CN106000450A - Preparation method of catalyst for hydrating cyclohexene - Google Patents
Preparation method of catalyst for hydrating cyclohexene Download PDFInfo
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- CN106000450A CN106000450A CN201610343622.3A CN201610343622A CN106000450A CN 106000450 A CN106000450 A CN 106000450A CN 201610343622 A CN201610343622 A CN 201610343622A CN 106000450 A CN106000450 A CN 106000450A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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Abstract
The invention provides a preparation method of a catalyst for hydrating cyclohexene. According to the preparation method, a commercial sodium-type ZSM-5 (Zeolite Socony Mobil-5) molecular sieve is treated by using appropriate alkaline liquor, so as to increase the porosity and the lipophilicity of the molecular sieve; afterwards, the modification is carried out by adopting elements of P, La and the like in a combinative manner, so as to modulate and increase the acidity and the hydrothermal stability of the molecular sieve. When the catalyst is applied to the hydration of the cyclohexene to prepare cyclohexanol, the percent conversion of the cyclohexene and the selectivity of the cyclohexanol can be drastically increased, and the reaction stability of the catalyst can be drastically improved. The preparation method of the catalyst, which is provided by the invention, is simple, safe and controllable in operating process, and is easy to realize in an industry.
Description
Technical field
The invention belongs to molecular sieve catalyst preparing technical field, especially relate to a kind of cyclohexene hydration and use
The preparation method of catalyst.
Background technology
Cyclohexene direct hydration is the important method preparing important industrial chemicals Hexalin.This method overcomes
Tradition is prepared after hexamethylene present in the cyclohexane oxidation technique of Hexalin mixes with air and is easily formed
Explosive mixture, production process poor stability, energy consumption are high and process raw material phenol price is high, and hydrogen disappears
Many deficiencies such as consumption is big, have that production line is safe, energy-conservation, carbon atom good economy performance, environmental friendliness
Without advantages such as garbages, commercial Application demonstrates advantage, thus enjoys people to pay close attention to and pay attention to.
Cyclohexene hydration is typical Protic Acid Catalyzed reaction, and mineral acid, benzenesulfonic acid, ion can be used to hand over
Change resin and molecular sieve etc. as catalyst.Mineral acid and benzenesulfonic acid are studied relatively as hydration homogeneous catalyst
Early, but course of reaction need to be carried out in the presence of strong inorganic acid is such as sulphuric acid, thus equipment corrosion is serious, unfavorable
In commercial production.Strong-acid ion exchange resin is as hydration catalyst poor heat stability, and separating technology is multiple
Miscellaneous, it is also unsuitable for commercial Application.Zeolite molecular sieve as water catalysts first by Japan Asahi Chemical Industry
Company applied for a patent in nineteen eighty-three, and successfully by its industrialization.Particularly ZSM-5 zeolite molecular sieve,
Having preferable hydrothermal stability and higher mechanical strength, its ten-ring channel diameter is
0.53nm～0.56nm, with molecular diameter sizableness (the respectively 0.58nm of cyclohexene and Hexalin
And 0.60nm), therefore hydration reaction is had preferably shape selectivity, is obtaining the most widely
Application.
Patent CN1414933A, CN103288600A disclose the method producing cyclohexene.Use
ZSM-5 zeolite is catalyst, and uses organic solvent in reaction system, such as isophorone, ethylidene
Glycol list phenyl ether, Polyethylene Glycol or isophorone etc. improve the conversion ratio of cyclohexene.
Patent 200410048354.X discloses the preparation method of a kind of small-grain ZSM-5.It is characterized in that:
By silica alumina ratio be 20～600, granularity be that the Alusil granule of 20～300 mixes with the aqueous solution of organic formwork agent
Close, in the presence of with or without crystal seed hydrothermal crystallizing synthesis, during without sodium ion raw material, because of without entering
Row ammonium exchanges.This catalyst can be used for cyclohexene hydration reaction, and in embodiment, the conversion ratio of cyclohexene is 7%
Left and right.
Patent 200710087075 discloses preparation method and the ring thereof of a kind of fine grain strong acid type molecular sieve
Hexene hydration performance.It is characterized in that, building-up process is without using organic formwork agent, it is not required that carry out height
Temperature roasting, can effectively control molecular sieve particle diameter in 0.01～0.5 μm, and its Hexalin yield is up to 14.9%.
But this invention needs to use ultrasonic technology before crystallization, and molecular sieve particle diameter is little, hold during industrial application
Easily cause molecular sieve to run off.
Patent 201410050168 discloses catalyst and the application of a kind of preparing cyclohexanol by cyclohexene hydration reaction.
It is characterized in that: used catalyst is with HZSM-5 as carrier, with niobium for modified active component, and use
Silylating reagent carries out surface and modifies to strengthen oleophylic performance.At reaction temperature is 80～180 DEG C, system
The cyclohexene conversion rate of standby catalyst reaches more than 15%, and Hexalin selectivity reaches more than 99%.But this patent
After middle catalyst preparation process is complicated, and silylating reagent is modified, need with organic reagent such as carbon tetrachloride
, there is potential safety hazard in washing, is also not suitable for industry amplification.
It addition, patent CN102259025A, CN104549434A and Master's thesis " ZSM-5 changes
Property for cyclohexene hydration " (the few China of Zhengzhou University sieve, 2010) and " P-H2O2Process ZSM-5
The impact of molecular sieve catalytic cyclohexene hydration performance " (Beijing University of Chemical Technology king obviously, 2011) disclose
With report by B-acid type N, N, N-trimethyl-N-sulphur butyl-ammonium hydrogen sulfate ionic liquid, Ce, La,
Ti, trim,ethylchlorosilane, P, steam treatment and H2O2ZSM-5 zeolite is modified by process etc.,
Improve the cyclohexene hydration activity of ZSM-5 catalyst.
In sum, for improving the effectiveness of cyclohexene hydration reaction in currently available technology, mainly take
Two kinds of means, one is to add the cosolvent such as organic solvent such as alcohol, ketone in reaction system to improve cyclohexene
Dissolubility；Two is that molecular sieve catalyst itself is carried out modification, as introduced parent at molecular sieve surface
Oiliness silylation groups strengthens molecular sieve lipophile；Be introduced directly into metal ion Ni, Ti, La and Fe,
The regulation zeolite acidity such as nonmetallic ion P and B and pore passage structure；Regulate point by controlling synthesis condition
Son sieve particle diameter.Although taking both the above means can improve having of cyclohexene hydration reaction to a certain extent
Effect property, but there is also some problems, can bring to late-stage products separation as reaction system adds cosolvent
Difficulty, can not effectively be applied in actual industrial production；On molecular sieve direct carried metal and
Nonmetallic ion, not only affects its acidity, also affects pore passage structure, and catalyst activity improves limited；Adopt
Although can effectively reduce production cost with without template system synthesis of molecular sieve, reduce environmental nuisance, Jin Jintong
Cross and control synthesis condition and carry out the Molecular regulator sieve molecular sieve particle size uniformity that obtains of particle diameter and need to improve, raw
Repeatability and the stability produced still are not known, and the hydrothermal stability of molecular sieve is relatively poor, catalyst activity
Can not effectively improve.Therefore, it is necessary to develop more efficient cyclohexene hydration catalyst.
Summary of the invention
In view of this, it is contemplated that propose the preparation method of a kind of cyclohexene hydration catalyst, to solve
Certainly deficiency of the prior art, the catalyst prepared by the method is suitable in commercial production.
For reaching above-mentioned purpose, the technical scheme is that and be achieved in that:
The preparation method of a kind of cyclohexene hydration catalyst, comprises the steps,
(1) Na-ZSM-5 molecular sieve appropriate alkaline liquor is processed certain time at a certain temperature, and
Sieve sample after filtering, wash, being dried to obtain base extraction；
(2) by molten with the acid of 0.1～2.0mol/L for the sieve sample after step (1) gained base extraction
Liquid or ammonium salt solution, at 20～120 DEG C, carry out ion and exchange 0.5～8 hour, through washing, are dried also
Roasting 3～8 hours at 500～600 DEG C, prepare Hydrogen ZSM-5 zeolite catalyst；
(3) by gained Hydrogen ZSM-5 zeolite catalyst in step (2), with the modified unit prepared
Element saline solution be modified, more scrubbed, dry, roasting, obtain cyclohexene hydration catalyst；
Preferably, the saline solution of described modifying element is ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, nitric acid
One or more any mixture in lanthanum, cerous nitrate, bismuth nitrate.
Preferably, in described step (1), the concentration range of described alkali liquor is 0～3.0mol/L；Na-ZSM-5
Molecular sieve is 0.05～1 with the mass ratio of alkali liquor；Described treatment temperature is 20～200 DEG C；During described process
Between be 0.5～50h.
Preferably, in described step (1), described alkali liquor is sodium hydroxide, Lithium hydrate, hydroxide
Potassium, sodium metaaluminate, potassium metaaluminate, ammonia, methylamine, ethamine, propylamine, diethylamine, triethylamine, just
One or more any mixture in butylamine, di-n-butylamine, Tri-n-Propylamine.
Preferably, in described step (2), described acid solution be hydrochloric acid, nitric acid, sulphuric acid, acetic acid,
Citric acid or phosphoric acid；Described ammonium salt solution is ammonium nitrate, ammonium sulfate, ammonium phosphate or ammonium chloride solution.
Preferably, in institute's step (3), method of modifying is infusion process or ion exchange；Preferably,
Infusion process is incipient impregnation or excess dipping.
Preferably, in described step (3), when method of modifying is infusion process or ion exchange, described
Concentration of salt solution is 0.1～3.0mol/L, and modification temperature is 20～150 DEG C, and modification time is 0.5～50 little
Time, molecular sieve is 0.1～1.0 with the mass ratio of the saline solution of modifying element.
Preferably, in described step (3), described sintering temperature is 400～650 DEG C, and roasting time is
2～6 hours.
Preferably, in described step (3), the cyclohexene hydration catalyst of described final preparation changes
The weight/mass percentage composition of property ion is 0.1～3.0%.
Prepared by the preparation method that present invention also offers a kind of cyclohexene hydration catalyst as above
Catalyst application in preparing cyclohexanol by cyclohexene hydration reaction.
Relative to prior art, the preparation method of a kind of cyclohexene hydration catalyst of the present invention,
Have the advantage that the method for modifying that the invention provides cyclohexene hydration ZSM-5 catalyst, work
Skill process is simple, handling by force, the catalyst first prepared through base extraction has porous, exposes
More acid site and silicone hydroxyl position, enhance the lipophile of molecular sieve and the diffusivity of reaction molecular；
Then in conjunction with ion modification, modulation is acid and improves the hydrothermal stability of molecular sieve itself, Jin Er great
Improve greatly the catalysis activity of catalyst, improve the reaction stability of catalyst.Reuse catalyst
5～8 times, performance is basically unchanged, and this method for preparing catalyst can be promoted the use of in the industry, can be from all
The circulating load of upper reduction raw material cyclohexene, extends the service life of catalyst, and then reduces production one-tenth
This.
Detailed description of the invention
Below by example, the present invention is described in further details, but the present invention is not by these embodiments
Restriction.
Comparative example:
The 50g business hydration ammonium nitrate solution of Na-ZSM-5 molecular sieve 400ml 0.8mol/L is existed
Carry out ion at 40 DEG C to exchange 6 hours, through washing, be dried and roasting 6 hours at 550 DEG C,
Prepare Hydrogen ZSM-5 zeolite catalyst, catalyst as a comparison, be labeled as DB-1.
Embodiment 1
By the 50g business hydration sodium hydroxide solution of Na-ZSM-5 molecular sieve 300ml 0.2mol/L
Stir process 3 hours at 50 DEG C, the sieve sample after filtering, wash, being dried to obtain process.
The ammonium nitrate solution of sieve sample 400ml 0.8mol/L carries out at 40 DEG C ion, and to exchange 6 little
Time, through washing, it is dried and roasting 6 hours at 550 DEG C, prepares the catalysis of Hydrogen ZSM-5 zeolite
Agent (HZSM-5 zeolite catalyst).
Weigh 15g HZSM-5 zeolite catalyst, be the lanthanum nitrate hexahydrate of 1.2% with 15ml mass fraction,
Room temperature incipient impregnation 12 hours, is then dried overnight sample at 110 DEG C, and roasts at 540 DEG C
Burn 3 hours, obtain modified catalyst, be labeled as GX-1.
Embodiment 2
Repeat embodiment 1, but change the sodium hydroxide solution of the 0.2mol/L in base extraction into 0.5
The Tri-n-Propylamine solution of mol/L, changes roasting at 540 DEG C in modification procedure into roasting 8 in 3 hours little
Time.Gained modified catalyst is labeled as GX-2.
Embodiment 3
Repeat embodiment 1, but change the sodium hydroxide solution of the 0.2mol/L in base extraction into 0.4
The n-butylamine solution of mol/L, by the lanthanum nitrate hexahydrate that 15ml mass fraction is 1.2% in modification procedure
Change the ammonium dihydrogen phosphate of 60ml 2.2% into, within 3 hours, change roasting at 540 DEG C into roasting 8 hours.
Gained modified catalyst is labeled as GX-3.
Embodiment 4
Repeat embodiment 1, but by the lanthanum nitrate hexahydrate that 15ml mass fraction is 1.2% in modification procedure
Change the bismuth nitrate solution of 60ml 0.6% into, within 3 hours, change roasting at 540 DEG C into roasting 6 hours.Institute
Obtain modified catalyst and be labeled as GX-4.
Embodiment 5
Repeat embodiment 1, but concentration 0.2mol/L of sodium hydroxide solution in base extraction is changed into
0.5mol/L, changes the lanthanum nitrate hexahydrate that 15ml mass fraction is 1.2% in modification procedure into 60ml
The cerous nitrate solution of 1.0%, changes roasting at 540 DEG C into roasting 6 hours in 3 hours.Gained Modified catalytic
Agent is labeled as GX-5.
Embodiment 6
Repeat embodiment 1, but concentration 0.2mol/L of sodium hydroxide solution in base extraction is changed into
0.5mol/L, changes the lanthanum nitrate hexahydrate that 15ml mass fraction is 1.2% in modification procedure into 60ml
The lanthanum nitrate hexahydrate of 1.2%, carry out excess dipping 3 hours, filter off unnecessary modification liquid, be dried overnight and in
Roasting 6 hours at 550 DEG C, obtain modified catalyst and are labeled as GX-6.
Compliance test result is tested:
It is used for being catalyzed cyclohexene water with the ZSM-5 zeolite catalyst obtained by comparative example by the inventive method
Close Hexalin processed reaction, verify the effect of the present invention.
Weigh above-mentioned each catalyst 15g, deionized water 45ml, cyclohexene 35ml, be sequentially added into 500ml
Autoclave, seals.Seal and be passed through high pure nitrogen displaced air.Reaction temperature is 120 DEG C, instead
Answering pressure is 0.6MPa, and rotating speed is 400r/min, after reacting 1 hour at 120 DEG C, from heating mantle
Interior taking-up autoclave, chilling is lowered the temperature.Pressure release, opens reactor, takes out reactant, stratification,
Taking upper oil phase to be analyzed by gas chromatogram, result see table 1.
Table 1 comparative example and the cyclohexene hydration Evaluation results of each embodiment synthetic catalyst
| Catalyst | Cyclohexene conversion rate % | Hexalin selectivity % |
| DB-1 | 9.23 | 99.21 |
| GX-1 | 10.96 | 99.23 |
| GX-2 | 12.58 | 99.57 |
| GX-3 | 13.12 | 99.35 |
| GX-4 | 11.54 | 99.28 |
| GX-5 | 12.85 | 99.27 |
| GX-6 | 13.01 | 99.52 |
From examples detailed above, the catalyst modification method technical process that the present invention provides is simple, handling
By force, modified catalyst has higher cyclohexene conversion rate and Hexalin selectivity, can fundamentally reduce
The circulating load of raw material cyclohexene, extends the service life of catalyst, and then reduces production cost.
The foregoing is only the preferred embodiment of the invention, not in order to limit the invention,
Within all spirit in the invention and principle, any modification, equivalent substitution and improvement etc. made,
Within should be included in the protection domain of the invention.
Claims (9)
1. the preparation method of a cyclohexene hydration catalyst, it is characterised in that: comprise the steps,
(1) Na-ZSM-5 molecular sieve appropriate alkaline liquor is processed certain time at a certain temperature, and
Sieve sample after filtering, wash, being dried to obtain base extraction；
(2) by molten with the acid of 0.1～2.0mol/L for the sieve sample after step (1) gained base extraction
Liquid or ammonium salt solution, at 20～120 DEG C, carry out ion and exchange 0.5～8 hour, through washing, are dried also
Roasting 3～8 hours at 500～600 DEG C, prepare Hydrogen ZSM-5 zeolite catalyst；
(3) by gained Hydrogen ZSM-5 zeolite catalyst in step (2), with the modified unit prepared
Element saline solution be modified, more scrubbed, dry, roasting, obtain cyclohexene hydration catalyst；
Preferably, the saline solution of described modifying element is ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, nitric acid
One or more any mixture in lanthanum, cerous nitrate, bismuth nitrate.
The preparation method of cyclohexene hydration catalyst the most according to claim 1, its feature exists
In: in described step (1), the concentration range of described alkali liquor is 0～3.0mol/L；Na-ZSM-5 divides
Son sieve is 0.05～1 with the mass ratio of alkali liquor；Described treatment temperature is 20～200 DEG C；The described process time
It is 0.5～50h.
The preparation method of cyclohexene hydration catalyst the most according to claim 1, its feature exists
In: in described step (1), described alkali liquor is sodium hydroxide, Lithium hydrate, potassium hydroxide, inclined aluminum
Acid sodium, potassium metaaluminate, ammonia, methylamine, ethamine, propylamine, diethylamine, triethylamine, n-butylamine, two
One or more any mixture in n-butylamine, Tri-n-Propylamine.
The preparation method of cyclohexene hydration catalyst the most according to claim 1, its feature exists
In: in described step (2), described acid solution be hydrochloric acid, nitric acid, sulphuric acid, acetic acid, citric acid or
Phosphoric acid；Described ammonium salt solution is ammonium nitrate, ammonium sulfate, ammonium phosphate or ammonium chloride solution.
The preparation method of cyclohexene hydration catalyst the most according to claim 1, its feature exists
In: in institute's step (3), method of modifying is infusion process or ion exchange；Preferably, infusion process is
Incipient impregnation or excess dipping.
The most according to claim 1 or 5, the preparation method of cyclohexene hydration catalyst, it is special
Levy and be: in described step (3), when method of modifying is infusion process or ion exchange, described salt is molten
Liquid concentration is 0.1～3.0mol/L, and modification temperature is 20～150 DEG C, and modification time is 0.5～50 hour,
Molecular sieve is 0.1～1.0 with the mass ratio of the saline solution of modifying element.
The preparation method of cyclohexene hydration catalyst the most according to claim 1, its feature exists
In: in described step (3), described sintering temperature is 400～650 DEG C, and roasting time is 2～6 hours.
The preparation method of cyclohexene hydration catalyst the most according to claim 1, its feature exists
In: in described step (3), modified ion in the cyclohexene hydration catalyst of described final preparation
Weight/mass percentage composition is 0.1～3.0%.
9. according to the preparation method system of the cyclohexene hydration catalyst described in any one of claim 1～8
The application in preparing cyclohexanol by cyclohexene hydration reaction of the standby catalyst.
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Cited By (8)
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| CN107876082A (en) * | 2017-11-01 | 2018-04-06 | 中国石油大学(华东) | A kind of molecular sieves of alkali modification ZSM 5 and its preparation method and application |
| CN109759130A (en) * | 2019-01-30 | 2019-05-17 | 江苏黄马化工有限公司 | A kind of regeneration method inactivating aluminium si molecular sieves |
| CN110981718A (en) * | 2019-12-04 | 2020-04-10 | 万华化学集团股份有限公司 | Method for preparing 3-hydroxypropionic acid by continuous hydration of acrylic acid |
| CN112175177A (en) * | 2020-10-15 | 2021-01-05 | 贵州省材料技术创新基地 | Catalyst and preparation method thereof, and preparation method of polylactic acid |
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| CN115591539A (en) * | 2022-10-21 | 2023-01-13 | 神马实业股份有限公司（Cn） | Catalyst for direct hydration reaction of cyclohexene and preparation method thereof |
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