CN104086373B - A kind of sheet Al-SBA-15 mesopore molecular sieve catalyzes and synthesizes the method for Bisphenol F - Google Patents
A kind of sheet Al-SBA-15 mesopore molecular sieve catalyzes and synthesizes the method for Bisphenol F Download PDFInfo
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- CN104086373B CN104086373B CN201410318627.1A CN201410318627A CN104086373B CN 104086373 B CN104086373 B CN 104086373B CN 201410318627 A CN201410318627 A CN 201410318627A CN 104086373 B CN104086373 B CN 104086373B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
The invention discloses and a kind ofly prepare the method that sheet Al-SBA-15 mesoporous molecular sieve catalyst catalyzes and synthesizes Bisphenol F.With polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (Pluronic123) for template, with tetraethoxy (TEOS) for silicon source, take aluminum isopropylate as aluminium source, under very rare low concentration of hydrochloric acid, add basic zirconium chloride, obtain sheet Al-SBA-15 mesoporous molecular sieve catalyst by hydrothermal method.With phenol, formaldehyde for raw material, with sheet Al-SBA-15 mesopore molecular sieve for catalyzer, Bisphenol F is obtained through condensation reaction, Bisphenol F yield reaches 98.8%, catalyst activity is high, in catalyst preparing and bis-phenol building-up process, all do not use other solvent, environmental protection, catalyst preparing cost is low, and is easy to Separation and Recovery and reusable.
Description
Technical field
The present invention relates to a kind of method catalyzing and synthesizing Bisphenol F.
Background technology
Bisphenol F is a kind of important chemical intermediate, due to its chemical structure feature, be suitable for preparing low viscosity epoxy resin, its finished product is all better than bisphenol A epoxide resin at aspect of performances such as thermotolerance, wet fastness, insulativity, processibility and injection moulding casting, especially it is convenient to injection moulding casting flowing, can adds the feature even not adding thinner less, be particularly suitable for the machine-shaping of wind turbine blade epoxy resin, greatly reduce environmental pollution, improve processing environment.
Patent US4400554, CN200810072071, JP58177928 report the method catalyzing and synthesizing Bisphenol F with mineral acids such as phosphoric acid, hydrochloric acid, sulfuric acid respectively, and mineral acid catalysis yield is high, but serious to equipment corrosion, side reaction is many.The method that it is catalyst bisphenol synthesis F that patent JP9255606, JP08198790, JP08268943, JP55124730 report with oxalic acid and oxalate respectively, catalytic reaction condition is gentle, comparatively light to equipment corrosion, but side reaction still many, phenol formaldehyde ratio is high, yield is low.The method that it is catalyst bisphenol synthesis F that patent CN102491879A reports with aluminum chloride and titanium tetrachloride modified synergic Zeo-karb, but the stability of aluminum chloride and titanium tetrachloride modified synergic Zeo-karb is still waited to improve.Patent CN102584541A reports the method that Bisphenol F is prepared in the catalysis of a kind of 1-alkyl-3-methylimidazole acidic ionic liquid, but ionic-liquid catalyst cost is higher, and washing recovery still exists certain influence.Patent CN101987812A discloses a kind of method that mesopore molecular sieve catalyzes and synthesizes Bisphenol F, and this method catalyzer is easy to Separation and Recovery, but the reaction times longer (4 ~ 6 hours).Common SBA-15 mesopore molecular sieve exterior appearance is bar-shaped or fibrous, because of its molecular sieve pore passage its long axis direction parallel (Zhao, D. .Science1998 is waited, 279,548.), so molecular sieve analog duct is longer, be generally micron order, this materially increases reactant and the diffusional resistance of reaction product molecule in molecular sieve pore passage, too increases the probability that molecular sieve pore passage is blocked simultaneously, have impact on the performance of catalyst activity.
The present invention is directed to common this defect of SBA-15 mesopore molecular sieve, provide a kind of sheet Al-SBA-15 mesoporous molecular sieve catalyst with short straight pore passage structure to catalyze and synthesize the method for Bisphenol F.
Summary of the invention
The technical problem to be solved in the present invention is: for the defect in common SBA-15 mesopore molecular sieve elongated hole road, a kind of sheet Al-SBA-15 mesoporous molecular sieve catalyst of short straight hole road is provided to catalyze and synthesize the method for Bisphenol F, the probability that the rate of diffusion of accelerated reaction thing in duct is blocked with reducing duct.
A kind of sheet Al-SBA-15 mesopore molecular sieve is the object of the present invention is to provide to catalyze and synthesize the novel method of Bisphenol F.
Technical scheme of the present invention is:
1. a sheet Al-SBA-15 mesopore molecular sieve catalyzes and synthesizes the method for Bisphenol F, sheet Al-SBA-15 mesoporous molecular sieve catalyst and phenol is the steps include: to join in the reactor with whipping appts, after being fully uniformly mixed, slowly add the formalin that mass percent is 35 ~ 40% again, stirring reaction, in pure formaldehyde, the mass ratio of the quality aldehyde of added catalyzer and formaldehyde is 0.1 ~ 0.5: 1, the mol ratio of phenol and formaldehyde is 6 ~ 30: 1, temperature of reaction is 50 ~ 110 DEG C, reaction times is 15 ~ 120 minutes, after reaction terminates, cooling leaves standstill, filtering separation reclaims catalyzer, the catalyzer reclaimed is through washing with alcohol, for lower secondary response after drying, filtrate is reclaimed after excessive phenol through underpressure distillation, obtain Bisphenol F product.
2. a kind of sheet Al-SBA-15 mesopore molecular sieve according to 1 catalyzes and synthesizes the method for Bisphenol F, it is characterized in that: the preparation method of described sheet Al-SBA-15 mesoporous molecular sieve catalyst is:
The first step: join in the hydrochloric acid soln of 0.03 ~ 0.1mol/L by aluminum isopropylate, tetraethoxy by the mol ratio of 0.02 ~ 0.2: 1, abundant stirring and dissolving is solution A; Join in the hydrochloric acid soln of aforementioned same concentrations by basic zirconium chloride and polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer (Pluronic123), abundant stirring and dissolving is solution B; Be the volume ratio of 1: 7 by solution A and solution B, solution A slowly joined in solution B under abundant agitation condition, obtain mixture C, in mixture C, the mol ratio of each component is: tetraethoxy: aluminum isopropylate: basic zirconium chloride: Pluronic123: H
2o: HCl is 1: 0.02 ~ 0.2: 0.046: 0.016: 205: 0.11 ~ 0.37;
Second step: the first step gained mixture C is stirred 20 ~ 30 hours at 30 ~ 45 DEG C, proceed in teflon-lined water heating kettle again, crystallization 40 ~ 50 hours are left standstill at 90 ~ 120 DEG C of temperature, filter, filter cake washes with water, drying, 450 ~ 650 DEG C of roasting temperatures 5 ~ 8 hours, i.e. obtained sheet Al-SBA-15 mesoporous molecular sieve catalyst.
3. the method according to 1 or 2, is characterized in that: the Si/Al mol ratio of prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is 10 ~ 40: 1.
4. the method according to 1 or 2, is characterized in that: in pure formaldehyde, and the mass ratio of added sheet Al-SBA-15 mesoporous molecular sieve catalyst and formaldehyde is 0.2 ~ 0.5: 1.
5. the method according to 1 or 2, is characterized in that: in pure formaldehyde, and the mol ratio of added phenol and formaldehyde is 10 ~ 30: 1.
6. the method according to 1 or 2, is characterized in that: temperature of reaction is 80 ~ 100 DEG C.
7. the method according to 1 or 2, is characterized in that: the reaction times is 60 ~ 90 minutes.
The present invention has following technical superiority and beneficial effect:
(1) the sheet Al-SBA-15 mesopore molecular sieve thickness prepared by is 300 ~ 500nm, namely there is short straight pore passage structure, diffusional resistance in molecular sieve pore passage of reactant and product molecule and the blocked probability of molecular sieve pore passage can be reduced, catalyzer shows higher catalytic activity in reaction process, and Bisphenol F yield reaches 98.8%;
(2) use mass percent in catalyst preparation process be 37% hydrochloric acid very rare low-concentration hcl of 120 ~ 390 times, do not use other solvent, environmental protection, preparation cost is low.
(3) catalyzer is easy to Separation and Recovery and reusable.
Accompanying drawing explanation
Fig. 1 is the small angle x-ray diffraction (SAXD) spectrogram (XRD) of described sheet Al-SBA-15 mesoporous molecular sieve catalyst;
Fig. 2 is the N2 adsorption-desorption curve (BET) of described sheet Al-SBA-15 mesoporous molecular sieve catalyst;
Fig. 3 is the pore size distribution curve (BET) of described sheet Al-SBA-15 mesoporous molecular sieve catalyst;
Fig. 4 is the stereoscan photograph (SEM) of described sheet Al-SBA-15 mesoporous molecular sieve catalyst;
Fig. 5 is the transmission electron microscope photo (TEM) of described sheet Al-SBA-15 mesoporous molecular sieve catalyst.
Embodiment
Below by embodiment, the specific embodiment of the invention is explained.
Embodiment 1
(1) preparation of sheet Al-SBA-15 mesoporous molecular sieve catalyst
The first step: 9 grams of tetraethoxys and 0.44 gram of aluminum isopropylate are joined in the hydrochloric acid soln of 20mL0.03mol/L, abundant stirring and dissolving is solution A, 4 grams of Pluronic123 and 0.64 gram basic zirconium chlorides are joined in the hydrochloric acid soln of 140mL0.03mol/L, abundant stirring and dissolving is solution B, solution A is slowly joined in solution B under abundant agitation condition, obtains mixture C;
Second step: the first step gained mixture C is stirred 24 hours at 35 DEG C, proceed in teflon-lined water heating kettle again, 100 DEG C of standing crystallization 48 hours, filter, filter cake washed 3 times, dry, 550 DEG C of roastings 6 hours, obtain 3 grams of sheet Al-SBA-15 mesoporous molecular sieve catalysts, wherein the Si/Al mol ratio of catalyzer is 20: 1.
(2) testing and characterization of sheet Al-SBA-15 mesoporous molecular sieve catalyst
Fig. 1 small angle x-ray diffraction (SAXD) spectrogram shows that prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst has very regular pore passage structure;
Fig. 2 is typical IV type N2 adsorption-desorption isothermal curve, shows that prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is orderly mesoporous material;
Fig. 3 shows that prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst pore size distribution is very narrow, and mainly concentrate between 7 ~ 9nm, mean diameter is 7.9nm;
BET Determination of Specific Surface Area, the specific surface area obtaining prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is 769m
2/ g, pore volume are 1.38cm
3/ g;
Fig. 4 stereoscan photograph shows that the pattern of prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is hexagonal flake;
Fig. 5 transmission electron microscope photo shows that prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst has very straight duct, and length is 300 ~ 500nm.
(3) Bisphenol F synthesis
Take 0.93 gram of sheet Al-SBA-15 mesoporous molecular sieve catalyst and 250 grams of phenol add in two mouthfuls of flasks, stir at temperature of reaction 90 DEG C, under whipped state, slowly add 7.2 gram mass percentage ratios is again the formalin of 37%, namely phenol and formaldehyde mole ratio are 30: 1, the mass ratio of catalyst levels and formaldehyde is 0.35: 1, react 1 hour, terminate reaction, cooling leaves standstill, filtering separation reclaims catalyzer, the catalyzer reclaimed is through washing with alcohol, for lower secondary response after drying, filtrate is reclaimed after excessive phenol through underpressure distillation, obtain Bisphenol F product, Bisphenol F yield is 95.2%.
Embodiment 2
With embodiment 1, its difference is that aluminum isopropylate consumption is 0.176 gram in the first step of preparation sheet Al-SBA-15 mesoporous molecular sieve catalyst, the Si/Al mol ratio of prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is 50: 1, and obtaining Bisphenol F yield is 80.6%.
Embodiment 3
With embodiment 1, its difference is that aluminum isopropylate consumption is 1.76 grams in the first step of preparation sheet Al-SBA-15 mesoporous molecular sieve catalyst, the Si/Al mol ratio of prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is 5: 1, and obtaining Bisphenol F yield is 80.5%.
Embodiment 4
With embodiment 1, its difference is that the consumption of sheet Al-SBA-15 mesoporous molecular sieve catalyst is 0.27 gram, and the mass ratio of catalyzer and formaldehyde (in pure formaldehyde) is 0.1: 1, and obtaining Bisphenol F yield is 79.2%.
Embodiment 5
With embodiment 1, its difference is that the consumption of sheet Al-SBA-15 mesoporous molecular sieve catalyst is 1.33 grams, and the mass ratio of catalyzer and formaldehyde (in pure formaldehyde) is 0.5: 1, and obtaining Bisphenol F yield is 98.8%.
Embodiment 6
With embodiment 1, its difference be mass percent be 37% formaldehyde consumption be 35.94 grams, the mol ratio of phenol and formaldehyde (in pure formaldehyde) is 6: 1, and obtaining Bisphenol F yield is 61.3%.
Embodiment 7
With embodiment 1, its difference is that temperature of reaction is 60 DEG C, and obtaining Bisphenol F yield is 56.8%.
Embodiment 8
With embodiment 1, its difference is that temperature of reaction is 110 DEG C, and obtaining Bisphenol F yield is 97.4%.
Embodiment 9
With embodiment 1, its difference is that the reaction times is 15 minutes, and obtaining Bisphenol F yield is 89.4%.
Embodiment 10
Embodiment 1, its difference is that the reaction times is 120 minutes, and obtaining Bisphenol F yield is 96.0%.
Embodiment 11
With embodiment 1, its difference is that catalyzer is that after using for the 1st time, Separation and Recovery re-uses for the 2nd time, and obtaining Bisphenol F yield is 93.8%.
Embodiment 12
With embodiment 1, its difference is not add basic zirconium chloride in the process of preparation sheet Al-SBA-15 mesoporous molecular sieve catalyst, and obtained common Al-SBA-15 mesopore molecular sieve, obtaining Bisphenol F yield is 86.0%.
Above embodiment 1 ~ 10 catalyzes and synthesizes the reaction conditions parameter of Bisphenol F and the results are shown in table 1, and wherein formaldehyde is in pure formaldehyde.
Table 1
Above embodiment 11 ~ 12 catalyzes and synthesizes the reaction conditions parameter of Bisphenol F and the results are shown in table 2, and wherein formaldehyde is in pure formaldehyde.
Table 2
Claims (5)
1. a sheet Al-SBA-15 mesopore molecular sieve catalyzes and synthesizes the method for Bisphenol F, sheet Al-SBA-15 mesoporous molecular sieve catalyst and phenol is the steps include: to join in the reactor with whipping appts, after being fully uniformly mixed, slowly add the formalin that mass percent is 35 ~ 40% again, stirring reaction, in pure formaldehyde, the mass ratio of added catalyzer and formaldehyde is 0.1 ~ 0.5: 1, the mol ratio of phenol and formaldehyde is 6 ~ 30: 1, temperature of reaction is 50 ~ 110 DEG C, reaction times is 15 ~ 120 minutes, after reaction terminates, cooling leaves standstill, filtering separation reclaims catalyzer, the catalyzer reclaimed is through washing with alcohol, for lower secondary response after drying, filtrate is reclaimed after excessive phenol through underpressure distillation, obtain Bisphenol F product,
The preparation method of described sheet Al-SBA-15 mesoporous molecular sieve catalyst is:
The first step: by aluminum isopropylate and tetraethoxy by 0.02 ~ 0.2: 1 mol ratio join in the hydrochloric acid soln of 0.03 ~ 0.1mol/L, abundant stirring and dissolving is solution A; Join in the hydrochloric acid soln of aforementioned same concentrations by basic zirconium chloride and polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer Pluronic123, abundant stirring and dissolving is solution B; Be the volume ratio of 1: 7 according to solution A than solution B, solution A slowly joined in solution B under abundant agitation condition, obtain mixture C, in mixture C, the mol ratio of each component is: tetraethoxy: aluminum isopropylate: basic zirconium chloride: Pluronic123: H
2o: HCl is 1: 0.02 ~ 0.2: 0.046: 0.016: 205: 0.11 ~ 0.37;
Second step: the first step gained mixture C is stirred 20 ~ 30 hours at 30 ~ 45 DEG C, proceed in teflon-lined water heating kettle again, crystallization 40 ~ 50 hours are left standstill at 90 ~ 120 DEG C of temperature, filter, filter cake washes with water, drying, 450 ~ 650 DEG C of roasting temperatures 5 ~ 8 hours, i.e. obtained sheet Al-SBA-15 mesoporous molecular sieve catalyst;
The Si/Al mol ratio of prepared sheet Al-SBA-15 mesoporous molecular sieve catalyst is 10 ~ 40: 1;
The orifice throat length scope 300 ~ 500nm of described sheet Al-SBA-15 mesoporous molecular sieve catalyst.
2. method according to claim 1, is characterized in that: in pure formaldehyde, and the mass ratio of added sheet Al-SBA-15 mesoporous molecular sieve catalyst and formaldehyde is 0.2 ~ 0.5: 1.
3. method according to claim 1, is characterized in that: in pure formaldehyde, and the mol ratio of added phenol and formaldehyde is 10 ~ 30: 1.
4. method according to claim 1, is characterized in that: temperature of reaction is 80 ~ 100 DEG C.
5. method according to claim 1, is characterized in that: the reaction times is 60 ~ 90 minutes.
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| CN105566069B (en) * | 2015-12-09 | 2018-04-03 | 湘潭大学 | A kind of catalyst bisphenol synthesis F of phosphotungstic acid modified short-bore road HPW Zr/SBA 15 method |
| CN106582776B (en) * | 2016-11-18 | 2019-08-16 | 湘潭大学 | A kind of Sn-Zr/SBA-15 mesoporous molecular sieve catalyst and the preparation method and application thereof |
| CN109482223B (en) * | 2017-09-13 | 2021-12-17 | 国家能源投资集团有限责任公司 | Coal ash-based denitration catalyst, preparation method thereof and denitration method |
| CN109880529B (en) * | 2017-12-06 | 2021-12-07 | 中国石油化工股份有限公司 | Tung oil based dimer acid and synthesis method thereof |
| CN109437223A (en) * | 2018-11-06 | 2019-03-08 | 中国神华能源股份有限公司 | It is a kind of to utilize Al-SBA-15 molecular sieve made from white clay and preparation method thereof |
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| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN101987812A (en) * | 2009-08-02 | 2011-03-23 | 中国石油化工集团公司 | Method for preparing bisphenol F |
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| US7041774B2 (en) * | 2003-09-30 | 2006-05-09 | General Electric Company | Functionalized zeolite compositions and methods for their preparation and use |
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| US5304688A (en) * | 1993-04-13 | 1994-04-19 | The Dow Chemical Company | Process for the preparation of bishydroxy aromatic compounds |
| CN1356265A (en) * | 2001-08-20 | 2002-07-03 | 复旦大学 | Process for preparing shape-controllable big-pore mesoporous molecular sieve |
| CN101987812A (en) * | 2009-08-02 | 2011-03-23 | 中国石油化工集团公司 | Method for preparing bisphenol F |
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