CN104815612B - Preparation method of molecular sieve adsorbent for metacresol and paracresol adsorption separation, and adsorbent prepared thereby - Google Patents
Preparation method of molecular sieve adsorbent for metacresol and paracresol adsorption separation, and adsorbent prepared thereby Download PDFInfo
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Abstract
The invention relates to the field of petroleum and chemical engineering, and specifically relates to a preparation method of a molecular sieve adsorbent for metacresol and paracresol adsorption separation, and relates to the adsorbent prepared thereby. The method comprises the following steps: 1) preparing a molecular sieve raw powder; 2) forming the molecular sieve, including using SiO2.H2O as a forming binder for roll forming (or extrusion forming); and 3) modifying the surface of the molecular sieve, including using Si(OCH3)4 as a liquid-phase deposition agent to repeatedly and sequentially apply chemical liquid phase deposition, high-temperature steam treatment and calcination to the formed molecular sieve. The molecular sieve adsorbent having a silica-alumina ratio of 300-400, a particle size or a strip size of 1.5-2.0mm, and a mechanical strength of more than 10N/mm2 can be obtained by the provided method. By examining the separation property to the metacresol/paracresol system of the molecular sieve with a static liquid phase adsorption method, the paracresol adsorption capacity takes up 95% and more of the total molecular sieve adsorption capacity, without basically absorbing the metacresol. Therefore, the molecular sieve can be applied to the liquid phase adsorption operations of an industrial fixed bed or a simulation moving bed or chromatography preparation, thereby achieving the adsorption separation of the metacresol/paracresol.
Description
Technical field
The present invention relates to oil, chemical field, more particularly to it is a kind of for, the molecular sieve adsorption of paracresol adsorbing separation
The preparation method and its adsorbent of agent.
Background technology
Middle coalite tar is product of the coal in middle low temperature distillation, pyrolytic process, the phenolic material in middle coalite tar
Matter content is very high, and aldehydes matter is the industrial chemicals that there is economic worth pole, from coal tar extract natural phenolic product cost with
Being compared as Material synthesis phenol products with oil product has larger advantage, wherein cresols include orthoresol, paracresol and
Three kinds of isomers of cresols, it is industrial to be difficult to use distillation etc. conventional because the boiling point of metacresol and paracresol is close (0.4 DEG C of difference)
Method is isolated, so many cresols form of mixtures mixed with metacresol and paracresol of industrial products are present, and chemistry is closed
Generally needed with the single compound of paracresol or metacresol as raw material into industrial, so Cresol Isomeric Compound in cresols mixture
Separation be low boiling phenols separate key, the separation method that can be used at present mainly have perfectly crystallization process, complexing addition process,
Alkylation partition method, wherein adsorption method of separation, one of adsorbing separation method that process energy consumption is low, product purity is high owned by France, its core
The heart is the development and utilization of adsorbent.
The content of the invention
The present invention provide it is a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation.Mainly solve
Technical problem be realize liquid phase adsorption separation is carried out to the cresols mixture containing metacresol and paracresol, be separately recovered purity
Metacresol higher and the industrial production of paracresol.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
The adsorbent of molecular sieve preparation method of adsorbing separation is carried out to the cresols mixture containing metacresol and paracresol, its
Essential characteristic is as follows：
The main making step of the adsorbent of molecular sieve has：Molecular screen primary powder makes, molecular sieve molded, molecular sieve surface
It is modified.
The molecular screen primary powder makes to be included using silica gel (SiO2·H2O it is) silicon source, using aluminium hydroxide (AI (OH)3)
It is silicon source, it is template to use TPAOH (TPAOH), it is crystallization auxiliary to use potassium fluoride (KF), using hydro-thermal side
Method carries out crystallization synthesis, and crystallization products therefrom is carried out into filtration under diminished pressure, and filter cake is washed with deionized in filter process, will wash
Filtering gained filter cake obtains molecular screen primary powder by smashing the low temperature drying and high-temperature roasting that certain hour is carried out after dissipating.
It is described molecular sieve molded including the molecular screen primary powder is made into the molecular screen primary powder for obtaining using silica gel (SiO2·
H2O) for shaping adhesive is well mixed, roller forming or the extruded moulding on extruder are carried out on bowling machine, and carry out
The low temperature drying and high-temperature roasting of a period of time are that can obtain molded molecular sieve.
The surface modification of the adsorbent of molecular sieve is included the molecular sieve molded molded molecular sieve for obtaining
First use Si (OCH3)4For liquid deposition agent carries out chemical liquid deposition (CLD) treatment, passed through successively after chemical liquid deposition treatment
High-temperature roasting and high-temperature vapor are processed, and then return again to carry out chemical liquid deposition (CLD) treatment.This process is repeated several times,
Most afterwards through be dried to obtain for, the adsorbent of molecular sieve of paracresol adsorbing separation.
Further：The molecular screen primary powder is made using the synthesis of hydrothermal method crystallization, in mass, hydrothermal crystallizing synthesis
Charge ratio is Si02·H20：Potassium fluoride：Aluminium hydroxide：TPAOH is 1：1.5：0.35：0.125, remaining for go from
Sub- water, that is, meet hydrothermal method crystallization synthesis system be：
SiO2-1.5KF-0.35Al(OH)3-0.125TPAOH-30H2O。
Further：The drying temperature that the molecular screen primary powder makes is 80 DEG C, and drying time is not less than 10 hours, roasting temperature
It is 550 DEG C to spend, and roasting time is not less than 6 hours.
Further：The molecular sieve molded molecular screen primary powder and shaping adhesive silica gel (SiO2·H2O) it is in mass ratio
3:1~1.5 ratio is well mixed, and roller forming or the extruded moulding on extruder are then carried out on bowling machine.
Further：When the molecular sieve molded use roller forming, the pellet that should be rolled out to bowling machine is sieved, small
Continue to roll shaping in the particle return bowling machine of 1.5mm, the particle more than 2mm smashes return bowling machine after dissipating and continues to roll into
Type, choosing the particle of 1.5-2mm carries out the low temperature drying and high-temperature roasting of certain hour, normal temperature is naturally cooled to after roasting, i.e.,
Can obtain molded molecular sieve；When the molecular sieve molded use extruded moulding, it is 1.5- that should set extrusion circle rule footpath
2.0mm, then circle bar is carried out the low temperature drying and high-temperature roasting of certain hour, the absorption of normal temperature will be naturally cooled to after roasting
Agent circle bar is cut into the billet of 2-3mm length, you can obtain molded molecular sieve.
Further：The molecular sieve molded drying temperature is 80 DEG C, and drying time is not less than 8 hours, and sintering temperature is
550 DEG C, roasting time is not less than 6 hours.
Further：Chemical liquid deposition (CLD) treatment of the surface modification is first by the molded molecular sieve
By solid-liquid volume ratio 1:5 ratio mixes with deionized water, then in the ratio of 0.6 milliliter of liquid deposition agent/gram molded molecular sieve
Add liquid deposition agent Si (OCH3)4。
Further：The surface modification of the adsorbent of molecular sieve is after chemical liquid deposition treatment successively through high temperature
Roasting and high-temperature vapor treatment, then return again to carry out chemical liquid deposition treatment, this process repeatedly, until molecular sieve
The rate of body weight gain of dry molecular sieves is 3-4% afterwards before modified on surface.
Present invention also offers the adsorbent of molecular sieve prepared according to the above method.
The beneficial effects of the invention are as follows：It is 300-400, particle diameter (or bar footpath) to use the present invention and can obtain a kind of silica alumina ratio
1.5-2.0mm, mechanical strength is 10N/mm2Adsorbent of molecular sieve；The molecular sieve is investigated using static liquid phase adsorption method to inhale
Between attached dose pair/separating property of paracresol system, paracresol adsorbance accounts for more than the 95% of the total adsorbance of molecular sieve, and pair between first
Phenolic group is not originally adsorbed, it is possible to achieve/adsorbing separation of paracresol.
The present invention relates to the adsorbent of molecular sieve that makes of adsorbent of molecular sieve preparation method, can apply to industrial
Fixed bed or Simulation moving bed or preparative chromatography liquid phase adsorption separation operation, relatively relax operating condition under realize
The separation of metacresol and paracresol in cresols mixture, has the advantages that energy consumption is low, flow is simple and operating cost is low.
Brief description of the drawings
Fig. 1 be offer of the invention it is a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation
Schematic flow sheet.
Specific embodiment
Principle of the invention and feature are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
The purpose of the adsorbent of molecular sieve preparation method that the present invention is provided：Come from molecular dimension and power diameter order
Say it is metacresol>Paracresol, a kind of molecular sieve of channel diameter between metacresol and paracresol is prepared by method for optimizing
Adsorbent, allows paracresol to be adsorbed to adsorbent of molecular sieve endoporus, and metacresol is not adsorbed, and realizes to metacresol and right
The shape-selective adsorbing separation of cresols.
The principle of adsorbent of molecular sieve preparation method that the present invention is provided is：Efficient raw material is selected to be wanted beneficial to satisfaction is prepared
The molecular sieve crystal asked；The method of selection should be as far as possible simple and easy to do, is beneficial to industrialized production.
As shown in figure 1, it is a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is main to make
Step has：Molecular screen primary powder makes, molecular sieve molded, surface modification；
The primary raw material that optimization molecular screen primary powder makes has：Using silica gel (Si02.H20) it is silicon source, using aluminium hydroxide
(AI(OH)3) it is silicon source, it is template to use TPAOH (TPAOH), and it is crystallization auxiliary to use potassium fluoride (KF)；
Optimization molecular screen primary powder make raw material proportion of composing be：
SiO2-1.5KF-0.35Al(OH)3-0.125TPAOH-30H2O
The use hydrothermal method crystallization synthesis that optimization molecular screen primary powder makes.
The principle of primary raw material made using above-mentioned optimization molecular screen primary powder is：It is preferred that using silica gel (Si02.H20) it is
Silicon source because use silica gel can be obtained for silicon source preferable crystallinity, average grain size and surface area molecular sieve it is brilliant
Body；It is preferred that using aluminium hydroxide (AI (OH)3) be silicon source because aluminium hydroxide not only provide the structure ion aluminium of molecular sieve from
Son (Al3+), and the hydroxyl (OH for bringing into-) more silicon sources can be dissolved and silicon source is beneficial to crystallization process；It is preferred that using
TPAOH (TPAOH) is template because template cation tetrapropyl amine (TPA+) it is more conducive to guiding generation spy
Determine duct, specific skeleton and the larger molecular sieve crystal of surface area, and the hydroxyl (OH for bringing into-) more silicon can be dissolved
Source and silicon source are beneficial to crystallization process；It is preferred that using potassium fluoride (KF) for crystallization auxiliary because potassium ion (K+) poly- beneficial to crystal
Collection growth, and fluorine ion (F-) template cation can be balanced, reduce the defect of molecular sieve crystal.
Use the principle of the raw material proportion of composing that above-mentioned optimization molecular screen primary powder makes for：Preferred SiO2With Al (OH)3Throw
Material ratio is 1:0.35 (mass ratio), conversion to SiO2/Al203Ratio is 4.37, and beneficial to generation, surface area is larger, crystal size
Moderate molecular sieve crystal, the high silica alumina ratio molecular sieve crystal of, acid relatively low and spherical complexion relatively strong beneficial to generation hydrophobicity, together
When also ensure SiO2Have compared with high usage；Preferred H20/Si02Ratio is 30:1 (mass ratio), can prevent crystallization building-up process
Middle nucleus agglomerates into larger zeolite crystal, while a certain degree of beneficial to being carried out when hydrothermal method crystallization synthesizes
Stirring, preferred H20/Si02Ratio is conducive to efficiently synthesizing for molecular sieve crystal；In preferred SiO2With Al (OH)3Rate of charge
Example and H20/Si02In the case of ratio, crystal size, surface area, pore size and frame configuration according to generation are preferably obtained
KF SiOs corresponding with TPAOH2Ingredient proportion be respectively 1.5:1 and 0.125:1.
Use that above-mentioned optimization molecular screen primary powder makes use the principle that hydrothermal method crystallization synthesizes for：Hydrothermal method is handle
Used as solvent, by the reaction raw materials dispersion of synthesis of molecular sieve in aqueous, water can produce certain pressure to water at high temperature,
Molecular sieve crystal is generated under the conditions of uniform temperature.The characteristics of hydrothermal method is that product is purer, crystal formation is controllable, dispersed high, production
Low cost, it is easy to industrialized production.
The molecular sieve molded use silica gel (SiO of the adsorbent of molecular sieve2·H2O) for shaping adhesive carry out spin into
Type, its cardinal principle is：Using silica gel (SiO2·H2O) be shaping adhesive can avoid other shaping adhesives bring into it is new
Influence of the element ion to molecular sieve composition, configuration etc., while also improving the SiO of molecular sieve2/Al203Ratio；Using spin
The general principle of shaping is after molecular screen primary powder is soaked through shaping adhesive, to be rolled into a ball under surface tension and capillary force action
Poly-, molecular screen primary powder is gradually and poly- parcel turns into larger spheroid in the rolling；Spheroidal adsorbent obtained by from apparent
Uniform particle sizes, the granule strength after roasting is high, beneficial to the filling during use and service life is more long；Simultaneously because spin
The process is simple of shaping, equipment used is less, is easy to industrialized production.
Or the method that extruded moulding can also be selected, it is molecular screen primary powder through shaping using the general principle of roller forming
After adhesive wetting, can reunite under surface tension and capillary force action, round bar is then extruded under certain mechanical pressure
Shape, the molecular sieve for being using extruded moulding beneficial effect compact density under external force extruding is higher, while having machinery higher
Intensity, while molding production process is also relatively simple, equipment used is less, is easy to industrialized production.
The surface modification is that the molecular sieve of shaping uses Si (OCH3)4For liquid deposition agent carries out chemical liquid phase
Deposition (CLD), carries out high-temperature vapor treatment, the cardinal principle of the surface modification again after high-temperature roasting after deposition
It is：Because pore-forming inhomogeneities present in molecular screen primary powder crystallization building-up process and following process are to aperture, the destruction in duct,
Have impact on the shape-selective absorption property of adsorbent of molecular sieve, it is necessary on the premise of pore volume and internal surface of hole property is not changed modulation hole
Footpath and recovery duct, while also needing to the SiO for continuing to adjust adsorbent of molecular sieve2/Al203Ratio and acidity.It is of the invention preferably to divide
Sub- size is than the larger deposition agent Si (OCH that can not enter duct3)4Silicone grease sedimentary is formed on molecular sieve crystal surface, is realized
Modulation to molecular sieve bore diameter simultaneously improves surface flatness；It is preferred that using liquid phase deposition because its operation and equipment are with respect to it
His deposition process is simple, and energy consumption is relatively low and works well, and is easy to industrialized production；High temperature is preferably used after chemical liquid deposition
Steam treatment can not only utilize high-temperature water vapor dredging, repair the duct for being blocked in above process and being destroyed, and
And by high-temperature water vapor dealuminzation and deacidification, further adjust the SiO of adsorbent of molecular sieve2/Al203Ratio and acidity.
The cardinal principle of above-mentioned prioritization scheme has belonged to it is known in the art, will not be repeated here.
In particular it relates to arrive it is a kind of for, the making side of the adsorbent of molecular sieve of paracresol adsorbing separation
Method, comprises the following steps：
(1) molecular screen primary powder makes：First by quantitative crystallization auxiliary potassium fluoride in the stainless steel cauldron of band stirring
(KF) be dissolved in filtering cleaning return filtrate, then sequentially add a certain proportion of template TPAOH (TPAOH),
Silica gel (Si02.H20), aluminium hydroxide (AI (OH)3), 170 DEG C of crystallization are heated to after being stirred 1 hour under normal temperature 24 hours, crystallization knot
Normal temperature is cooled down to after beam, by products therefrom filtration under diminished pressure, filter cake is washed with deionized in filter process, filtrate returns to not
Rust steel reactor is used for dispensing.Washing and filtering gained filter cake is smash and dried and be calcined after dissipating, and drying temperature is 80 DEG C, during drying
Between be 12 hours, sintering temperature be 550 DEG C, roasting time be 8 hours, filter cake drying and roasting after can molecular screen primary
Powder.
(2) it is molecular sieve molded：By the molecular screen primary powder obtained by step (1) and shaping adhesive silica gel (SiO2·H2O) press
3:1 ratio is well mixed.When the method using roller forming, put into and shaping is rolled on bowling machine, the grain of shaping will be rolled
Material is sieved, and the particle less than 1.5mm returns to bowling machine to be continued to roll shaping, and the particle more than 2mm is smash after dissipating and returns to spin
Machine continues to roll shaping, and the particle for choosing 1.5-2mm is dried, is calcined, and drying temperature is 80 DEG C, and drying time is 8 hours,
Sintering temperature is 550 DEG C, and roasting time is 6 hours, normal temperature is naturally cooled to after roasting and can obtain molded molecular sieve；Work as use
During the method for extruded moulding, it is 1.5-2.0mm to set extrusion circle rule footpath, is then dried circle bar, is calcined, drying temperature
It it is 80 DEG C, drying time is 8 hours, sintering temperature is 550 DEG C, and roasting time is 6 hours, and normal temperature is naturally cooled to after roasting
Adsorbent circle bar is cut into the billet of 2-3mm length, you can obtain molded molecular sieve；
(3) surface modification：The molded molecular sieve that step (2) is obtained, by solid-to-liquid ratio 1:5 ratio and deionization
Water mixes, then adds deposition agent Si (OCH in the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve3)4, uniformly stir at normal temperatures
Mixing carries out the 1st chemical deposition for 6 hours.Molded molecular sieve after 1st chemical deposition is put into tube heater with 5 DEG C/minute
The speed of clock is warming up to 500 DEG C and is calcined 3 hours, then is passed through temperature and is carried out at the 1st water vapour higher than 750 DEG C of superheated vapour
Reason, the 1st steam treatment time is 3 hours, is calcined 3 hours at 500 DEG C again after the 1st steam treatment, natural after roasting
Normal temperature is cooled to by solid-to-liquid ratio 1:5 ratio mixes with deionized water, then by the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve
Example adds deposition agent Si (OCH3)4, at normal temperatures uniform stirring carry out within 6 hours the 2nd chemical deposition.After 2nd chemical deposition
Molded molecular sieve is put into tube heater and is warming up to 500 DEG C with 5 DEG C/min of speed and is calcined 3 hours, then is passed through temperature and is higher than
750 DEG C of superheated vapour carries out the 2nd steam treatment, and the 2nd steam treatment time is 3 hours, at the 2nd water vapour
After reason again 500 DEG C be calcined 3 hours ... this process is repeated several times, until dry molecular sieves after molecular sieve surface before processing
Rate of body weight gain is that 3-4% can be dried to obtain finished product adsorbent of molecular sieve.
In view of the test condition limitation that may be present of actual molecules sieve adsorbant industrial production, present invention provides right
The adsorbent of molecular sieve easily realizes the main apparent index of detection, the i.e. mechanical strength of adsorbent of molecular sieve and static liquid phase
Adsorption separation performance.
The mechanical strength of the adsorbent of molecular sieve is measured using particle equipment to test mechanical performance, and method has belonged to ability
Well known to domain, repeat no more.
The adsorbent of molecular sieve for/the static liquid phase adsorption separation performance of two systems of paracresol uses static liquid
Phase determination of adsorption method, specially：Sorbent molecule sieves samples and cresols adsorption liquid consumption is respectively 0.5 gram and 2.5ml, first
Phenol adsorption liquid contains to, each 3% (w t) of metacresol, and solvent selects 1,3,5- trimethylbenzenes.Sorbent molecule sieve sample is first at 500 DEG C
Activated 6 hours in Muffle furnace, be positioned in cresols adsorption liquid and reach adsorption equilibrium, adsorption temp is 30 DEG C, time of equilibrium adsorption
48 hours, the change in concentration of Isomers in front and rear solution is adsorbed with gas chromatography analysis, calculate sorbent molecule sieve sample
Adsorbance.
The present invention is further described below by example, but the present invention is not limited to this.
Embodiment 1
Prepare in the present inventive method it is a kind of for, the ball-type adsorbent of molecular sieve of paracresol adsorbing separation.
(1) molecular screen primary powder makes：First by quantitative crystallization auxiliary potassium fluoride in the stainless steel cauldron of band stirring
(KF) filtrate that filtering cleaning is returned is dissolved in, template TPAOH (TPAOH), silica gel is then proportionally added into
(Si02.H20), aluminium hydroxide (AI (OH)3), 170 DEG C of crystallization are heated to after being stirred 1 hour under normal temperature 24 hours, after crystallization terminates
Normal temperature is cooled down to, by products therefrom filtration under diminished pressure, filter cake is washed with deionized in filter process, filtrate returns to stainless steel
Reactor is used for dispensing.Washing and filtering gained filter cake is smash and dried and be calcined after dissipating, and drying temperature is 80 DEG C, and drying time is
12 hours, sintering temperature was 550 DEG C, and roasting time is 8 hours, and molecular screen primary powder can be obtained after filter cake drying and roasting.
(2) it is molecular sieve molded：By the molecular screen primary powder obtained by step (1) and shaping adhesive silica gel (SiO2·H2O) press
3:1 ratio be well mixed, put on bowling machine roll shaping, will roll shaping pellet sieved, less than 1.5mm
Grain returns to bowling machine continuation rolling shaping, and the particle more than 2mm is smash and returned after dissipating bowling machine continuation rolling shaping, chooses 1.5-
The particle of 2mm is dried, is calcined, and drying temperature is 80 DEG C, and drying time is 8 hours, and sintering temperature is 550 DEG C, during roasting
Between be 6 hours, normal temperature is naturally cooled to after roasting and can obtain molded molecular sieve.
(3) surface modification：The molded molecular sieve that step (2) is obtained, by solid-to-liquid ratio 1:5 ratio and deionization
Water mixes, then adds deposition agent Si (OCH in the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve3)4, uniformly stir at normal temperatures
Mixing carries out the 1st chemical deposition for 6 hours.Molded molecular sieve after 1st chemical deposition is put into tube heater with 5 DEG C/minute
The speed of clock is warming up to 500 DEG C and is calcined 3 hours, then is passed through temperature and is carried out at the 1st water vapour higher than 750 DEG C of superheated vapour
Reason, the 1st steam treatment time is 3 hours, is calcined 3 hours at 500 DEG C again after the 1st steam treatment, natural after roasting
Normal temperature is cooled to by solid-to-liquid ratio 1:5 ratio mixes with deionized water, then by the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve
Example adds deposition agent Si (OCH3)4, at normal temperatures uniform stirring carry out within 6 hours the 2nd chemical deposition.After 2nd chemical deposition
Molded molecular sieve is put into tube heater and is warming up to 500 DEG C with 5 DEG C/min of speed and is calcined 3 hours, then is passed through temperature and is higher than
750 DEG C of superheated vapour carries out the 2nd steam treatment, and the 2nd steam treatment time is 3 hours, at the 2nd water vapour
After reason again 500 DEG C be calcined 3 hours ... this step is repeated several times, until dry molecular sieves after molecular sieve surface before processing
Rate of body weight gain is 3-4%, then dries 4 hours and can obtain finished product adsorbent of molecular sieve.
Finished product adsorbent of molecular sieve sample is carried out into mechanical strength measure using particle equipment to test mechanical performance, its machine is measured
Tool intensity is mechanical strength>10N/mm2。
By finished product adsorbent of molecular sieve sample using static liquid phase adsorption method determine its for/two systems of paracresol
Static liquid phase adsorption separation performance, measures the finished product adsorbent of molecular sieve sample paracresol adsorbance and accounts for the total adsorbance of molecular sieve
More than 95%, and metacresol is not adsorbed substantially, it is possible to achieve/adsorbing separation of paracresol.
Embodiment 2
Prepare in the present inventive method it is a kind of for, the stripe shape adsorbent of molecular sieve of paracresol adsorbing separation.
By the method for example 1 prepare it is a kind of for, the stripe shape adsorbent of molecular sieve of paracresol adsorbing separation, unlike
Step (2), molecular sieve molded (step (2)) of the adsorbent of molecular sieve use bar shaped extruded moulding, and control strip footpath is 1.5-
2.0mm.Molecular screen primary powder and shaping adhesive silica gel (SiO that will be resulting2·H2O 3) are pressed:1 ratio is well mixed, and is squeezing
Go out extruded moulding on machine, then bar shaped molecular sieve be dried, be calcined, drying temperature is 80 DEG C, drying time is 8 hours,
Sintering temperature is 550 DEG C, and roasting time is 6 hours, and normal temperature is naturally cooled to after roasting, and it is short that strip catalyst is cut into 2-3mm
Bar, you can obtain molded molecular sieve.
Finished product adsorbent of molecular sieve sample is carried out into mechanical strength measure using particle equipment to test mechanical performance, its machine is measured
Tool intensity is mechanical strength>11N/mm2。
By finished product adsorbent of molecular sieve sample using static liquid phase adsorption method determine its for/two systems of paracresol
Static liquid phase adsorption separation performance, measures the finished product adsorbent of molecular sieve sample paracresol adsorbance and accounts for the total adsorbance of molecular sieve
More than 95%, and metacresol is not adsorbed substantially, it is possible to achieve/adsorbing separation of paracresol.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (9)
1. it is a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterised in that including following step
Suddenly：
1) molecular screen primary powder makes
The molecular screen primary powder makes to be included using SiO2·H2O is silicon source, uses aluminium hydroxide for silicon source, using tetrapropyl hydrogen
Amine-oxides are template and to use potassium fluoride be crystallization auxiliary, and crystallization synthesis is carried out with hydro-thermal method, and crystallization products therefrom is carried out
Filtration under diminished pressure, is washed with deionized filter cake in filter process, by washing and filtering gained filter cake smash dissipate after carry out low temperature drying and
High-temperature roasting, obtains final product molecular screen primary powder；
2) it is molecular sieve molded
It is described molecular sieve molded including by step 1) molecular screen primary powder that obtains uses silica gel SiO2·H2O is mixed for shaping adhesive
Close uniform, roller forming or the extruded moulding on extruder carried out on bowling machine, and carry out low temperature drying and high-temperature roasting,
Obtain final product molded molecular sieve；
3) surface modification
The surface modification is included step 2) molded molecular sieve that obtains first uses Si (OCH3)4It is liquid deposition agent
Chemical liquid deposition treatment is carried out, is processed through high-temperature roasting and high-temperature vapor successively after chemical liquid deposition treatment, Ran Houzai
Come back for chemical liquid deposition treatment, this process is repeated several times, most afterwards through be dried to obtain for, paracresol adsorbing separation
Adsorbent of molecular sieve, wherein, the mode of the high-temperature vapor treatment is：Enter water-filling with the superheated vapour higher than 750 DEG C to steam
Vapour treatment, the steam treatment time is 3 hours.
2. it is according to claim 1 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, its feature
It is：By quality ratio, the step 1) in hydrothermal crystallizing synthesis dispensing SiO2·H2O ：Potassium fluoride：Aluminium hydroxide：4 third
Base ammonium hydroxide is 1：1.5：0.35：0.125, remaining is deionized water.
3. it is according to claim 2 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is special
Levy and be, the step 2) molecular screen primary powder and shaping adhesive SiO2·H2O is 3 in mass ratio:The mixing of 1~1.5 ratio is equal
It is even, roller forming or the extruded moulding on extruder are then carried out on bowling machine.
4. it is according to claim 3 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, its feature
Be, the step 3) chemical liquid deposition treatment be first by the molded molecular sieve by solid-liquid volume ratio 1:5 ratio with
Deionized water mixes, then adds liquid deposition agent Si (OCH in the ratio of 0.6 milliliter of liquid deposition agent/gram molded molecular sieve3)4。
5. it is according to claim 4 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, its feature
Be, the step 3) in processed through high-temperature roasting and high-temperature vapor successively after chemical liquid deposition treatment, then return again to
Carry out chemical liquid deposition treatment, this process repeatedly, the rate of body weight gain of dry molecular sieves before and after surface modification
It is 3~4%.
6. according to claim 1 to 5 it is any it is described for, the making side of the adsorbent of molecular sieve of paracresol adsorbing separation
Method, it is characterised in that：The step 1) drying temperature be 80 DEG C, drying time is not less than 10 hours, and sintering temperature is 550
DEG C, roasting time is not less than 6 hours.
7. according to claim 1 to 5 it is any it is described for, the making side of the adsorbent of molecular sieve of paracresol adsorbing separation
Method, it is characterised in that when step 2) using roller forming when, the pellet that bowling machine is rolled out is sieved, less than 1.5mm
Grain return bowling machine continue roll shaping, the particle more than 2mm smash dissipate after return bowling machine continue roll shaping, choose 1.5~
The particle of 2mm carries out low temperature drying and high-temperature roasting, and normal temperature is naturally cooled to after roasting, obtains final product molded molecular sieve；When step 2)
During using extruded moulding, it is 1.5~2.0mm to control extrusion circle rule footpath, and circle bar then is carried out into low temperature drying and high-temperature roasting,
The adsorbent circle bar that normal temperature will be naturally cooled to after roasting is cut into the billet of 2~3mm length, you can obtain molded molecular sieve.
8. according to claim 1 to 5 it is any it is described for, the making side of the adsorbent of molecular sieve of paracresol adsorbing separation
Method, it is characterised in that the step 2) drying temperature be 80 DEG C, drying time is not less than 8 hours, sintering temperature be 550 DEG C,
Roasting time is not less than 6 hours.
9. it is a kind of prepared according to any described preparation method of claim 1 to 8 for, paracresol adsorbing separation
Adsorbent of molecular sieve.
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| CN106943993B (en) * | 2017-04-03 | 2019-11-12 | 上海复榆新材料科技有限公司 | Separate paracresol and the zeolite adsorbent of meta position Cresol Isomeric Compound and preparation method thereof |
| CN107879900B (en) * | 2017-12-22 | 2024-05-14 | 中触媒新材料股份有限公司 | Process method for separating and purifying cresol mixed isomer |
| CN110511122B (en) * | 2018-05-22 | 2022-03-11 | 中国石油化工股份有限公司 | Method for separating cresol isomer by liquid phase adsorption |
| CN110511121B (en) * | 2018-05-22 | 2022-02-08 | 中国石油化工股份有限公司 | Method for separating p-cresol by liquid phase adsorption |
| CN110511118B (en) * | 2018-05-22 | 2022-02-08 | 中国石油化工股份有限公司 | Method for separating paracresol by liquid phase adsorption |
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| CN111167404A (en) * | 2020-01-10 | 2020-05-19 | 上海航中实业有限公司 | Molecular sieve of commercial vehicle brake system and preparation method thereof |
| CN113731352A (en) * | 2021-06-23 | 2021-12-03 | 浙江环化科技有限公司 | Adsorbent and method for adsorbing and separating m-cresol and p-cresol by using same |
| CN116474715A (en) * | 2022-01-15 | 2023-07-25 | 中国石油化工股份有限公司 | Spherical material and preparation method thereof |
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