CN106622350B - The method that transition metal modified Si-Al molecular sieve and its catalytic esterification prepares ester - Google Patents
The method that transition metal modified Si-Al molecular sieve and its catalytic esterification prepares ester Download PDFInfo
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- 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
- B01J29/42—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 iron group metals, noble metals or copper
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- 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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- 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
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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Abstract
The invention discloses a kind of method that transition metal modified Si-Al molecular sieve and its catalytic esterification prepare ester, the molecular sieve then with the method for wet impregnation, is modified and is obtained to Si-Al molecular sieve using transition metal by hydrothermal synthesis method synthesizing Si-Al molecular sieve；Using the molecular sieve as catalyst, catalyst, water entrainer, alcohol compound, the carboxylic acid compound of reacting dose is taken to be placed in the back flow reaction device with water segregator, mixed；The temperature of reaction system is controlled under stiring at 40~120 DEG C and 1~12h of sustained response to get.Molecular sieve of the present invention as catalyst in the esterification reaction, with the excellent reactivity worth such as reaction-ure conversion-age height and target product selectivity height, improve the conversion ratio of raw material and the selectivity of target product ester, at a lower temperature, carboxylic acid high conversion rate is up to 96.5%, also greater than 99%, catalytic effect significantly improves ester selectivity.
Description
Technical field
The present invention relates to solid catalyst preparation and applied technical field, specifically a kind of transition metal modified sial point
The method that son sieve and its catalytic esterification prepare ester.
Background technique
Ester is a kind of important Organic Ingredients, and it is fragrant to be widely used in solvent, plasticizer, resin, coating, essence
Material, cosmetics, medicine, surfactant and reaction intermediate etc., and esterification is prepare Ester important
Approach.Traditional esterification is to use sulfuric acid for catalyst using corresponding carboxylic acid and alcohol as raw material, and the method catalyst price is low
Honest and clean, catalytic activity is high, and production cost is low, but there are side reactions more, aftertreatment technology complexity, equipment seriously corroded, spent acid are discharged
The defects of polluting environment.In recent years, it is made great progress with the esterification process and technique of the catalysis such as solid acid, ionic liquid,
Increase substantially esterification yied, the quality of esterification products is also obviously improved.
The Chinese invention patent that application publication number is CN1323655 is disclosed is with ferric sulfate, zirconyl nitrate, sodium metasilicate etc.
A kind of SO is made in raw material4 2-/Fe2O3-ZrO2-SiO2Solid acid is simultaneously catalyzed acetic acid/esterified by butyl alcohol reaction, butyl acetate yield and choosing
Selecting property can respectively reach 93.3% and 96%.Application publication number is the Chinese invention patent of CN101703940 with organic titanium esters, organic
A kind of SO is made by hydro-thermal method for raw material in estersil etc.4 2-/TiO2-SiO2Novel solid acid, in a reflux unit be catalyzed acetic acid/
N-butanol esterification, n-butyl acetate yield and selectivity can respectively reach 98.9% and 99.5%.Application publication number is
The Chinese invention patent of CN101049573 discloses a kind of conjunction of the Bronsted of alkyl pyrrolidone group containing N- acid ion liquid
The catalytic performance in esterification is carried out at method and its in aliphatic or aromatic acid and straight chain alcohol or branched-chain alcoho, in the reactant
In system, ionic-liquid catalyst has 90~100% high conversion and 100% selectivity.Application publication number is CN1156717
Chinese invention patent disclose using acetic acid and n-butanol as raw material, and add and a kind of can generate azeotropic mixture with raw material and product
Azeotropic additive, at a kind of Ti being carried on molecular sieve, Zr, Zn, the mixed oxide solid acid effect of Al, gas-solid is opposite
N-butyl acetate should be produced, reactant, which is condensed, in reaction process continuously separates water phase, and unreacted raw material returns to circulation and makes
With n-butyl acetate yield can reach 98%.Microporous and Mesoporous Materials (2016), doi:
Zhu etc. is reported in H in 10.1016/j.micromeso.2016.01.0382SO4It is catalyzed in the esterification of carboxylic acid and alcohol and adds
Enter mordenite membrane and the water that reaction generates continuously is removed by pervaporation, the conversion ratio of alcohol can be greatly improved, in optimization
Under experiment condition, value is up to 98%.
From document disclosed above it is found that solid acid or ionic liquid-catalyzed esterification catalytic activity with higher and steady
It is qualitative, but catalyst preparation is complicated in reported catalyst system, and higher cost, reaction process needs a large amount of organic solvents, after
Handle cumbersome, and catalyst activity component is easy to run off, and regeneration is difficult, easily colours product.Therefore, it researches and develops novel, efficient, green
The catalyst of color has extremely important realistic meaning to the industrial development of state's lactone is accelerated.
Summary of the invention
The purpose of the present invention is to provide a kind of high conversion, highly selective transition metal modified Si-Al molecular sieve and
The method that its catalytic esterification prepares ester.
To achieve the above object, the invention provides the following technical scheme:
Transition metal modified Si-Al molecular sieve first uses hydrothermal synthesis method synthesizing Si-Al molecular sieve, then the side with wet impregnation
Method is modified Si-Al molecular sieve using transition metal and obtains, specific preparation step are as follows:
(1) hydrothermal synthesis: using TPAOH as template, precursor liquid is by TEOS, Al (NO3)3·9H2O, NaOH and TPAOH
Composition.With feed molar proportion for 1 SiO2: 0.0026~0.033 Al2O3: 0.25 TPAOH:0.05 Na2O:80H2O is 180
Hydrothermal synthesis Si-Al molecular sieve under the conditions of DEG C, gained molecular sieve 1.5M NH4NO3Solion exchanges twice, washes, dry,
Roast to obtain Si-Al molecular sieve original powder.
(2) wet impregnation is modified: a certain amount of citric acid is dissolved in deionized water, according to citric acid and transition metal from
The molar ratio of son is 1.5:1, and the soluble salt solutions containing transition metal ions are added thereto, is evenly stirred until completely molten
Xie Hou, the ammonium hydroxide that brand-new is added dropwise adjust pH=8, Si-Al molecular sieve original powder are then added, magnetic agitation 4h then will be molten
Liquid is placed in 80 DEG C of water-bath and at the uniform velocity stirs 10-15h, until there is the wet gel of sticky shape, is set after vacuum drying
In Muffle furnace after 300 DEG C of pre-burnings, then 600 DEG C of roasting 2h, prepare transition metal modified Si-Al molecular sieve.
As a further solution of the present invention: the transition metal is one in V, Mn, Fe, Co, Cu, Zr, Mo and Ce
Kind or two or more mixtures.
As a further solution of the present invention: the Si-Al molecular sieve is the HZSM-5 molecular sieve of MFI type, described
The silica alumina ratio of HZSM-5 molecular sieve is (30~380): 1.
The method that the transition metal modified Si-Al molecular sieve catalytic esterification prepares ester, with transition metal modified silicon
Aluminum molecular screen is catalyst, specific steps are as follows: negates the catalyst that should be measured, water entrainer, alcohol compound, carboxylic acid compound and sets
In the back flow reaction device with water segregator, mixing；The temperature of reaction system is controlled under stiring at 40~120 DEG C and is continued
React 1~12h to get.
As a further solution of the present invention: the carboxylic acid compound is formic acid, acetic acid, propionic acid, benzoic acid, 2- pyrrole
Pyridine formic acid, p-methylbenzoic acid, ethanedioic acid, malonic acid, succinic acid, cinnamic acid, benzoic acid, terephthalic acid (TPA), phthalic acid,
The mixture of one or more of oxalic acid, oleic acid, parachlorobenzoic-acid, 4- methoxyphenylacetic acid, salicylic acid, acrylic acid；
The alcohol compound is methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, n-hexyl alcohol, benzyl alcohol, ethylene glycol, the tert-butyl alcohol, 2- methoxy
The mixture of one or more of base benzyl alcohol, glycerol, octanol；The water entrainer be benzene, toluene, dichloroethanes,
The mixture of one or more of dimethylbenzene and carbon tetrachloride.
As a further solution of the present invention: the propyl alcohol is isopropanol；The butanol is n-butanol；Described is pungent
Alcohol is n-octyl alcohol；The amylalcohol is isoamyl alcohol.
As a further solution of the present invention: the volume mass ratio of the water entrainer and carboxylic acid compound is
The mass ratio of (0.01~1.34) ml:1 g, the catalyst and carboxylic acid compound is (0.002~0.2): 1, it is described
Alcohol compound and carboxylic acid compound molar ratio be (0.5~3.0): 1.
As a further solution of the present invention: the mass ratio of the water entrainer and carboxylic acid compound be (0.01~
0.2) mass ratio of ml:1g, the catalyst and carboxylic acid compound is (0.01~0.2): 1, the alcohols chemical combination
The molar ratio of object and carboxylic acid compound is (0.8~3.0): 1.
As a further solution of the present invention: the temperature of the reaction system at 60~120 DEG C and sustained response 1~
12h。
Application of the transition metal modified Si-Al molecular sieve in terms of catalytic esterification prepares ester.
Compared with prior art, the beneficial effects of the present invention are:
In transition metal modified Si-Al molecular sieve catalyst preparation process provided by the present invention, it need to only pass through simple water
Thermal synthesis, then using wet impregnation method it is carried out it is transition metal modified can be prepared by catalyst, process preparation is simple, reaction item
Part is mild, environmentally protective, corrosion-free to equipment, and catalyst thermal stability is high, and there is no inactivation (active components in catalysis reaction
It is lost) phenomenon, post catalyst reaction separation is simple, just Ke Xunhuanliyong after washing and drying, long service life.
Transition metal modified Si-Al molecular sieve provided by the invention in the esterification reaction, has reactant as catalyst
The excellent reactivity worth such as high conversion rate and target product selectivity height improves the conversion ratio and target product ester of raw material
Selectivity, at a lower temperature, carboxylic acid high conversion rate is up to 96.5%, and also greater than 99%, catalytic effect significantly improves ester selectivity.It should
Method solves in esterification traditional processing technology the deficiencies such as environmental pollution is serious, yield is low, has good industrial application
Prospect.
Detailed description of the invention
Fig. 1 is the XRD diagram of the modified HZSM-5 molecular sieve catalyst of iron used by embodiment 1；
Fig. 2 is the SEM figure of the modified HZSM-5 molecular sieve catalyst of iron used by embodiment 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The structural analysis of reaction product is using the RTx-5MS type for preparing 30m long in the following embodiment and comparative examples of the present invention
The Shimadzu GC/MS of capillary chromatographic column (30m × 0.25mm × 0.25 μm) and hydrogen flame ionization detector (FID)
(6890N/5973N) gas phase-mass spectrograph combined instrument.The analysis of target product selectivity and yield is using the SE-30 for configuring 30m long
The good fortune of type capillary chromatographic column (30m × 0.32mm × 0.33 μm) and hydrogen flame ionization detector (FID) founds GC9790 type gas phase
Chromatograph.
Embodiment 1
In the embodiment of the present invention, first using TPAOH as template, precursor liquid is by TEOS, Al (NO3)3·9H2O, NaOH,
It is formed with TPAOH.With feed molar proportion for 1 SiO2: 0.0033 Al2O3: 0.25 TPAOH:0.05 Na2O:80 H2O exists
Hydrothermal synthesis Si-Al molecular sieve under the conditions of 180 DEG C.Gained molecular sieve 1.5M NH4NO3Solion exchanges twice, washes, and does
It is dry, roast Si/Al=150 molecular screen primary powder.Then a certain amount of citric acid is dissolved in deionized water again, according to lemon
The molar ratio of lemon acid and transition metal ions is 1.5:1, is added contains Fe (NO thereto3)3Solution is evenly stirred until completely molten
Xie Hou, the ammonium hydroxide that brand-new is added dropwise adjust pH=8, Si-Al molecular sieve original powder are then added, magnetic agitation 4h then will be molten
Liquid is placed in 80 DEG C of water-bath and at the uniform velocity stirs 10~15h, until there is the wet gel of sticky shape, is set after vacuum drying
In Muffle furnace after 300 DEG C of pre-burnings, then 600 DEG C of roasting 2h, prepare the modified Si-Al molecular sieve of Fe.
Please refer to Fig. 1 and Fig. 2: Fig. 1 is the XRD spectra of 1 products therefrom of embodiment, it can be seen that product is with HZSM-5's
Characteristic diffraction peak, and crystallinity with higher；Fig. 2 is the SEM photograph of 1 products therefrom of embodiment, it can be seen that sample is in
Existing uniform sheet shape pattern.
Modified HZSM-5(silica alumina ratio Si/Al=150 of the iron) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: modified HZSM-5(silica alumina ratio Si/Al=150 of iron are sequentially added into reaction unit) molecular sieve 0.2g, acetic acid
7.50g(0.125mol), n-butanol 18.5g(0.25mol), water liquid benzene 10ml, after reacting 2h at 115 DEG C under stiring,
Gas chromatograph-mass spectrometer (GC-MS) analysis as the result is shown product be target product n-butyl acetate, gas chromatographic analysis the result shows that
The conversion ratio of toluene is 93.5%, and the selectivity and yield of n-butyl acetate are respectively 100% and 93.5%.
Embodiment 2
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0067 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are ammonium metavanadate, and other operations are analogous to embodiment 1, obtain the modified HZSM- of vanadium
5(silica alumina ratio Si/Al=75) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=75 of the vanadium) the molecular sieve catalytic esterification method for preparing ester is specific to walk
Suddenly molecular sieve 0.05g, formic acid 9.20g are as follows: modified HZSM-5(silica alumina ratio Si/Al=75 of vanadium are sequentially added into reaction unit)
(0.20mol), isopropanol 9.61g(0.16mol), water entrainer carbon tetrachloride 2ml, after reacting 6h at 80 DEG C under stiring, gas
Product is target product isopropyl formate to the analysis of phase chromatograph-mas spectrometer as the result is shown, and gas chromatographic analysis is the result shows that first
The conversion ratio of acid is 78.5%, and the selectivity and yield of isopropyl formate are respectively 99.0% and 77.7%.
Embodiment 3
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.017 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are cobalt nitrate, and other operations are analogous to embodiment 1, obtain cobalt improved HZSM-5
(silica alumina ratio Si/Al=30) molecular sieve.
Cobalt improved HZSM-5(silica alumina ratio Si/Al=30) the molecular sieve catalytic esterification method for preparing ester is specific to walk
Suddenly molecular sieve 0.05g are as follows: cobalt improved HZSM-5(silica alumina ratio Si/Al=30 are sequentially added into reaction unit), benzoic acid
24.40g(0.20mol), ethyl alcohol 27.64g(0.60mol), water entrainer toluene 4ml, after reacting 6h at 75 DEG C under stiring, gas
Product is target product ethyl benzoate to the analysis of phase chromatograph-mas spectrometer as the result is shown, and gas chromatographic analysis is the result shows that benzene
The conversion ratio of formic acid is 92.8%, and the selectivity and yield of ethyl benzoate are respectively 99.0% and 91.9%.
Embodiment 4
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0036 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are zirconium chloride, and other operations are analogous to embodiment 1, obtain the HZSM-5 of modified zirconia
(silica alumina ratio Si/Al=140) molecular sieve.
HZSM-5(silica alumina ratio Si/Al=140 of the modified zirconia) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: HZSM-5(silica alumina ratio Si/Al=140 of modified zirconia are sequentially added into reaction unit) molecular sieve 0.10g, propionic acid
14.80g(0.20mol), n-butanol 16.31g(0.22mol), water entrainer toluene 4ml, after reacting 6h at 75 DEG C under stiring,
Gas chromatograph-mass spectrometer (GC-MS) analysis as the result is shown product be target product n-butyl propionate, gas chromatographic analysis the result shows that
The conversion ratio of benzoic acid is 89.5%, and the selectivity and yield of n-butyl propionate are respectively 98.0% and 87.8%.
Embodiment 5
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0013 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are zirconium chloride, and other operations are analogous to embodiment 1, obtain the HZSM-5 of modified zirconia
(silica alumina ratio Si/Al=380) molecular sieve.
HZSM-5(silica alumina ratio Si/Al=380 of the modified zirconia) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: HZSM-5(silica alumina ratio Si/Al=380 of modified zirconia are sequentially added into reaction unit) molecular sieve 0.05g, cinnamic acid
14.82g(0.10mol), isobutanol 8.89g(0.12mol), water entrainer dimethylbenzene 5ml reacts 6h at 108 DEG C under stiring
Afterwards, product is target product isobutyl cinnamate, gas chromatographic analysis result as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The conversion ratio for showing cinnamic acid is 95.5%, and the selectivity and yield of isobutyl cinnamate are respectively 99.0% and 94.5%.
Embodiment 6
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0033 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are ammonium molybdate, and other operations are analogous to embodiment 1, obtain the modified HZSM-5 of molybdenum
(silica alumina ratio Si/Al=150) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=150 of the molybdenum) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: modified HZSM-5(silica alumina ratio Si/Al=150 of molybdenum are sequentially added into reaction unit) molecular sieve 0.20g, 2- pyridine
Formic acid 12.31g(0.10mol), methanol 9.61g(0.30mol), water entrainer dichloroethanes 10ml is anti-at 65 DEG C under stiring
After answering 2h, product is target product 2- pyridine carboxylic acid methyl esters, gas-chromatography point as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
Analysis is the result shows that the conversion ratio of 2- pyridine carboxylic acid is the selectivity of 90.7%, 2- pyridine carboxylic acid methyl esters and yield is respectively 98.0% He
88.9%。
Embodiment 7
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0033 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are cerous chloride, and other operations are analogous to embodiment 1, obtain cerium modified HZSM-
5(silica alumina ratio Si/Al=150) molecular sieve.
Cerium modified HZSM-5(silica alumina ratio Si/Al=150) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: cerium modified HZSM-5(silica alumina ratio Si/Al=150 are sequentially added into reaction unit) molecular sieve 0.20g, to methyl
Benzoic acid 13.61g(0.10mol), ethyl alcohol 9.20g(0.20mol), water entrainer toluene 10ml reacts at 75 DEG C under stiring
After 3h, product is target product ethyl p-methyl benzoate, gas-chromatography point as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The result shows that the conversion ratio of p-methylbenzoic acid is 94.7%, the selectivity and yield of ethyl p-methyl benzoate are respectively for analysis
98.5% and 93.3%.
Embodiment 8
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0033 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are cerous chloride, and other operations are analogous to embodiment 1, obtain cerium modified HZSM-
5(silica alumina ratio Si/Al=150) molecular sieve.
Cerium modified HZSM-5(silica alumina ratio Si/Al=150) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: cerium modified HZSM-5(silica alumina ratio Si/Al=150 are sequentially added into reaction unit) molecular sieve 0.20g, oxalic acid
18.01g(0.20mol), methanol 9.61g(0.30mol), water entrainer dichloroethanes 10ml reacts 2h at 60 DEG C under stiring
Afterwards, product is target product dimethyl oxalate, gas chromatographic analysis result table as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The bright conversion ratio to oxalic acid is 96.5%, and the selectivity and yield of dimethyl oxalate are respectively 99.2% and 95.7%.
Embodiment 9
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.017 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are cobalt nitrate, and other operations are analogous to embodiment 1, obtain cobalt improved HZSM-5
(silica alumina ratio Si/Al=30) molecular sieve.
Cobalt improved HZSM-5(silica alumina ratio Si/Al=30) the molecular sieve catalytic esterification method for preparing ester is specific to walk
Suddenly molecular sieve 0.30g, oleic acid 28.25g are as follows: cobalt improved HZSM-5(silica alumina ratio Si/Al=30 are sequentially added into reaction unit)
(0.10mol), glycerol 18.42g(0.20mol), water entrainer carbon tetrachloride 10ml, after reacting 6h at 120 DEG C under stiring, gas
Product is target product methyl stearate to the analysis of phase chromatograph-mas spectrometer as the result is shown, and gas chromatographic analysis is the result shows that oil
The conversion ratio of acid is 91.7%, and the selectivity and yield of methyl stearate are respectively 98.5% and 90.3%.
Embodiment 10
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0033 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are manganese acetylacetonate, and other operations are analogous to embodiment 1, obtain cobalt improved
HZSM-5(silica alumina ratio Si/Al=150) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=150 of the manganese) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: modified HZSM-5(silica alumina ratio Si/Al=150 of manganese are sequentially added into reaction unit) molecular sieve 0.20g, to chlorobenzene
Formic acid 15.66g(0.10mol), n-butanol 14.82g(0.20mol), water entrainer dimethylbenzene 10ml, under stiring at 120 DEG C
After reacting 5h, product is target product to chlorobenzoic acid N-butyl, gas-chromatography as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The result shows that the conversion ratio of parachlorobenzoic-acid is 93.3%, selectivity and yield to chlorobenzoic acid N-butyl are respectively 99.0% for analysis
With 89.4%.
Embodiment 11
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0033 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are manganese acetylacetonate, and other operations are analogous to embodiment 1, obtain cobalt improved
HZSM-5(silica alumina ratio Si/Al=150) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=150 of the manganese) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: modified HZSM-5(silica alumina ratio Si/Al=150 of manganese are sequentially added into reaction unit) molecular sieve 0.20g, 4- methoxy
Base phenylacetic acid 15.21g(0.10mol), methanol 9.61g(0.30mol), water liquid benzene 10ml reacts at 120 DEG C under stiring
After 6h, product is target product 4- methoxyphenylacetic acid methyl esters, gas-chromatography as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
Analysis is the result shows that the conversion ratio of 4- methoxyphenylacetic acid is the selectivity and yield point of 93.1%, 4- methoxyphenylacetic acid methyl esters
It Wei 99.0% and 92.2%.
Embodiment 12
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0033 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are zirconium chloride, and other operations are analogous to embodiment 1, obtain cobalt improved HZSM-5
(silica alumina ratio Si/Al=150) molecular sieve.
HZSM-5(silica alumina ratio Si/Al=150 of the modified zirconia) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: HZSM-5(silica alumina ratio Si/Al=150 of modified zirconia are sequentially added into reaction unit) molecular sieve 0.20g, salicylic acid
27.62g(0.20mol), methanol 17.78g(0.24mol), water liquid benzene 10ml, after reacting 3h at 90 DEG C under stiring, gas
Phase chromatograph-mas spectrometer analysis as the result is shown product be target product butyl salicylate, gas chromatographic analysis the result shows that
The salicylic conversion ratio of 4- is 90.7%, and the selectivity and yield of butyl salicylate are respectively 97.4% and 88.3%.
Embodiment 13
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.017 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are cobalt nitrate, and other operations are analogous to embodiment 1, obtain cobalt improved HZSM-5
(silica alumina ratio Si/Al=30) molecular sieve.
Cobalt improved HZSM-5(silica alumina ratio Si/Al=30) the molecular sieve catalytic esterification method for preparing ester is specific to walk
Suddenly molecular sieve 0.10g are as follows: cobalt improved HZSM-5(silica alumina ratio Si/Al=30 are sequentially added into reaction unit), benzoic acid
12.21g(0.10mol), n-octyl alcohol 14.33g(0.11mol), water entrainer dimethylbenzene 10ml reacts 4h at 90 DEG C under stiring
Afterwards, product is target product benzoic acid n-octyl, gas chromatographic analysis result as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The conversion ratio for showing benzoic acid is 88.5%, and the selectivity and yield of benzoic acid n-octyl are respectively 98.2% and 86.7%.
Embodiment 14
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0067 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are ferric nitrate, and other operations are analogous to embodiment 1, obtain the modified HZSM-5 of iron
(silica alumina ratio Si/Al=75) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=75 of the iron) the molecular sieve catalytic esterification method for preparing ester is specific to walk
Suddenly molecular sieve 0.05g, acetic acid 12.00g are as follows: modified HZSM-5(silica alumina ratio Si/Al=75 of iron are sequentially added into reaction unit)
(0.20mol), isoamyl alcohol 8.82g(0.10mol), water liquid benzene 10ml, after reacting 4h at 105 DEG C under stiring, gas phase color
Product is target product isoamyl acetate to the analysis of spectrum-mass spectrometer as the result is shown, and gas chromatographic analysis is the result shows that acetic acid
Conversion ratio is 94.8%, and the selectivity and yield of isoamyl acetate are respectively 99.0% and 93.9%.
Embodiment 15
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0067 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are ferric nitrate, and other operations are analogous to embodiment 1, obtain the modified HZSM-5 of iron
(silica alumina ratio Si/Al=75) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=75 of the iron) the molecular sieve catalytic esterification method for preparing ester is specific to walk
Suddenly molecular sieve 0.10g are as follows: modified HZSM-5(silica alumina ratio Si/Al=75 of iron are sequentially added into reaction unit), malonic acid
10.04g(0.10mol), ethyl alcohol 13.80g(0.30mol), water liquid benzene 10ml, after reacting 3h at 75 DEG C under stiring, gas
Phase chromatograph-mas spectrometer analysis as the result is shown product be target product diethyl malonate, gas chromatographic analysis the result shows that
The conversion ratio of malonic acid is 95.0%, and the selectivity and yield of diethyl malonate are respectively 99.5% and 94.5%.
Embodiment 16
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0067 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are ammonium metavanadate, and other operations are analogous to embodiment 1, obtain the modified HZSM- of iron
5(silica alumina ratio Si/Al=75) molecular sieve.
Modified HZSM-5(silica alumina ratio Si/Al=100 of the vanadium) the molecular sieve catalytic esterification method for preparing ester, specifically
Step are as follows: modified HZSM-5(silica alumina ratio Si/Al=100 of vanadium are sequentially added into reaction unit) molecular sieve 0.05g, acrylic acid
14.41g(0.20mol), methanol 7.69g(0.24mol), water liquid benzene 10ml, after reacting 2h at 65 DEG C under stiring, gas phase
Product is target product methyl acrylate as the result is shown for chromatograph-mas spectrometer analysis, and gas chromatographic analysis is the result shows that propylene
The conversion ratio of acid is 95.6%, and the selectivity and yield of methyl acrylate are respectively 99.0% and 94.6%.
Embodiment 17
It is 1 SiO according to feed molar proportion in the embodiment of the present invention2: 0.0071 Al2O3: 0.25 TPAOH:0.05
Na2O:80 H2O, transition metal solubility solution are ferric nitrate, manganese acetylacetonate mixed liquor, and other operations are analogous to embodiment 1,
Obtain modified HZSM-5(silica alumina ratio Si/Al=70 of ferrimanganic) molecular sieve.
Composite modified HZSM-5(silica alumina ratio Si/Al=70 of the ferrimanganic) the molecular sieve catalytic esterification method for preparing ester,
Specific steps are as follows: composite modified HZSM-5(silica alumina ratio Si/Al=70 of ferrimanganic are sequentially added into reaction unit) molecular sieve
0.20g, acetic acid 12.01g(0.20mol), n-butanol 17.79g(0.24mol), water liquid benzene 10ml, under stiring in 110 DEG C
After lower reaction 3h, product is target product n-butyl acetate, gas-chromatography point as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The result shows that the conversion ratio of toluene is 94.7%, the selectivity and yield of n-butyl acetate are respectively 99.5% and 94.2% for analysis.
Comparative example 1
The side that this comparative example is reported according to Applied Catalysis A:General, 2006,297:182-188
Method prepares HZSM-5(silica alumina ratio Si/Al=12.5), by obtained catalyst HZSM-5 0.20g addition reaction unit, then plus
Enter acetic acid 12.01g(0.20mol), n-butanol 17.78g(0.24mol), water liquid benzene 10ml reacts at 75 DEG C under stiring
After 6h, product is target product n-butyl acetate, gas chromatographic analysis result as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The conversion ratio for showing acetic acid is 36.5%, and the selectivity and yield of methyl acrylate are respectively 99.0% and 36.1%.
Comparative example 2
The method that this comparative example is reported according to Applied Catalysis A:General, 2005,288:25-33
Prepare Al-MCM-41(silica alumina ratio Si/Al=25), reaction unit is added in obtained catalyst Al-MCM-41 0.20g, then
Acetic acid 12.01g(0.20mol is added), n-butanol 14.82g(0.20mol), water liquid benzene 10ml, under stiring at 125 DEG C
After reacting 6h, product is target product n-butyl acetate, gas chromatographic analysis as the result is shown for gas chromatograph-mass spectrometer (GC-MS) analysis
The result shows that the conversion ratio of acetic acid is 65.0%, the selectivity and yield of methyl acrylate are respectively 99.0% and 64.4%.
It can be seen that made from the method for the present invention from above-described embodiment and comparative example through the metal-modified silicoaluminophosphate molecular of transition
Sifter device has unique physico-chemical structure feature, be applied to esterification in, can it is highly selective, be prepared with high yield carboxylate.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (7)
1. a kind of preparation method for the transition metal modified Si-Al molecular sieve for preparing ester for catalytic esterification, which is characterized in that
Hydrothermal synthesis method synthesizing Si-Al molecular sieve is first used, then with the method for wet impregnation, Si-Al molecular sieve is changed using transition metal
Property and obtain, specific preparation step are as follows:
(1) hydrothermal synthesis: using TPAOH as template, precursor liquid is by TEOS, Al (NO3)3·9H2O, NaOH and TPAOH group
At；With feed molar proportion for 1 SiO2: 0.0026~0.033 Al2O3: 0.25 TPAOH:0.05 Na2O:80H2O is at 180 DEG C
Under the conditions of hydrothermal synthesis Si-Al molecular sieve, gained molecular sieve 1.5M NH4NO3Solion exchanges twice, washes, dry, roasting
Burn to obtain Si-Al molecular sieve original powder；
(2) wet impregnation is modified: a certain amount of citric acid being dissolved in deionized water, according to citric acid and transition metal ions
Molar ratio is 1.5:1, and the soluble salt solutions containing transition metal ions are added thereto, are evenly stirred until after being completely dissolved,
The ammonium hydroxide that brand-new is added dropwise adjusts pH=8, Si-Al molecular sieve original powder is then added, then solution is placed in by magnetic agitation 4h
10~15h is at the uniform velocity stirred in 80 DEG C of water-bath, until there is the wet gel of sticky shape, places it in Muffle furnace after vacuum drying
In after 300 DEG C of pre-burnings, then 550 DEG C of roasting 2h prepare transition metal modified Si-Al molecular sieve；
The Si-Al molecular sieve is the HZSM-5 molecular sieve of MFI type, the silica alumina ratio of the HZSM-5 molecular sieve be (30~
380): 1；
The transition metal is one of V, Co, Zr, Mo, Ce.
2. a kind of method that catalytic esterification prepares ester, which is characterized in that using transition metal modified Si-Al molecular sieve as catalyst,
Specific steps are as follows: negate the catalyst that should be measured, water entrainer, alcohol compound, carboxylic acid compound and be placed in returning with water segregator
It flows in reaction unit, mixing；The temperature of reaction system is controlled under stiring at 40~120 DEG C and 1~12 h of sustained response, i.e.,
?；
The transition metal modified Si-Al molecular sieve is by the transition metal described in claim 1 for preparing ester for catalytic esterification
The preparation method of modified Si-Al molecular sieve is made.
3. the method that catalytic esterification according to claim 2 prepares ester, which is characterized in that the carboxylic acid compound is
One of formic acid, propionic acid, benzoic acid, 2- pyridine carboxylic acid, p-methylbenzoic acid, cinnamic acid, oxalic acid, salicylic acid, acrylic acid or
Two or more mixtures；The alcohol compound is one of methanol, ethyl alcohol, propyl alcohol, butanol；The water entrainer
For one of benzene, toluene, dichloroethanes, dimethylbenzene and carbon tetrachloride.
4. the method that catalytic esterification according to claim 3 prepares ester, which is characterized in that the propyl alcohol is isopropanol；
The butanol is n-butanol or isobutanol.
5. the method that catalytic esterification according to claim 2 prepares ester, which is characterized in that the water entrainer and carboxylic acids
The volume mass ratio of compound is (0.01~1.34) ml:1g, the mass ratio of the catalyst and carboxylic acid compound
For (0.002~0.2): 1, the molar ratio of the alcohol compound and carboxylic acid compound is (0.5~3.0): 1.
6. the method that catalytic esterification according to claim 5 prepares ester, which is characterized in that the water entrainer and carboxylic acids
The mass ratio of compound is (0.01~0.2) ml:1g, and the mass ratio of the catalyst and carboxylic acid compound is
(0.01~0.2): 1, the molar ratio of the alcohol compound and carboxylic acid compound is (0.8~3.0): 1.
7. the method that catalytic esterification according to claim 2 prepares ester, which is characterized in that the temperature of the reaction system
At 60~120 DEG C and 1~12h of sustained response.
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