CN104815612A - 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, particularly relate to a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation and adsorbent thereof.
Background technology
Middle coalite tar is that coal is in middle low temperature distillation, product in pyrolytic process, aldehydes matter content in middle coalite tar is very high, aldehydes matter is the industrial chemicals that there is economic worth pole, from coal tar, extract natural phenolic product cost and be have larger advantage compared with Material synthesis phenol products with oil product, wherein cresols comprises orthoresol, paracresol and metacresol three kinds of isomers, due to the boiling point close (differing 0.4 DEG C) of metacresol and paracresol, the conventional methods such as industrial very difficult distillation are isolated, so the cresols form of mixtures that industrial products mix mainly with metacresol and paracresol exists, and chemical synthesis industry usually needs with the single compound of paracresol or metacresol for raw material, so the separation of Cresol Isomeric Compound is the key that low boiling phenols is separated in cresols mixture, the separation method that can adopt at present mainly contains perfectly crystallization process, complexing addition process, alkylation partition method, adsorption method of separation, wherein adsorbing separation process owned by France energy consumption is low, one of method that product purity is high, its core is the development and utilization of adsorbent.
Summary of the invention
The invention provides a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation.The technical problem mainly solved realizes carrying out liquid phase adsorption separation to the cresols mixture containing metacresol and paracresol, reclaims the industrial production of the higher metacresol of purity and paracresol respectively.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
Cresols mixture containing metacresol and paracresol is carried out to the adsorbent of molecular sieve preparation method of adsorbing separation, its essential characteristic is as follows:
The main making step of described adsorbent of molecular sieve has: molecular screen primary powder makes, molecular sieve molded, surface modification.
Described molecular screen primary powder makes to comprise and adopts silica gel (SiO
2h
2o) be silicon source, adopt aluminium hydroxide (AI (OH)
3) be aluminium source, TPAOH (TPAOH) is adopted to be template, potassium fluoride (KF) is adopted to be crystallization auxiliary, hydrothermal method is adopted to carry out crystallization synthesis, crystallization products therefrom is carried out filtration under diminished pressure, spend deionized water filter cake in filter process, washing and filtering gained filter cake is smash loose after carry out the low temperature drying of certain hour and high-temperature roasting molecular screen primary powder.
Described molecular screen primary powder to be made the molecular screen primary powder obtained and adopts silica gel (SiO by described molecular sieve molded comprising
2h
2o) for shaping adhesive mixes, bowling machine carries out roller forming or extruded moulding on extruder, and carry out the low temperature drying of a period of time and high-temperature roasting can obtain molded molecular sieve.
The surface modification of described adsorbent of molecular sieve comprises the described molecular sieve molded molded molecular sieve obtained first is adopted Si (OCH
3)
4for liquid deposition agent carry out chemical liquid deposition (CLD) process, successively through high-temperature roasting and high-temperature vapor process after chemical liquid deposition process, and then return carry out chemical liquid deposition (CLD) process.This process repeatedly repeats, finally by drying obtain for, the adsorbent of molecular sieve of paracresol adsorbing separation.
Further: described molecular screen primary powder makes and adopts the synthesis of hydrothermal method crystallization, in mass, the charge ratio of hydrothermal crystallizing synthesis is Si0
2h
20: potassium fluoride: aluminium hydroxide: TPAOH is 1:1.5:0.35:0.125, all the other are deionized water, and the system namely meeting the synthesis of hydrothermal method crystallization is:
SiO
2-1.5KF-0.35Al(OH)
3-0.125TPAOH-30H
2O。
Further: the bake out temperature that described molecular screen primary powder makes is 80 DEG C, and drying time is not less than 10 hours, and sintering temperature is 550 DEG C, and roasting time is not less than 6 hours.
Further: described molecular sieve molded molecular screen primary powder and shaping adhesive silica gel (SiO
2h
2o) mix for 3:1 ~ 1.5 ratio in mass ratio, on bowling machine, then carry out roller forming or extruded moulding on extruder.
Further: when described molecular sieve molded employing roller forming, the pellet that reply bowling machine rolls out sieves, the particle being less than 1.5mm returns bowling machine continuation and rolls shaping, the particle being greater than 2mm smash loose after return bowling machine and continue to roll shaping, the particle choosing 1.5-2mm carries out low temperature drying and the high-temperature roasting of certain hour, naturally cool to normal temperature after roasting, can molded molecular sieve be obtained; When described molecular sieve molded employing extruded moulding, should arrange and extrude round rule footpath is 1.5-2.0mm, then circle bar is carried out low temperature drying and the high-temperature roasting of certain hour, the adsorbent circle bar naturally cooling to normal temperature is cut into the billet of 2-3mm length, can molded molecular sieve be obtained after roasting.
Further: described molecular sieve molded bake out temperature is 80 DEG C, and drying time is not less than 8 hours, sintering temperature is 550 DEG C, and roasting time is not less than 6 hours.
Further: chemical liquid deposition (CLD) process of described surface modification first the ratio of described molded molecular sieve in solid-liquid volume ratio 1:5 is mixed with deionized water, then add liquid deposition agent Si (OCH in the ratio of 0.6 milliliter of liquid deposition agent/gram molded molecular sieve
3)
4.
Further: the surface modification of described adsorbent of molecular sieve after chemical liquid deposition process successively through high-temperature roasting and high-temperature vapor process, and then return and carry out chemical liquid deposition process, this process repeatedly, until the rate of body weight gain of dry molecular sieves is 3-4% before and after surface modification.
Present invention also offers the adsorbent of molecular sieve prepared according to said method.
The invention has the beneficial effects as follows: adopting the present invention can obtain a kind of silica alumina ratio is 300-400, and particle diameter (or bar footpath) 1.5-2.0mm, mechanical strength is 10N/mm
2adsorbent of molecular sieve; Adopt static liquid phase adsorption method to investigate between described adsorbent of molecular sieve pair the/separating property of paracresol system, paracresol adsorbance accounts for more than 95% of the total adsorbance of molecular sieve, and does not substantially adsorb metacresol, between can realizing/and the adsorbing separation of paracresol.
The adsorbent of molecular sieve that the adsorbent of molecular sieve preparation method that the present invention relates to makes, industrial fixed bed or liquid phase adsorption separation operation that is simulation moving-bed or preparative chromatography can be applied to, under the operating condition comparatively relaxed, realize being separated of metacresol in cresols mixture and paracresol, there is the advantage that energy consumption is low, flow process is simple and operating cost is low.
Accompanying drawing explanation
Fig. 1 for of the present invention provide a kind of for, the schematic flow sheet of the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation.
Detailed description of the invention
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
The object of adsorbent of molecular sieve preparation method provided by the invention: be metacresol > paracresol from molecular dimension and power diameter order, the adsorbent of molecular sieve of a kind of channel diameter between metacresol and paracresol is prepared by method for optimizing, allow paracresol can be adsorbed to adsorbent of molecular sieve endoporus, and metacresol is not adsorbed, realize selecting shape adsorbing separation to metacresol and paracresol.
The principle of adsorbent of molecular sieve preparation method provided by the invention is: select efficient raw material to be beneficial to the molecular sieve crystal prepared and meet the demands; The method selected should be as far as possible simple and easy to do, is beneficial to suitability for industrialized production.
As shown in Figure 1, a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, main making step has: molecular screen primary powder makes, molecular sieve molded, surface modification;
The primary raw material optimizing molecular screen primary powder making has: adopt silica gel (Si0
2.H
20) be silicon source, adopt aluminium hydroxide (AI (OH)
3) be aluminium source, adopt TPAOH (TPAOH) to be template, adopt potassium fluoride (KF) to be crystallization auxiliary;
The raw material proportion of composing optimizing molecular screen primary powder making is:
SiO
2-1.5KF-0.35Al(OH)
3-0.125TPAOH-30H
2O
Optimize the employing hydrothermal method crystallization synthesis that molecular screen primary powder makes.
The principle of the primary raw material adopting above-mentioned optimization molecular screen primary powder to make is: preferably adopt silica gel (Si0
2.H
20) for silicon source is because of adopting silica gel to be the molecular sieve crystal that silicon source can obtain good degree of crystallinity, average grain size and surface area; Preferred employing aluminium hydroxide (AI (OH)
3) for aluminium source be because aluminium hydroxide not only provides the structure ion aluminium ion (Al of molecular sieve
3+), and the hydroxyl (OH brought into
-) more silicon source can be dissolved and aluminium source is beneficial to crystallization process; Preferred employing TPAOH (TPAOH) for template be because template cation tetrapropyl amine (TPA
+) be more conducive to the larger molecular sieve crystal of the specific duct of guiding generation, specific skeleton and surface area, and the hydroxyl (OH brought into
-) more silicon source can be dissolved and aluminium source is beneficial to crystallization process; Preferred employing potassium fluoride (KF) for crystallization auxiliary be because potassium ion (K
+) be beneficial to crystal accumulation growth, and fluorine ion (F
-) template cation can be balanced, reduce the defect of molecular sieve crystal.
The principle of the raw material proportion of composing adopting above-mentioned optimization molecular screen primary powder to make is: preferred SiO
2with Al (OH)
3ingredient proportion is 1:0.35 (mass ratio), and conversion is to SiO
2/ Al
20
3ratio is 4.37, is beneficial to and generates the molecular sieve crystal that surface area is comparatively large, crystal size is moderate, is beneficial to the high silica alumina ratio molecular sieve crystal generating comparatively strong, the acid lower and spherical complexion of hydrophobicity, also ensures SiO simultaneously
2there is comparatively high usage; Preferred H
20/Si0
2ratio is 30:1 (mass ratio), can prevent nucleus in crystallization building-up process from occurring to reunite and form larger zeolite crystal, is beneficial to the stirring carried out when hydrothermal method crystallization is synthesized to a certain degree, preferred H simultaneously
20/Si0
2ratio is conducive to the efficient synthesis of molecular sieve crystal; At preferred SiO
2with Al (OH)
3ingredient proportion and H
20/Si0
2when ratio, preferably obtain the corresponding SiO of KF and TPAOH according to the crystal size generated, surface area, pore size and frame configuration
2ingredient proportion be respectively 1.5:1 and 0.125:1.
The principle of the employing hydrothermal method crystallization synthesis adopting above-mentioned optimization molecular screen primary powder to make is: hydrothermal method is as solvent using water, by the dispersion of the reaction raw materials of synthesis of molecular sieve in aqueous, water at high temperature can produce certain pressure, under uniform temperature condition, generate molecular sieve crystal.The feature of hydrothermal method is that product is purer, crystal formation is controlled, dispersiveness is high, production cost is low, is convenient to suitability for industrialized production.
The molecular sieve molded employing silica gel (SiO of described adsorbent of molecular sieve
2h
2o) for shaping adhesive carries out roller forming, its cardinal principle is: adopt silica gel (SiO
2h
2o) for shaping adhesive can avoid other shaping adhesives to bring the impact of new element ion on molecular sieve composition, configuration etc. into, also improve the SiO of molecular sieve simultaneously
2/ Al
20
3ratio; Adopt the general principle of roller forming be molecular screen primary powder after shaping adhesive is wetting, can reunite under surface tension and capillary force action, molecular screen primary powder is gradually and poly-parcel becomes larger spheroid in the rolling; From apparent obtained spheroidal adsorbent uniform particle sizes, the granule strength after roasting is high, be beneficial to filling in use procedure and also service life longer; Technique simultaneously due to roller forming is simple, and equipment used is less, is convenient to suitability for industrialized production.
Or also can select the method for extruded moulding, the general principle of roller forming is adopted to be that molecular screen primary powder is after shaping adhesive is wetting, can reunite under surface tension and capillary force action, then under certain mechanical pressure, round strip is extruded into, the molecular sieve adopting extruded moulding beneficial effect to be is higher in external force extruding compacted under density, and have higher mechanical strength, molding production process is also comparatively simple simultaneously simultaneously, equipment used is less, is convenient to suitability for industrialized production.
Described surface modification is that shaping molecular sieve adopts Si (OCH
3)
4for chemical liquid deposition (CLD) is carried out in liquid deposition agent, after high-temperature roasting, high-temperature vapor process is carried out again after deposition, the cardinal principle of described surface modification is: because the pore-forming inhomogeneities that exists in molecular screen primary powder crystallization building-up process and following process are to the destruction in aperture, duct, what have impact on adsorbent of molecular sieve selects shape absorption property, need pore size controlling and recovery duct under the prerequisite not changing pore volume and internal surface of hole character, also need the SiO continuing adjustment adsorbent of molecular sieve simultaneously
2/ Al
20
3ratio and acidity.Deposition agent Si (the OCH in what the preferred molecular dimension of the present invention was larger can not enter duct
3)
4form silicone grease sedimentary deposit on molecular sieve crystal surface, realize the modulation of molecular sieve bore diameter and improve surface flatness; Preferred employing liquid phase deposition is that energy consumption is lower and respond well, is convenient to suitability for industrialized production because its operation other deposition process relative to equipment are simple; The duct preferably adopting high-temperature water vapor process that high-temperature water vapor not only can be utilized to dredge after chemical liquid deposition, repair in process above blocking and destroy, and by high-temperature water vapor dealuminzation and deacidification, the SiO of adjustment adsorbent of molecular sieve further
2/ Al
20
3ratio and acidity.
The cardinal principle of above-mentioned prioritization scheme has belonged to well known in the art, does not repeat them here.
Particularly, the present invention relates to a kind of for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, comprise the steps:
(1) molecular screen primary powder makes: first quantitative crystallization auxiliary potassium fluoride (KF) is dissolved in the filtrate of filtering and cleaning and returning in the stainless steel cauldron of band stirring, then adds a certain proportion of template TPAOH (TPAOH), silica gel (Si0 successively
2.H
20), aluminium hydroxide (AI (OH)
3), stir under normal temperature after 1 hour and be heated to 170 DEG C of crystallization 24 hours, crystallization terminates rear cooling and is down to normal temperature, by products therefrom filtration under diminished pressure, spends deionized water filter cake in filter process, and filtrate turns back to stainless steel cauldron for batching.Washing and filtering gained filter cake smash loose after carry out drying and roasting, bake out temperature is 80 DEG C, and drying time is 12 hours, and sintering temperature is 550 DEG C, and roasting time is 8 hours, after filter cake drying and roasting molecular screen primary powder.
(2) molecular sieve molded: the molecular screen primary powder that step (1) is obtained and shaping adhesive silica gel (SiO
2h
2o) mix in 3:1 ratio.When adopting the method for roller forming, put into bowling machine rolls shaping, sieved by the shaping pellet of rolling, the particle being less than 1.5mm returns bowling machine and continues to roll shaping, the particle being greater than 2mm smash loose after return bowling machine and continue to roll shaping, the particle choosing 1.5-2mm carries out drying, roasting, baking temperature is 80 DEG C, and drying time is 8 hours, and sintering temperature is 550 DEG C, roasting time is 6 hours, naturally cools to normal temperature and can obtain molded molecular sieve after roasting; When adopting the method for extruded moulding, it is 1.5-2.0mm that round rule footpath is extruded in setting, then circle bar is carried out drying, roasting, baking temperature is 80 DEG C, drying time is 8 hours, and sintering temperature is 550 DEG C, and roasting time is 6 hours, the adsorbent circle bar naturally cooling to normal temperature after roasting is cut into the billet of 2-3mm length, can obtain molded molecular sieve;
(3) surface modification: molded molecular sieve step (2) obtained, mixes with deionized water in the ratio of solid-to-liquid ratio 1:5, then add deposition agent Si (OCH in the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve
3)
4, uniform stirring carries out the 1st chemical deposition for 6 hours at normal temperatures.Molded molecular sieve after 1st chemical deposition is put into tube heater with the ramp to 500 of 5 DEG C/min DEG C roasting 3 hours, pass into temperature again and carry out the 1st steam treatment higher than the superheated vapour of 750 DEG C, 1st steam treatment time is 3 hours, again 500 DEG C of roastings 3 hours after 1st steam treatment, naturally cool to normal temperature after roasting to mix with deionized water in the ratio of solid-to-liquid ratio 1:5, then add deposition agent Si (OCH in the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve
3)
4, uniform stirring carries out the 2nd chemical deposition for 6 hours at normal temperatures.Molded molecular sieve after 2nd chemical deposition puts into tube heater with the ramp to 500 of 5 DEG C/min DEG C roasting 3 hours, pass into temperature again and carry out the 2nd steam treatment higher than the superheated vapour of 750 DEG C, 2nd steam treatment time is 3 hours, again 500 DEG C of roastings 3 hours after 2nd steam treatment ... this process repeatedly repeats, until the rate of body weight gain of dry molecular sieves is that 3-4% drying can obtain finished product adsorbent of molecular sieve before and after molecular sieve surface process.
Consider the test condition restriction that actual molecules sieve adsorbant industrial production may exist, present invention provides and the main apparent index that detects, the i.e. mechanical strength of adsorbent of molecular sieve and static liquid phase adsorption separation performance are easily realized to described adsorbent of molecular sieve.
The mechanical strength of described adsorbent of molecular sieve adopts particle equipment to test mechanical performance to measure, and method has belonged to well known in the art, repeats no more.
Described adsorbent of molecular sieve for/the static liquid phase adsorption separation performance of paracresol two individual system adopts static liquid phase adsorption method to measure, be specially: sorbent molecule sieve samples and cresols adsorption liquid consumption are respectively 0.5 gram and 2.5ml, cresols adsorption liquid is containing to, each 3% (the w t) of metacresol, solvent selects 1,3,5-trimethylbenzene.Sorbent molecule sieve sample first activates 6 hours in 500 DEG C of Muffle furnaces, be positioned in cresols adsorption liquid and reach adsorption equilibrium, adsorption temp is 30 DEG C, time of equilibrium adsorption 48 hours, by the change in concentration of Isomers in solution before and after gas chromatography analysis absorption, calculate the adsorbance of sorbent molecule sieve sample.
Further describe the present invention below by example, but the present invention is not limited to this.
Embodiment 1
By method of the present invention prepare a kind of for, the ball-type adsorbent of molecular sieve of paracresol adsorbing separation.
(1) molecular screen primary powder makes: first quantitative crystallization auxiliary potassium fluoride (KF) is dissolved in the filtrate of filtering and cleaning and returning in the stainless steel cauldron of band stirring, then adds template TPAOH (TPAOH), silica gel (Si0 in proportion
2.H
20), aluminium hydroxide (AI (OH)
3), stir under normal temperature after 1 hour and be heated to 170 DEG C of crystallization 24 hours, crystallization terminates rear cooling and is down to normal temperature, by products therefrom filtration under diminished pressure, spends deionized water filter cake in filter process, and filtrate turns back to stainless steel cauldron for batching.Washing and filtering gained filter cake smash loose after carry out drying and roasting, bake out temperature is 80 DEG C, and drying time is 12 hours, and sintering temperature is 550 DEG C, and roasting time is 8 hours, after filter cake drying and roasting molecular screen primary powder.
(2) molecular sieve molded: the molecular screen primary powder that step (1) is obtained and shaping adhesive silica gel (SiO
2h
2o) mix in 3:1 ratio, put into bowling machine rolls shaping, sieved by the shaping pellet of rolling, the particle being less than 1.5mm returns bowling machine and continues to roll shaping, the particle being greater than 2mm smash loose after return bowling machine and continue to roll shaping, the particle choosing 1.5-2mm carries out drying, roasting, baking temperature is 80 DEG C, and drying time is 8 hours, and sintering temperature is 550 DEG C, roasting time is 6 hours, naturally cools to normal temperature and can obtain molded molecular sieve after roasting.
(3) surface modification: molded molecular sieve step (2) obtained, mixes with deionized water in the ratio of solid-to-liquid ratio 1:5, then add deposition agent Si (OCH in the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve
3)
4, uniform stirring carries out the 1st chemical deposition for 6 hours at normal temperatures.Molded molecular sieve after 1st chemical deposition is put into tube heater with the ramp to 500 of 5 DEG C/min DEG C roasting 3 hours, pass into temperature again and carry out the 1st steam treatment higher than the superheated vapour of 750 DEG C, 1st steam treatment time is 3 hours, again 500 DEG C of roastings 3 hours after 1st steam treatment, naturally cool to normal temperature after roasting to mix with deionized water in the ratio of solid-to-liquid ratio 1:5, then add deposition agent Si (OCH in the ratio of 0.6 milliliter of deposition agent/gram molded molecular sieve
3)
4, uniform stirring carries out the 2nd chemical deposition for 6 hours at normal temperatures.Molded molecular sieve after 2nd chemical deposition puts into tube heater with the ramp to 500 of 5 DEG C/min DEG C roasting 3 hours, pass into temperature again and carry out the 2nd steam treatment higher than the superheated vapour of 750 DEG C, 2nd steam treatment time is 3 hours, again 500 DEG C of roastings 3 hours after 2nd steam treatment ... this step repeatedly repeats, until the rate of body weight gain of dry molecular sieves is 3-4% before and after molecular sieve surface process, then drying can obtain finished product adsorbent of molecular sieve in 4 hours.
Adopt particle equipment to test mechanical performance to carry out mechanical strength mensuration in finished product adsorbent of molecular sieve sample, recording its mechanical strength is mechanical strength >10N/mm
2.
Finished product adsorbent of molecular sieve sample is adopted static liquid phase adsorption method measure its for/the static liquid phase adsorption separation performance of paracresol two individual system, record described finished product adsorbent of molecular sieve sample paracresol adsorbance and account for more than 95% of the total adsorbance of molecular sieve, and metacresol is not adsorbed substantially, between can realizing/adsorbing separation of paracresol.
Embodiment 2
By method of the present invention prepare a kind of for, the stripe shape adsorbent of molecular sieve of paracresol adsorbing separation.
By the method for example 1 prepare a kind of for, the stripe shape adsorbent of molecular sieve of paracresol adsorbing separation, unlike step (2), molecular sieve molded (step (2)) of described adsorbent of molecular sieve adopt bar shaped extruded moulding, and control strip footpath is 1.5-2.0mm.Be about to obtained molecular screen primary powder and shaping adhesive silica gel (SiO
2h
2o) mix in 3:1 ratio, extruded moulding on extruder, then bar shaped molecular sieve is carried out drying, roasting, baking temperature is 80 DEG C, and drying time is 8 hours, and sintering temperature is 550 DEG C, roasting time is 6 hours, naturally cool to normal temperature after roasting, strip catalyst is cut into 2-3mm billet, can molded molecular sieve be obtained.
Adopt particle equipment to test mechanical performance to carry out mechanical strength mensuration in finished product adsorbent of molecular sieve sample, recording its mechanical strength is mechanical strength >11N/mm
2.
Finished product adsorbent of molecular sieve sample is adopted static liquid phase adsorption method measure its for/the static liquid phase adsorption separation performance of paracresol two individual system, record described finished product adsorbent of molecular sieve sample paracresol adsorbance and account for more than 95% of the total adsorbance of molecular sieve, and metacresol is not adsorbed substantially, between can realizing/adsorbing separation of paracresol.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that, comprise the following steps:
1) molecular screen primary powder makes
Described molecular screen primary powder makes to comprise and adopts SiO
2h
2o is silicon source, adopts aluminium hydroxide to be aluminium source, adopts TPAOH to be template and adopt potassium fluoride to be crystallization auxiliary, crystallization synthesis is carried out with hydro-thermal method, crystallization products therefrom is carried out filtration under diminished pressure, deionized water filter cake is spent in filter process, washing and filtering gained filter cake is smash after faling apart and carry out low temperature drying and high-temperature roasting, obtain molecular screen primary powder;
2) molecular sieve molded
Describedly molecular sieve moldedly comprising step 1) molecular screen primary powder that obtains adopts silica gel SiO
2h
2o is that shaping adhesive mixes, and bowling machine carries out roller forming or extruded moulding on extruder, and carries out low temperature drying and high-temperature roasting, obtain molded molecular sieve;
3) surface modification
Described surface modification comprises step 2) molded molecular sieve that obtains first adopts Si (OCH
3)
4for chemical liquid deposition process is carried out in liquid deposition agent, successively through high-temperature roasting and high-temperature vapor process after chemical liquid deposition process, and then return and carry out chemical liquid deposition process, this process repeatedly repeats, finally by drying obtain for, the adsorbent of molecular sieve of paracresol adsorbing separation.
2. according to claim 1 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that: by quality ratio, described step 1) in the batching Si0 of hydrothermal crystallizing synthesis
2h
20: potassium fluoride: aluminium hydroxide: TPAOH is 1:1.5:0.35:0.125, all the other are deionized water, and the system of hydro-thermal method crystallization synthesis is:
SiO
2-1.5KF-0.35Al(OH)
3-0.125TPAOH-30H
2O。
3. according to claim 2 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that, described step 2) molecular screen primary powder and shaping adhesive SiO
2h
2o mixes for 3:1 ~ 1.5 ratio in mass ratio, on bowling machine, then carries out roller forming or extruded moulding on extruder.
4. according to claim 3 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that, described step 3) chemical liquid deposition process be first the ratio of described molded molecular sieve in solid-liquid volume ratio 1:5 is mixed with deionized water, then add liquid deposition agent Si (OCH in the ratio of 0.6 milliliter of liquid deposition agent/gram molded molecular sieve
3)
4.
5. according to claim 4 for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that, described step 3) in after chemical liquid deposition process successively through high-temperature roasting and high-temperature vapor process, and then return and carry out chemical liquid deposition process, this process repeatedly, until the rate of body weight gain of dry molecular sieves is 3 ~ 4% before and after surface modification.
6. according to claim 1 to 5 arbitrary described for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that: described step 1) bake out temperature be 80 DEG C, drying time is not less than 10 hours, and sintering temperature is 550 DEG C, and roasting time is not less than 6 hours.
7. according to claim 1 to 5 arbitrary described for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that, when step 2) adopt roller forming time, the pellet that bowling machine rolls out is sieved, the particle being less than 1.5mm returns bowling machine and continues to roll shaping, the particle being greater than 2mm smash loose after return bowling machine and continue to roll shaping, the particle choosing 1.5 ~ 2mm carries out low temperature drying and high-temperature roasting, naturally cool to normal temperature after roasting, obtain molded molecular sieve; When step 2) adopt extruded moulding time, it is 1.5 ~ 2.0mm that round rule footpath is extruded in control, then circle bar is carried out low temperature drying and high-temperature roasting, the adsorbent circle bar naturally cooling to normal temperature is cut into the billet of 2 ~ 3mm length, can molded molecular sieve be obtained after roasting.
8. according to claim 1 to 5 arbitrary described for, the preparation method of the adsorbent of molecular sieve of paracresol adsorbing separation, it is characterized in that, described step 2) bake out temperature be 80 DEG C, drying time is not less than 8 hours, sintering temperature is 550 DEG C, and roasting time is not less than 6 hours.
9. one kind according to the arbitrary described preparation method of claim 1 to 8 prepare for, the adsorbent of molecular sieve of paracresol adsorbing separation.
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| CN105540705A (en) * | 2016-01-19 | 2016-05-04 | 东华大学 | Method and device for preparing solid adsorbent via thermocatalysis of high-concentration nonylphenol polyoxyethylene ether wastewater |
| CN106943993A (en) * | 2017-04-03 | 2017-07-14 | 上海复榆新材料科技有限公司 | Separate zeolite adsorbent of paracresol and meta Cresol Isomeric Compound and preparation method thereof |
| CN107879900A (en) * | 2017-12-22 | 2018-04-06 | 中触媒新材料股份有限公司 | A kind of process of cresols mixed isomers separating-purifying |
| CN110339809A (en) * | 2019-08-13 | 2019-10-18 | 淄博齐创化工科技开发有限公司 | A kind of adsorbent and preparation method for VOCs absorption |
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| CN110511118A (en) * | 2018-05-22 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of method of liquid phase adsorption separation paracresol |
| CN111111630A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for recycling waste powder in production process of adsorbent for simulated moving bed |
| 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 |
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| CN105540705A (en) * | 2016-01-19 | 2016-05-04 | 东华大学 | Method and device for preparing solid adsorbent via thermocatalysis of high-concentration nonylphenol polyoxyethylene ether wastewater |
| CN106943993A (en) * | 2017-04-03 | 2017-07-14 | 上海复榆新材料科技有限公司 | Separate zeolite adsorbent of paracresol and meta Cresol Isomeric Compound and preparation method thereof |
| CN107879900A (en) * | 2017-12-22 | 2018-04-06 | 中触媒新材料股份有限公司 | A kind of process of cresols mixed isomers separating-purifying |
| 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 |
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| 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 |
| CN111111630A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for recycling waste powder in production process of adsorbent for simulated moving bed |
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