CN108946761A - A kind of preparation method and application of high dispersive ZSM-5 molecular sieve - Google Patents
A kind of preparation method and application of high dispersive ZSM-5 molecular sieve Download PDFInfo
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Abstract
The present invention provides a kind of preparation method and application of high dispersive ZSM-5 molecular sieve, preparation method includes: three steps such as the preparation of crystal seed, the preparation of silica-alumina gel and preparation of high dispersive ZSM-5 molecular sieve；It is simple that the present invention prepares high dispersive ZSM-5 step, it is easily operated, only in the preparation of crystal seed use small amount organic formwork agent, no template silica-alumina gel preparation in introduce organic additive can synthesize particle surface be nanoscale, large specific surface area, good dispersion, uniform particle sizes, regular appearance ZSM-5 molecular sieve；This molecular sieve of application establishes a kind of method for preparing cyclohexanol by cyclohexene direct hydration, not only cyclohexene conversion rate with higher and cyclohexanol are selective for the catalyst, but also settling property is preferable as catalyst to the present invention again.
Description
Technical field
The invention belongs to molecular sieve catalyst preparation technical fields, more particularly, to a kind of high dispersive ZSM-5 molecular sieve
Preparation method and application, more specifically, being mainly used for being catalyzed the preparation method of the molecular sieve of cyclohexene hydration cyclohexanol.
Background technique
Cyclohexene direct hydration is an important method for preparing important industrial chemicals cyclohexanol.The method overcomes traditional system
Hexamethylene present in the cyclohexane oxidation technique of standby cyclohexanol is with easily forming explosive mixture, production process peace after air mixing
Full property is poor, energy consumption is high and process raw material phenol price is high, and many deficiencies such as hydrogen gas consumption is big, have production line it is safe,
The advantages that energy conservation, carbon atom good economy performance, environmental-friendly no waste, advantage is shown in industrial application, thus by people
Pay close attention to and pay attention to.
Cyclohexene hydration is typical Protic Acid Catalyzed reaction, and mineral acid, benzene sulfonic acid, ion exchange resin can be used and divide
Son sieve etc. is used as catalyst.Mineral acid and benzene sulfonic acid are more early as hydration homogeneous catalyst research, but reaction process need to be in strong nothing
It is carried out in the presence of machine acid such as sulfuric acid, thus equipment seriously corroded, it is unfavorable for industrial production.Strong-acid ion exchange resin is as water
It is poor to close catalyst thermal stability, separating technology is complicated, is also unsuitable for industrial application.Zeolite molecular sieve is first as water catalysts
It is first applied for a patent by Japanese chemical company of Asahi Chemical Industry in nineteen eighty-three, and is successfully industrialized.Especially ZSM-5 zeolite molecule
Sieve has preferable hydrothermal stability and higher mechanical strength, and ten-ring channel diameter is 0.53nm~0.56nm, with ring
The molecular diameter sizableness (respectively 0.58nm and 0.60nm) of hexene and cyclohexanol, therefore have to hydration reaction preferable
Shape selectivity is having been more and more widely used.
Patent CN1414933A, CN103288600A discloses the method for production cyclohexene.It the use of ZSM-5 zeolite is catalysis
Agent, and organic solvent is used in the reaction system, such as isophorone, ethylidene glycol list phenyl ether, polyethylene glycol or different Fo Er
Ketone etc. improves the conversion ratio of cyclohexene.
Patent 200410048354.X CN1715186A discloses a kind of preparation method of small-grain ZSM-5.Its feature
Be: the Alusil particle that silica alumina ratio is 20~600, granularity is 20~300 mixed with the aqueous solution of organic formwork agent, having or
Hydrothermal crystallizing synthesizes in the presence of no crystal seed, in the process without sodium ion raw material, because without carrying out ammonium exchange.The catalyst can be used for
Cyclohexene hydration reaction, the conversion ratio of cyclohexene is 7% or so in embodiment.
200710087075 CN101041442A of patent disclose a kind of fine grain strong acid type molecular sieve preparation method and
Its cyclohexene hydration performance.It is characterized in that synthesis process without using organic formwork agent, does not need to carry out high-temperature roasting yet, it can
Effectively control molecular sieve partial size is at 0.01~0.5 μm, and cyclohexanol yield is up to 14.9%.But it is needed before crystallization in the invention
Using ultrasonic technology, and molecular sieve partial size is small, and when industrial application be easy to cause molecular sieve to be lost.
201410050168 CN103785451A of patent disclose a kind of preparing cyclohexanol by cyclohexene hydration reaction catalyst and
Using.It is characterized in that: used catalyst is using niobium as modified active component, and to use silylating reagent using HZSM-5 as carrier
It is surface modified to enhance oleophylic performance.In the case where reaction temperature is 80~180 DEG C, the cyclohexene conversion rate for preparing catalyst reaches
15% or more, cyclohexanol is selective up to 99% or more.But catalyst preparation process is complicated in the patent, and silylating reagent is modified
Afterwards, it needs to be washed with organic reagent such as carbon tetrachloride, there are security risks, are also not suitable for industrial amplification.
In addition, " ZSM-5 is modified to be used for cyclohexene water for patent CN102259025A, CN104549434A and Master's thesis
Conjunction " (the few China of Zhengzhou University sieve) 2010 and " influence that P-H2O2 processing is catalyzed cyclohexene hydration performance to ZSM-5 molecular sieve " (north
Capital university of chemical technology king is obviously) 2011 disclose and report with B acid type N, N, N- trimethyl-N- sulphur butyl-ammonium hydrogen sulfate ionic liquid
Body, Ce, La, Ti, trim,ethylchlorosilane, P, steam treatment and H2O2Processing etc. is modified ZSM-5 zeolite, improves ZSM-5
The cyclohexene hydration activity of catalyst.
In conclusion being the validity for improving cyclohexene hydration reaction in currently available technology, two kinds of means are mainly taken,
First is that the organic solvents such as cosolvent such as alcohol, ketone are added in the reaction system to improve the solubility of cyclohexene；Second is that molecular sieve
Catalyst itself carries out modification, and it is lipophilic such as to introduce lipophilic silylation groups enhancing molecular sieve in molecular sieve surface；Draw
Enter metal ion Ni, Ti, La and Fe, nonmetallic ion P and B etc. and adjusts zeolite acidity and cellular structure；Item is synthesized by control
Part adjusts molecular sieve partial size.Although taking both the above means that can improve the effective of cyclohexene hydration reaction to a certain extent
Property, but there is also some problems, can bring difficulty to late-stage products separation as cosolvent is added in reaction system, in actual industrial
It can not effectively be applied in production；Carried metal and nonmetallic ion on molecular sieve, under the conditions of hydration reaction, these
Ion is easy to fall loss, can not fundamentally improve catalyst activity；Using no template system synthesis of molecular sieve although energy
Production cost is effectively reduced, reduces environmental nuisance, adjusts the molecule that molecular sieve partial size obtains only by control synthesis condition
Sieve particle size uniformity need to be improved, and the repeatability and stability of production are not known still, and the hydrothermal stability of molecular sieve is relatively
Difference, catalyst activity can not effectively improve.Applicant passes through the study found that hydration must have with ZSM-5 catalyst
Suitable silica alumina ratio and partial size, nanometer and big partial size ZSM-5 molecular sieve are not particularly suited for hydration reaction system.Partial size is too small, work
It is unfavorable for settling in industry production；Partial size is too big, and specific surface area is relatively small, and activity is not enough.Therefore, it is necessary to develop it is more efficient i.e.
Active high, good dispersion cyclohexene hydration catalyst.
In the prior art, there are mainly three types of the preparation methods of high dispersive ZSM-5: first is that passing through control aging and crystallization item
Part；Second is that introducing surfactant in crystallization process；Third is that introducing organic agent after the completion of crystallization, these methods can obtain height
The ZSM-5 molecular sieve of dispersion, but gained sample or silica alumina ratio height or partial size are small, are not suitable for cyclohexene hydration reaction,
And the synthesis process that has is time-consuming and laborious is also unsuitable for industrial amplification.
Summary of the invention
In view of this, the present invention is directed to propose a kind of preparation method and application of high dispersive ZSM-5 molecular sieve.After study
It was found that using less amount of organic formwork agent in crystal seed preparation, one-step synthesis table can be gone out in subsequent no template system
Face is nanoscale particle agglomeration, but lower than external surface area effective rate of utilization；And it is a small amount of by only being introduced when gel is prepared
It is nanoscale, large specific surface area, good dispersion, uniform particle sizes, regular appearance that organic additive, which can synthesize particle surface,
ZSM-5 molecular sieve.Here, crystal seed can provide a large amount of nucleus for no template system, avoid in synthesis process using largely having
Machine template；Gel using organic surface active agent is to be dissolved in synthetic system based on surfactant and formed glue in preparing
Beam is coated on zeolite crystal surface, and then inhibits the growth and reunion of molecular sieve.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of high dispersive ZSM-5 molecular sieve, including following preparation step,
(1) preparation of crystal seed: silicon source, silicon source, organic amine and deionized water are stirred, colloidal sol is made into, in 20~150
1~30h of aging at DEG C, obtains seed-solution；
(2) preparation of silicon-aluminum sol: silicon source being dispersed in water, lye is slowly added to, and is sufficiently stirred at 20~120 DEG C
0.5~10h obtains solution A；Silicon source is dispersed in water, is sufficiently stirred, solution B is obtained；Then solution B is slowly added into
In solution A, and pH value is adjusted 8~14 with acid solution, be stirred to react 1~20h at room temperature, uniform silicon-aluminum sol is made；
(3) seed-solution prepared by step (1) preparation of high dispersive ZSM-5 molecular sieve: is slowly added into step (2)
In the silicon-aluminum sol of preparation, 1~10h is sufficiently stirred at 20~120 DEG C, adds organic additive and is filled at 20~120 DEG C
Divide 0.5~10h of stirring that homogeneous gel is made, then gel is transferred in crystallizing kettle and carries out hydrothermal crystallizing, the solid after crystallization
By being filtered, washed, being dried to obtain zeolite product, finally using the acid solution of 0.1~2.0mol/L or ammonium salt solution 20~
0.5~8h of ion exchange is carried out to zeolite powder at 120 DEG C, 3~8h is roasted by washing, drying and at 450~650 DEG C,
High dispersive ZSM-5 molecular sieve is made.
Preferably, the organic additive can be neopelex, lauryl sodium sulfate, fatty alcohol ether sulfuric acid
Sodium, α-sodium olefin sulfonate, sodium cetanesulfonate, 16/Cetyltrimethylammonium bromide, 16/octadecyl trimethyl
One or more of ammonium chloride etc., preferably neopelex, lauryl sodium sulfate, fatty alcohol ether sulfuric acid
One or more of sodium, α-sodium olefin sulfonate, sodium cetanesulfonate, cetyl trimethylammonium bromide.It is described to have
The additional amount of machine additive is the 1%~30% of sieve and silica-sesquioxide total amount, the amount of the preferably described organic additive is 1%~
10%.
Preferably, in the step (1), in the crystal seed preparation, the molar ratio of each substance is SiO2/Al2O3=20~
500, H2O/SiO2=10~50, M/SiO2=0.05~1.0, M indicate organic amine.
Preferably, in the step (2), in the silica-alumina gel, the molar ratio of each substance is SiO2/Al2O3=20~
100, H2O/SiO2=20~100, R2O/SiO2=0.1~1.0, R indicate alkali metal.
Preferably, in the step (3), the Seed charge is the 1%~30% of sieve and silica-sesquioxide gross mass；It is described
Crystallization temperature range is 100~200 DEG C, and crystallization time is 10~200h.
Preferably, in the step (1) and step (2), source of aluminium is aluminium isopropoxide, aluminum sulfate, diaspore, chlorination
One or more of aluminium, aluminum nitrate, sodium metaaluminate, aluminium hydroxide, aluminium secondary butylate, aluminium citrate, aluminium borate；The silicon
Source is one or more of silica solution, waterglass, white carbon black, solid silicone.
Preferably, in the step (1), the organic amine is tetrapropyl oxyammonia, 4-propyl bromide, methylamine, second
One or more of amine, propylamine, n-butylamine, triethylamine, ethylenediamine, Tri-n-Propylamine.
Preferably, in the step (2), the lye is sodium hydroxide, lithium hydroxide, potassium hydroxide, one in ammonium hydroxide
Kind is two or more；The acid solution be one or both of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, boric acid or phosphoric acid with
On.
Preferably, in the step (3), the acid solution is hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid or phosphoric acid；Institute
Stating ammonium salt solution is ammonium nitrate, ammonium sulfate, ammonium phosphate or ammonium chloride.
The molecular sieve that the present invention is prepared using the preparation method of high dispersive ZSM-5 molecular sieve as described above again is as catalysis
Agent establishes a kind of method for preparing cyclohexanol by cyclohexene direct hydration, and not only settling property is preferable for the catalyst, but also has
There are higher cyclohexene conversion rate and cyclohexanol selectivity.
Present invention provides a kind of methods of preparing cyclohexanol by cyclohexene hydration reaction, include the following steps, by water, cyclohexene
With catalyst according to mass ratio be 1:(0.1~1.0): (0.1~0.5) is added to autoclave, seals and is passed through High Purity Nitrogen
Gas displaced air, reaction temperature are 80~200 DEG C, and reaction pressure is 0.2~1.0MPa, and revolving speed is 100~1000r/min, instead
It is 0.5~5h between seasonable；The catalyst is molecule prepared by the preparation method of high dispersive ZSM-5 molecular sieve as described above
Sieve.
Compared with the existing technology, the preparation method and application of a kind of high dispersive ZSM-5 molecular sieve of the present invention, has
Following advantage:
(1) the present invention provides the preparation method of high dispersive ZSM-5 catalyst, step is simple, at low cost, can be in the industry
Using；The molecular sieve that the present invention synthesizes is subsphaeroidal nanocrystal agglomerated particle, large specific surface area, epigranular, pattern rule
Whole, good dispersion.
(2) present invention this molecular sieve of application establishes one kind by cyclohexene direct hydration and prepares hexamethylene as catalyst
The method of alcohol, catalyst cyclohexene conversion rate with higher and cyclohexanol selectivity；Work can not only be reduced using the present invention
The race damage of catalyst in industry production, and process for synthetic catalyst is simple, at low cost, can promote in industrial application.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
The X-ray diffractogram of 1 gained sieve sample of Fig. 1 embodiment.
Fig. 2 is electron scanning micrograph (the SEM) (amplification 3000 of 1 gained sieve sample (ZM-1) of embodiment
Times).
The electron scanning micrograph (SEM) (7500 times of amplification) of 1 gained sieve sample (ZM-1) of Fig. 3 embodiment
Specific embodiment
The present invention is described in further details below by example.
Embodiment 1
By ethyl orthosilicate (TEOS), tetrapropyl oxyammonia (TPAOH), aluminium isopropoxide, deionized water according to molar ratio
Example is stirred for 1:0.25:0.03:20, uniform colloidal sol is made, aging 10 hours, obtain seed-solution at 100 DEG C.
By 150g silica solution (technical grade, SiO2>=30wt%) it is scattered in 60g desalted water, 80g mass point is then added
The NaOH solution that number is 15%, is sufficiently stirred 0.5 hour at room temperature, and solution A is made；The sulphur for being 98% by 3.6g mass fraction
Acid, 70g desalted water and the mixing of 8.0g aluminum sulfate, stirring sufficiently dissolution 0.5 hour, is made B solution at room temperature；B solution is slow
It is added in solution A, stir thoroughly at room temperature 1h, adds 2.0g neopelex 1h is sufficiently stirred at room temperature and be made equal
Gel, is then transferred in synthesis reactor by even gel, the stirring ageing 12h at 100 DEG C, then is warming up to 170 DEG C of stirring crystallization
20h is cooled to room temperature, and is filtered, washed.Filter cake is dried overnight at 110 DEG C and obtains ZSM-5 sample after roasting 3h at 550 DEG C
Product are labeled as ZM-1, and test relative crystallinity is 98%, and it is 2~3 μm that scanning electron microscope, which characterizes sample granularity, nearly spherical morphology, nitrogen
The specific surface area of gas physical absorption test sample is 530m2/g。
Embodiment 2
Tetrapropylammonium hydroxide is changed to 4-propyl bromide when repeating embodiment 1, but preparing crystal seed, in silica-alumina gel
2.0g neopelex is added and 1g sodium cetanesulfonate 2h is sufficiently stirred at 50 DEG C, homogeneous gel, crystallization is made
After obtain ZSM-5 sample, be labeled as ZM-2, test relative crystallinity be 98%, crystal phase is close with embodiment 1, scanning electron microscope table
Levying sample granularity is 3 μm or so, nearly spherical morphology, and the specific surface area of nitrogen physisorption test sample is 510m2/g。
Embodiment 3
Tetrapropylammonium hydroxide is changed to Tri-n-Propylamine when repeating embodiment 1, but preparing presoma, is added in silica-alumina gel
Enter 2.5g cetyl trimethylammonium bromide and homogeneous gel is made in stir thoroughly at room temperature 2h, obtains ZSM-5 sample after crystallization, mark
It is denoted as ZM-3, test relative crystallinity is 96%, and crystal phase is close with embodiment 1, and it is 1~2 μm that scanning electron microscope, which characterizes sample granularity,
Left and right, nearly spherical morphology, the specific surface area of nitrogen physisorption test sample are 540m2/g。
Embodiment 4
Embodiment 1 is repeated, 1.5g lauryl sodium sulfate and 1.5g α-sodium olefin sulfonate are added in silica-alumina gel in room
Temperature is sufficiently stirred 2h and homogeneous gel is made, and obtains ZSM-5 sample after crystallization, is labeled as ZM-4, and test relative crystallinity is 98%,
It is 2~3 μm or so that scanning electron microscope, which characterizes sample granularity, and the specific surface area of nearly spherical morphology, nitrogen physisorption test sample is
520m2/g。
Embodiment 5
Embodiment 1 is repeated, 2.0g neopelex and 2.0g sodium cetanesulfonate are added in silica-alumina gel
2h is sufficiently stirred in 40 DEG C, homogeneous gel is made, obtain ZSM-5 sample after crystallization, be labeled as ZM-5, test relative crystallinity is
97%, it is 3~4 μm or so that scanning electron microscope, which characterizes sample granularity, nearly spherical morphology, the specific surface of nitrogen physisorption test sample
Product is 510m2/g。
Performance detection experiment
Experiment one
It is 8 that the HCl solution of the 0.8mol/L of embodiment ZM-1~5, liquid, which are consolidated mass ratio, and ion friendship is carried out at 80 DEG C
It changes, repeated exchanged 2 times, is then filtered, washed to neutrality, is dried overnight at 100 DEG C, and roasted 5 hours at 550 DEG C, made
Obtain Hydrogen ZSM-5 zeolite catalyst.Sample is respectively labeled as: HZM-1, HZM-2, HZM-3, HZM-4 and HZM-5.
Experiment two
This experiment is in order to illustrate ZSM-5 molecular sieve obtained by the method for the present invention and comparative example method for being catalyzed cyclohexene
It is hydrated the effect of cyclohexanol reaction processed.
Above-mentioned each catalyst 30g, deionized water 90ml, cyclohexene 65ml are weighed, 500ml autoclave is sequentially added,
It seals and is passed through high pure nitrogen displaced air.Reaction temperature is 120 DEG C, reaction pressure 0.6MPa, revolving speed 400r/min,
After reacting 1 hour at 120 DEG C, autoclave, chilling cooling are taken out out of heating mantle.Reaction kettle is opened in pressure release, takes out reaction
Object, stratification take upper oil phase to be analyzed by gas-chromatography, as a result see the table below 1.In addition, also to these catalyst into
It has gone settling property test (being evaluated with the rate of recovery of post catalyst reaction, the rate of recovery is higher, then settling property is better).
It is catalyzed after each embodiment synthetic catalyst of table 1 and the cyclohexene hydration Evaluation results of commercially available business agent and reaction
The agent rate of recovery
| Catalyst | Cyclohexene conversion rate % | Cyclohexanol selectivity % | Rate of recovery % |
| Commercially available business agent | 10.32 | 99.25 | 92.5 |
| HZM-1 | 12.28 | 99.42 | 97.3 |
| HZM-2 | 12.56 | 99.28 | 96.2 |
| HZM-3 | 11.52 | 99.24 | 95.8 |
| HZM-4 | 12.05 | 99.38 | 96.4 |
| HZM-5 | 12.24 | 99.52 | 97.2 |
By examples detailed above it is found that no template system provided by the invention, which introduces organic additive, is hydrated use come synthesizing cyclohexene
High dispersive ZSM-5 catalyst, preparation process is simple, and the molecular sieve synthesized is subsphaeroidal nanometer agglomerated particle, specific surface
Long-pending big, epigranular, good dispersion, suitable for using in the industry.In addition, the molecular sieve can be used as cyclohexene hydration cyclohexanol
Catalyst, cyclohexene conversion rate with higher and cyclohexanol selectivity, cyclohexene conversion rate is up to 12% or more, cyclohexanol
Selectivity is up to 99% or more, and the settling property of catalyst is preferable.
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on should be included in the invention
Protection scope within.
Claims (10)
1. a kind of preparation method of high dispersive ZSM-5 molecular sieve, it is characterised in that: including following preparation step,
(1) preparation of crystal seed: silicon source, silicon source, organic amine and deionized water being stirred, colloidal sol is made into, at 20~150 DEG C
1~30h of aging, obtains seed-solution；
(2) preparation of silicon-aluminum sol: silicon source being dispersed in water, lye is slowly added to, and is sufficiently stirred 0.5 at 20~120 DEG C
~10h, obtains solution A；Silicon source is dispersed in water, is sufficiently stirred, solution B is obtained；Then solution B is slowly added into solution
In A, and pH value is adjusted 8~14 with acid solution, be stirred to react 1~20h at room temperature, uniform silicon-aluminum sol is made；
(3) seed-solution prepared by step (1) preparation of high dispersive ZSM-5 molecular sieve: is slowly added into step (2) preparation
Silicon-aluminum sol in, 1~10h is sufficiently stirred at 20~120 DEG C, adds organic additive and is sufficiently stirred at 20~120 DEG C
It mixes 0.5~10h and homogeneous gel is made, then gel is transferred in crystallizing kettle and carries out hydrothermal crystallizing, the solid after crystallization passes through
It is filtered, washed, is dried to obtain zeolite product, finally using the acid solution of 0.1~2.0mol/L or ammonium salt solution at 20~120 DEG C
Under 0.5~8h of ion exchange is carried out to zeolite powder, 3~8h is roasted by washing, drying and at 450~650 DEG C, height is made
Disperse ZSM-5 molecular sieve；Preferably, the organic additive is neopelex, lauryl sodium sulfate, fatty alcohol
Ether sodium sulfate, α-sodium olefin sulfonate, sodium cetanesulfonate, 16/Cetyltrimethylammonium bromide, 16/octadecyl
One or more of trimethyl ammonium chloride etc.；The additional amount of the organic additive is sieve and silica-sesquioxide gross mass
1%~30%；Preferably 1%~10%.
2. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (1)
In, in the seed-solution, the molar ratio of each substance is SiO2/Al2O3=20~500, H2O/SiO2=10~50, M/SiO2=
0.05~1.0, M indicate organic amine.
3. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (2)
In, in the silicon-aluminum sol, the molar ratio of each substance is SiO2/Al2O3=20~100, H2O/SiO2=20~100, R2O/
SiO2=0.1~1.0, R indicate alkali metal.
4. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (3)
In, the Seed charge is the 1%~30% of sieve and silica-sesquioxide gross mass；The crystallization temperature range is 100~200 DEG C,
Crystallization time is 10~200h.
5. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (1) with
And in step (2), source of aluminium be aluminium isopropoxide, aluminum sulfate, diaspore, aluminium chloride, aluminum nitrate, sodium metaaluminate, aluminium hydroxide,
One or more of aluminium secondary butylate, aluminium citrate, aluminium borate, aluminum sulfate；The silicon source is ethyl orthosilicate, silicon is molten
One or more of glue, waterglass, white carbon black, solid silicone.
6. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (1)
In, the organic amine is tetrapropyl oxyammonia, 4-propyl bromide, methylamine, ethamine, propylamine, n-butylamine, triethylamine, second two
One or more of amine, Tri-n-Propylamine.
7. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (2)
In, the lye is one or more of sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide；The acid solution is salt
One or more of acid, nitric acid, sulfuric acid, acetic acid, citric acid, boric acid or phosphoric acid.
8. the preparation method of high dispersive ZSM-5 molecular sieve according to claim 1, it is characterised in that: the step (3)
In, the acid solution is hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid or phosphoric acid；The ammonium salt solution is ammonium nitrate, ammonium sulfate, phosphorus
Sour ammonium or ammonium chloride.
9. the molecular sieve of the preparation method preparation of described in any item high dispersive ZSM-5 molecular sieves is being urged according to claim 1~8
Change the application in cyclohexene hydration cyclohexanol.
10. a kind of method of preparing cyclohexanol by cyclohexene hydration reaction, it is characterised in that: include the following steps, by water, cyclohexene and urge
Agent is 1:(0.1~1.0 according to mass ratio): (0.1~0.5) is added to autoclave, seals and is passed through high pure nitrogen and sets
It ventilates, reaction temperature is 80~200 DEG C, and reaction pressure is 0.2~1.0MPa, and revolving speed is 100~1000r/min, when reaction
Between be 0.5~5h；The catalyst is the preparation side according to high dispersive ZSM-5 molecular sieve according to any one of claims 1 to 8
The molecular sieve of method preparation.
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Cited By (6)
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| CN109759043A (en) * | 2019-02-13 | 2019-05-17 | 郑州大学 | A kind of preparation method of solid acid catalyst and preparation method thereof and D-pHPG |
| CN110054199A (en) * | 2019-06-11 | 2019-07-26 | 兰州理工大学 | A kind of method of green energy conservation synthesis Fe-ZSM-5 molecular sieve |
| CN111302358A (en) * | 2020-03-05 | 2020-06-19 | 华东理工大学 | Binder-free FAU type molecular sieve particles and preparation method and application thereof |
| CN111450875A (en) * | 2020-04-29 | 2020-07-28 | 烟台大学 | Preparation method of cyclohexene hydration liquid-liquid amphiphilic catalyst |
| CN113559919A (en) * | 2021-06-18 | 2021-10-29 | 烟台大学 | Preparation method of OTS-HZSM-5 molecular sieve and application of molecular sieve in cyclohexene hydration |
| CN116199235A (en) * | 2023-03-10 | 2023-06-02 | 天津大学 | Sulfonated amphiphilic HZSM-5, preparation method and application thereof |
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| CN102962091A (en) * | 2012-11-23 | 2013-03-13 | 中国天辰工程有限公司 | Preparation method of ZSM-5 (zeolites synthesized by mobil-5) molecular sieve catalyst with small grain diameter |
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| CN109759043A (en) * | 2019-02-13 | 2019-05-17 | 郑州大学 | A kind of preparation method of solid acid catalyst and preparation method thereof and D-pHPG |
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| CN111302358A (en) * | 2020-03-05 | 2020-06-19 | 华东理工大学 | Binder-free FAU type molecular sieve particles and preparation method and application thereof |
| CN111450875A (en) * | 2020-04-29 | 2020-07-28 | 烟台大学 | Preparation method of cyclohexene hydration liquid-liquid amphiphilic catalyst |
| CN113559919A (en) * | 2021-06-18 | 2021-10-29 | 烟台大学 | Preparation method of OTS-HZSM-5 molecular sieve and application of molecular sieve in cyclohexene hydration |
| CN116199235A (en) * | 2023-03-10 | 2023-06-02 | 天津大学 | Sulfonated amphiphilic HZSM-5, preparation method and application thereof |
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Application publication date: 20181207 |