CN109772261A - 5A adsorbent of molecular sieve and its preparation method and application - Google Patents
5A adsorbent of molecular sieve and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to adsorbent of molecular sieve fields, specifically disclose a kind of 5A adsorbent of molecular sieve and its preparation method and application, 5A adsorbent of molecular sieve of the invention, in terms of the dry weight of adsorbent, 5A molecular sieve content in the adsorbent is more than 92 weight %, percentage of damage of the adsorbent at 250N 6.9% hereinafter, and the adsorbent n-pentadecane adsorbance be 103mg/g or more.5A adsorbent of molecular sieve provided by the invention is high with molecular sieve content, intensity is good, large amount of adsorption, the absorption particularly suitable for n-pentadecane.
Description
Technical field
The present invention relates to adsorbent of molecular sieve fields, and in particular to a kind of 5A adsorbent of molecular sieve and preparation method thereof and answers
With.
Background technique
N-alkane is important industrial chemicals, is its important means of production using molecular sieve adsorbing separation.5A molecular sieve
Mean molecule aperture is 5A, and the molecular diameter of n-alkane is less than 5A in petroleum oil product, can enter molecular sieve pore passage.And it is other
The molecular diameter of isoparaffin, cycloalkane, aromatic hydrocarbons etc. is both greater than 5A, according to the characterization of adsorption of molecular sieve, is made using 5A molecular sieve
It can be separated from petroleum oil product for adsorbent and absorb n-alkane.
CN87105499A discloses a kind of preparation method of binder-free spherical model-A molecular sieves, and this method is with Inorganic Ammonium
Salt, inorganic acid, waterglass are raw material, prepare silica hydrogel bead with oil-drop method, are washed, soak surface-active
Agent, dry, roasting are made low bulk silicon oxide pellets, silicon oxide pellets and sodium aluminate solution are mixed, one
Determine aging at temperature, crystallization, so that silica is essentially converted to 4A molecular sieve, then become 5A molecular sieve through calcium exchange.The work
Skill brings two big pollutions in process of production, and the pollution control difficulty generated is larger, and the especially use of inorganic ammonium salt will
Reluctant ammonia-nitrogen sewage is generated, the use of surfactant keeps the COD of sewage exceeded.
CN201310516673.8 discloses a kind of method that rolling ball method prepares 5A adsorbent, by that will contain 4A molecular sieve
Roller forming is carried out with the powder of binder to be then dried, roast and obtain matrix pellet, later carries out matrix pellet in advance
It carries out turning brilliant after wet, calcium exchange, drying, roast so that the 5A adsorbent of molecular sieve that the method according to the invention is prepared.But
This method still remains larger room for promotion in terms of turning crystalline substance, adsorbent.(carbon number is greater than 14 positive structure to especially heavy wax
Alkane) absorption aspect wretched insufficiency.
Summary of the invention
That the purpose of the present invention is to provide a kind of molecular sieve contents is high, intensity is good, large amount of adsorption, especially suitable for weight wax
The 5A adsorbent of molecular sieve product and its preparation method and application of (especially n-pentadecane) absorption.
To realize foregoing purpose, according to the first aspect of the invention, the present invention provides a kind of 5A adsorbent of molecular sieve,
In, in terms of the dry weight of adsorbent, the 5A molecular sieve content in the adsorbent is more than 92 weight %, and the adsorbent is in 250N
Under percentage of damage 6.9% hereinafter, and the adsorbent n-pentadecane adsorbance be 103mg/g or more.
According to the second aspect of the invention, the present invention provides a kind of method for preparing 5A adsorbent of molecular sieve, this method packet
It includes:
(1) powder containing 4A molecular sieve and binder source is subjected to roller forming and obtains bead；The bead is carried out
Dry, roasting obtains matrix pellet；
(2) matrix pellet is prewetted, then carries out a turn crystalline substance and the binder in the matrix pellet is converted substantially
For 4A molecular sieve, 4A molecular sieve beads are obtained；
(3) the 4A molecular sieve beads are washed, then carries out calcium and exchanges to obtain 5A molecular sieve beads；By the 5A molecule
Drying after bead is washed is sieved, vacuum baking is then carried out；
Wherein, it prewets and successively undergoes stage (1) and stage (2), wherein the ambient humidity in stage (1) is 10-50%RH,
The ambient humidity in stage (2) is 50-99%RH.
According to the third aspect of the invention we, the present invention provides a kind of 5A molecular sieve suction being prepared by method of the invention
Attached dose.
According to the fourth aspect of the invention, the answering in weight wax absorption the present invention provides a kind of 5A adsorbent of molecular sieve
With.
5A adsorbent of molecular sieve of the invention has 5A molecular sieve content height, weight wax (especially n-pentadecane) adsorbance
Greatly, the advantages that adsorption efficiency is high, intensity is good.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of 5A adsorbent of molecular sieve (hereinafter also referred to as adsorbent), wherein with the dry of adsorbent
Restatement, more than 92 weight %, percentage of damage of the adsorbent at 250N exists the 5A molecular sieve content in the adsorbent
6.9% hereinafter, and the adsorbent n-pentadecane adsorbance be 103mg/g or more.
According to the present invention, in terms of the dry weight of adsorbent, the 5A molecular sieve content in the adsorbent more than 92 weight %,
Preferably 96 weight % or more.
In terms of the dry weight of adsorbent, the specific example of the 5A molecular sieve content in the adsorbent for example: 92
Weight %, 93 weight %, 94 weight %, 95 weight %, 96 weight %, 96.5 weight %, 96.6 weight %, 96.8 weight %,
96.9 weight %, 97.0 weight %, 97.1 weight %, 97.2 weight %, 97.5 weight %, 97.7 weight %, 97.9 weight %,
98.1 weight %, 98.1 weight %, 98.3 weight %, 98.5 weight %, 98.8 weight %, 99 weight % or 99.5 weight %
Deng.
Molecular sieve content in above-mentioned adsorbent is carried out by test method as defined in ASTM D5357-2003 (2008) e1
Test.
According to the present invention, the n-pentadecane adsorbance of the 5A adsorbent of molecular sieve is preferably in 105mg/g or more, more preferably
For 105-111mg/g.
The specific example of n-pentadecane adsorbance as the 5A adsorbent of molecular sieve for example: 103mg/g,
104mg/g、105mg/g、105.1mg/g、105.3mg/g、105.5mg/g、105.7mg/g、105.9mg/g、106mg/g、
106.2mg/g、106.5mg/g、106.8mg/g、107mg/g、107.1mg/g、107.2mg/g、107.3mg/g、107.5mg/
g、107.8mg/g、108mg/g、108.2mg/g、108.4mg/g、108.6mg/g、108.8mg/g、109mg/g、109.5mg/
G, 110mg/g, 110.1mg/g, 110.5mg/g or 111mg/g etc..
In the present invention, the n-pentadecane adsorbance of the 5A adsorbent of molecular sieve is measured using following methods: at 25 DEG C, being inhaled
Attached dose: adsorption liquid=1:2 (weight ratio), the isooctane solution containing 16% n-pentadecane is that adsorption criteria is molten by weight percentage
Liquid, after stirring 15 minutes, adsorbance of the measurement adsorbent to n-pentadecane in standard solution.
In the present invention, percentage of damage of the adsorbent at 250N is 6.9% hereinafter, preferably 5-6%.
As percentage of damage of the adsorbent at 250N specific example for example: 6.9%, 6.5%,
6.3%, 6%, 5.9%, 5.8%, 5.7%, 5.6%, 5.5%, 5.4%, 5.3%, 5.2%, 5.1% or 5.8% etc..
The measuring method of percentage of damage of the adsorbent at 250N is using DL-II type detector for strength of particles (Dalian
The production of chemical research designing institute), about 1.5 milliliters of adsorbents are packed into stainless steel cylinder, is saturated naturally through air, crosses 297 microns
Sieve weighing.One thimble being interference fitted with stainless steel cylinder of installation when measurement, pushes primary in pre-set pressure
After pour out adsorbent, after 297 microns sieves weigh, the adsorbent in the case where setting pressure is calculated according to the reduction amount of adsorbent
Percentage of damage.
In the present invention, in terms of dry weight, in the adsorbent other than 5A molecular sieve, remaining is binder and/or pore-creating
Agent.
In addition, the present invention to the water content of the adsorbent without particular/special requirement, such as with total restatement of adsorbent, adsorbent
In water content in 5 weight % hereinafter, preferably 1-4 weight %.
In the present invention, igloss amount of the 5A adsorbent of molecular sieve at 580 DEG C is in 5 mass % hereinafter, preferably 1-4 matter
Measure %.
In the present invention, the 5A adsorbent of molecular sieve water content is indicated with the igloss amount after 580 DEG C, 1.5 hours, i.e. calcination
The ratio of quality before the mass decrement of 5A adsorbent of molecular sieve afterwards and the calcination of 5A adsorbent of molecular sieve.
, according to the invention it is preferred to which the average crystal grain diameter of the 5A adsorbent of molecular sieve is 0.1-3.5 μm, more preferably
0.5-1.5 μm, further preferably 0.6-0.9 μm.
, according to the invention it is preferred in the 5A adsorbent of molecular sieve, n (SiO2)/n(Al2O3) molar ratio be 1.92-2.2,
More preferably 1.95-2.
, according to the invention it is preferred to which the specific surface area of the 5A adsorbent of molecular sieve is greater than 500m2/ g, more preferably 505-
550m2/ g, further preferably 508-520m2/g。
, according to the invention it is preferred to zeolite crystal range 0.44-0.68 part mass hundred in the 5A adsorbent of molecular sieve
Divide than being greater than 50%, more preferably 51-60%, further preferably 51-55%.
Concrete example as zeolite crystal range 0.44-0.68 part mass percentage in the 5A adsorbent of molecular sieve
Son for example: 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60% etc..
The present invention provides a kind of methods for preparing 5A adsorbent of molecular sieve, this method comprises:
(1) powder containing 4A molecular sieve and binder source is subjected to roller forming and obtains bead；The bead is carried out
Dry, roasting obtains matrix pellet；
(2) matrix pellet is prewetted, then carries out a turn crystalline substance and the binder in the matrix pellet is converted substantially
For 4A molecular sieve, 4A molecular sieve beads are obtained；
(3) the 4A molecular sieve beads are washed, then carries out calcium and exchanges to obtain 5A molecular sieve beads；By the 5A molecule
Drying after bead is washed is sieved, vacuum baking is then carried out；
Wherein, it prewets and successively undergoes stage (1) and stage (2), wherein the ambient humidity in stage (1) is 10-50%RH,
The ambient humidity in stage (2) is 50-99%RH.
A kind of more preferable embodiment according to the present invention, the ambient humidity in stage (1) are 20-30%RH, the stage (2)
Ambient humidity is 80-90%RH.
According to the method for the present invention, as long as guaranteeing first to prewet by abovementioned steps before carrying out matrix pellet to turn brilliant
The purpose of the present invention can be thus achieved, and for the present invention, in order to further increase the 5A molecular sieve being finally prepared absorption
Heavy wax (especially n-pentadecane) adsorbance of agent, is preferably subjected to after the prewetting of stage (1) and stage (2) that water contains in matrix pellet
Amount is 17 weight % or more, preferably 18-23 weight %.
According to the method for the present invention, RH refers to relative humidity, refers specifically to contained steam vapour amount in environmental air
With the percentage of air contained saturated steam amount in the same circumstances.
In the present invention, what turn crystalline substance was well known to those skilled in the art turns crystal technique, refers specifically to viscous by that will contain
The matrix pellet of knot agent carries out alkali process and binder is made to be converted into 4A molecular sieve.
According to the method for the present invention, the purpose of the present invention can be achieved according to present invention technical solution above-mentioned, for this
Invention, in order to further increase heavy wax (especially n-pentadecane) adsorbance for the 5A adsorbent of molecular sieve being prepared, preferably
The average crystal grain diameter of 4A molecular sieve described in step (1) is 0.2-2.1 μm, preferably 0.5-1.5 μm, more preferably 0.6-
1.4μm.It can be improved and be prepared into for 5A adsorbent of molecular sieve of the invention using the 4A system with molecular sieve for preparing of aforementioned average crystal grain diameter
Heavy wax (especially n-pentadecane) adsorbance of the 5A adsorbent of molecular sieve arrived.
According to the method for the present invention, the methanol adsorption amount of further preferred step (1) the 4A molecular sieve is 160-
190mg/g, more preferably 180-190mg/g.
With the method for the invention it is preferred to containing also containing in 4A molecular sieve and the powder in binder source described in step (1)
Have auxiliary agent (such as can be pore creating material), the preferably described pore creating material is one of lignin, sodium cellulosate and sesbania powder or more
Kind.By the heap ratio that the adjustable 5A adsorbent of molecular sieve of pore creating material is added in powder.
According to the method for the present invention, 4A molecular sieve in the powder, binder source content optional wider range, specifically
It is referred to prior art progress, for the present invention, in a preferred embodiment of the invention, 4A molecule in the preferably described powder
The content of sieve is 90-99 weight %, and the content in binder source is 0.5-9 weight %, and the content of pore creating material is 0.1-8 weight %.
In the present invention, the preparation method containing 4A molecular sieve, the powder in binder source (or also containing auxiliary agent) can
With referring to the prior art carry out, such as can by 4A molecular sieve powder, adhesive powder, auxiliary agent powder batch mixer (for example,
Twin screw compounder) middle mixing 1-5 hours.In this regard, those skilled in the art can know, details are not described herein by the present invention.
The method that the powder containing 4A molecular sieve and binder source carries out roller forming is referred in the present invention existing
Technology carries out, such as can carry out as follows: described will contain 4A molecular sieve, binder source (or also containing auxiliary agent)
Powder is sent into spin pot (such as coating pan, preferably spin pot bore are 0.5-2.5m, more preferably 1.0-1.2m), and then one
Bian Jiashui carries out roller forming on one side, wherein the operating condition in preferred spin pot includes: that revolving speed is 30-40 revs/min, adds water
Speed is subject to the total material moisture of spin and improves 3-5 weight % per hour, when the moisture of the total material of spin reaches 45-50 weight
When measuring %, stops plus water then proceedes to rotation roller forming 3-5 hours.For the present invention, the preferably described roller forming condition makes
The partial size for obtaining the bead that roller forming obtains is 0.3-0.9mm, and the water content of bead is 42-44 weight %.
According to the method for the present invention, optional wider range of the type in the binder source can be converted by turning crystalline substance
Binder (for example, clay and/or Alusil) in the binder source of 4A molecular sieve is used equally for the present invention, for the present invention,
Under preferable case, binder source described in step (1) is one of kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite or more
Kind.
According to the method for the present invention, the method that the 5A molecular sieve beads are dried is referred in step (3) existing
There is technology progress, however the present inventor has found in the course of the research, if 5A molecular sieve beads progress microwave is done
Dry heavy wax (especially n-pentadecane) adsorbance that can greatly improve the 5A adsorbent of molecular sieve being finally prepared.Therefore,
For the present invention, microwave drying will be carried out after 5A molecular sieve beads washing in preferred steps (3), and preferably microwave drying
Condition makes the water content of the 5A molecular sieve beads below 18 weight %.
According to the method for the present invention, the method for the microwave drying is known in the art, and details are not described herein by the present invention,
For the present invention, in preferred steps (3) by the 5A molecular sieve beads carry out microwave drying condition include: micro-wave oven power
It is 100-500 kilowatts, preferably 250-400 kilowatts, in the process using purification wind, a large amount of steam bands that microwave heating is generated
It walks, purification general mood amount control is in 100-1000m3/ hour, preferably 600-800m3/ hour；The purification wind can be for example sky
Gas, the preferably described purification wind are that dew point is controlled at 50 DEG C to subzero 50 DEG C, preferably 20 DEG C to subzero 10 DEG C of air.
According to the method for the present invention, in step (3) by the 5A molecular sieve beads at vacuum degree -80~-100KPa, into
Row vacuum baking is to activate dehydration, and the condition of the more preferably roasting makes the water content of the 5A molecular sieve beads after roasting exist
2.0 weight % or less.For the present invention, the condition of the preferably described roasting includes: and the temperature roasted is 200-600 DEG C, preferably
It is 250-350 DEG C；The vacuum degree of roasting is -80~-100KPa, preferably -85~-95KPa；The time of roasting is 1-5 hours,
Preferably 2-3 hours.
The roasting apparatus that can satisfy aforementioned roasting condition is, for example, vacuum baking furnace.
According to the method for the present invention, the present invention to the operating condition of the vacuum baking furnace without particular/special requirement, as long as can be real
The existing purpose of the present invention, for the present invention, the volume of the preferably described vacuum baking furnace is 0.1-18m3, more preferably 1-
2.8m3.The vacuum degree of roasting is -80~-100KPa, preferably -85~-95KPa.
According to the method for the present invention, turn brilliant method for the matrix pellet after described prewet in step (2) can join
It is selected according to the prior art, the various rotating crystal methods of the prior art are used equally for the present invention.For the present invention, preferred steps
(2) matrix pellet after described prewet turn the 80 weight % that brilliant condition makes the binder in the matrix pellet in
It is converted into 4A molecular sieve above.
It is further preferably described to turn brilliant and carry out as follows for the present invention: by after described prewet matrix pellet with
Stage (I) and stage (II) are successively undergone in sodium hydrate aqueous solution contact, the contact, and the temperature in stage (I) is 5-50 DEG C, rank
The temperature of section (II) is 90-100 DEG C.It carries out turning crystalline substance according to abovementioned steps, can be further improved adsorbent counterweight wax (especially
N-pentadecane) adsorbance.
A kind of more preferable embodiment according to the present invention, the time in stage (I) are 1-10 hours, preferably 3-6 hours；
The time in stage (II) is 1-6 hours, preferably 2-3 hours.
According to the method for the present invention, the condition that the matrix pellet after described prewet is contacted with sodium hydrate aqueous solution is also wrapped
Include: the concentration of sodium hydrate aqueous solution is 0.1-0.25mol/L, preferably 0.13-0.15mol/L；Sodium hydrate aqueous solution with
It is described prewet after matrix pellet volume ratio be 1-9:1, preferably 2-3:1.
According to the method for the present invention, step (3) the calcium exchange is referred to prior art progress, and the calcium of the prior art is handed over
The method of changing is used equally for the present invention, and for the present invention, preferred steps (3) the calcium exchange carries out as follows: by the water
4A molecular sieve beads after washing are contacted with calcium chloride water, and the condition of the preferably described contact includes: the dense of calcium chloride water
Degree is 0.1-1.2mol/L, preferably 0.5-0.6mol/L；Calcium chloride water and the 4A molecular sieve beads after the washing
Volume ratio is 1-9:1, preferably 2-3:1；The temperature of contact is 50-150 DEG C, preferably 95-99 DEG C；Time is 1-16 hours,
Preferably 3-5 hours.
According to the method for the present invention, the container that the calcium is used interchangeably in the present invention, such as can be in kettle without particular/special requirement
It is carried out in formula container or pillar container, for the present invention, the preferably described calcium exchange carries out in pillar container.
According to needs, method of the invention further includes will be described before the bead for obtaining step (1) is dried
Bead carries out Shape correction (this field is also commonly referred to as polishing treatment).
Shaping (also referred to as polishing) refers to for bead being placed in trimmer in the present invention, and after starting device, bead is in shaping
Rubbed with the hands in machine examine, blow boiling, extruding, polishing make the inside of bead become that more matter is close, surface becomes more smooth step.Specifically may be used
To be realized as follows: a certain amount of bead being placed in trimmer, first low speed opens trimmer, pre- to small ball warp
High-speed cruising, those skilled in the art can know that details are not described herein to this again after processing.
In the present invention, method that is dry described in step (1), roasting is referred to prior art progress, wherein described
Dry to be dried using the drying means of foregoing microwave drying, the roasting can also be using as previously described
The method of roasting roasted in vertical heater.
In the present invention, the purpose for washing the 4A molecular sieve beads in step (3) is primarily to washing removing
Free sodium ion, and purpose that the 5A molecular sieve beads are washed is primarily to washing removing chloride ion, in this regard,
Those skilled in the art can know that details are not described herein by the present invention, also no longer carry out in a specific embodiment of the present invention strong
It adjusts.
The present invention provides a kind of 5A adsorbent of molecular sieve being prepared by method of the invention.
The 5A adsorbent of molecular sieve that the method according to the invention is prepared, in terms of the dry weight of adsorbent, the adsorbent
In 5A molecular sieve content more than 92 weight %, preferably 96 weight % or more.
In terms of the dry weight of adsorbent, the specific example of the 5A molecular sieve content in the adsorbent for example: 92
Weight %, 93 weight %, 94 weight %, 95 weight %, 96 weight %, 96.5 weight %, 96.6 weight %, 96.8 weight %,
96.9 weight %, 97.0 weight %, 97.1 weight %, 97.2 weight %, 97.5 weight %, 97.7 weight %, 97.9 weight %,
98.1 weight %, 98.1 weight %, 98.3 weight %, 98.5 weight %, 98.8 weight %, 99 weight % or 99.5 weight %
Deng.
Molecular sieve content in above-mentioned adsorbent is carried out by test method as defined in ASTM D5357-2003 (2008) e1
Test.
The n-pentadecane adsorbance for the 5A adsorbent of molecular sieve that the method according to the invention is prepared be 103mg/g with
On, preferably 105mg/g or more, more preferably 105-111mg/g.
The specific example of n-pentadecane adsorbance as the 5A adsorbent of molecular sieve for example: 103mg/g,
104mg/g、105mg/g、105.1mg/g、105.3mg/g、105.5mg/g、105.7mg/g、105.9mg/g、106mg/g、
106.2mg/g、106.5mg/g、106.8mg/g、107mg/g、107.1mg/g、107.2mg/g、107.3mg/g、107.5mg/
g、107.8mg/g、108mg/g、108.2mg/g、108.4mg/g、108.6mg/g、108.8mg/g、109mg/g、109.5mg/
G, 110mg/g, 110.1mg/g, 110.5mg/g or 111mg/g etc..
In the present invention, the n-pentadecane adsorbance of the 5A adsorbent of molecular sieve is measured using following methods: at 25 DEG C, being inhaled
Attached dose: adsorption liquid=1:2 (weight ratio), the isooctane solution containing 16% n-pentadecane is that adsorption criteria is molten by weight percentage
Liquid, after stirring 15 minutes, adsorbance of the measurement adsorbent to n-pentadecane in standard solution.
Percentage of damage of the 5A adsorbent of molecular sieve that the method according to the invention is prepared at 250N 6.9% hereinafter,
Preferably 5-6%.
As percentage of damage of the 5A adsorbent of molecular sieve at 250N specific example for example: 6.9%,
6.5%, 6.3%, 6%, 5.9%, 5.8%, 5.7%, 5.6%, 5.5%, 5.4%, 5.3%, 5.2%, 5.1% or 5.8%
Deng.
The measuring method of percentage of damage of the adsorbent at 250N is using DL-II type detector for strength of particles (Dalian
The production of chemical research designing institute), about 1.5 milliliters of adsorbents are packed into stainless steel cylinder, is saturated naturally through air, crosses 297 microns
Sieve weighing.One thimble being interference fitted with stainless steel cylinder of installation when measurement, pushes primary in pre-set pressure
After pour out adsorbent, after 297 microns sieves weigh, the adsorbent in the case where setting pressure is calculated according to the reduction amount of adsorbent
Percentage of damage.
In the present invention, in terms of dry weight, in the adsorbent other than 5A molecular sieve, remaining is binder and/or pore-creating
Agent.
In addition, the present invention to the water content of the adsorbent without particular/special requirement, such as with total restatement of adsorbent, adsorbent
In water content in 5 weight % hereinafter, preferably 1-4 weight %.
In the present invention, igloss amount of the 5A adsorbent of molecular sieve at 580 DEG C is in 5 mass % hereinafter, preferably 1-4 matter
Measure %.
In the present invention, the 5A adsorbent of molecular sieve water content is indicated with the igloss amount after 580 DEG C, 1.5 hours, i.e. calcination
The ratio of quality before the mass decrement of 5A adsorbent of molecular sieve afterwards and the calcination of 5A adsorbent of molecular sieve.
, according to the invention it is preferred to which the average crystal grain diameter of the 5A adsorbent of molecular sieve is 0.1-3.5 μm, more preferably
0.5-1.5 μm, further preferably 0.6-0.9 μm.
, according to the invention it is preferred in the 5A adsorbent of molecular sieve, n (SiO2)/n(Al2O3) molar ratio be 1.92-2.2,
More preferably 1.95-2.
, according to the invention it is preferred to which the specific surface area of the 5A adsorbent of molecular sieve is greater than 500m2/ g, more preferably 505-
550m2/ g, further preferably 508-520m2/g。
, according to the invention it is preferred to zeolite crystal range 0.44-0.68 part mass hundred in the 5A adsorbent of molecular sieve
Divide than being greater than 50%, more preferably 51-60%, further preferably 51-55%.
Concrete example as zeolite crystal range 0.44-0.68 part mass percentage in the 5A adsorbent of molecular sieve
Son for example: 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59% or 60% etc..
The present invention also provides the application of 5A adsorbent of molecular sieve of the invention in n-pentadecane absorption.
The present invention will be described in detail by the following examples, but the present invention is not limited in following embodiments.
In following embodiment and comparative example,
The n-pentadecane adsorbance of 5A adsorbent of molecular sieve is measured using following methods: at 25 DEG C, adsorbent: adsorption liquid=
1:2 (weight ratio), the isooctane solution containing 16% n-pentadecane is adsorption criteria solution by weight percentage, is stirred 15 minutes
Afterwards, adsorbance of the measurement adsorbent to n-pentadecane in standard solution.
Calcium exchange rate refers to the percentage that the sodium ion in molecular sieve is replaced by calcium ion, according to professional standard Q/
The method of SH349550 measures.
Average crystal grain diameter is measured using scanning electron microscope observation method.
The measuring method of percentage of damage of the adsorbent at 250N is using DL-II type detector for strength of particles (Dalian chemical industry
Studying and designing institute's production), about 1.5 milliliters of adsorbents are packed into stainless steel cylinder, is saturated naturally through air, crosses 297 microns of sieve
Weighing.One thimble being interference fitted with stainless steel cylinder of installation when measurement, falls after pre-set pressure pushes once
Adsorbent out is weighed after 297 microns of sieves, calculates being crushed in the case where set pressure adsorbent according to the reduction amount of adsorbent
Rate.Wherein, percentage of damage is lower, and intensity is better.
Molecular sieve content in adsorbent is tested according to test method as defined in ASTM D5357-2003 (2008) e1.
Spherical diameter uses vernier caliper measurement, and directly reading obtains.
Embodiment 1
(1) (water content is 21 weight % to the commercially available 4A molecular screen primary powder 400kg for taking by levigate processing, and average crystal grain is straight
Diameter is 0.7 μm, and methanol adsorption amount be 181mg/g), kaolin 20kg (water content be 22 weight %), sesbania powder pore creating material 10kg
It is put into twin screw compounder and mixes 3 hours, take out the material 50kg mixed, be put into the spin pot (sugar-coat that bore is 1.2m
Pot) in, carrying out roller forming production bead, (operating condition in spin pot includes: that revolving speed control is 30 revs/min, adds water speed
Degree is subject to material moisture and improves 3-5 weight % per hour, when material final moisture reaches 45-50 weight %, stop plus
Water, then keeping spin pot pot body revolving speed is 30-40 revs/min, is continued to rotate 3-5 hours), it is 0.3- when ball grows to diameter
It when 1.0mm, is processed by shot blasting 1-2 hours, screening obtains bead sample, in the method, in 20 mouthfuls of identical spin pots
It carries out roller forming and makes bead, 1 ton of bead is finally prepared (water content is 43 weight %, diameter 0.3-0.9mm)；
By the bead carry out microwave drying (drying condition include: power be 300 kilowatts, in drying process with purification wind,
The a large amount of steam generated in drying process are taken away, purification wind is air of the dew point control at 0 DEG C or so, purification general mood amount control
In 800m3/ hour), so that bead water content is reduced to 17 mass %, then bead is sent into meshbeltfurnace and is roasted (roasting
Condition includes: that temperature is 550-560 DEG C, and the time is 2.2 hours), finally obtain matrix pellet (water content is 2.3 weight %)；
(2) stage (1), stage (2) is successively undergone to prewet the matrix pellet, the stage ambient humidity of (1) is
The ambient humidity of 20%RH, stage (2) are 90%RH, and matrix pellet water content is made to reach 20 weight %；Then it will prewet
Matrix pellet, which is sent into synthesis reactor, contacts two sections turns of progress brilliant processing (wherein, sodium hydrate aqueous solutions with sodium hydrate aqueous solution
Volume ratio with the matrix pellet after described prewet is 2.5, and the concentration of sodium hydrate aqueous solution is 0.12mol/L, wherein first
Duan Wendu is 30 DEG C, and the time is 3 hours, and second segment temperature is 97 DEG C, and the time is 2 hours), so that binder is largely converted into 4A
(binder of about 80 weight % is converted into 4A molecular sieve to molecular sieve, wherein calculates binder by the variation of methanol adsorption amount
It is converted into the amount of 4A molecular sieve, if the content of 4A molecular sieve in powder is 94 weight %, the content of binder is 5 weight %, is made
The content of hole agent is 1 weight %, and the methanol adsorption amount of initial 4A molecular sieve is 180mg/g, then the binder of 80 weight % turns
The raising value of adsorbance is X=(180*5) * 0.8/94=7.66mg/g when turning to 4A molecular sieve), obtain 4A molecular sieve beads；
(3) the 4A molecular sieve beads are washed to remove free sodium ion, it is then that the 4A molecular sieve after washing is small
Ball is sent into column reactor and is contacted with calcium chloride water to carry out calcium ion-exchanged, wherein calcium chloride water concentration is
The volume ratio of 4A molecular sieve beads after 0.55mol/L, calcium chloride water and the washing is 2, and time of contact is 3.5 small
When, Contact Temperature is 95 DEG C, repeats several times, so that the calcium exchange rate of 4A molecular sieve beads is reached 90%, obtain 5A molecule
Sieve bead；Then the 5A molecular sieve beads are washed with removing chloride ion, then carrying out microwave drying, (drying condition includes:
Power is 300 kilowatts, with purification wind in drying process, a large amount of steam generated in drying process is taken away, purification wind is dew point
The air at 0 DEG C or so is controlled, purification general mood amount control is in 800m3/ hour), so that 5A molecular sieve beads water content is reduced to 18
Weight % or less；Finally enter vacuum activating furnace (chemical, Sinopec Nanjing Chemical Industrial Co., Ltd, producer) progress
To activate dehydration, (wherein, the volumetric void fraction of vacuum drying oven is 2.2m for roasting3, temperature is 350 DEG C, and vacuum degree is -90~-100KPa,
Calcining time is 2 hours), obtaining 5A molecular sieve beads adsorbent, (water content of adsorbent is 3.0 weight %, with adsorbent
Dry weight meter, 5A molecular sieve content are 96.8 weight %, and diameter 0.3-0.9mm, adsorbent average grain diameter is 0.7 μm, n
(SiO2)/n(Al2O3) molar ratio be 1.98, specific surface area 520m2/ g, zeolite crystal range are the part 0.44-0.68 matter
Measuring percentage is 55%, 1) other relevant natures such as n-pentadecane adsorbance etc. are shown in Table.
Embodiment 2
5A adsorbent of molecular sieve bead is prepared according to the method for embodiment 1, unlike, the stage ambient humidity of (1) is
The ambient humidity of 30%RH, stage (2) are 80%RH, and matrix pellet water content is made to reach 20 weight %；Remaining condition is all the same,
Obtaining 5A molecular sieve beads adsorbent, (water content of adsorbent is 2.8 weight %, and in terms of the dry weight of adsorbent, 5A molecular sieve contains
Amount is 97.0 weight %, and diameter 0.3-0.9mm, adsorbent average grain diameter is 0.7 μm, n (SiO2)/n(Al2O3) molar ratio is
1.99, specific surface area 517m2/ g, zeolite crystal range are that 0.44-0.68 part mass percentage is 53%, relevant nature
1) such as n-pentadecane adsorbance is shown in Table.
Embodiment 3
5A adsorbent of molecular sieve bead is prepared according to the method for embodiment 1, unlike,
The matrix pellet prewetted is sent into synthesis reactor to contact with sodium hydrate aqueous solution and turn brilliant processing, wherein
Sodium hydrate aqueous solution and the volume ratio of the matrix pellet after described prewet are 2.5, and the concentration of sodium hydrate aqueous solution is
0.12mol/L, wherein temperature is 96 DEG C, and the time is 3 hours.Remaining condition is all the same, obtains 5A molecular sieve beads adsorbent
(water content of adsorbent is 2.9 weight %, and in terms of the dry weight of adsorbent, 5A molecular sieve content is 97.0 weight %, and diameter is
0.3-0.9mm, adsorbent average grain diameter are 0.8 μm, n (SiO2)/n(Al2O3) molar ratio be 2.00, specific surface area 515m2/
G, zeolite crystal range are that 0.44-0.68 part mass percentage is 53%, and relevant nature such as n-pentadecane adsorbance etc. is shown in
Table 1).
Embodiment 4
5A adsorbent of molecular sieve bead is prepared according to the method for embodiment 1, unlike, the temperature of vacuum drying oven is 350 DEG C,
Vacuum degree is -80~-90KPa, and calcining time is 2 hours, remaining condition is all the same, obtains 5A molecular sieve beads adsorbent and (inhales
Attached dose of water content is 3.1 weight %, and in terms of the dry weight of adsorbent, 5A molecular sieve content is 96.8 weight %, diameter 0.3-
0.9mm, adsorbent average grain diameter are 0.7 μm, n (SiO2)/n(Al2O3) molar ratio be 1.99, specific surface area 511m2/ g, point
It is 51% that son sieve grain colony, which is 0.44-0.68 part mass percentage, 1) relevant nature such as n-pentadecane adsorbance etc. is shown in Table.
Embodiment 5
5A adsorbent of molecular sieve bead is prepared according to the method for embodiment 1, unlike, by the matrix in step (2)
The condition that bead is prewetted makes the matrix pellet water content after prewetting be 15.6 weight %, remaining condition is all the same, obtains 5A points
(water content of adsorbent is 2.9 weight % to son sieve bead adsorbent, and in terms of the dry weight of adsorbent, 5A molecular sieve content is 96.6
Weight %, diameter 0.3-0.9mm, adsorbent average grain diameter are 0.7 μm, n (SiO2)/n(Al2O3) molar ratio be 1.99, compare table
Area is 509m2/ g, zeolite crystal range are that 0.44-0.68 part mass percentage is 51%, relevant nature for example positive 15
1) alkane adsorbance etc. is shown in Table.
Comparative example 1
5A adsorbent of molecular sieve bead is prepared according to the method for embodiment 1, unlike, the only environmental wet in stage (1)
Degree makes matrix pellet water content reach 20 weight % for 90%RH without stage (2)；Remaining condition is all the same, obtains 5A molecule
Sieving bead adsorbent, (water content of adsorbent is 2.9 weight %, and in terms of the dry weight of adsorbent, 5A molecular sieve content is 96.3 weights
%, diameter 0.3-0.9mm are measured, adsorbent average grain diameter is 0.7 μm, n (SiO2)/n(Al2O3) molar ratio be 1.99, specific surface
Product is 496m2/ g, zeolite crystal range are that 0.44-0.68 part mass percentage is 47%, relevant nature such as n-pentadecane
1) adsorbance etc. is shown in Table.
Comparative example 2
5A adsorbent of molecular sieve bead is prepared according to the method for embodiment 1, unlike, step (2) is without prewetting, directly
It taps into row and turns crystalline substance, remaining condition is all the same, and obtaining 5A molecular sieve beads adsorbent, (adsorbent average grain diameter is 0.8 μm, n
(SiO2)/n(Al2O3) molar ratio be 1.99, specific surface area 489m2/ g, zeolite crystal range are the part 0.44-0.68 matter
Measuring percentage is 44%, 1) relevant nature such as n-pentadecane adsorbance etc. is shown in Table.
Table 1
The 5A adsorbent of molecular sieve bead that the method according to the invention is prepared it can be seen from result in table 1 is just
Pentadecane adsorbance is small compared to the 5A adsorbent of molecular sieve that the method according to the prior art is prepared in 103mg/g or more
Ball n-pentadecane adsorbance is much higher, and small compared to the 5A adsorbent of molecular sieve that the method according to the prior art is prepared
The intensity of ball, 5A molecular sieve beads of the invention increases, it can be seen that, the 5A molecular sieve that method of the invention is prepared
Adsorbent is particularly well suited as positive structure pentadecane adsorbent and uses.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (14)
1. a kind of 5A adsorbent of molecular sieve, which is characterized in that in terms of the dry weight of adsorbent, the 5A molecular sieve in the adsorbent contains
Amount more than 92 weight %, percentage of damage of the adsorbent at 250N 6.9% hereinafter, and the adsorbent n-pentadecane
Adsorbance is 103mg/g or more.
2. 5A adsorbent of molecular sieve according to claim 1, wherein the 5A molecular sieve content in the adsorbent is in 96 weights
Measure % or more；
Preferably, percentage of damage of the adsorbent at 250N is 5-6%；
Preferably, igloss amount of the 5A adsorbent of molecular sieve at 580 DEG C is 2-4 mass %；
Preferably, the n-pentadecane adsorbance of the adsorbent is 105-111mg/g；
Preferably, zeolite crystal range 0.44-0.68 part mass percentage is greater than 50% in 5A adsorbent of molecular sieve.
3. a kind of method for preparing 5A adsorbent of molecular sieve, which is characterized in that this method comprises:
(1) powder containing 4A molecular sieve and binder source is subjected to roller forming and obtains bead；The bead is dried,
Roasting obtains matrix pellet；
(2) matrix pellet is prewetted, then carries out a turn crystalline substance and the binder in the matrix pellet is made to be substantially transitioned to 4A
Molecular sieve obtains 4A molecular sieve beads；
(3) the 4A molecular sieve beads are washed, then carries out calcium and exchanges to obtain 5A molecular sieve beads；The 5A molecular sieve is small
It is dry after ball washing, then carry out vacuum baking；
Wherein, it prewets and successively undergoes stage (1) and stage (2), wherein the ambient humidity in stage (1) is 10-50%RH, stage
(2) ambient humidity is 50-99%RH.
4. according to the method described in claim 3, wherein, the ambient humidity in stage (1) is 20-30%RH, the environment in stage (2)
Humidity is 80-90%RH.
5. the method according to claim 3 or 4, wherein experience stage (1) and stage (2), prewet after in matrix pellet
Water content is 18-23 weight %.
6. the method according to claim 3 or 4, wherein carry out the matrix pellet after described prewet in step (2) to turn crystalline substance
Condition make the 80 weight % or more of the binder in the matrix pellet be converted into 4A molecular sieve.
7. the method according to claim 3 or 4, wherein described turn of crystalline substance carries out as follows: by the base after described prewet
Matter bead is contacted with sodium hydrate aqueous solution, and the contact successively undergoes stage (I) and stage (II), the stage temperature of (I) are
5-50 DEG C, the temperature in stage (II) is 90-100 DEG C.
8. according to the method described in claim 7, wherein, the time in stage (I) is 1-10 hours, preferably 3-6 hours；Stage
(II) time is 1-6 hours, preferably 2-3 hours.
9. according to the method described in claim 7, wherein, the matrix pellet after described prewet is contacted with sodium hydrate aqueous solution
Condition further include: the concentration of sodium hydrate aqueous solution be 0.1-0.25mol/L, sodium hydrate aqueous solution and it is described prewet after
The volume ratio of matrix pellet is 1-9:1.
10. the method according to claim 3 or 4, wherein the average crystal grain diameter of the 4A molecular sieve is 0.2-2.1 μm,
Preferably 0.5-1.5 μm.
11. the method according to claim 3 or 4, wherein contain 4A molecular sieve and binder source described in step (1)
Also contain pore creating material in powder；
It is preferred that the content of 4A molecular sieve is 90-99 weight % in the powder, the content in binder source is 0.5-9 weight %, is made
The content of hole agent is 0.1-8 weight %；
It is preferred that the pore creating material is one of lignin, sodium cellulosate and sesbania powder or a variety of；The binder source is kaolinite
One of the sweet soil of soil, sheep and diatomite are a variety of.
12. the method according to claim 3 or 4, wherein in step (3), the vacuum degree of the vacuum baking is -80~-
100KPa。
13. the 5A adsorbent of molecular sieve that the method as described in any one of claim 3-12 is prepared.
14. application of the 5A adsorbent of molecular sieve described in claim 1,2 or 13 in n-pentadecane absorption.
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| 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 |
| CN114682235A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of molecular sieve adsorbent |
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| CN103566888A (en) * | 2012-08-02 | 2014-02-12 | 中国石油化工股份有限公司 | Activation method for p-xylene adsorbent carrier and preparation method of p-xylene adsorbent |
| CN103933932A (en) * | 2012-10-29 | 2014-07-23 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method thereof |
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| CN103566888A (en) * | 2012-08-02 | 2014-02-12 | 中国石油化工股份有限公司 | Activation method for p-xylene adsorbent carrier and preparation method of p-xylene adsorbent |
| CN103933932A (en) * | 2012-10-29 | 2014-07-23 | 中国石油化工股份有限公司 | 5A molecular sieve adsorbent and preparation method thereof |
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| CN114426283A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | 5A molecular sieve, preparation method and application thereof, and method for separating normal paraffin and isoparaffin in gasoline |
| 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 |
| CN114682235A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Preparation method of molecular sieve adsorbent |
| CN114682235B (en) * | 2020-12-31 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of molecular sieve adsorbent |
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