CN107457004B - Spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method - Google Patents
Spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method Download PDFInfo
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- CN107457004B CN107457004B CN201610392157.2A CN201610392157A CN107457004B CN 107457004 B CN107457004 B CN 107457004B CN 201610392157 A CN201610392157 A CN 201610392157A CN 107457004 B CN107457004 B CN 107457004B
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000002253 acid Substances 0.000 title claims abstract description 43
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 title claims abstract description 39
- 239000011148 porous material Substances 0.000 claims abstract description 102
- 238000000034 method Methods 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000002808 molecular sieve Substances 0.000 claims abstract description 38
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000009826 distribution Methods 0.000 claims abstract description 37
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 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 32
- 239000012065 filter cake Substances 0.000 claims description 30
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000005642 Oleic acid Substances 0.000 claims description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 24
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 24
- 229910002027 silica gel Inorganic materials 0.000 claims description 23
- 239000000741 silica gel Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 12
- 235000019353 potassium silicate Nutrition 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 239000007853 buffer solution Substances 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 9
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 9
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- -1 isopropyl ester Chemical class 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000007974 sodium acetate buffer Substances 0.000 description 4
- 101150116295 CAT2 gene Proteins 0.000 description 3
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention relates to catalyst fields, and in particular to it is a kind of spherical shape montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method.Wherein, disclose a kind of spherical montmorillonite mesoporous composite material and preparation method thereof, the spherical montmorillonite mesoporous composite material prepared by this method, loaded catalyst containing the spherical shape montmorillonite mesoporous composite material, the preparation method of the loaded catalyst, the loaded catalyst prepared by this method, the application of the loaded catalyst in the esterification reaction.Wherein, the composite material contains montmorillonite and the meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels.The conversion ratio of reaction raw materials can be significantly improved in acid isopropyl preparation process as loaded catalyst made of carrier using composite material provided by the invention.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of spherical shape montmorillonite mesoporous composite material, the spherical shape montmorillonite
The preparation method of mesoporous composite material, the spherical montmorillonite mesoporous composite material prepared by this method contain the spherical shape montmorillonite
The loaded catalyst of mesoporous composite material, the preparation method of the loaded catalyst, the supported catalyst prepared by this method
Agent, the application of the loaded catalyst in the esterification reaction, and prepare using the loaded catalyst side of acid isopropyl
Method.
Background technique
Acid isopropyl is transparent oily liquid, can be dissolved each other with animal and vegetable oil, and the coefficient of dispersion is big, and spreadability is good, can be
Thin electrolyte film is formed on skin, and there is skin care effect.With the rapid development of chemical industry, the demand to acid isopropyl is continuous
Increase.Under normal circumstances, acid isopropyl is made by esterification under the effect of the catalyst by oleic acid and isopropanol.It passes
System is liquid organic acid for oleic acid and the catalyst of isopropanol esterification, but because the pair that its corrosiveness is big, causes is anti-
Product separates the defects of complicated and liquid waste processing is difficult and its use is caused to be subject to certain restrictions after Ying Duo, reaction.With
Increase of the whole world to Catalytic processes greenization attention degree, solid acid catalysis technique replace liquid acid Catalytic processes gesture must
Row.
In existing loaded catalyst, meso-porous molecular sieve material is as carrier.Meso-porous molecular sieve material has duct
Orderly, the advantages that aperture is adjustable, specific surface area and hole appearance are larger, so that being made using these meso-porous molecular sieve materials as carrier
Loaded catalyst show lot of advantages in preparation process in organic catalytic reaction, for example, catalytic activity is high, secondary anti-
Should less, post-processing it is simple etc., however, big specific surface area and high hole hold so that these meso-porous molecular sieve materials have it is stronger
Water suction, moisture absorption ability, reunite in catalytic reaction process to will lead to these loaded catalysts, and then reduce oleic acid
The conversion ratio of oleic acid in isopropyl ester preparation process.Therefore, a kind of novel acid isopropyl that is used to prepare further is developed
Catalyst becomes problem in the urgent need to address.
Summary of the invention
The purpose of the invention is to overcome making using loaded catalyst made of existing meso-porous molecular sieve material
The lower defect of reaction raw materials conversion ratio during standby acid isopropyl provides a kind of spherical montmorillonite Jie for being suitable as carrier
Hole composite material, the preparation method of the spherical shape montmorillonite mesoporous composite material, the spherical montmorillonite prepared by this method are mesoporous multiple
Condensation material, the loaded catalyst containing the spherical shape montmorillonite mesoporous composite material, the preparation method of the loaded catalyst, by
The loaded catalyst of this method preparation, the application of the loaded catalyst in the esterification reaction, and urged using the support type
The method that agent prepares acid isopropyl.
In order to achieve the above object, the present inventor after research by having found, with three pore size distribution of one-dimensional channels
Montmorillonite is introduced in the meso-porous molecular sieve material of structure, enters montmorillonite in the duct of meso-porous molecular sieve material, and should
The spherical shape for being not susceptible to reunite is made in mesoporous composite material, can retain the high-specific surface area, big of meso-porous molecular sieve material in this way
Kong Rong, large aperture and have the characteristics that three pore size distribution structure of one-dimensional channels, and the reunion of meso-porous molecular sieve material can be reduced, increases
Add its mobility；Simultaneously as binder is introduced in meso-porous molecular sieve material, so that sphere intensity increases, it can as carrier
With repeated multiple times use, so as to substantially reduce use cost.In addition, being urged using support type made of the mesoporous composite material
Agent can significantly improve the conversion ratio of reaction raw materials when being used to prepare acid isopropyl.
For this purpose, the present invention provides a kind of spherical montmorillonite mesoporous composite materials, wherein the spherical shape montmorillonite is composite mesoporous
Material contains montmorillonite and the meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels, and the spherical shape montmorillonite is mesoporous
The average grain diameter of composite material be 30-60 micron, specific surface area be 100-600 meters squared per gram, pore volume for 0.5-1.5 milliliters/
Gram, aperture is in tri-modal distribution, and three peaks respectively correspond the first most probable pore size, the second most probable pore size and third most probable hole
Diameter, first most probable pore size are 1-10 nanometers, and second most probable pore size is 15-30 nanometers, the third most probable
Aperture is 40-55 nanometers.
The present invention also provides a kind of method for preparing spherical montmorillonite mesoporous composite material, this method includes following step
It is rapid:
(1) providing meso-porous molecular sieve material or preparation with three pore size distribution structure of one-dimensional channels has one-dimensional channels three
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b, montmorillonite and binder are subjected to mixing and ball milling in ball grinder, and will
Obtained slurry, is then spray-dried by the solid powder obtained after ball milling water slurrying；
Wherein, above-mentioned steps make the average grain diameter of the spherical montmorillonite mesoporous composite material be 30-60 microns, compare table
Area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks respectively correspond the
One most probable pore size, the second most probable pore size and third most probable pore size, first most probable pore size is 1-10 nanometers, described
Second most probable pore size is 15-30 nanometers, and the third most probable pore size is 40-55 nanometers.
The present invention also provides the spherical montmorillonite mesoporous composite materials prepared by the above method.
The present invention also provides a kind of loaded catalyst, which contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein the carrier is the spherical montmorillonite mesoporous composite material according to the present invention.
The present invention also provides a kind of methods for preparing loaded catalyst, this method comprises: by carrier, p-methyl benzenesulfonic acid
It is uniformly mixed with water, and obtained mixture is spray-dried, wherein the carrier is the spherical shape according to the present invention
Montmorillonite mesoporous composite material.
The present invention also provides the loaded catalysts prepared by the above method.
The present invention also provides the application of above-mentioned loaded catalyst in the esterification reaction.
The present invention also provides a kind of preparation methods of acid isopropyl, this method comprises: in the presence of a catalyst,
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, wherein the catalyst is the present invention
The loaded catalyst.
Spherical shape montmorillonite mesoporous composite material provided by the invention combines Jie with three pore size distribution structure of one-dimensional channels
The advantages of porous molecular sieve material, montmorillonite and ball type carrier, so that the spherical shape montmorillonite mesoporous composite material is suitable as bearing
The carrier of supported catalyst is especially suitable as the load of the loaded catalyst used in acid isopropyl preparation process
Body.
In loaded catalyst of the present invention, the spherical montmorillonite mesoporous composite material as carrier has mesoporous
The characteristics of porous structure of molecular screen material, and be also loaded p-methyl benzenesulfonic acid so that the loaded catalyst both had it is negative
The advantages of supported catalyst such as catalytic activity it is high, side reaction is few, post-processing is simple so that the loaded catalyst be used for it is oily
It not will lead to equipment corrosion when in isopropyl propionate preparation process not only, but also the conversion ratio of reaction raw materials can be significantly improved.
In addition, the loaded catalyst can be with when the method by spray drying prepares the loaded catalyst
It is used repeatedly, and still can obtain higher reaction raw materials conversion ratio during recycling.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of spherical montmorillonite mesoporous composite material according to the present invention；
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical montmorillonite mesoporous composite material according to the present invention；
Fig. 3 is the graph of pore diameter distribution of spherical montmorillonite mesoporous composite material according to the present invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of spherical montmorillonite mesoporous composite materials, wherein the spherical shape montmorillonite mesoporous composite material
Meso-porous molecular sieve material containing montmorillonite and with three pore size distribution structure of one-dimensional channels, and the spherical shape montmorillonite is composite mesoporous
The average grain diameter of material is 30-60 microns, and specific surface area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g,
Aperture is in tri-modal distribution, and three peaks respectively correspond the first most probable pore size, the second most probable pore size and third most probable pore size, institute
Stating the first most probable pore size is 1-10 nanometers, and second most probable pore size is 15-30 nanometers, and the third most probable pore size is
40-55 nanometers.
Spherical shape montmorillonite mesoporous composite material according to the present invention has three pore size distribution structure of one-dimensional channels, particle
Average grain diameter measured using laser fineness gage, specific surface area, pore volume and most probable pore size are surveyed according to nitrogen adsorption methods
?.In the present invention, the average grain diameter is average grain diameter.
Spherical shape montmorillonite mesoporous composite material according to the present invention, by by spherical montmorillonite mesoporous composite material
Particle size controls within above range, it can be ensured that and the spherical shape montmorillonite mesoporous composite material is not susceptible to reunite, and
And it is used as loaded catalyst made of carrier and reaction raw materials conversion ratio in acid isopropyl preparation process can be improved.
When the spherical montmorillonite mesoporous composite material specific surface area less than 100 meters squared per grams and/or pore volume less than 0.5 milliliter/
Gram when, the catalytic activity for being used as loaded catalyst made of carrier can significantly reduce；When the spherical montmorillonite is mesoporous
When the specific surface area of composite material is greater than 600 meters squared per grams and/or pore volume greater than 1.5 mls/g, it is used as carrier system
At loaded catalyst reunion is easy to happen in acid isopropyl preparation process, to influence acid isopropyl preparation process
In reaction raw materials conversion ratio.
Preferably, the average grain diameter of the spherical montmorillonite mesoporous composite material is 45-55 microns, specific surface area 120-
300 meters squared per grams, pore volume are 0.8-1.4 mls/g, and first most probable pore size is 5-10 nanometers, and described second most may be used
Several apertures are 20-28 nanometers, and the third most probable pore size is 42-50 nanometers.
It is highly preferred that the average grain diameter of the spherical shape montmorillonite mesoporous composite material is 50-52 microns, specific surface area is
140-200 meters squared per gram, pore volume be 1.1-1.3 mls/g, first most probable pore size be 7-9 nanometers, described second
Most probable pore size is 21-25 nanometers, and the third most probable pore size is 44-48 nanometers.
According to the present invention, relative to the mesopore molecular sieve described in 100 parts by weight with three pore size distribution structure of one-dimensional channels
Material, the content of the montmorillonite are 1-100 parts by weight, preferably 25-100 parts by weight.
In the present invention, the spherical montmorillonite mesoporous composite material can also contain the titanium dioxide introduced by silica gel
Silicon." silica being introduced by silica gel " refers in the preparation process of the spherical montmorillonite mesoporous composite material, by silicon
Glue is as the silica component for preparing raw material and bringing into the spherical montmorillonite mesoporous composite material finally prepared.In the spherical shape
In montmorillonite mesoporous composite material, relative to the mesoporous molecular described in 100 parts by weight with three pore size distribution structure of one-dimensional channels
Material is sieved, the content of the silica introduced by silica gel can be 1-200 parts by weight, preferably 50-150 parts by weight,
More preferably 75-150 parts by weight.
In the present invention, the meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels can be normal for this field
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
The present invention also provides a kind of method for preparing spherical montmorillonite mesoporous composite material, this method includes following step
It is rapid:
(1) providing meso-porous molecular sieve material or preparation with three pore size distribution structure of one-dimensional channels has one-dimensional channels three
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and montmorillonite are subjected in ball grinder mixing and ball milling, and will be obtained after ball milling
Obtained slurry, is then spray-dried by the solid powder arrived water slurrying；
Wherein, above-mentioned steps make the average grain diameter of the spherical montmorillonite mesoporous composite material be 30-60 microns, compare table
Area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks respectively correspond the
One most probable pore size, the second most probable pore size and third most probable pore size, first most probable pore size is 1-10 nanometers, described
Second most probable pore size is 15-30 nanometers, and the third most probable pore size is 40-55 nanometers.
Preferably, the average grain diameter of the spherical montmorillonite mesoporous composite material is 45-55 microns, specific surface area 120-
300 meters squared per grams, pore volume are 0.8-1.4 mls/g, and first most probable pore size is 5-10 nanometers, and described second most may be used
Several apertures are 20-28 nanometers, and the third most probable pore size is 42-50 nanometers.
It is highly preferred that the average grain diameter of the spherical shape montmorillonite mesoporous composite material is 50-52 microns, specific surface area is
140-200 meters squared per gram, pore volume be 1.1-1.3 mls/g, first most probable pore size be 7-9 nanometers, described second
Most probable pore size is 21-25 nanometers, and the third most probable pore size is 44-48 nanometers.
In step (1), the process with the filter cake of meso-porous molecular sieve material of three pore size distribution structure of one-dimensional channels is prepared
May include: in the presence of trimethylpentane and ethyl alcohol, template is contacted with silicon source in acidic aqueous solution, and
The mixture obtained after contact is subjected to crystallization and filtering.
The template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane molar ratio can be 1:100-500:200-
500:50-200, preferably 1:180-400:250-400:70-150.
The template can be various templates commonly used in the art.Preferably, the template is three block
Copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template can be commercially available (for example, can be purchased from
Aldrich, trade name P123, molecular formula EO20PO70EO20), it can also be prepared by existing various methods
It arrives.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-
The average molecular weight of polyoxypropylene polyoxyethylene calculates to obtain.
The acidic aqueous solution can be various acidic aqueous solutions commonly used in the art, and pH value can be 1-6, excellent
It is selected as 3-5.It is highly preferred that the acidic aqueous solution is the acetic acid and sodium acetate buffer solution that pH value is 1-6.
In step (1), the condition of the contact may include: that temperature is 10-60 DEG C, and the time is 10-72 hours, pH value
For 1-7；Preferably, temperature is 15-40 DEG C, and the time is 10-20 hours, pH value 3.5-5.5.In order to be more advantageous between each substance
Uniform mixing, the contact preferably carries out under agitation.The dosage of the acid solution is preferably so that haptoreaction body
The pH value of system is 1-7.
In step (1), the condition of the crystallization may include: that temperature is 30-150 DEG C, and the time is 10-72 hours.It is excellent
In the case of choosing, the condition of the crystallization includes: that temperature is 40-100 DEG C, and the time is 10-48 hours.The crystallization passes through hydro-thermal crystalline substance
Change method is implemented.
During above-mentioned preparation has the filter cake of the meso-porous molecular sieve material of three pore size distribution structure of one-dimensional channels, pass through
Filtering with the process for obtaining filter cake may include: after filtration, wash that (washing times can be 2- repeatedly with deionized water
10) it, is then filtered.
In step (1), " providing the meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels " be can be directly
The product for weighing or choosing the meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels is also possible to preparation with one-dimensional
The meso-porous molecular sieve material of three pore size distribution structure of duct.The meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels
Preparation method can implement according to the conventional method, for example, preparation method may include: according to the above method preparation have
The filter cake of the meso-porous molecular sieve material of three pore size distribution structure of one-dimensional channels then by gained filtration cakes torrefaction, and will obtain after drying
Product in template removal.The condition of the removed template method may include: that temperature is 300-600 DEG C, time 10-80
Hour.
In step (2), the process for preparing the filter cake of silica gel may include: to carry out waterglass and inorganic acid and polyalcohol
Contact, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass is contacted with inorganic acid and polyalcohol, can be according to the routine for preparing silica gel
It is suitably determined in technique.Under preferable case, the condition that waterglass is contacted with inorganic acid and polyalcohol may include: that temperature is
10-60 DEG C, preferably 20-40 DEG C；Time is 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.
In order to be more advantageous to the uniform mixing between each substance, waterglass and inorganic acid and the catalytic process of polyalcohol are excellent
Choosing carries out under agitation.
The waterglass is the aqueous solution of sodium metasilicate, and concentration can be 10-50 weight %, preferably 12-30 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and hydrochloric acid
At least one of.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.The nothing
The dosage of machine acid is preferably so that the pH value of the haptoreaction system of waterglass and inorganic acid is 2-4.
In step (2), the polyalcohol can be at least one of for ethylene glycol, propylene glycol and glycerine, preferably
Ethylene glycol and/or glycerine, more preferably glycerine.
In step (2), the weight ratio of the waterglass, inorganic acid and polyalcohol can be 3-8:1-3:1, preferably 3-
7:1-2:1, more preferably 4-6:1:1.
In step (2), " providing silica gel ", which can be, directly weighs or chooses silica gel product, is also possible to prepare silica gel.
The method for preparing silica gel can be implemented according to the conventional method, such as may include: the filter cake that silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
In step (3), relative to the component a of 100 parts by weight, the dosage of the component b is 1-200 parts by weight,
Preferably 50-150 parts by weight, more preferably 75-150 parts by weight；The dosage of the montmorillonite is 1-100 parts by weight, preferably
25-100 parts by weight；The dosage of the binder is 10-100 parts by weight, preferably 10-80 parts by weight, more preferably 10-40 weight
Measure part.
Preferably, the binder is polyvinyl alcohol and/or polyethylene glycol, most preferably polyvinyl alcohol.
In step (3), the ball milling can carry out in the ball mill, and the inner wall of ball grinder is preferably in the ball mill
The diameter of agate liner, the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be closed according to the size of ball grinder
1 abrading-ball usually can be used in the selection of reason ground, the ball grinder for being 50-150mL for size；The material of the abrading-ball can be
Agate, ceramics etc., preferably agate.The condition of the ball milling may include: that the revolving speed of abrading-ball is 200-800r/min, ball grinder
Interior temperature is 15-100 DEG C, and the time of ball milling is 0.1-100h；Preferably, the revolving speed of abrading-ball is 300-500r/min, ball milling
Temperature in tank is 40-80 DEG C, and the time of ball milling is 0.5-10h.
In step (3), by the process of the solid powder water slurrying obtained after ball milling can at 25-60 DEG C into
Row.In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.1-2, preferably 1:0.3-1, more preferably
For 1:0.5-1.
In step (3), the spray drying can be implemented according to conventional mode, for example, can in atomizer into
Row.The condition of the spray drying may include: that temperature is 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-
13000r/min。
In step (3), when the filter that the component a is the meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels
Cake, when the component b is the filter cake of silica gel, namely when step (1) is that preparation has the mesoporous of three pore size distribution structure of one-dimensional channels
The process of the filter cake of molecular screen material, when step (2) is the process for the filter cake for preparing silica gel, the spherical shape montmorillonite is composite mesoporous
The preparation method of material can also include: to remove mould from the product that spray drying obtains after the spray drying of step (3)
Plate agent.The condition of the removed template method may include: that temperature is 300-600 DEG C, and the time is 10-80 hours；It is preferred that situation
Under, temperature is 450-550 DEG C, and the time is 15-70 hours.
The present invention also provides the spherical montmorillonite mesoporous composite materials prepared by the above method.
The present invention also provides a kind of loaded catalyst, which contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein the carrier is above-mentioned spherical montmorillonite mesoporous composite material provided by the invention.
In the loaded catalyst, there is no particular limitation for the content of the carrier and p-methyl benzenesulfonic acid, Ke Yigen
It is suitably determined according to the loaded catalyst of this field routine, for example, using the total weight of the loaded catalyst as base
Standard, the content of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The content of the carrier is 50-99 weight
Measure %, preferably 50-95 weight %.
In the present invention, the loaded catalyst can be prepared according to various methods commonly used in the art, only be needed
On the carrier by p-methyl benzenesulfonic acid load.
In a preferred embodiment, in order to make the loaded catalyst of preparation may be repeated utilization, and
Higher reaction raw materials conversion ratio still can be obtained during recycling, the method for preparing loaded catalyst include: by
Carrier, p-methyl benzenesulfonic acid and water are uniformly mixed, and obtained mixture is spray-dried, wherein the carrier is this hair
The above-mentioned spherical montmorillonite mesoporous composite material of bright offer.
It is above-mentioned prepare loaded catalyst during, on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid,
The dosage of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The dosage of the carrier can be 50-99 weight
Measure %, preferably 50-95 weight %.
The spray drying can be implemented according to conventional mode, such as can carry out in atomizer.It is described spraying dry
Dry condition may include: that temperature is 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；Under preferable case,
The condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min.
The present invention also provides the loaded catalysts prepared by above-mentioned spray drying process.
The present invention also provides the application of above-mentioned loaded catalyst in the esterification reaction.
The present invention also provides a kind of preparation methods of acid isopropyl, this method comprises: in the presence of a catalyst,
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, wherein the catalyst is the present invention
The loaded catalyst.
In the preparation method of the acid isopropyl, there is no particular limitation for the dosage of oleic acid and isopropanol, as long as energy
Enough reactions obtain acid isopropyl, but in order to improve the utilization rate of raw material, under preferable case, mole of oleic acid and isopropanol
Than for 1:0.5-10, preferably 1:1-5.
Also there is no particular limitation for the dosage of the catalyst, can be carried out according to conventional acid isopropyl preparation process
Suitably determine.Under preferable case, relative to the oleic acid of 100 parts by weight, the dosage of the catalyst is 1-15 parts by weight, more excellent
It is selected as 2-14 parts by weight.
In the acid isopropyl preparation process, in order to be more advantageous to the progress of esterification, the reaction temperature can
Think 25-200 DEG C, preferably 100-150 DEG C；Reaction time can be 0.5-20 hours, preferably 2-15 hours.
After the preparation method of the acid isopropyl can also be included in esterification, to final reaction mixture
Suction filtration separation is carried out, and isolated solid product will be filtered and be dried in vacuo 1-24 hours at 25-200 DEG C；It is preferred that in 50-
It is dried in vacuo 6-10 hours at 150 DEG C, to recycle catalyst.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, average molecular weight
Mn is 5800.
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from U.S. Kang Ta company
It is carried out on attached instrument, wherein before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient exists
Purchased from being carried out on Agilent company, Britain 7890A/5973N gas chromatograph-mass spectrometer.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of oleic acid and the selectivity of acid isopropyl are according to following
Formula is calculated.
The conversion ratio (%) of oleic acid=(content of oleic acid in dosage-reaction product of oleic acid) ÷ oleic acid dosage ×
100%
The theoretical yield of selectivity (%)=acid isopropyl actual production ÷ acid isopropyl of acid isopropyl ×
100%
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment be used to illustrate spherical montmorillonite mesoporous composite material and loaded catalyst of the invention and they
Preparation method.
(1) spherical montmorillonite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol) ethyl alcohol is added
Into 28mL, the acetic acid and sodium acetate buffer that pH value is 4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) four is added thereto
Methoxy silane stirs 20h under conditions of 15 DEG C, pH value are 4.5, then obtained solution is transferred in reaction kettle,
At 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filter and obtain with three hole of one-dimensional channels
The filter cake A1 of the meso-porous molecular sieve material of distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
5:1:1 carries out mixing and the haptoreaction 2h at 30 DEG C, then adjusts pH value to 3, then with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains the filter of silica gel
Cake B1.
Together by 10g filter cake A1,10g filter cake B1 and the 10g montmorillonite and 5g binder polyvinyl alcohol (PVA) of above-mentioned preparation
Be put into 100mL ball grinder (wherein, the material of ball grinder and abrading-ball is agate, and the diameter of abrading-ball is 3mm, and quantity is 1,
Revolving speed is 400r/min).Ball grinder is closed, temperature is to obtain 30g solid powder ball milling 1 hour at 60 DEG C in ball grinder；It will
The solid powder is dissolved in 30g deionized water, is spray-dried at 200 DEG C in the case where revolving speed is 12000r/min；It will do by spraying
The product obtained after dry is calcined for 24 hours at 500 DEG C in Muffle furnace, removed template method, obtains 28g with three hole of one-dimensional channels point
The spherical montmorillonite mesoporous composite material C1 of cloth structure.
(2) loaded catalyst is prepared
At 25 DEG C, the 30g spherical shape montmorillonite mesoporous composite material C1 and p-methyl benzenesulfonic acid that will be prepared in above-mentioned steps (1)
It is put into togerther in deionized water, stirring to dissolution, and the weight ratio of spherical shape montmorillonite mesoporous composite material C1 and p-methyl benzenesulfonic acid
For 50:50, the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, spraying in the case where revolving speed is 12000r/min at 200 DEG C
It is dry, obtain loaded catalyst Cat-1.
With XRD, scanning electron microscope and U.S.'s Kang Ta company Atsorb-1 type instrument come to the support type Catalyzed by p-Toluenesulfonic Acid
Agent is characterized.
Fig. 1 is X-ray diffracting spectrum, and for the XRD spectra of spherical montmorillonite mesoporous composite material C1, abscissa is 2 θ, is indulged
Coordinate is intensity.By the low-angle spectral peak that occurs in XRD spectra it is found that spherical shape montmorillonite mesoporous composite material C1 has mesoporous material
Expect three pore size distribution structure of specific one-dimensional channels.
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical montmorillonite mesoporous composite material C1.As seen from the figure, spherical
The microscopic appearance of montmorillonite mesoporous composite material C1 is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 3 is the pore size distribution curve of spherical montmorillonite mesoporous composite material C1.
The pore structure parameter of spherical montmorillonite mesoporous composite material C1 and loaded catalyst Cat-1 is as shown in table 1 below.
Table 1
*: it respectively is the first most probable pore size, the second most probable pore size and third most probable pore size, is used between them
Comma separates.
By spherical montmorillonite mesoporous composite material it can be seen from the data of upper table 1 after loading p-methyl benzenesulfonic acid, compare table
Area and pore volume are reduced, and it is mesoporous multiple that this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical montmorillonite
The inside of condensation material.
Comparative example 1
Spherical montmorillonite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different,
It is added without montmorillonite during mesoporous composite material of the preparation as carrier, so that mesoporous composite material D1 be made respectively and bear
Supported catalyst Cat-D-1.
Comparative example 2
Spherical montmorillonite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different,
During preparing loaded catalyst, (Jilin University's high-tech is purchased from the rodlike mesoporous silicon oxide SBA-15 of identical weight
Skill limited liability company) the filter cake A1 with the meso-porous molecular sieve material of three pore size distribution structure of one-dimensional channels is replaced, thus respectively
Mesoporous composite material D2 and loaded catalyst Cat-D-2 is made.
Comparative example 3
Spherical montmorillonite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, the difference is that
The material of ball grinder is polytetrafluoroethylene (PTFE) during preparation is used as the mesoporous composite material of carrier, and Material quality of grinding balls is agate.
To which mesoporous composite material D3 and loaded catalyst Cat-D-3 be made respectively.
Comparative example 4
Spherical montmorillonite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different,
The step of not being spray-dried during preparing loaded catalyst, and only loaded p-methyl benzenesulfonic acid by the method impregnated
On spherical montmorillonite mesoporous composite material, so that loaded catalyst Cat-D-4 be made.
Embodiment 2
The present embodiment be used to illustrate spherical montmorillonite mesoporous composite material and loaded catalyst of the invention and they
Preparation method.
(1) spherical montmorillonite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethyl alcohol is added to
In 28mL, the acetic acid and sodium acetate buffer that pH value is 5, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 3.04g (0.02mol) four is added thereto
Methoxy silane stirs 15h under conditions of 25 DEG C, pH value are 5.5, then obtained solution is transferred in reaction kettle,
Crystallization 10h at 100 DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain with three hole of one-dimensional channels
The filter cake A2 of the meso-porous molecular sieve material of distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
4:1:1 carries out mixing and the haptoreaction 1.5h at 40 DEG C, then adjusts pH value to 2, so with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered afterwards, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B2.
20g filter cake A2,15g filter cake B2 and the 15g montmorillonite and 2g binder PVA of above-mentioned preparation are put into togerther 100mL
(wherein, the material of ball grinder and abrading-ball is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, and revolving speed is in ball grinder
300r/min).Ball grinder is closed, temperature is ball milling 0.5h at 80 DEG C in ball grinder, obtains 50g solid powder；By the solid
Powder is dissolved in 36g deionized water, is spray-dried at 250 DEG C in the case where revolving speed is 11000r/min；It will be obtained after spray drying
To product 15h is calcined at 550 DEG C in Muffle furnace, removed template method obtains 30g spherical shape montmorillonite mesoporous composite material
C2。
(2) loaded catalyst is prepared
At 25 DEG C, the 20g spherical shape montmorillonite mesoporous composite material C2 and p-methyl benzenesulfonic acid that will be prepared in above-mentioned steps (1)
It is put into togerther in deionized water, stirring to dissolution, and the weight ratio of spherical shape montmorillonite mesoporous composite material C2 and p-methyl benzenesulfonic acid
For 95:5, the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, is done by spraying at 150 DEG C in the case where revolving speed is 13000r/min
It is dry, obtain loaded catalyst Cat-2.
Table 2
*: it respectively is the first most probable pore size, the second most probable pore size and third most probable pore size, is used between them
Comma separates.
By spherical montmorillonite mesoporous composite material it can be seen from the data of upper table 2 after loading p-methyl benzenesulfonic acid, compare table
Area and pore volume are reduced, and it is mesoporous multiple that this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical montmorillonite
The inside of condensation material.
Embodiment 3
The present embodiment be used to illustrate spherical montmorillonite mesoporous composite material and loaded catalyst of the invention and they
Preparation method.
(1) spherical montmorillonite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethyl alcohol is added to
In 28mL, the acetic acid and sodium acetate buffer that pH value is 3, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 4.56g (0.03mol) tetramethyl is added thereto
Oxysilane stirs 10h under conditions of 40 DEG C, pH value are 3.5, then obtained solution is transferred in reaction kettle, 40
Crystallization 48h at DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain with three hole of one-dimensional channels point
The filter cake A3 of the meso-porous molecular sieve material of cloth structure.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
6:1:1 carries out mixing and the haptoreaction 3h at 20 DEG C, then adjusts pH value to 4, then with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains the filter of silica gel
Cake B3.
20g filter cake A3,30g filter cake B3 and the 5g montmorillonite and 8g binder PVA of above-mentioned preparation are put into togerther 100mL ball
(wherein, the material of ball grinder and abrading-ball is agate, and the diameter of abrading-ball is 3mm, and quantity is 1, revolving speed 500r/ in grinding jar
min).Ball grinder is closed, temperature is ball milling 10h at 40 DEG C in ball grinder, obtains 55g solid powder；The solid powder is molten
Solution is spray-dried at 150 DEG C in the case where revolving speed is 13000r/min in 30g deionized water；The production that will be obtained after spray drying
Object calcines 70h in Muffle furnace at 450 DEG C, and removed template method obtains 33g spherical shape montmorillonite mesoporous composite material C3.
(2) loaded catalyst is prepared
At 25 DEG C, the 20g spherical shape montmorillonite mesoporous composite material C3 and p-methyl benzenesulfonic acid that will be prepared in above-mentioned steps (1)
It is put into togerther in deionized water, stirring to dissolution, and the weight ratio of spherical shape montmorillonite mesoporous composite material C3 and p-methyl benzenesulfonic acid
For 85:15, the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, spraying in the case where revolving speed is 11000r/min at 250 DEG C
It is dry, obtain loaded catalyst Cat-3.
The pore structure parameter of spherical montmorillonite mesoporous composite material C3 and loaded catalyst Cat-3 is as shown in table 3 below.
Table 3
*: it respectively is the first most probable pore size, the second most probable pore size and third most probable pore size, is used between them
Comma separates.
By spherical montmorillonite mesoporous composite material it can be seen from the data of upper table 3 after loading p-methyl benzenesulfonic acid, compare table
Area and pore volume are reduced, and it is mesoporous multiple that this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical montmorillonite
The inside of condensation material.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used to illustrate the application and the system of acid isopropyl of the loaded catalyst provided by the invention
Preparation Method.
Loaded catalyst Cat-1 prepared by embodiment 1 is dried in vacuo 6h at 150 DEG C, after being cooled to room temperature, is weighed
0.5g is sequentially added oleic acid 6g (0.02mol) in there-necked flask, and isopropanol 2.8g (0.047mol), Cat-1 0.5g are heated to
75 DEG C, after reacting 0.5h, centrifuge separation utilizes gas chromatographic analysis reaction product liquid ingredient, oleic acid conversion 99.9%, oleic acid
Isopropyl ester selectivity 100%, solid catalyst Cat-1 is dried in vacuo 6h at 150 DEG C, sharp again after recycling after being cooled to room temperature
With.
EXPERIMENTAL EXAMPLE 2-3 and Experimental comparison's example 1-4
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, the difference is that using embodiment 2-3 and comparison respectively
The loaded catalyst of example 1-4 preparation replaces the loaded catalyst Cat-1.As a result, the oleic acid being respectively calculated turns
Rate and acid isopropyl selective data are as shown in table 4 below.
Table 4
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 99.9% | 100% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 99% | 100% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 99% | 100% |
| Experimental comparison's example 1 | Cat-D-1 | 93% | 96% |
| Experimental comparison's example 2 | Cat-D-2 | 91% | 97% |
| Experimental comparison's example 3 | Cat-D-3 | 80% | 87% |
| Experimental comparison's example 4 | Cat-D-4 | 75% | 95% |
EXPERIMENTAL EXAMPLE 4-6 and Experimental comparison's example 5-8
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, the difference is that respectively with from EXPERIMENTAL EXAMPLE 1-3
The loaded catalyst Cat-1 is replaced with the catalyst of Experimental comparison's example 1-4 recycling.As a result, the oleic acid being respectively calculated
Conversion ratio and acid isopropyl selective data it is as shown in table 5 below.
Table 5
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 4 | The Cat-1 of recycling | 95% | 100% |
| EXPERIMENTAL EXAMPLE 5 | The Cat-2 of recycling | 90% | 100% |
| EXPERIMENTAL EXAMPLE 6 | The Cat-3 of recycling | 85% | 100% |
| Experimental comparison's example 5 | The Cat-D-1 of recycling | 83% | 90% |
| Experimental comparison's example 6 | The Cat-D-2 of recycling | 45% | 92% |
| Experimental comparison's example 7 | The Cat-D-3 of recycling | 40% | 80% |
| Experimental comparison's example 8 | The Cat-D-4 of recycling | 50% | 90% |
Using the spherical montmorillonite mesoporous composite material conduct of the invention it can be seen from the data of above-mentioned table 4 and 5
Loaded catalyst made of carrier can significantly improve the conversion ratio of reaction raw materials in acid isopropyl preparation process.And
And when the method by spray drying prepares the loaded catalyst, the loaded catalyst may be repeated benefit
With, and higher reaction raw materials conversion ratio still can be obtained during recycling.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (32)
1. a kind of spherical shape montmorillonite mesoporous composite material, which is characterized in that it is de- that the spherical shape montmorillonite mesoporous composite material contains illiteracy
Stone and meso-porous molecular sieve material with three pore size distribution structure of one-dimensional channels, and the spherical shape montmorillonite mesoporous composite material is flat
Equal partial size is 30-60 microns, and specific surface area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in three
Peak distribution, and three peaks respectively correspond the first most probable pore size, the second most probable pore size and third most probable pore size, described first most
Can several apertures be 1-10 nanometer, second most probable pore size be 15-30 nanometers, the third most probable pore size is received for 40-55
Rice；Relative to described in 100 parts by weight with three pore size distribution structure of one-dimensional channels meso-porous molecular sieve material, the montmorillonite
Content is 25-100 parts by weight.
2. a kind of method for preparing spherical montmorillonite mesoporous composite material, method includes the following steps:
(1) providing meso-porous molecular sieve material or preparation with three pore size distribution structure of one-dimensional channels has three hole of one-dimensional channels point
The filter cake of the meso-porous molecular sieve material of cloth structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b, montmorillonite and binder are subjected to mixing and ball milling in ball grinder, and by ball milling
Obtained slurry, is then spray-dried by the solid powder obtained afterwards water slurrying；
Wherein, above-mentioned steps make the average grain diameter of the spherical montmorillonite mesoporous composite material be 30-60 microns, specific surface area
For 100-600 meters squared per gram, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks respectively correspond first most
Can several apertures, the second most probable pore size and third most probable pore size, first most probable pore size be 1-10 nanometers, described second
Most probable pore size is 15-30 nanometers, and the third most probable pore size is 40-55 nanometers；
In step (2), the process for preparing the filter cake of silica gel includes: that in the presence of a mineral acid, waterglass and polyalcohol are carried out
Contact, and the mixture obtained after contact is filtered, the polyalcohol be in ethylene glycol, propylene glycol and glycerine at least
One kind, the weight ratio of the waterglass, inorganic acid and polyalcohol are 3-8:1-3:1；
In step (3), the dosage of the component a relative to 100 parts by weight, the dosage of the montmorillonite is 25-100 weight
Part.
3. according to the method described in claim 2, wherein, in step (3), the use of the component a relative to 100 parts by weight
Amount, the dosage of the component b are 1-200 parts by weight, and the dosage of the binder is 10-100 parts by weight.
4. according to the method described in claim 3, wherein, the dosage of the component a relative to 100 parts by weight, the component b
Dosage be 75-150 parts by weight；The dosage of the binder is 10-80 parts by weight.
5. the method according to claim 3 or 4, wherein the binder is polyvinyl alcohol and/or polyethylene glycol.
6. according to the method described in claim 5, wherein, the binder is polyvinyl alcohol.
7. according to the method described in claim 2, wherein, in step (1), preparing the mesoporous of three pore size distribution structure of one-dimensional channels
The process of the filter cake of molecular screen material includes: in acidic aqueous solution, in the presence of trimethylpentane and ethyl alcohol, by template
It is contacted with silicon source, and the mixture obtained after contact is subjected to crystallization and filtering.
8. according to the method described in claim 7, wherein, template, ethyl alcohol, trimethylpentane and silicon source molar ratio be 1:
100-500:200-500:50-200.
9. according to the method described in claim 8, wherein, template, ethyl alcohol, trimethylpentane and silicon source molar ratio be 1:
180-400:250-400:70-150.
10. method according to claim 8 or claim 9, wherein the template is triblock copolymer polyoxyethylene-polyoxy
Proplyene-polyoxyethylene；The silicon source is tetramethoxy-silicane；The acidic aqueous solution is the acetic acid and sodium acetate that pH value is 1-6
Buffer solution.
11. the condition of the contact includes: that temperature is 10-60 DEG C according to the method described in claim 8, wherein, the time is
10-72 hours, pH value 1-7；The condition of the crystallization includes: that temperature is 30-150 DEG C, and the time is 10-72 hours.
12. according to the method described in claim 2, wherein, the condition of the contact includes: that temperature is 10-60 DEG C, time 1-
5 hours, pH value 2-4；The inorganic acid is at least one of sulfuric acid, nitric acid and hydrochloric acid.
13. according to the method described in claim 2, wherein, the polyalcohol is ethylene glycol and/or glycerine.
14. according to the method described in claim 2, wherein, in step (3), the condition of the ball milling includes: the revolving speed of abrading-ball
For 200-800r/min, the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hours.
15. according to the method for claim 14, wherein the ball grinder is agate jar.
16. according to the method for claim 15, wherein the condition of the spray drying includes: 100-300 DEG C of temperature, is turned
Speed is 10000-15000r/min.
17. the method according to any one of claim 2-4, wherein the component a is with three hole of one-dimensional channels point
The filter cake of the meso-porous molecular sieve material of cloth structure, the component b are the filter cake of silica gel.
18. according to the method for claim 17, wherein the preparation method of the spherical shape montmorillonite mesoporous composite material is also wrapped
It includes: after the spray-drying process of step (3), the removed template method from the product that spray drying obtains.
19. according to the method for claim 18, wherein the condition of the removed template method includes: that temperature is 300-600
DEG C, the time is 10-80 hours.
20. the spherical montmorillonite mesoporous composite material of the preparation of the method as described in any one of claim 2-19.
21. a kind of loaded catalyst, which contains the p-methyl benzenesulfonic acid of carrier and load on the carrier, feature
It is, the carrier is spherical montmorillonite mesoporous composite material described in claims 1 or 20.
22. loaded catalyst according to claim 21, wherein using the total weight of the loaded catalyst as base
Standard, the content of the p-methyl benzenesulfonic acid are 1-50 weight %, and the content of the carrier is 50-99 weight %.
23. loaded catalyst according to claim 22, wherein using the total weight of the loaded catalyst as base
Standard, the content of the p-methyl benzenesulfonic acid are 5-50 weight %, and the content of the carrier is 50-95 weight %.
24. a kind of preparation method of loaded catalyst, which is characterized in that this method comprises: by carrier, p-methyl benzenesulfonic acid and water
It is uniformly mixed, and obtained mixture is spray-dried, wherein the carrier is spherical shape described in claims 1 or 20
Montmorillonite mesoporous composite material.
25. according to the method for claim 24, wherein right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 1-50 weight %, and the dosage of the carrier is 50-99 weight %.
26. according to the method for claim 25, wherein right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 5-50 weight %, and the dosage of the carrier is 50-95 weight %.
27. the loaded catalyst of the preparation of the method as described in any one of claim 24-26.
28. the application of loaded catalyst in the esterification reaction described in any one of claim 21-23 and 27.
29. a kind of preparation method of acid isopropyl, wherein this method comprises: in the presence of a catalyst, in esterification
Under the conditions of, contact oleic acid and isopropanol, to obtain acid isopropyl, which is characterized in that the catalyst is claim 21-
Loaded catalyst described in any one of 23 and 27.
30. preparation method according to claim 29, wherein the molar ratio of oleic acid and isopropanol is 1:0.5-10.
31. preparation method according to claim 29, wherein relative to the oleic acid of 100 parts by weight, the use of the catalyst
Amount is 1-15 parts by weight.
32. preparation method according to claim 31, wherein relative to the oleic acid of 100 parts by weight, the use of the catalyst
Amount is 2-14 parts by weight.
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| CN104248985A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method |
| CN104415795A (en) * | 2013-09-11 | 2015-03-18 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and supported catalyst, and preparation methods and application of spherical zeolite mesoporous composite material and supported catalyst, and preparation method of ethyl acetate |
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| CN104248985A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method |
| CN104415795A (en) * | 2013-09-11 | 2015-03-18 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and supported catalyst, and preparation methods and application of spherical zeolite mesoporous composite material and supported catalyst, and preparation method of ethyl acetate |
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