CN107457005A - Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method - Google Patents
Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method Download PDFInfo
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- CN107457005A CN107457005A CN201610392567.7A CN201610392567A CN107457005A CN 107457005 A CN107457005 A CN 107457005A CN 201610392567 A CN201610392567 A CN 201610392567A CN 107457005 A CN107457005 A CN 107457005A
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- pore size
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- mesoporous composite
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 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 103
- 238000000034 method Methods 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 58
- 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 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000012065 filter cake Substances 0.000 claims description 30
- 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 30
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 23
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 23
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 23
- 239000005642 Oleic acid Substances 0.000 claims description 23
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 23
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 23
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 23
- 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 19
- 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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 239000000243 solution Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000007974 sodium acetate buffer Substances 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000000126 substance 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 239000002994 raw material Substances 0.000 abstract description 12
- 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
- 238000011084 recovery Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005516 engineering process 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004064 recycling Methods 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
- 239000003643 water by type Substances 0.000 description 3
- 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
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000002156 mixing Methods 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
- 238000005507 spraying Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-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
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 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
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant 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
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction 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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 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
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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/51—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/643—
-
- B01J35/647—
-
- 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
- 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
Abstract
The present invention relates to catalyst field, and in particular to the preparation method of a kind of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl.Wherein, disclose a kind of spherical diatomite mesoporous composite material and preparation method thereof, the spherical diatomite mesoporous composite material prepared by this method, loaded catalyst containing the spherical diatomite 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 contains diatomite and the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three.The conversion ratio of reaction raw materials can be significantly improved in acid isopropyl preparation process as loaded catalyst made of carrier using composite provided by the invention.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of spherical diatomite mesoporous composite material, the spherical diatomite
The preparation method of mesoporous composite material, the spherical diatomite mesoporous composite material prepared by this method, contains the spherical diatomite
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 technology
Acid isopropyl is transparent oily liquid, can be dissolved each other with animal and vegetable oil, and its coefficient of dispersion is big, and spreadability is good, can be
Thin electrolyte film is formed on skin, there is skin care effect.It is continuous to the demand of acid isopropyl with developing rapidly for chemical industry
Increase.Generally, acid isopropyl is made by oleic acid and isopropanol in the presence of catalyst by esterification.Pass
The be used for oleic acid and the catalyst of isopropanol esterification of system are liquid organic acid, but because the pair that its corrosiveness is big, triggers is anti-
Product separation is complicated after Ying Duo, reaction and causes its use to be subject to certain restrictions the defects of liquid waste processing difficulty.With
Increase of the whole world to Catalytic processes greenization attention degree, solid acid catalysis technique substitution liquid acid Catalytic processes gesture must
OK.
In existing loaded catalyst, meso-porous molecular sieve material is as carrier.Meso-porous molecular sieve material has duct
In order, the advantages that aperture is adjustable, specific surface area and pore volume are larger so that be made using these meso-porous molecular sieve materials as carrier
Preparation technology of the loaded catalyst in organic catalytic reaction in show lot of advantages, for example, catalytic activity is high, secondary anti-
Should less, post processing it is simple etc., however, make it that these meso-porous molecular sieve materials have stronger for big specific surface area and high pore volume
Water suction, moisture absorption ability, so as to which these loaded catalysts can be caused to reunite in catalytic reaction process, and then reduce oleic acid
The conversion ratio of oleic acid in isopropyl ester preparation technology.Therefore, further develop and a kind of new be used to prepare acid isopropyl
Catalyst turns into the problem of in the urgent need to address.
The content of the invention
The invention aims to overcome making using loaded catalyst made of existing meso-porous molecular sieve material
The defects of reaction raw materials conversion ratio is relatively low during standby acid isopropyl, there is provided a kind of spherical diatomite for being suitable as carrier is situated between
Hole composite material, the preparation method of the spherical diatomite mesoporous composite material, the spherical diatomite prepared by this method are mesoporous multiple
Condensation material, the loaded catalyst containing the spherical diatomite mesoporous composite material, the preparation method of the loaded catalyst, by
Loaded catalyst prepared by this method, 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 the pore size distribution of one-dimensional channels three
Diatomite is introduced in the meso-porous molecular sieve material of structure, diatomite is entered in the duct of meso-porous molecular sieve material, and should
Mesoporous composite material, which is made, to be not susceptible to reunite spherical, can so retain the high-specific surface area, big of meso-porous molecular sieve material
Pore volume, large aperture and there is the pore size distribution structure of one-dimensional channels three, the reunion of meso-porous molecular sieve material can be reduced again, increase
Add its mobility；Simultaneously as binding agent is introduced in meso-porous molecular sieve material so that spheroid intensity increases, can as carrier
With repeated multiple times use, so as to substantially reduce use cost.In addition, urged using support type made of the mesoporous composite material
Agent can significantly improve the conversion ratio of reaction raw materials when for preparing acid isopropyl.
Therefore, the invention provides a kind of spherical diatomite mesoporous composite material, wherein, the spherical diatomite is composite mesoporous
Material contains diatomite and the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three, and the spherical diatomite is mesoporous
The average grain diameter of composite is 30-60 microns, and specific surface area is 100-600 meters squared per grams, pore volume be 0.5-1.5 milliliters/
Gram, aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable hole respectively
Footpath, first most probable pore size are 1-5 nanometers, and second most probable pore size is 6-10 nanometers, the 3rd most probable hole
Footpath is 40-45 nanometers.
Present invention also offers a kind of method for preparing spherical diatomite mesoporous composite material, this method includes following step
Suddenly：
(1) meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three is provided or prepared with one-dimensional channels three
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, component b, diatomite and the binding agent are mixed in ball grinder and ball milling, and will
Obtained slurry, is then spray-dried by the solid powder obtained after ball milling water slurrying；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical diatomite mesoporous composite material is 30-60 microns, compare table
Area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture be in tri-modal distribution, and three peaks respectively corresponding the
One most probable pore size, the second most probable pore size and the 3rd most probable pore size, first most probable pore size is 1-5 nanometers, described
Second most probable pore size is 6-10 nanometers, and the 3rd most probable pore size is 40-45 nanometers.
Present invention also offers the spherical diatomite mesoporous composite material prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein, the carrier is the spherical diatomite mesoporous composite material according to the present invention.
Present invention also offers a kind of method for preparing loaded catalyst, this method includes：By carrier, p-methyl benzenesulfonic acid
It is well mixed with water, and obtained mixture is spray-dried, wherein, the carrier is according to the described spherical of the present invention
Diatomite mesoporous composite material.
Present invention also offers the loaded catalyst prepared by the above method.
Present invention also offers the application of above-mentioned loaded catalyst in the esterification reaction.
Present invention also offers a kind of preparation method of acid isopropyl, this method includes：In the presence of a catalyst, exist
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, wherein, the catalyst is the present invention
Described loaded catalyst.
Spherical diatomite mesoporous composite material provided by the invention combines Jie with the pore size distribution structure of one-dimensional channels three
The advantages of porous molecular sieve material, diatomite and ball type carrier so that the spherical diatomite mesoporous composite material is suitable as bearing
The carrier of supported catalyst, particularly it is suitable as the load of loaded catalyst used in acid isopropyl preparation process
Body.
In loaded catalyst of the present invention, the spherical diatomite mesoporous composite material as carrier has mesoporous
The characteristics of loose structure of molecular screen material, but also it is loaded with p-methyl benzenesulfonic acid so that the loaded catalyst had both had 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 is for oil
Equipment corrosion will not only be caused when in isopropyl propionate preparation process, but also the conversion ratio of reaction raw materials can be significantly improved.
In addition, when preparing the loaded catalyst by the method for spray drying, the loaded catalyst can be with
It is used repeatedly, and higher reaction raw materials conversion ratio still can be obtained during recycling.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, 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 diatomite mesoporous composite material according to the present invention；
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of the microscopic appearance of spherical diatomite mesoporous composite material according to the present invention；
Fig. 3 is the graph of pore diameter distribution of spherical diatomite mesoporous composite material according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of spherical diatomite mesoporous composite material, wherein, the spherical diatomite mesoporous composite material
Meso-porous molecular sieve material containing diatomite and with the pore size distribution structure of one-dimensional channels three, and the spherical diatomite is composite mesoporous
The average grain diameter of material is 30-60 microns, and specific surface area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g,
Aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size, institute respectively
It is 1-5 nanometers to state the first most probable pore size, and second most probable pore size is 6-10 nanometers, and the 3rd most probable pore size is
40-45 nanometers.
Spherical diatomite mesoporous composite material according to the present invention has the pore size distribution structure of one-dimensional channels three, its 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 particulate diameter.
Spherical diatomite mesoporous composite material according to the present invention, by by spherical diatomite mesoporous composite material
Particle size is controlled within above range, it can be ensured that and the spherical diatomite mesoporous composite material is not susceptible to reunite, and
And it is used as loaded catalyst made of carrier and can improves reaction raw materials conversion ratio in acid isopropyl preparation process.
When the specific surface area of the spherical diatomite mesoporous composite material be less than 100 meters squared per grams and/or pore volume be less than 0.5 milliliter/
Gram when, being used as the catalytic activity of loaded catalyst made of carrier can significantly reduce；When the spherical diatomite is mesoporous
When the specific surface area of composite is more than 600 meters squared per grams and/or pore volume more than 1.5 mls/g, carrier system is used as
Into loaded catalyst easily reunite in acid isopropyl preparation process, so as to influence acid isopropyl preparation process
In reaction raw materials conversion ratio.
Preferably, the average grain diameter of the spherical diatomite mesoporous composite material is 47-53 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 2-4 nanometers, and described second most may be used
Several apertures are 7-9 nanometers, and the 3rd most probable pore size is 41-44 nanometers.
It is highly preferred that the average grain diameter of the spherical diatomite mesoporous composite material is 48-52 microns, specific surface area is
180-220 meters squared per grams, pore volume are 1-1.2 mls/g, and first most probable pore size is 2-3 nanometers, and described second most
Can several apertures be 8-9 nanometers, the 3rd most probable pore size is 42-43 nanometers.
According to the present invention, relative to the mesopore molecular sieve described in 100 parts by weight with the pore size distribution structure of one-dimensional channels three
Material, the diatomaceous content are 1-100 parts by weight, preferably 25-100 parts by weight.
In the present invention, the spherical diatomite mesoporous composite material can also contain the titanium dioxide introduced by silica gel
Silicon." silica being introduced into by silica gel " refers in the preparation process of the spherical diatomite mesoporous composite material, by silicon
The silica component that glue is brought into as preparing raw material in the spherical diatomite mesoporous composite material finally prepared.Described spherical
In diatomite mesoporous composite material, relative to the mesoporous molecular described in 100 parts by weight with the pore size distribution structure of one-dimensional channels three
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 the pore size distribution structure of one-dimensional channels three can be that this area is normal
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
Present invention also offers a kind of method for preparing spherical diatomite mesoporous composite material, this method includes following step
Suddenly：
(1) meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three is provided or prepared with one-dimensional channels three
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, the component b and diatomite is mixed in ball grinder and ball milling, and will be after ball milling
Obtained slurry, is then spray-dried by the solid powder arrived water slurrying；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical diatomite mesoporous composite material is 30-60 microns, compare table
Area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture be in tri-modal distribution, and three peaks respectively corresponding the
One most probable pore size, the second most probable pore size and the 3rd most probable pore size, first most probable pore size is 1-5 nanometers, described
Second most probable pore size is 6-10 nanometers, and the 3rd most probable pore size is 40-45 nanometers.
Preferably, the average grain diameter of the spherical diatomite mesoporous composite material is 47-53 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 2-4 nanometers, and described second most may be used
Several apertures are 7-9 nanometers, and the 3rd most probable pore size is 41-44 nanometers.
It is highly preferred that the average grain diameter of the spherical diatomite mesoporous composite material is 48-52 microns, specific surface area is
180-220 meters squared per grams, pore volume are 1-1.2 mls/g, and first most probable pore size is 2-3 nanometers, and described second most
Can several apertures be 8-9 nanometers, the 3rd most probable pore size is 42-43 nanometers.
In step (1), the process of the filter cake of the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three is prepared
It can include：In acidic aqueous solution, in the presence of trimethylpentane and ethanol, template is contacted with silicon source, and
The mixture obtained after contact is subjected to crystallization and filtering.
The template, ethanol, the mol ratio of trimethylpentane and tetramethoxy-silicane 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 into by existing various methods
Arrive.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template according to polyoxyethylene-
The mean molecule quantity of polyoxypropylene polyoxyethylene calculates to obtain.
The acidic aqueous solution can be various acidic aqueous solutions commonly used in the art, and its pH value can be 1-6, excellent
Elect 3-5 as.It is highly preferred that acetic acid and sodium acetate buffer solution that it is 1-6 that the acidic aqueous solution, which is pH value,.
In step (1), the condition of the contact can include：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 beneficial between each material
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 can include：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：Temperature is 40-100 DEG C, and the time is 10-48 hours.The crystallization is brilliant by hydro-thermal
Change method is implemented.
During the filter cake in above-mentioned preparation with the meso-porous molecular sieve material of the pore size distribution structure of one-dimensional channels three, pass through
Filtering can be included with obtaining the process of filter cake：After filtration, wash that (washing times can be 2- repeatedly with deionized water
10), then filtered.
In step (1), " providing the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three " can be direct
Weigh or choose the product of the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three or prepare with one-dimensional
The meso-porous molecular sieve material of the pore size distribution structure of duct three.The meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three
Preparation method can implement according to the conventional method, for example, its preparation method can include：Being prepared according to the above method has
The filter cake of the meso-porous molecular sieve material of the pore size distribution structure of one-dimensional channels three, then by gained filtration cakes torrefaction, and it will be obtained after drying
Product in template removal.The condition of the removed template method can include：Temperature is 300-600 DEG C, time 10-80
Hour.
In step (2), preparing the process of the filter cake of silica gel can include：Waterglass and inorganic acid and polyalcohol are carried out
Contact, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass contacts with inorganic acid and polyalcohol, can be according to the routine for preparing silica gel
Suitably determined in technique.Under preferable case, the condition that waterglass contacts with inorganic acid and polyalcohol can include：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 beneficial for the uniform mixing between each material, waterglass and inorganic acid and the catalytic process of polyalcohol are excellent
Choosing is carried out under agitation.
The waterglass is the aqueous solution of sodium metasilicate, and its 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 ethylene glycol, propane diols and glycerine, be 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), " offer silica gel " can directly be weighed or choose silica gel product or prepare silica gel.
Preparing the method for silica gel can implement according to the conventional method, such as can include：The filter cake of 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 diatomaceous dosage is 1-100 parts by weight, is preferably
25-100 parts by weight；The dosage of the binding agent is 10-100 parts by weight, preferably 10-80 parts by weight, and more preferably 10-40 is heavy
Measure part.
Preferably, the binding agent is polyvinyl alcohol and/or polyethylene glycol, most preferably polyvinyl alcohol.
In step (3), the ball milling can be carried out in ball mill, and the inwall of ball grinder is preferably in the ball mill
Agate liner, the diameter of 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
The selection of reason ground, for the ball grinder that size is 50-150mL, it can generally use 1 abrading-ball；The material of the abrading-ball can be
Agate, ceramics etc., preferably agate.The condition of the ball milling can include：The rotating 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 rotating 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), the process of the solid powder water slurrying obtained after ball milling can be entered at 25-60 DEG C
OK.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 the mode of routine, such as can enter in atomizer
OK.The condition of the spray drying can include：Temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes：Temperature is 150-250 DEG C, and the rotating 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 the pore size distribution structure of one-dimensional channels three
Cake, when the component b is the filter cake of silica gel, namely it is mesoporous with the pore size distribution structure of one-dimensional channels three to prepare when step (1)
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 diatomite is composite mesoporous
The preparation method of material can also include：After the spray drying of step (3), mould is removed in the product obtained from spray drying
Plate agent.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is 10-80 hours；Preferable situation
Under, temperature is 450-550 DEG C, and the time is 15-70 hours.
Present invention also offers the spherical diatomite mesoporous composite material prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein, the carrier is above-mentioned spherical diatomite 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
Suitably determined according to the conventional loaded catalyst in this area, for example, using the gross 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 weights
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
By p-methyl benzenesulfonic acid load on the carrier.
In a preferred embodiment, in order that the loaded catalyst prepared may be repeated utilization, and
Still higher reaction raw materials conversion ratio can be obtained during recycling, preparing the method for loaded catalyst includes：Will
Carrier, p-methyl benzenesulfonic acid and water are well mixed, and obtained mixture is spray-dried, wherein, the carrier is this hair
The above-mentioned spherical diatomite 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 weights
Measure %, preferably 50-95 weight %.
The spray drying can be implemented according to the mode of routine, such as can be carried out in atomizer.The spraying is dry
Dry condition can include：Temperature is 100-300 DEG C, and the rotating speed of rotation can be 10000-15000r/min；Under preferable case,
The condition of the spray drying includes：Temperature is 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
Present invention also offers the loaded catalyst prepared by above-mentioned spray drying process.
Present invention also offers the application of above-mentioned loaded catalyst in the esterification reaction.
Present invention also offers a kind of preparation method of acid isopropyl, this method includes：In the presence of a catalyst, exist
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, wherein, the catalyst is the present invention
Described 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 the acid isopropyl preparation technology of routine
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
Elect 2-14 parts by weight as.
In the acid isopropyl preparation process, in order to be more beneficial for 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.
The preparation method of the acid isopropyl is additionally may included in after esterification terminates, to final reactant mixture
Suction filtration separation is carried out, and isolated solid product will be filtered 1-24 hours are dried in vacuo at 25-200 DEG C；It is preferred that in 50-
6-10 hours are dried in vacuo at 150 DEG C, to reclaim 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 material for being 9003-11-6 in the registration number of U.S. chemical abstract, mean molecule quantity
Mn is 5800.
In following examples and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on D8Advance X-ray diffractometer；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
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 companies of Britain 7890A/5973N gas chromatograph-mass spectrometers.
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 dosage of the conversion ratio (%) of oleic acid=(content of oleic acid in dosage-reaction product of oleic acid) ÷ oleic acid ×
100%
The theoretical yield of the actual production ÷ acid isopropyls of selectivity (%)=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 for illustrate the present invention spherical diatomite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical diatomite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol) ethanol is added
Into 28mL, the acetic acid and sodium acetate buffer that pH value is 4, at 15 DEG C stirring be completely dissolved to P123, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then add 2.13g (0.014mol) four thereto
Methoxy silane, 20h is stirred under conditions of being 4.5 in 15 DEG C, pH value, then obtained solution is transferred in reactor,
Crystallization 24h at 60 DEG C, then carry out filtering and and be washed with deionized 4 times, then filter and obtain with the hole of one-dimensional channels three
The filter cake A1 of the meso-porous molecular sieve material of distributed architecture.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
5：1：1 is mixed and the haptoreaction 2h at 30 DEG C, then adjusts pH value to 3 with the sulfuric acid that concentration is 98 weight %, then
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter of silica gel
Cake B1.
By 10g filter cake A1,10g filter cake B1 and the 10g diatomite and 5g binding agents polyvinyl alcohol (PVA) of above-mentioned preparation together
Be put into 100mL ball grinders (wherein, the material of ball grinder and abrading-ball is agate, and a diameter of 3mm of abrading-ball, quantity is 1,
Rotating speed is 400r/min).Ball grinder is closed, temperature is ball milling 1 hour at 60 DEG C in ball grinder, obtains 30g solid powders；Will
The solid powder is dissolved in 30g deionized waters, is spray-dried at 200 DEG C in the case where rotating speed is 12000r/min；Spraying is dry
The product obtained after dry calcines 24h in Muffle furnace at 500 DEG C, and removed template method, obtaining 28g has the hole of one-dimensional channels three point
The spherical diatomite mesoporous composite material C1 of cloth structure.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical diatomite mesoporous composite material C1 of 30g and p-methyl benzenesulfonic acid that will be prepared in above-mentioned steps (1)
It is put into together in deionized water, stirring to dissolving, and the weight ratio of spherical diatomite mesoporous composite material C1 and p-methyl benzenesulfonic acid
For 50：50, the mol ratio of deionized water and p-methyl benzenesulfonic acid is 25：1, sprayed at 200 DEG C in the case where rotating speed is 12000r/min
Dry, obtain loaded catalyst Cat-1.
With XRD, ESEM and U.S.'s Kang Ta companies Atsorb-1 types instrument come to the support type Catalyzed by p-Toluenesulfonic Acid
Agent is characterized.
Fig. 1 is X-ray diffracting spectrum, is spherical diatomite mesoporous composite material C1 XRD spectra, and abscissa is 2 θ, is indulged
Coordinate is intensity.From the low-angle spectral peak occurred in XRD spectra, spherical diatomite mesoporous composite material C1 has mesoporous material
The pore size distribution structure of one-dimensional channels three specific to material.
Fig. 2 is the SEM scanning electron microscope (SEM) photographs of spherical diatomite mesoporous composite material C1 microscopic appearance.As seen from the figure, it is spherical
Diatomite mesoporous composite material C1 microscopic appearance is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 3 is spherical diatomite mesoporous composite material C1 pore size distribution curve.
Spherical diatomite mesoporous composite material C1 and loaded catalyst Cat-1 pore structure parameter are as shown in table 1 below.
Table 1
*：The first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively are, is used between them
Comma separates.
Spherical diatomite mesoporous composite material compares table after p-methyl benzenesulfonic acid is loaded it can be seen from the data of upper table 1
Area and pore volume have reduced, and it is mesoporous multiple that this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical diatomite
The inside of condensation material.
Comparative example 1
Spherical diatomite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, it is different,
Diatomite is added without during mesoporous composite material of the preparation as carrier, so as to which mesoporous composite material D1 be made respectively and bear
Supported catalyst Cat-D-1.
Comparative example 2
Spherical diatomite 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 bar-shaped mesoporous silicon oxide SBA-15 of identical weight
Skill limited company) instead of the filter cake A1 of the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three, so as to respectively
Mesoporous composite material D2 and loaded catalyst Cat-D-2 is made.
Comparative example 3
Spherical diatomite mesoporous composite material and loaded catalyst are prepared according to the method for embodiment 1, except that,
The material of ball grinder is polytetrafluoroethylene (PTFE) during the mesoporous composite material as carrier is prepared, and Material quality of grinding balls is agate.
So as to which mesoporous composite material D3 and loaded catalyst Cat-D-3 be made respectively.
Comparative example 4
Spherical diatomite 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 for dipping
On spherical diatomite mesoporous composite material, so as to which loaded catalyst Cat-D-4 be made.
Embodiment 2
The present embodiment be used for illustrate the present invention spherical diatomite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical diatomite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethanol is added to
In 28mL, the acetic acid and sodium acetate buffer that pH value is 5, at 15 DEG C stirring be completely dissolved to P123, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then add 3.04g (0.02mol) four thereto
Methoxy silane, 15h is stirred under conditions of being 5.5 in 25 DEG C, pH value, then obtained solution is transferred in reactor,
Crystallization 10h at 100 DEG C, then carry out filtering and and be washed with deionized 4 times, then filter and obtain with the hole of one-dimensional channels three
The filter cake A2 of the meso-porous molecular sieve material of distributed architecture.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
4：1：1 is mixed and the haptoreaction 1.5h at 40 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %, so
Obtained reaction mass is filtered afterwards, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains silica gel
Filter cake B2.
20g filter cake A2,15g filter cake B2 and the 15g diatomite and 2g binding agents PVA of above-mentioned preparation are put into 100mL together
(wherein, the material of ball grinder and abrading-ball is agate, and a diameter of 3mm of abrading-ball, quantity is 1, and rotating 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 powders；By the solid
Powder is dissolved in 36g deionized waters, is spray-dried at 250 DEG C in the case where rotating 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, obtain the spherical diatomite mesoporous composite materials of 30g
C2。
(2) loaded catalyst is prepared
At 25 DEG C, the spherical diatomite mesoporous composite material C2 of 20g and p-methyl benzenesulfonic acid that will be prepared in above-mentioned steps (1)
It is put into together in deionized water, stirring to dissolving, and the weight ratio of spherical diatomite mesoporous composite material C2 and p-methyl benzenesulfonic acid
For 95：5, the mol ratio of deionized water and p-methyl benzenesulfonic acid is 25：1, spray and do in the case where rotating speed is 13000r/min at 150 DEG C
It is dry, obtain loaded catalyst Cat-2.
Table 2
*：The first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively are, is used between them
Comma separates.
Spherical diatomite mesoporous composite material compares table after p-methyl benzenesulfonic acid is loaded it can be seen from the data of upper table 2
Area and pore volume have reduced, and it is mesoporous multiple that this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical diatomite
The inside of condensation material.
Embodiment 3
The present embodiment be used for illustrate the present invention spherical diatomite mesoporous composite material and loaded catalyst and they
Preparation method.
(1) spherical diatomite mesoporous composite material is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethanol is added to
In 28mL, the acetic acid and sodium acetate buffer that pH value is 3, at 15 DEG C stirring be completely dissolved to P123, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then add 4.56g (0.03mol) tetramethyl thereto
TMOS, 10h is stirred under conditions of being 3.5 in 40 DEG C, pH value, then obtained solution is transferred in reactor, 40
Crystallization 48h at DEG C, then carry out filtering and and be washed with deionized 4 times, then filter and obtain with the hole of one-dimensional channels three point
The filter cake A3 of the meso-porous molecular sieve material of cloth structure.
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as
6：1：1 is mixed and the haptoreaction 3h at 20 DEG C, then adjusts pH value to 4 with the sulfuric acid that concentration is 98 weight %, then
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter of silica gel
Cake B3.
20g filter cake A3,30g filter cake B3 and the 5g diatomite and 8g binding agents PVA of above-mentioned preparation are put into 100mL balls together
(wherein, the material of ball grinder and abrading-ball is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating 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 powders；The solid powder is molten
Solution is spray-dried in 30g deionized waters at 150 DEG C in the case where rotating speed is 13000r/min；The production that will be obtained after spray drying
Thing calcines 70h in Muffle furnace at 450 DEG C, removed template method, obtains the spherical diatomite mesoporous composite material C3 of 33g.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical diatomite mesoporous composite material C3 of 20g and p-methyl benzenesulfonic acid that will be prepared in above-mentioned steps (1)
It is put into together in deionized water, stirring to dissolving, and the weight ratio of spherical diatomite mesoporous composite material C3 and p-methyl benzenesulfonic acid
For 85：15, the mol ratio of deionized water and p-methyl benzenesulfonic acid is 25：1, sprayed at 250 DEG C in the case where rotating speed is 11000r/min
Dry, obtain loaded catalyst Cat-3.
Spherical diatomite mesoporous composite material C3 and loaded catalyst Cat-3 pore structure parameter are as shown in table 3 below.
Table 3
*：The first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively are, is used between them
Comma separates.
Spherical diatomite mesoporous composite material compares table after p-methyl benzenesulfonic acid is loaded it can be seen from the data of upper table 3
Area and pore volume have reduced, and it is mesoporous multiple that this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical diatomite
The inside of condensation material.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for application and the system of acid isopropyl for illustrating 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, weighed
0.5g, oleic acid 6g (0.02mol) is sequentially added in there-necked flask, isopropanol 2.8g (0.047mol), Cat-1 0.5g, is heated to
75 DEG C, after reacting 0.5h, centrifuge, utilize gas chromatographic analysis reaction product liquid composition, oleic acid conversion 99.9%, oleic acid
Isopropyl ester selectivity 99%, solid catalyst Cat-1 is dried in vacuo 6h at 150 DEG C, sharp again after recovery 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, except that, respectively with embodiment 2-3 and contrast
Loaded catalyst prepared by example 1-4 replaces the loaded catalyst Cat-1.As a result, the oleic acid being each 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% | 99% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 99% | 99% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 99% | 99% |
| Experimental comparison's example 1 | Cat-D-1 | 97% | 96% |
| Experimental comparison's example 2 | Cat-D-2 | 95% | 95% |
| Experimental comparison's example 3 | Cat-D-3 | 97% | 97% |
| Experimental comparison's example 4 | Cat-D-4 | 98% | 96% |
EXPERIMENTAL EXAMPLE 4-6 and Experimental comparison's example 5-8
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, except 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 recovery.As a result, the oleic acid being each 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 recovery | 90% | 98% |
| EXPERIMENTAL EXAMPLE 5 | The Cat-2 of recovery | 80% | 99% |
| EXPERIMENTAL EXAMPLE 6 | The Cat-3 of recovery | 72% | 100% |
| Experimental comparison's example 5 | The Cat-D-1 of recovery | 70% | 88% |
| Experimental comparison's example 6 | The Cat-D-2 of recovery | 60% | 87% |
| Experimental comparison's example 7 | The Cat-D-3 of recovery | 52% | 90% |
| Experimental comparison's example 8 | The Cat-D-4 of recovery | 40% | 95% |
Using the spherical diatomite mesoporous composite material conduct of the present 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 preparing the loaded catalyst by the method for spray drying, the loaded catalyst may be repeated profit
With, and higher reaction raw materials conversion ratio still can be obtained during recycling.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 equally be considered as content disclosed in this invention.
Claims (19)
1. a kind of spherical diatomite mesoporous composite material, it is characterised in that the spherical diatomite mesoporous composite material contains diatom
Soil and the meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three, and the spherical diatomite mesoporous composite material is flat
Equal particle diameter is 30-60 microns, and specific surface area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in three
Peak is distributed, and three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size respectively, and described first most
Can several apertures be 1-5 nanometers, second most probable pore size is 6-10 nanometers, and the 3rd most probable pore size is 40-45 nanometers.
2. composite according to claim 1, wherein, relative to having the hole of one-dimensional channels three described in 100 parts by weight
The meso-porous molecular sieve material of distributed architecture, the diatomaceous content are 1-100 parts by weight, preferably 25-100 parts by weight.
3. a kind of method for preparing spherical diatomite mesoporous composite material, this method comprise the following steps：
(1) meso-porous molecular sieve material with the pore size distribution structure of one-dimensional channels three is provided or prepared with the hole of one-dimensional channels three point
The filter cake of the meso-porous molecular sieve material of cloth structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) by the component a, component b, diatomite and the binding agent are mixed in ball grinder and ball milling, and by ball milling
Obtained slurry, is then spray-dried by the solid powder obtained afterwards water slurrying；
Wherein, above-mentioned steps cause the average grain diameter of the spherical diatomite mesoporous composite material to be 30-60 microns, specific surface area
For 100-600 meters squared per grams, pore volume is 0.5-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to first most respectively
Can several apertures, the second most probable pore size and the 3rd most probable pore size, first most probable pore size is 1-5 nanometers, described second
Most probable pore size is 6-10 nanometers, and the 3rd most probable pore size is 40-45 nanometers.
4. the method according to claim 11, wherein, in step (3), relative to the component a of 100 parts by weight use
Amount, the dosage of the component b is 1-200 parts by weight, preferably 75-150 parts by weight；The diatomaceous dosage is 1-100 weights
Measure part, preferably 25-100 parts by weight；The dosage of the binding agent is 10-100 parts by weight, preferably 10-80 parts by weight；
Preferably, the binding agent is polyvinyl alcohol and/or polyethylene glycol, more preferably polyvinyl alcohol.
5. according to the method for claim 3, wherein, in step (1), prepare the mesoporous of the pore size distribution structure of one-dimensional channels three
The process of the filter cake of molecular screen material includes：In acidic aqueous solution, in the presence of trimethylpentane and ethanol, by template
Contacted with silicon source, and the mixture obtained after contact is subjected to crystallization and filtering.
6. according to the method for claim 5, wherein, template, ethanol, the mol ratio of trimethylpentane and silicon source are 1：
100-500：200-500：50-200, preferably 1：180-400：250-400：70-150；
Preferably, the template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；The silicon source is tetramethyl
TMOS；The acidic aqueous solution is the acetic acid and sodium acetate buffer solution that pH value is 1-6；
Preferably, the condition of the contact includes：Temperature is 10-60 DEG C, and the time is 10-72 hours, pH value 1-7；The crystalline substance
The condition of change includes：Temperature is 30-150 DEG C, and the time is 10-72 hours.
7. according to the method for claim 3, wherein, in step (2), preparing the process of the filter cake of silica gel includes：In nothing
In the presence of machine acid, waterglass is contacted with polyalcohol, and the mixture obtained after contact is filtered.
8. according to the method for claim 7, wherein, the condition of the contact includes：Temperature is 10-60 DEG C, time 1-5
Hour, pH value 2-4；The inorganic acid is at least one of sulfuric acid, nitric acid and hydrochloric acid；The polyalcohol is ethylene glycol, third
At least one of glycol and glycerine, preferably ethylene glycol and/or glycerine；
Preferably, the weight ratio of the waterglass, inorganic acid and polyalcohol is 3-8：1-3：1.
9. according to the method for claim 3, wherein, in step (3), the condition of the ball milling includes：The rotating 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；
Preferably, the ball grinder is agate jar；
Preferably, the condition of the spray drying includes：100-300 DEG C of temperature, rotating speed 10000-15000r/min.
10. the method according to claim 3 or 4, wherein, the component a is with the pore size distribution structure of one-dimensional channels three
The filter cake of meso-porous molecular sieve material, the component b are the filter cake of silica gel；
Preferably, the preparation method of the spherical diatomite mesoporous composite material also includes：Spray-drying process in step (3)
Afterwards, removed template method in the product obtained from spray drying；
It is highly preferred that the condition of the removed template method includes：Temperature is 300-600 DEG C, and the time is 10-80 hours.
11. the spherical diatomite mesoporous composite material prepared as the method described in any one in claim 3-10.
12. a kind of loaded catalyst, the catalyst contains the p-methyl benzenesulfonic acid of carrier and load on the carrier, its feature
It is, the carrier is the spherical diatomite mesoporous composite material described in any one in claim 1-2 and 11.
13. loaded catalyst according to claim 12, wherein, using the gross weight of the loaded catalyst as base
Standard, the content of the p-methyl benzenesulfonic acid is 1-50 weight %, preferably 5-50 weight %；The content of the carrier is 50-99 weights
Measure %, preferably 50-95 weight %.
14. a kind of preparation method of loaded catalyst, it is characterised in that this method includes：By carrier, p-methyl benzenesulfonic acid and water
It is well mixed, and obtained mixture is spray-dried, wherein, the carrier is any one in claim 1-2 and 11
Spherical diatomite mesoporous composite material described in.
15. the method according to claim 11, wherein, it is right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 1-50 weight %, preferably 5-50 weight %；The dosage of the carrier is 50-99 weight %, preferably
For 50-95 weight %.
16. the loaded catalyst prepared as the method described in claims 14 or 15.
17. the application of loaded catalyst in the esterification reaction in claim 12-13 and 16 described in any one.
18. a kind of preparation method of acid isopropyl, wherein, this method includes：In the presence of a catalyst, in esterification
Under the conditions of, contact oleic acid and isopropanol, to obtain acid isopropyl, it is characterised in that the catalyst is claim 12-
Loaded catalyst in 13 and 16 described in any one.
19. preparation method according to claim 18, wherein, the mol ratio of oleic acid and isopropanol is 1：0.5-10；It is preferred that
Ground, relative to the oleic acid of 100 parts by weight, the dosage of the catalyst is 1-15 parts by weight, more preferably 2-14 parts by weight.
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| CN114425433A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Propylene catalyst containing diatomite mesoporous composite material, preparation method of propylene catalyst and method for preparing propylene by MTBE (methyl tert-butyl ether) cracking |
| CN115337921A (en) * | 2021-05-12 | 2022-11-15 | 中国石油化工股份有限公司 | Supported esterification catalyst, preparation method and application thereof |
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