CN103506156A - Heterogeneous acid catalyst, and preparation method and application thereof - Google Patents
Heterogeneous acid catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003377 acid catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000005886 esterification reaction Methods 0.000 claims abstract description 38
- 239000013335 mesoporous material Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 230000032050 esterification Effects 0.000 claims description 35
- 239000002608 ionic liquid Substances 0.000 claims description 30
- 230000004048 modification Effects 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims description 13
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 206010067171 Regurgitation Diseases 0.000 abstract description 2
- 238000006277 sulfonation reaction Methods 0.000 abstract description 2
- 239000011831 acidic ionic liquid Substances 0.000 abstract 1
- 239000002638 heterogeneous catalyst Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 63
- 239000003054 catalyst Substances 0.000 description 27
- 238000001035 drying Methods 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000013019 agitation Methods 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 230000006837 decompression Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a heterogeneous acid catalyst which is formed by linking an acidic ionic liquid on a mesoporous material through chemical bonds. The invention further provides a preparation method of the heterogeneous acid catalyst and the application of the heterogeneous acid catalyst in a catalytic esterification reaction. The heterogeneous acid catalyst is simple in preparation method and stable in structure, can be used as a heterogeneous catalyst to be repeatedly used, and is high in catalytic efficiency. Side reactions such as oxidation reactions, sulfonation reactions and the like are not likely to happen when the heterogeneous acid catalyst is used for synthesize an ester. A catalyzed product is good in quality, no acid regurgitation phenomenon happens, the heterogeneous acid catalyst does not corrode equipment, recycle is easy after a catalytic reaction, and the cost of an esterification reaction is greatly reduced.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly a kind of heterogeneous acid catalyst, also relates to the preparation method of this catalyst, also relates to the application of this catalyst in catalytic esterification.
Background technology
Hydroxycarboxylic acid esters is the broad-spectrum organic compound of a class, in food, medical treatment, daily use chemicals etc. industry, all has been widely used.Present industrial hydroxycarboxylic acid esters mainly adopts catalysis process synthetic, and its catalyst be take the concentrated sulfuric acid as main, and the method exists following shortcoming: 1. the concentrated sulfuric acid has strong oxidizing property, can cause a lot of side reaction generations and the generation of carbonization, makes product color burn; 2. the concentrated sulfuric acid is larger to equipment corrosion; 3. the discharge environmental pollution of a large amount of spent acid is larger.Therefore finding new esterification catalyst becomes one of current study hotspot.
Ionic liquid is with its good stability, stronger catalytic activity and the low-corrosiveness of equipment is become to the study hotspot of catalyst for esterification reaction in recent years.Yet ionic liquid is because it is homogeneous catalyst, more difficult recovery, has therefore limited its application.
Mesoporous material refers to that aperture is the porous material of 2～50nm, and because its loose structure also obtains research and development very widely in application aspect catalyst, but mesoporous material self is acid not enough with respect to esterification.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide a kind of novel heterogeneous acid catalyst.
The second object of the present invention is to provide the preparation method of above-mentioned catalyst.
The 3rd object of the present invention is to provide the application process of above-mentioned catalyst in catalytic esterification.
Technical scheme: a kind of heterogeneous acid catalyst provided by the invention, for acidic ion liquid by chemical bond linkage on mesoporous material.
Wherein, described acidic ion liquid is made by following methods: N-allyl imidazole is reacted with PS or Isosorbide-5-Nitrae-butane sultone, make precursor salt; By adding the acid reaction of equimolar amounts in precursor salt, make ionic liquid again.
Wherein, described mesoporous material is the SBA-15 of modification, and the SBA-15 of described modification is made by following methods: using γ-mercaptopropyl trimethoxysilane as modifier, using tetraethyl orthosilicate as silicon source, using P123 as template, and in aqueous hydrochloric acid solution, reaction makes the SBA-15 of modification.
The present invention also provides the preparation method of above-mentioned heterogeneous acid catalyst, comprises the following steps:
(1) preparation of mesoporous material: using γ-mercaptopropyl trimethoxysilane as modifier, using tetraethyl orthosilicate as silicon source, using P123 as template, reaction makes the SBA-15 of modification in aqueous hydrochloric acid solution;
(2) preparation of ionic liquid: N-allyl imidazole is reacted with PS or Isosorbide-5-Nitrae-butane sultone, make precursor salt; By adding the acid reaction of equimolar amounts in precursor salt, make ionic liquid again;
(3) preparation of heterogeneous acid catalyst: the SBA-15 of modification, ionic liquid and initator are mixed, and reaction makes heterogeneous acid catalyst.
Wherein, in step (1), the mass ratio of γ-mercaptopropyl trimethoxysilane, tetraethyl orthosilicate and P123 is (10-20): (40-70): (20-50): 1000, preferred mass is than for (10-15): (50-60): (30-40): 1000, and more preferably 12.88:54.64:32:1000; The molar concentration of described aqueous hydrochloric acid solution is 1.0-3.0mol/L, preferably 1.5-2.5mol/L, more preferably 1.9mol/L; The molecular weight of described P123 is 5800; Reaction condition is 90-110 ℃ of standing 18-30h after 30-50 ℃ of stirring 16-24h.
Wherein, in the preparation feedback of step (2) precursor salt, the mol ratio of N-allyl imidazole and PS or Isosorbide-5-Nitrae-butane sultone is 1:1; Reaction temperature is 20-30 ℃; Reaction time is 18-30h.
Wherein, in the preparation feedback of step (2) ionic liquid, described acid is hydrochloric acid, sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phosphotungstic acid or silico-tungstic acid, and the mole of described acid is 1:1 with the mole of precursor salt ratio; Reaction temperature is room temperature; Reaction time is 16-24h.
Wherein, in step (3), described initator is azodiisobutyronitrile, oxidation cyclohexanone, dibenzoyl peroxide, TBHP or ABVN; The mol ratio of sulfydryl amount, ionic liquid and initator in the SBA-15 of modification is (1～2): 1:(0.1～0.2); Reaction temperature is 90-110 ℃; Reaction time is 18-30h.
The present invention also provides the application of above-mentioned heterogeneous acid catalyst in catalytic esterification.
Described application, in esterification system, the mol ratio of alcohol and carboxylic acid is (0.1～10): 1; In esterification system, also comprise band aqua, described band aqua is toluene or cyclohexane.
Beneficial effect: heterogeneous acid catalyst preparation method provided by the invention is simple, structure temperature, and can be used as that heterogeneous catalysis repeatedly reuses, catalytic efficiency is high, use the side reactions such as the synthetic ester of this catalyst is difficult for being oxidized, sulfonation, catalyst article quality is good, without the generation of sour regurgitation phenomenon, corrosion-free to equipment, easy to be recycled after catalytic reaction, greatly reduce the cost of esterification.
This catalyst is for to be connected to ionic liquid on mesoporous material by chemical bond-linking, the acidity of existing ionic liquid and the architectural characteristic of mesoporous material, being conducive to reaction carries out, it is again heterogeneous solid catalyst, recyclable repeatedly utilization, thereby can effectively reduce the discharge of spent acid, environmentally friendly.
The specific embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment, process conditions and result thereof be only for the present invention is described, and should also can not limit the present invention described in detail in claims.
Embodiment 1
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having the 1.9M HCl aqueous solution and the 4g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 6.83g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 1.61g) add stirring.Remain on after stirring 20h at 40 ℃ and be warming up to 24h under 100 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template, reclaims solid matter washing several times, and drying under reduced pressure at 60 ℃ is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 3g N-allyl imidazole and 3.39g1,3-propane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 24h at 25 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; The concentrated sulfuric acid of getting 1.4g is dissolved in 30ml water, and the solid stirring at room 20h making before adding removes to anhydrate by decompression and obtains ionic liquid and be designated as IL-H
2sO
4.
The preparation method of heterogeneous acid catalyst, step is as follows: by what make, containing sulfydryl SBA-15 mesoporous material 3.7g(, approximately contain sulfydryl 0.0082mol) and 2.29g ionic liquid IL-H
2sO
4in 50ml pressure bottle, add 20ml acetonitrile and 0.2g AIBN(azodiisobutyronitrile) stirring reaction 24h at 100 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 2
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having the 3.0M HCl aqueous solution and the 2.5g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 5.0g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 1.25g) add stirring.Remain on after stirring 20h at 40 ℃ and be warming up to 24h under 100 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template, reclaims solid matter washing several times, and drying under reduced pressure at 60 ℃ is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 3g N-allyl imidazole and 3.39g1,3-propane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 30h at 20 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; The dry solid obtaining is got to 1g and is taken at the phosphotungstic acid 4.33g(crystallization water yield of drying at 110 ℃ and by TG/DTA, measure), be dissolved in stirring at room 20h in 30ml water, by decompression, remove to anhydrate and obtain ionic liquid and be designated as IL-H
3pW
12o
40.
The preparation method of heterogeneous acid catalyst, step is as follows: by what make, containing sulfydryl SBA-15 mesoporous material 3.7g(, approximately contain sulfydryl 0.0082mol) and 10.05g ionic liquid IL-H
3pW
12o
40in 50ml pressure bottle, add 20ml acetonitrile and 0.2g AIBN(azodiisobutyronitrile) stirring reaction 24h at 100 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 3
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having 1.5M HCl solution and the 6.25g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 8.75g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 2.5g) add stirring.Remain on after stirring 24h at 30 ℃ and be warming up to 30h under 90 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template, reclaims solid matter washing several times, and drying under reduced pressure at 60 ℃ is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 3g N-allyl imidazole and 3.39g1,3-propane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 18h at 30 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; The dry solid obtaining is got to 1g and is taken at the silico-tungstic acid 3.285g(crystallization water yield of drying at 110 ℃ and by TG/DTA, measure), be dissolved in stirring at room 20h in 30ml water, by decompression, remove to anhydrate and obtain ionic liquid and be designated as IL-H
4(SiW
3o
10)
4.
The preparation method of heterogeneous acid catalyst, step is as follows: by what make, containing sulfydryl SBA-15 mesoporous material 3.7g(, approximately contain sulfydryl 0.0082mol) and 8.08g ionic liquid IL-H
4(SiW
3o
10)
4in 50ml pressure bottle, add 20ml acetonitrile and 0.2g AIBN(azodiisobutyronitrile) stirring reaction 30h at 90 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 4
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having 2.5M HCl solution and the 3.75g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 6.25g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 1.875g) add stirring.Remain on after stirring 16h at 50 ℃ and be warming up to 18h under 110 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template, reclaims solid matter washing several times, and drying under reduced pressure at 60 ℃ is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 3g N-allyl imidazole and 3.39g1,3-propane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 18h at 30 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; The dry solid obtaining is got to 1g and got p-methyl benzenesulfonic acid 0.75g, be dissolved in stirring at room 20h in 30ml water, by decompression, remove to anhydrate and obtain ionic liquid and be designated as IL-TsOH.
The preparation method of heterogeneous acid catalyst, step is as follows: by make containing sulfydryl SBA-15 mesoporous material 3.7g(approximately containing sulfydryl 0.0082mol) with 3.3g ionic liquid IL-TsOH as in 50ml pressure bottle, add 20ml acetonitrile and 0.2g AIBN(azodiisobutyronitrile) stirring reaction 18h at 110 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 5
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having 1.0M HCl solution and the 5.0g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 7.5g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 1.5g) add stirring.Remain on after stirring 20h at 40 ℃ and be warming up to 24h under 100 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template.Reclaim solid matter washing several times, drying under reduced pressure at 60 ℃, is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 3g N-allyl imidazole and 3.39g1,3-propane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 18h at 30 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; The dry solid obtaining is got to 1g and got phosphoric acid 0.14g, be dissolved in stirring at room 20h in 30ml water, by decompression, remove to anhydrate and obtain ionic liquid and be designated as IL-H
3pO
4.
The preparation method of heterogeneous acid catalyst, step is as follows: by what make, containing sulfydryl SBA-15 mesoporous material 3.7g(, approximately contain sulfydryl 0.0082mol) and 0.27g ionic liquid IL-H
3pO
4in 50ml pressure bottle, add 20ml acetonitrile and 0.2g AIBN(azodiisobutyronitrile) stirring reaction 30h at 90 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 6
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having the 1.9M HCl aqueous solution and the 4g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 6.83g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 1.61g) add stirring.Remain on after stirring 20h at 40 ℃ and be warming up to 24h under 100 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template, reclaims solid matter washing several times, and drying under reduced pressure at 60 ℃ is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 20mmol N-allyl imidazole and 20mmol1,4-butane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 24h at 25 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; By the sulfuric acid stirring at room 20h of the solid making before and equimolar amounts, by decompression, remove to anhydrate and obtain ionic liquid and be designated as IL-H
2sO
4.
The preparation method of heterogeneous acid catalyst, step is as follows: get containing sulfydryl SBA-15 mesoporous material (containing sulfydryl 10mmol) and 10mmol ionic liquid IL-H
2sO
4in 50ml pressure bottle, add 20ml acetonitrile and 0.2mmol oxidation cyclohexanone stirring reaction 24h at 100 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 7
The preparation of the SBA-15 of mesoporous material modification, step is as follows: toward having the 1.9M HCl aqueous solution and the 4g P123(M=5800 that adds 125g in the 250mL there-necked flask of magnetic agitation, thermometer), stirring and dissolving at 40 ℃, adds the TEOS(tetraethyl orthosilicate of 6.83g) after hydrolysis 45min by MPTMS(γ-mercaptopropyl trimethoxysilane of 1.61g) add stirring.Remain on after stirring 20h at 40 ℃ and be warming up to 24h under 100 ℃ of static conditions, reclaim solid product.The 20h that refluxes in 500ml absolute ethyl alcohol removes template, reclaims solid matter washing several times, and drying under reduced pressure at 60 ℃ is the SBA-15 of modification.
The preparation of acidic ion liquid, step is as follows: get 20mmol N-allyl imidazole and 20mmol1,4-butane sultone, in 100ml there-necked flask, adds 30ml acetonitrile to stir 24h at 25 ℃, filtration is by acetonitrile washing several for the solid product obtaining, drying under reduced pressure at 60 ℃; By the sulfuric acid stirring at room 20h of the solid making before and equimolar amounts, by decompression, remove to anhydrate and obtain ionic liquid and be designated as IL-H
2sO
4.
The preparation method of heterogeneous acid catalyst, step is as follows: get containing sulfydryl SBA-15 mesoporous material (containing sulfydryl 10mmol) and 5mmol ionic liquid IL-H
2sO
4in 50ml pressure bottle, add 20ml acetonitrile and 0.1mmol dibenzoyl peroxide stirring reaction 24h at 100 ℃.By the product obtaining methanol wash several times, 60 ℃ of drying under reduced pressure, obtain heterogeneous acid catalyst.
Embodiment 8
Substantially the same manner as Example 7, difference is only: adopt TBHP to replace dibenzoyl peroxide.Embodiment 9
Substantially the same manner as Example 7, difference is only: adopt azo two cyanogen in different heptan to replace dibenzoyl peroxide.Embodiment 10
The application of heterogeneous acid catalyst in catalytic esterification, the heterogeneous acid catalyst that embodiment 1 to 5 is obtained drops into reaction in the following manner:
A) alcohol is placed in reactor;
B) heterogeneous acid catalyst is placed in reactor, and it is even to make it dispersed with stirring;
C) reaction carboxylic acid used is added in reactor according to the mol ratio of calculating;
D) under certain temperature and pressure condition, reaction is carried out, refrigerated separation, obtains product ester after completion of the reaction.
Particularly:
In having the 250mL there-necked flask of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add 10g
(47.6mmol) monohydrate potassium, 17.641g(238mmol) n-butanol (acid alcohol is than 1:5), add 1g heterogeneous acid catalyst of the present invention simultaneously, the water that heating return stirring generates reaction separates from water knockout drum, every 1h, survey an acid number, the mensuration of acid number is auspicious in GB/T1668-2008, and reaction 4h calculates esterification yield, and esterification yield computing formula is
The esterification yield of table 1 heterogeneous acid catalyst catalytic esterification of the present invention
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Catalyst 5 |
| Esterification yield | 96.9% | 97.1% | 95.6% | 92.0% | 97.7% |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Catalyst 10 |
| Esterification yield | 95.7% | 95.1% | 96.1% | 94.9% | 96.5% |
Having electromagnetic agitation, thermometer, reflux condensing tube, adds 10g(49.5mmol in the 250mL there-necked flask of water knockout drum) decanedioic acid, 25.74g(198mmol) n-octyl alcohol (acid alcohol is than 1:4), adds 10ml toluene, fills it up with toluene in water knockout drum.In simultaneous reactions bottle, add 1g heterogeneous acid catalyst of the present invention, heat return stirring the water of reaction generation is separated from water knockout drum, every 1h, survey an acid number, after reaction 6h, measure esterification yield, detection is the same with computational methods, the results are shown in Table 2.
The esterification yield of table 2 heterogeneous acid catalyst catalytic esterification of the present invention
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Catalyst 5 |
| Esterification yield | 97.3% | 98.1% | 96.7% | 95.0% | 98.4% |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Catalyst 10 |
| Esterification yield | 98.0% | 96.5% | 96.1% | 97.1% | 94.9% |
In having the 250mL there-necked flask of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add 50mmol monohydrate potassium, 500mmol n-butanol (acid alcohol is than 1:10), add 1g heterogeneous acid catalyst of the present invention simultaneously, the water that heating return stirring generates reaction separates from water knockout drum, every 1h, survey an acid number, the mensuration of acid number is auspicious in GB/T1668-2008, and reaction 4h calculates esterification yield, and esterification yield computing formula is
* 100%, the results are shown in Table 3.
The esterification yield of table 3 heterogeneous acid catalyst catalytic esterification of the present invention
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Catalyst 5 |
| Esterification yield | 99.9% | 100% | 99.8% | 99.7% | 100% |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Catalyst 10 |
| Esterification yield | 99.8% | 99.7% | 100% | 99.8% | 99.7% |
In having the 250mL there-necked flask of electromagnetic agitation, thermometer, reflux condensing tube, water knockout drum, add 50mmol monohydrate potassium, 5mmol n-butanol (acid alcohol is than 10:1), add 1g heterogeneous acid catalyst of the present invention simultaneously, the water that heating return stirring generates reaction separates from water knockout drum, every 1h, survey an acid number, the mensuration of acid number is auspicious in GB/T1668-2008, and reaction 4h calculates esterification yield
Esterification yield computing formula is
The esterification yield of table 4 heterogeneous acid catalyst catalytic esterification of the present invention
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Catalyst 5 |
| Esterification yield | 10.0% | 9.9% | 9.9% | 92.0% | 9.9% |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Catalyst 10 |
| Esterification yield | 9.9% | 9.9% | 9.9% | 9.9% | 9.9% |
Claims (10)
1. a heterogeneous acid catalyst, is characterized in that: for acidic ion liquid by chemical bond linkage on mesoporous material.
2. a kind of heterogeneous acid catalyst according to claim 1, is characterized in that: described acidic ion liquid is made by following methods: N-allyl imidazole is reacted with PS or Isosorbide-5-Nitrae-butane sultone, make precursor salt; By adding the acid reaction of equimolar amounts in precursor salt, make ionic liquid again.
3. a kind of heterogeneous acid catalyst according to claim 1, it is characterized in that: the SBA-15 that described mesoporous material is modification, the SBA-15 of described modification is made by following methods: using γ-mercaptopropyl trimethoxysilane as modifier, using tetraethyl orthosilicate as silicon source, using P123 as template, and in aqueous hydrochloric acid solution, reaction makes the SBA-15 of modification.
4. a preparation method for a kind of heterogeneous acid catalyst claimed in claim 1, is characterized in that: comprise the following steps:
(1) preparation of mesoporous material: using γ-mercaptopropyl trimethoxysilane as modifier, using tetraethyl orthosilicate as silicon source, using P123 as template, reaction makes the SBA-15 of modification in aqueous hydrochloric acid solution;
(2) preparation of ionic liquid: N-allyl imidazole is reacted with PS or Isosorbide-5-Nitrae-butane sultone, make precursor salt; By adding the acid reaction of equimolar amounts in precursor salt, make ionic liquid again;
(3) preparation of heterogeneous acid catalyst: the SBA-15 of modification, ionic liquid and initator are mixed, and reaction makes heterogeneous acid catalyst.
5. the preparation method of a kind of heterogeneous acid catalyst according to claim 4, it is characterized in that: in step (1), the mass ratio of γ-mercaptopropyl trimethoxysilane, tetraethyl orthosilicate, P123 and aqueous hydrochloric acid solution is (10-20): (40-70): (20-50): 1000; The molar concentration of described aqueous hydrochloric acid solution is 1.0-3.0mol/L; Reaction condition is 90-110 ℃ of standing 18-30h after 30-50 ℃ of stirring 16-24h.
6. the preparation method of a kind of heterogeneous acid catalyst according to claim 4, is characterized in that: in the preparation feedback of step (2) precursor salt, the mol ratio of N-allyl imidazole and PS or Isosorbide-5-Nitrae-butane sultone is 1:1; Reaction temperature is 20-30 ℃; Reaction time is 18-30h.
7. the preparation method of a kind of heterogeneous acid catalyst according to claim 4, it is characterized in that: in the preparation feedback of step (2) ionic liquid, described acid is hydrochloric acid, sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phosphotungstic acid or silico-tungstic acid, and in the mole of described acid and step (2), the mole ratio of precursor salt is 1:1; Reaction temperature is room temperature; Reaction time is 16-24h.
8. the preparation method of a kind of heterogeneous acid catalyst according to claim 4, it is characterized in that: in step (3), described initator is azodiisobutyronitrile, oxidation cyclohexanone, dibenzoyl peroxide, TBHP or ABVN; The mol ratio of sulfydryl amount, ionic liquid and initator in the SBA-15 of modification is (1～2): 1:(0.1～0.2); Reaction temperature is 90-110 ℃; Reaction time is 18-30h.
9. the application of heterogeneous acid catalyst claimed in claim 1 in catalytic esterification.
10. application as claimed in claim 9, is characterized in that: in esterification system, the mol ratio of alcohol and carboxylic acid is (0.1～10): 1; In esterification system, also comprise band aqua, described band aqua is toluene or cyclohexane.
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