554029A (en) * | 2016-11-14 | 2017-04-05 | 南开大学 | The compound FAU types molecular sieve of package metals chromic compound and its synthetic method |
| CN106622115A (en) * | 2016-12-30 | 2017-05-10 | 华南农业大学 | Potassium type heavy metal mesoporous adsorption material with molybdenum ore tailings as raw material, and preparation method and application thereof |
| CN106622115B (en) * | 2016-12-30 | 2019-05-07 | 华南农业大学 | It is a kind of based on the potassium type heavy metal mesoporous adsorption material and its preparation method and application that molybdenum ore tailings is raw material |
| KR20190126096A (en) * | 2017-03-17 | 2019-11-08 | 아르끄마 프랑스 | How to Synthesize Zeolite Crystals with Seeding Agent |
| KR102282810B1 (en) * | 2017-03-17 | 2021-07-27 | 아르끄마 프랑스 | Method for synthesizing zeolite crystals as a seeding agent |
| JP2020510602A (en) * | 2017-03-17 | 2020-04-09 | アルケマ フランス | Method for synthesizing zeolite crystals using seeding agent |
| CN109692657B (en) * | 2017-10-24 | 2022-03-11 | 中国石油化工股份有限公司 | Mesoporous X zeolite, adsorbent and preparation method of adsorbent |
| CN109692657A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of mesoporous X zeolite and adsorbent and sorbent preparation method |
| CN109748292A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve bar shaped agent and its extruded moulding methods and applications |
| CN109748292B (en) * | 2017-11-03 | 2021-02-05 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve striping agent and extrusion molding method and application thereof |
| CN110804204A (en) * | 2018-08-06 | 2020-02-18 | 南京理工大学 | Bacterial cellulose/X-type molecular sieve composite aerogel and preparation method thereof |
| CN109123775A (en) * | 2018-08-06 | 2019-01-04 | 江西中烟工业有限责任公司 | A kind of heating of the perfume (or spice) of solid-state containing herbal odor type pearl is not burnt cigarette and preparation method thereof |
| CN110564005A (en) * | 2019-08-28 | 2019-12-13 | 中国第一汽车股份有限公司 | Anion additive |
| CN110564005B (en) * | 2019-08-28 | 2021-04-09 | 中国第一汽车股份有限公司 | Anion additive |
| CN111378300A (en) * | 2020-03-20 | 2020-07-07 | 上海安费诺永亿通讯电子有限公司 | Laser-enhanced chemical plating filler and preparation method thereof, laser-enhanced chemical plating material and method for carrying out selective metallization on surface of laser-enhanced chemical plating material |
| CN111960430A (en) * | 2020-09-01 | 2020-11-20 | 常州工学院 | Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve |
| CN111960430B (en) * | 2020-09-01 | 2022-04-01 | 常州工学院 | Synthetic method and application of high-crystallinity hierarchical-pore LSX zeolite molecular sieve |
| CN114425297B (en) * | 2020-10-15 | 2024-03-12 | 中国石油化工股份有限公司 | Para-disubstituted benzene adsorbent and preparation method thereof |
| CN114425297A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Para-disubstituted benzene adsorbent and preparation method thereof |
| CN112246217A (en) * | 2020-10-30 | 2021-01-22 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for purifying VOCs (volatile organic compounds) in zeolite adsorption rotating wheel and preparation method thereof |
| CN114433017A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | High-strength molecular sieve adsorbent and preparation method thereof |
| CN114433017B (en) * | 2020-10-31 | 2023-07-28 | 中国石油化工股份有限公司 | High-strength molecular sieve adsorbent and preparation method thereof |
| CN112191280A (en) * | 2020-12-10 | 2021-01-08 | 苏州立昂新材料有限公司 | Continuous crystal transformation and ion exchange device and process |
| US11845073B1 (en) | 2020-12-10 | 2023-12-19 | Catlion Co., Ltd. | Continuous crystal transformation and ion exchange device and process |
| WO2022121223A1 (en) * | 2020-12-10 | 2022-06-16 | 苏州立昂新材料有限公司 | Continuous crystal transformation and ion exchange device and process |
| CN112958144A (en) * | 2021-02-07 | 2021-06-15 | 内蒙古师范大学 | Preparation method and application of X-type zeolite molecular sieve catalyst |
| CN112588258A (en) * | 2021-03-03 | 2021-04-02 | 苏州立昂新材料有限公司 | Composite A-type molecular sieve raw powder containing wave absorbing material and full-zeolite molecular sieve, and preparation method and application thereof |
| CN113083222A (en) * | 2021-03-30 | 2021-07-09 | 中触媒新材料股份有限公司 | Modified adsorbent for adsorption separation and preparation method and application thereof |
| CN113441111A (en) * | 2021-05-11 | 2021-09-28 | 常州大学 | Preparation method of modified metal organic framework material for adsorbing and separating BTEX in C8 aromatic hydrocarbon |
| CN113441111B (en) * | 2021-05-11 | 2023-09-22 | 常州大学 | Preparation method of modified metal organic framework material for adsorbing and separating BTEX in C8 aromatic hydrocarbon |
| CN114160096B (en) * | 2022-02-08 | 2022-05-17 | 中海油天津化工研究设计院有限公司 | Adsorbent for separating ethylbenzene from carbon octa-aromatic hydrocarbons and preparation method thereof |
| CN114160096A (en) * | 2022-02-08 | 2022-03-11 | 中海油天津化工研究设计院有限公司 | Adsorbent for separating ethylbenzene in carbon octaaromatic hydrocarbon and preparation method thereof |
| CN115970637A (en) * | 2022-07-29 | 2023-04-18 | 正大能源材料(大连)有限公司 | Adsorbent and preparation method and application thereof |
| CN115970637B (en) * | 2022-07-29 | 2023-08-08 | 正大能源材料(大连)有限公司 | Adsorbent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104477937A (en) | Mesoporous X-type molecular sieve, adsorbent based on molecular sieve, and preparation and application thereof | |
| CN103442800B (en) | Adhesive-free zeolite adsorbents, manufactures the method for adhesive-free zeolite adsorbents, and uses the adsorption separating method of this adhesive-free zeolite adsorbents | |
| US8530367B2 (en) | Agglomerated zeolitic adsorbents, their method of preparation and their uses | |
| US10722862B2 (en) | Zeolitic adsorbents, their process of preparation and their uses | |
| Shams et al. | Preparation of 5A zeolite monolith granular extrudates using kaolin: Investigation of the effect of binder on sieving/adsorption properties using a mixture of linear and branched paraffin hydrocarbons | |
| KR101923248B1 (en) | Emm-23 molecular sieve material, its synthesis and use | |
| CN104148010B (en) | Binder free height silicon MFI zeolite adsorbents and its preparation method | |
| CN101932380B (en) | Agglomerated zeolitic absorbents, method of preparing them and uses thereof | |
| US5567407A (en) | Li-exchanged low silica EMT-containing metallosilicates | |
| Rasouli et al. | Para-xylene adsorption separation process using nano-zeolite Ba-X | |
| KR101504054B1 (en) | Aluminosilicate x-type zeolite compositions with low lta-type zeolite | |
| Subhan et al. | Adsorption and reusability performance of hierarchically porous silica (MMZ) for the removal of MB dye from water | |
| CN103506069B (en) | A kind of dewaxing by molecular sieve adsorbent and preparation method thereof | |
| Esmaeili et al. | Synthesis and characterization of NaA zeolite nanoparticles from Hordeum vulgare L. husk for the separation of total petroleum hydrocarbon by an adsorption process | |
| Kimura et al. | Water adsorption behavior of ordered mesoporous silicas modified with an organosilane composed of hydrophobic alkyl chain and hydrophilic polyethylene oxide groups | |
| CN108262004A (en) | Paraxylene adsorbent and preparation method thereof | |
| CN108262005A (en) | A kind of bead adsorbent of adsorption stripping dimethyl benzene and preparation method thereof | |
| Rasouli et al. | Adsorptive separation of meta-xylene from C8 aromatics | |
| CN103028372B (en) | Binderless zeolite adsorbent and preparation method thereof | |
| KR20220025044A (en) | Composite bed cohesive adsorbent and method for preparing same | |
| US10981143B2 (en) | Binderless zeolitic adsorbents | |
| CN108525643B (en) | Paraxylene adsorbent and preparation method thereof | |
| Luchian et al. | Removal of Mn (II), Ni (II) and Cu (II) ions from white wine through ion exchange in microporous mordenite and mesoporous Al-MCM-41 | |
| CN103933928B (en) | Dehumidifying adsorbent and preparation method thereof | |
| US11033879B2 (en) | Binderless zeolitic adsorbents |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 201806 Jiading District, Shanghai, the town of Heng Yue Road, No. 258 Applicant after: Shanghai Luqiang New Materials Co., Ltd. Applicant after: Shanghai Chemical Research Institute Co., Ltd. Address before: 201806 Jiading District, Shanghai, the town of Heng Yue Road, No. 258 Applicant before: Shanghai Luqiang New Materials Co., Ltd. Applicant before: Shanghai Research Institute of Chemical Industry |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150401 |