CN107262157A - The preparation method of spherical mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl - Google Patents
The preparation method of spherical mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl Download PDFInfo
- Publication number
- CN107262157A CN107262157A CN201610213169.4A CN201610213169A CN107262157A CN 107262157 A CN107262157 A CN 107262157A CN 201610213169 A CN201610213169 A CN 201610213169A CN 107262157 A CN107262157 A CN 107262157A
- Authority
- CN
- China
- Prior art keywords
- weight
- meerschalminite
- composite material
- mesoporous composite
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 113
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 42
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- 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 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 35
- 239000004411 aluminium Substances 0.000 claims abstract description 35
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 27
- 239000004113 Sepiolite Substances 0.000 claims abstract description 24
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 24
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000012065 filter cake Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000000741 silica gel Substances 0.000 claims description 24
- 229910002027 silica gel Inorganic materials 0.000 claims description 24
- 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 24
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 230000002902 bimodal effect Effects 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 7
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 6
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 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
- 239000002002 slurry Substances 0.000 claims description 3
- 239000004575 stone 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
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000000243 solution Substances 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 101150116295 CAT2 gene Proteins 0.000 description 5
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 5
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 5
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007974 sodium acetate buffer Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007086 side reaction Methods 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001420 photoelectron spectroscopy Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 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
- 241001465754 Metazoa Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000004364 calculation method Methods 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
- 239000002274 desiccant Substances 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 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
- 239000003595 mist 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
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 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
- B01J29/03—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
- 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
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 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
- B01J35/643—Pore diameter less than 2 nm
-
- 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
- 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)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to catalyst field, and in particular to the preparation method of a kind of spherical mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl.Wherein, disclose a kind of spherical mesoporous composite material containing meerschalminite, the preparation method of the spherical mesoporous composite material containing meerschalminite, the spherical mesoporous composite material containing meerschalminite prepared by this method, loaded catalyst containing the spherical mesoporous composite material containing meerschalminite, 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 sepiolite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the content of aluminium element is 5 30 weight % in the composite.The loaded catalyst that the composite provided using the present invention is made as carrier can significantly improve the conversion ratio of reaction raw materials in acid isopropyl preparation process.
Description
Technical field
The present invention relates to catalyst field, and in particular to a kind of spherical mesoporous composite material containing meerschalminite,
The preparation method of the spherical mesoporous composite material containing meerschalminite, the spherical Hai Pao containing aluminium prepared by this method
Stone mesoporous composite material, the loaded catalyst containing the spherical mesoporous composite material containing meerschalminite should
The preparation method of loaded catalyst, the loaded catalyst prepared by this method, the loaded catalyst
Application in the esterification reaction, and the method for preparing using the loaded catalyst acid isopropyl.
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, paving
Malleability is good, thin electrolyte film can be formed on skin, with skin care effect.With the rapid hair of chemical industry
Exhibition, the demand to acid isopropyl is continuously increased.Generally, acid isopropyl is by oleic acid and isopropyl
Alcohol is made in the presence of catalyst by esterification.It is traditionally used for oleic acid and isopropyl alcohol esterification is anti-
The catalyst answered is liquid organic acid, but is produced because its corrosiveness is big, trigger side reaction is more, after reaction
Thing separation is complicated and the defect such as liquid waste processing difficulty and cause it using being subject to certain restrictions.With complete
Increase of the ball to Catalytic processes greenization attention degree, solid acid catalysis technique substitution liquid acid Catalytic processes
It is imperative.
In existing loaded catalyst, meso-porous molecular sieve material is used as carrier.Meso-porous molecular sieve material
Have the advantages that duct is orderly, aperture is adjustable, specific surface area and pore volume are larger so that mesoporous using these
In preparation technology of the loaded catalyst that molecular screen material is made as carrier in organic catalytic reaction
Lot of advantages is shown, for example, catalytic activity is high, side reaction is few, post processing is simple etc., however, greatly
Specific surface area and high pore volume enable these meso-porous molecular sieve materials have stronger water suction, the moisture absorption
Power, so that these loaded catalysts can be caused to reunite in catalytic reaction process, and then reduces oil
The conversion ratio of oleic acid in isopropyl propionate preparation technology.Therefore, further developing a kind of new is used to make
The problem of catalyst of standby acid isopropyl turns into the urgent need to address.
The content of the invention
The invention aims to overcome the support type being made of existing meso-porous molecular sieve material to urge
Agent relatively low defect of reaction raw materials conversion ratio during acid isopropyl is prepared is adapted to use there is provided one kind
Make the spherical mesoporous composite material containing meerschalminite of carrier, the spherical mesoporous composite material containing meerschalminite
Preparation method, the spherical mesoporous composite material containing meerschalminite prepared by this method is spherical containing aluminium containing this
The loaded catalyst of sepiolite mesoporous composite material, the preparation method of the loaded catalyst, by the party
Loaded catalyst prepared by method, the application of the loaded catalyst in the esterification reaction, and use should
The method that loaded catalyst prepares acid isopropyl.
In order to achieve the above object, the present inventor after research by having found, with one-dimensional channels
Sepiolite is introduced in the meso-porous molecular sieve material of diplopore distributed architecture, sepiolite is entered mesopore molecular sieve material
In the duct of material, and the mesoporous composite material is made to be not susceptible to reunite spherical, can so protected
Stay the high-specific surface area of meso-porous molecular sieve material, big pore volume, large aperture and with one-dimensional channels diplopore point
The features such as cloth structure, the reunion of meso-porous molecular sieve material can be reduced again, increase its mobility；Meanwhile, by
In introducing aluminium element in meso-porous molecular sieve material so that spheroid intensity is increased, can be repeatedly as carrier
It is used for multiple times, greatly reduces use cost.In addition, the support type being made of the mesoporous composite material
Catalyst can significantly improve the conversion ratio of reaction raw materials when for preparing acid isopropyl.
Therefore, the invention provides the spherical mesoporous composite material containing meerschalminite of one kind, wherein, this is spherical
Mesoporous composite material containing meerschalminite contains sepiolite and with the mesoporous of one-dimensional channels diplopore distributed architecture
Molecular screen material, and the average grain diameter of the spherical mesoporous composite material containing meerschalminite is 30-60 microns,
Specific surface area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution,
And it is bimodal correspond to the first most probable pore size and the second most probable pore size respectively, first most probable pore size is
1-10 nanometers, second most probable pore size is 40-42 nanometers；It is described spherical mesoporous multiple containing meerschalminite
The content of aluminium element is 5-30 weight %, preferably 10-29 weight % in condensation material.
Present invention also offers a kind of method for preparing the spherical mesoporous composite material containing meerschalminite, this method
Comprise the following steps：
(1) providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, is used as component a；
(2) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(3) the component a, the component b and sepiolite are mixed in high alumina ceramic ball grinder
And ball milling, and by the solid powder obtained after ball milling water slurrying, then obtained slurry is sprayed
Dry；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical mesoporous composite material containing meerschalminite is
30-60 microns, specific surface area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, hole
Footpath is in bimodal distribution, and it is bimodal correspond to the first most probable pore size and the second most probable pore size respectively, described the
One most probable pore size is 1-10 nanometers, and second most probable pore size is 40-42 nanometers；It is described spherical to contain
The content of aluminium element is 5-30 weight %, preferably 10-29 weight % in meerschalminite mesoporous composite material.
Present invention also offers the spherical mesoporous composite material containing meerschalminite prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains carrier and is supported on the load
P-methyl benzenesulfonic acid on body, wherein, the carrier is according to the described spherical containing meerschalminite Jie of the present invention
Hole composite material.
Present invention also offers a kind of method for preparing loaded catalyst, this method includes：By carrier,
P-methyl benzenesulfonic acid and water are well mixed, and obtained mixture is spray-dried, wherein, it is described to carry
Body is the spherical mesoporous composite material containing meerschalminite according to the present invention.
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 catalyst
In the presence of, under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl,
Wherein, the catalyst is loaded catalyst of the present invention.
Spherical mesoporous composite material containing meerschalminite according to the present invention, is combined with one-dimensional channels
The meso-porous molecular sieve material of diplopore distributed architecture, sepiolite, the advantage of aluminium element and ball type carrier, make
The carrier that the spherical mesoporous composite material containing meerschalminite is suitable as loaded catalyst is obtained, is particularly fitted
Share the carrier for the loaded catalyst for making to be used in acid isopropyl preparation process.
In loaded catalyst of the present invention, the spherical composite mesoporous containing meerschalminite of carrier is used as
The characteristics of material has the loose structure of meso-porous molecular sieve material, but also p-methyl benzenesulfonic acid is loaded with, make
Obtain the loaded catalyst and both had the advantages that loaded catalyst such as catalytic activity are high, side reaction is few, after
Handle simple etc., there is the catalytic performance of acid again so that the loaded catalyst is for acid isopropyl
Equipment corrosion will not only be caused when in preparation process, but also the conversion of reaction raw materials can be significantly improved
Rate.
In addition, when preparing the loaded catalyst by the method for spray drying, the support type is urged
Agent can be used repeatedly, and still can obtain during recycling higher anti-
Answer feed stock conversion.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with
Following embodiment is used to explain the present invention together, but is not construed as limiting the invention.
In accompanying drawing：
Fig. 1 is the X-ray diffraction of the spherical mesoporous composite material containing meerschalminite according to the present invention
Spectrogram；
Fig. 2 is the microscopic appearance of the spherical mesoporous composite material containing meerschalminite according to the present invention
SEM scanning electron microscope (SEM) photographs；
Fig. 3 is the graph of pore diameter distribution of the spherical mesoporous composite material containing meerschalminite according to the present invention.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides the spherical mesoporous composite material containing meerschalminite of one kind, wherein, this is spherical containing aluminium sea
Afrodite mesoporous composite material contains sepiolite and the mesopore molecular sieve with one-dimensional channels diplopore distributed architecture
Material, and the average grain diameter of the spherical mesoporous composite material containing meerschalminite is 30-60 microns, compares table
Area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and
Bimodal to correspond to the first most probable pore size and the second most probable pore size respectively, first most probable pore size is
1-10 nanometers, second most probable pore size is 40-42 nanometers；It is described spherical mesoporous multiple containing meerschalminite
The content of aluminium element is 5-30 weight %, preferably 10-29 weight % in condensation material.
Spherical mesoporous composite material containing meerschalminite according to the present invention has one-dimensional channels diplopore point
Cloth structure, the average grain diameter of its particle is measured using laser fineness gage, specific surface area, pore volume and
Most probable pore size is measured according to nitrogen adsorption methods.In the present invention, the average grain diameter is average grain
Diameter.
Spherical mesoporous composite material containing meerschalminite according to the present invention, by by spherical Hai Pao containing aluminium
The particle size of stone mesoporous composite material is controlled within above range, it can be ensured that described spherical containing aluminium sea
Afrodite mesoporous composite material is not susceptible to reunite, and be used as loaded catalyst that carrier is made can
To improve the reaction raw materials conversion ratio in acid isopropyl preparation process.When described spherical containing meerschalminite Jie
When the specific surface area of hole composite material is less than 100 meters squared per grams and/or pore volume less than 0.5 ml/g,
Being used as the catalytic activity for the loaded catalyst that carrier is made can significantly reduce；When described spherical containing aluminium
The specific surface area of sepiolite mesoporous composite material is more than 600 meters squared per grams and/or pore volume is more than 1.5 millis
Rise/gram when, be used as the loaded catalyst that carrier is made and easily sent out in acid isopropyl preparation process
It is raw to reunite, so as to influence the reaction raw materials conversion ratio in acid isopropyl preparation process.
In the preferred case, the average grain diameter of the spherical mesoporous composite material containing meerschalminite is 35-55
Micron, specific surface area is 100-500 meters squared per grams, and pore volume is 0.9-1.3 mls/g, described first
Most probable pore size is 2-10 nanometers, and second most probable pore size is 41-42 nanometers.
In the present invention, the aluminium element can enter by sepiolite and/or in high alumina ceramic ball grinder
The mode of row ball milling is introduced.The sepiolite can be sepiolite commonly used in the art, preferable case
Under, the content of aluminium element is 1-10 weight %, preferably 2-8 weight % in the sepiolite.Further
Preferably, described in the percentage by weight of aluminium element is more than in the spherical mesoporous composite material containing meerschalminite
The percentage by weight of aluminium element in sepiolite.
According to the present invention, relative to Jie described in 100 parts by weight with one-dimensional channels diplopore distributed architecture
Porous molecular sieve material, the content of the sepiolite is 1-100 parts by weight, preferably 25-100 parts by weight,
Preferably 15-50 parts by weight.
In the present invention, the spherical mesoporous composite material containing meerschalminite can also contain and be drawn by silica gel
The silica entered." silica introduced by silica gel " refers to described spherical containing meerschalminite Jie
In the preparation process of hole composite material, brought into by silica gel as preparing raw material finally prepare it is spherical containing aluminium sea
Silica component in afrodite mesoporous composite material.In the spherical mesoporous composite material containing meerschalminite
In, relative to the meso-porous molecular sieve material described in 100 parts by weight with one-dimensional channels diplopore distributed architecture,
The content of the silica introduced by silica gel can be 1-200 parts by weight, preferably 50-150 weights
Measure part, more preferably 75-150 parts by weight.
In the present invention, the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture can be
Meso-porous molecular sieve material commonly used in the art, and can prepare according to the conventional method.
Present invention also offers a kind of method for preparing the spherical mesoporous composite material containing meerschalminite, this method
Comprise the following steps：
(1) providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, is used as component a；
(2) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(3) the component a, the component b and sepiolite are mixed in high alumina ceramic ball grinder
And ball milling, and by the solid powder obtained after ball milling water slurrying, then obtained slurry is sprayed
Dry；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical mesoporous composite material containing meerschalminite is
30-60 microns, specific surface area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, hole
Footpath is in bimodal distribution, and it is bimodal correspond to the first most probable pore size and the second most probable pore size respectively, described the
One most probable pore size is 1-10 nanometers, and second most probable pore size is 40-42 nanometers；It is described spherical to contain
The content of aluminium element is 5-30 weight %, preferably 10-29 weight % in meerschalminite mesoporous composite material.
In the preferred case, the component a causes the flat of the spherical mesoporous composite material containing meerschalminite
Equal particle diameter is 35-55 microns, and specific surface area is 100-600 meters squared per grams, and pore volume is 0.8-1.2 milliliters
/ gram, first most probable pore size is 1-10 nanometers, and second most probable pore size is 42-44 nanometers.
In step (1), the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is prepared
The process of filter cake can include：In the presence of template, trimethylpentane and ethanol, by tetramethoxy
Silane is contacted with sour agent, and the mixture obtained after contact is carried out into 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
For triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template can be commercially available
(for example, Aldrich can be purchased from, trade name P123, molecular formula is EO20PO70EO20),
It can also be prepared by existing various methods.When the template be PULLRONIC F68-
During polyoxyethylene, molal quantity being averaged according to polyoxyethylene-poly-oxypropylene polyoxyethylene of the template
Molecular weight calculation is obtained.
The material or mixture that the sour agent can be used for adjusting pH value for various routines are (such as molten
Liquid).The sour agent is preferably used in form of an aqueous solutions, and its pH value can be 1-6, preferably 3-5.
It is highly preferred that acetic acid and sodium acetate buffer solution that it is 1-6 (more preferably 3-5) that the sour agent, which is pH value,.
The condition that tetramethoxy-silicane is contacted with sour agent can include：Temperature is 10-60 DEG C, and the time is
10-72 hours, pH value was 1-7.In order to be more beneficial for the uniform mixing between each material, four methoxy
Base silane is contacted with sour agent and preferably carried out under agitation.The consumption of the sour agent is preferably so that four methoxies
The pH value of base silane and the haptoreaction system of sour agent is 1-7.
The condition of the crystallization can include：Temperature is 30-150 DEG C, and the time is 10-72 hours.It is preferred that
In the case of, the condition of the crystallization includes：Temperature is 40-100 DEG C, and the time is 10-48 hours.It is described
Crystallization is implemented by hydrothermal crystallization method.
There is the mistake of the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture in above-mentioned preparation
Cheng Zhong, can be included by filtering with the process for obtaining filter cake：After filtration, with deionized water repeatedly
Wash (washing times can be 2-10), then carry out suction filtration.
In step (1), " meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is provided "
It can be the production for directly weighing or choosing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
The meso-porous molecular sieve material of product or preparation with one-dimensional channels diplopore distributed architecture.It is described to have
The preparation method of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture can be according to the conventional method
Implement, for example, its preparation method can include：Being prepared according to the above method has one-dimensional channels diplopore point
The filter cake of the meso-porous molecular sieve material of cloth structure, then by gained filtration cakes torrefaction, and will be obtained after drying
Template removal in product.The condition of the removed template method can include：Temperature is 300-600 DEG C,
Time is 10-80 hours.
In step (2), preparing the process of the filter cake of silica gel can include：By waterglass and inorganic acid
Contacted with glycerine, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass is contacted with inorganic acid and glycerine, can be according to preparing silicon
Suitably determined in the common process of glue.Under preferable case, waterglass is contacted with inorganic acid and glycerine
Condition can include：Temperature is 10-60 DEG C, preferably 20-40 DEG C；Time is 1-5 hours, is preferably
1.5-3 hour；PH value is 2-4.
In order to be more beneficial for the uniform mixing between each material, waterglass and inorganic acid and glycerine haptoreaction
Process preferably carry out under agitation.
The waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 weight %, be preferably
12-30 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can for sulfuric acid,
At least one of nitric acid and hydrochloric acid.The inorganic acid can be used in pure form, can also be with it
The form of the aqueous solution is used.The consumption of the inorganic acid is preferably so that the haptoreaction of waterglass and inorganic acid
The pH value of system is 2-4.
In step (2), " offer silica gel " can directly weigh or choose silica gel product, can also
It is to prepare silica gel.Preparing the method for silica gel can implement according to the conventional method, for example, can include：Root
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 consumption of the component b is
1-200 parts by weight, preferably 75-150 parts by weight；The consumption of the sepiolite is 1-100 parts by weight,
Preferably 25-100 parts by weight.
In step (3), there is no particular limitation for concrete operation method and condition of the present invention to ball milling,
It is defined by not destroying or not destroying carrier structure substantially and enter silica gel in carrier duct.Art technology
Personnel can select various suitable conditions to implement the present invention according to mentioned above principle.In preferred situation
Under, the ball milling can be carried out in ball mill, and the inwall of ball grinder is high alumina ceramic in the ball mill,
The diameter of abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can be entered according to the size of ball grinder
Row is reasonably selected, and for the ball grinder that size is 50-150ml, can generally use 1 abrading-ball；
The material of the abrading-ball is high alumina ceramic.In situations where it is preferred, aluminium element contains in the high alumina ceramic
Measure as 30-40 weight %.There is no particular limitation in source of the present invention to the high alumina ceramic ball grinder,
For example, can be by commercially available.The condition of the ball milling can include：The rotating speed of abrading-ball can be
300-500r/min；Temperature in high alumina ceramic ball grinder can be 15-100 DEG C, preferably 40-80 DEG C；
The time of ball milling can be 0.1-100 hours, preferably 0.5-10 hours.
In step (3), the process by the solid powder water slurrying obtained after ball milling can be at 25-60 DEG C
Lower progress.In pulping process, the weight ratio of the consumption of solid powder and water can be 1:0.1-2, it is excellent
Elect 1 as:0.3-1, more preferably 1:0.5-1.
In step (3), the spray drying can be implemented according to conventional mode, for example can be
Carried out in atomizer.The condition of the spray drying can include：Temperature is 100-300 DEG C, rotation
Rotating speed can be 10000-15000r/min；Under preferable case, the condition of the spray drying includes：Temperature
Spend for 150-250 DEG C, the rotating speed of rotation is 11000-13000r/min.
In step (3), when the component a is mesoporous point with one-dimensional channels diplopore distributed architecture
The filter cake of son sieve material, when the component b is the filter cake of silica gel, namely when step (1) has to prepare
There is the process of the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, step (2) is system
During the process of the filter cake of standby silica gel, the preparation method of the spherical mesoporous composite material containing meerschalminite may be used also
With including：After the spray drying of step (3), template is removed in the product obtained from spray drying
Agent.The condition of the removed template method can include：Temperature is 300-600 DEG C, and the time is that 10-80 is small
When；It is preferred that in the case of, temperature is 450-550 DEG C, and the time is 15-70 hours.
Present invention also offers the spherical mesoporous composite material containing meerschalminite prepared by the above method.
Present invention also offers a kind of loaded catalyst, the catalyst contains carrier and is supported on the load
P-methyl benzenesulfonic acid on body, wherein, the carrier is situated between for the above-mentioned spherical meerschalminite that contains that the present invention is provided
Hole composite material.
In the loaded catalyst, the content of the carrier and p-methyl benzenesulfonic acid is not limited particularly
It is fixed, can suitably it be determined according to the conventional loaded catalyst in this area, for example, with described negative
On the basis of the gross weight of supported catalyst, the content of p-methyl benzenesulfonic acid can be 1-50 weight %, be preferably
5-50 weight %；The content of the carrier is 50-99 weight %, preferably 50-95 weight %.
In the present invention, the loaded catalyst can be according to various method systems commonly used in the art
It is standby, it is only necessary to by p-methyl benzenesulfonic acid load on the carrier.
In a preferred embodiment, in order that the loaded catalyst prepared may be repeated profit
With, and higher reaction raw materials conversion ratio still can be obtained during recycling, prepare load
The method of type catalyst includes：Carrier, p-methyl benzenesulfonic acid and water are well mixed, and by obtained mixing
Thing is spray-dried, wherein, the carrier for the present invention provide it is above-mentioned it is spherical containing meerschalminite it is mesoporous
Composite.
It is above-mentioned prepare loaded catalyst during, with the carrier and total consumption of p-methyl benzenesulfonic acid
On the basis of, the consumption of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；It is described
The consumption of carrier can be 50-99 weight %, preferably 50-95 weight %.
The spray drying can be implemented according to conventional mode, for example, can be carried out in atomizer.Institute
Stating the condition of 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, 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 catalyst
In the presence of, under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl,
Characterized in that, the catalyst is loaded catalyst of the present invention.
In the preparation method of the acid isopropyl, the consumption of oleic acid and isopropanol is not limited particularly
It is fixed, acid isopropyl is obtained as long as can react, but in order to improve the utilization rate of raw material, preferably feelings
Under condition, the mol ratio of oleic acid and isopropanol is 1：0.5-10, preferably 1:1-5.
Also there is no particular limitation for the consumption of the catalyst, can be prepared according to conventional acid isopropyl
Technique is suitably determined.Under preferable case, relative to the oleic acid of 100 parts by weight, the catalyst
Consumption be 1-15 parts by weight, more preferably 2-14 parts by weight.
It is described anti-in order to be more beneficial for the progress of esterification in the acid isopropyl preparation process
It should be carried out preferably in there-necked flask, i.e. 25~100 DEG C of the reaction temperature.Reaction time can be 1-20
Hour, preferably 2-15 hours.
The preparation method of the acid isopropyl is additionally may included in after esterification terminates, to final anti-
Mixture is answered to carry out suction filtration separation, and vacuum is done at 25-200 DEG C by the isolated solid product of suction filtration
It is dry 1-24 hours；It is preferred that being dried in vacuo 6-10 hours at 50-150 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
Company, is abbreviated as P123, and molecular formula is EO20PO70EO20, it is in the registration number of U.S. chemical abstract
9003-11-6 material, average molecular mass Mn is 5800.
In following examples and comparative example, X-ray diffraction analysis are purchased from German Bruker AXS companies
Model D8Advance X-ray diffractometer on carry out；Scanning electron microscope analysis is purchased from U.S. FEI
Carried out in the model XL-30 of company SEM；Pore structure parameter is analyzed purchased from the U.S.
Carried out on the model Autosorb-1 of Kang Ta companies nitrogen adsorption desorption instrument, wherein, before being tested,
Sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient is purchased from Britain Agilent
Carried out on company's 7890A/5973N gas chromatograph-mass spectrometers.Aluminium content result is surveyed by XPS Analysis instrument
.
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of oleic acid and the selectivity of acid isopropyl
Calculated and obtained according to below equation.
Consumption × 100% of the conversion ratio (%) of oleic acid=(content of oleic acid in consumption-reaction product of oleic acid) ÷ oleic acid
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 is used to illustrate that the spherical mesoporous composite material containing meerschalminite and support type of the present invention to be urged
Agent and their preparation method.
(1) spherical mesoporous composite material containing meerschalminite is prepared
By 1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol)
Ethanol be added to 28ml, pH value be 4 acetic acid and sodium acetate buffer in, stirred at 15 DEG C to
P123 is completely dissolved, the solution obtained backward in add 6g (0.053mol) trimethylpentane,
Stir 8h at 15 DEG C, then add 2.13g (0.014mol) tetramethoxy-silicane thereto, 15 DEG C,
PH value be 4.5 under conditions of stir 20h, obtained solution is then transferred to polytetrafluoroethyllining lining
In reactor, the crystallization 24h at 60 DEG C, then carry out filtering and and be washed with deionized 4 times, so
Suction filtration obtains the filter cake A1 of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture afterwards.
The sulfuric acid solution and glycerine that the waterglass and concentration for being 15 weight % by concentration are 12 weight % with
Weight ratio is 5:1:1 is mixed and haptoreaction 2 hours at 30 DEG C, is then 98 weights with concentration
The sulfuric acid for measuring % adjusts pH value to 3, then carries out suction filtration to obtained reaction mass, and use distilled water
Washing to sodium ions content is 0.02 weight %, obtains the filter cake B1 of silica gel.
10g filter cake A1,10g filter cake B1 and 10g sepiolites of above-mentioned preparation are put into 100ml together
(wherein, the material of ball grinder and abrading-ball is high alumina ceramic, aluminium element in the high alumina ceramic in ball grinder
Content be 35 weight %, a diameter of 3mm of abrading-ball, quantity be 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 30 grams of deionized waters, is sprayed at 200 DEG C in the case where rotating speed is 12000r/min
Mist is dried；By the product obtained after spray drying in Muffle furnace at 500 DEG C calcine 24 hours, removing
Template, obtaining 28 grams has the spherical composite mesoporous containing meerschalminite of one-dimensional channels diplopore distributed architecture
Material C 1.According to the result of XPS Analysis, the content of aluminium is 18 weight % in C1.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical composite mesoporous materials containing meerschalminite of 30g that will be prepared in above-mentioned steps (1)
Material C1 is put into deionized water together with p-methyl benzenesulfonic acid, stirring to dissolving, and spherical containing meerschalminite
The weight ratio of mesoporous composite material C1 and p-methyl benzenesulfonic acid is 50:50, deionized water and p-methyl benzenesulfonic acid
Mol ratio is 25:1, it is spray-dried at 200 DEG C in the case where rotating speed is 12000r/min, obtains support type and urge
Agent Cat-1.
With XRD, ESEM and U.S.'s Kang Ta companies Atsorb-1 types instrument come to the support type to first
Benzene sulfonic acid catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, the XRD for being the spherical C1 of mesoporous composite material containing meerschalminite spectrums
Figure, abscissa is 2 θ, and ordinate is intensity.The low-angle spectral peak occurred in XRD spectra, ball
Shape mesoporous composite material containing meerschalminite C1 has one-dimensional channels diplopore distribution knot specific to mesoporous material
Structure.
Fig. 2 is the SEM ESEMs of the spherical C1 of mesoporous composite material containing meerschalminite microscopic appearance
Figure.As seen from the figure, the spherical C1 of mesoporous composite material containing meerschalminite microscopic appearance is that particle diameter is
30-60 μm of Mesoporous Spheres.
Fig. 3 is the spherical C1 of mesoporous composite material containing meerschalminite pore size distribution curve.
The spherical C1 of mesoporous composite material containing meerschalminite and loaded catalyst Cat-1 pore structure parameter
It is as shown in table 1 below.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Particle diameter (μm) |
| Composite C1 | 200 | 1.2 | 8,42 | 50 |
| Catalyst Cat-1 | 170 | 0.8 | 3,27 | 50 |
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Spherical mesoporous composite material containing meerschalminite is being loaded to toluene it can be seen from the data of upper table 1
After sulfonic acid, specific surface area and pore volume have reduced, and this explanation is during load-reaction to toluene
Sulfonic acid enters the inside of the spherical mesoporous composite material containing meerschalminite.
Comparative example 1
Spherical mesoporous composite material containing meerschalminite and supported catalyst are prepared according to the method for embodiment 1
Agent, it is different, sepiolite is added without during the mesoporous composite material as carrier is prepared, from
And mesoporous composite material D1 and loaded catalyst Cat-D-1 is made respectively.According to XPS Analysis
Result, the content of aluminium is 11 weight % in D1.
Comparative example 2
Spherical mesoporous composite material containing meerschalminite and supported catalyst are prepared according to the method for embodiment 1
Agent, it is different, during loaded catalyst is prepared, with the bar-shaped mesoporous dioxy of identical weight
SiClx SBA-15 (being purchased from high-tech limited company of Jilin University) replaces having one-dimensional channels diplopore
The filter cake A1 of the meso-porous molecular sieve material of distributed architecture, so that mesoporous composite material D2 is made respectively and negative
Supported catalyst Cat-D-2.According to the result of XPS Analysis, the content of aluminium is 12 weights in D2
Measure %.
Comparative example 3
Spherical mesoporous composite material containing meerschalminite and supported catalyst are prepared according to the method for embodiment 1
Agent, except that, the material of ball grinder is during the mesoporous composite material as carrier is prepared
Polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate.So as to which obtained mesoporous composite material D3 and support type are urged respectively
Agent Cat-D-3.According to the result of XPS Analysis, the content of aluminium is 4 weight % in D3.
Comparative example 4
Spherical mesoporous composite material containing meerschalminite and supported catalyst are prepared according to the method for embodiment 1
Agent, it is different, the step of not being spray-dried during preparing loaded catalyst, and only lead to
P-methyl benzenesulfonic acid is supported on spherical mesoporous composite material containing meerschalminite by the method for crossing dipping, so as to make
Obtain loaded catalyst Cat-D-4.
Embodiment 2
The present embodiment is used to illustrate that the spherical mesoporous composite material containing meerschalminite and support type of the present invention to be urged
Agent and their preparation method.
(1) spherical mesoporous composite material containing meerschalminite is prepared
By 1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol)
Ethanol be added to 28ml, pH value be 5 acetic acid and sodium acetate buffer in, stirred at 15 DEG C to
P123 is completely dissolved, the solution obtained backward in add 9.12g (0.08mol) trimethylpentane,
Stir 8h at 15 DEG C, then add 3.04g (0.02mol) tetramethoxy-silicane thereto, 25 DEG C,
PH value be 5.5 under conditions of stir 15h, obtained solution is then transferred to polytetrafluoroethyllining lining
In reactor, the crystallization 10h at 100 DEG C, then carry out filtering and and be washed with deionized 4 times,
Then suction filtration obtains the filter cake A2 of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture.
The sulfuric acid solution and glycerine that the waterglass and concentration for being 15 weight % by concentration are 12 weight % with
Weight ratio is 4:1:1 is mixed and haptoreaction 1.5 hours at 40 DEG C, is then 98 weights with concentration
The sulfuric acid for measuring % adjusts pH value to 2, then carries out suction filtration to obtained reaction mass, and use distilled water
Washing to sodium ions content is 0.02 weight %, obtains the filter cake B2 of silica gel.
20g filter cake A2,15g filter cake B2 and 15g sepiolites of above-mentioned preparation are put into 100ml together
(wherein, the material of ball grinder and abrading-ball is high alumina ceramic, aluminium element in the high alumina ceramic in ball grinder
Content be 35 weight %, a diameter of 3mm of abrading-ball, quantity be 1, rotating speed is 300r/min).
Ball grinder is closed, temperature is ball milling 0.5 hour at 80 DEG C in ball grinder, obtains 50g solid powders；
The solid powder is dissolved in 36 grams of deionized waters, at 250 DEG C in the case where rotating speed is 11000r/min
Spray drying；By the product obtained after spray drying in Muffle furnace at 550 DEG C calcine 15 hours, take off
Template agent removing, obtains 30 grams of spherical C2 of mesoporous composite material containing meerschalminite.According to photoelectron spectroscopy point
The content of aluminium is 10 weight % in the result of analysis, C2.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical composite mesoporous materials containing meerschalminite of 20g that will be prepared in above-mentioned steps (1)
Material C2 is put into deionized water together with p-methyl benzenesulfonic acid, stirring to dissolving, and spherical containing meerschalminite
The weight ratio of mesoporous composite material C2 and p-methyl benzenesulfonic acid is 95:5, deionized water and p-methyl benzenesulfonic acid
Mol ratio is 25:1, it is spray-dried at 150 DEG C in the case where rotating speed is 13000r/min, obtains support type and urge
Agent Cat-2.
The spherical C2 of mesoporous composite material containing meerschalminite and loaded catalyst Cat-2 pore structure parameter
It is as shown in table 2 below.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Particle diameter (μm) |
| Composite C2 | 270 | 1.3 | 9,41 | 52 |
| Catalyst Cat-2 | 240 | 0.9 | 3.5,32 | 45 |
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Spherical mesoporous composite material containing meerschalminite is being loaded to toluene it can be seen from the data of upper table 2
After sulfonic acid, specific surface area and pore volume have reduced, and this explanation is during load-reaction to toluene
Sulfonic acid enters the inside of the spherical mesoporous composite material containing meerschalminite.
Embodiment 3
The present embodiment is used to illustrate that the spherical mesoporous composite material containing meerschalminite and support type of the present invention to be urged
Agent and their preparation method.
(1) spherical mesoporous composite material containing meerschalminite is prepared
By 1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol)
Ethanol be added to 28ml, pH value be 3 acetic acid and sodium acetate buffer in, stirred at 15 DEG C to
P123 is completely dissolved, the solution obtained backward in add 5.7g (0.05mol) trimethylpentane,
Stir 8h at 15 DEG C, then add 4.56g (0.03mol) tetramethoxy-silicane thereto, 40 DEG C,
PH value be 3.5 under conditions of stir 10h, obtained solution is then transferred to polytetrafluoroethyllining lining
In reactor, the crystallization 48h at 40 DEG C, then carry out filtering and and be washed with deionized 4 times, so
Suction filtration obtains the filter cake A3 of the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture afterwards.
The sulfuric acid solution and glycerine that the waterglass and concentration for being 15 weight % by concentration are 12 weight % with
Weight ratio is 6:1:1 is mixed and haptoreaction 3 hours at 20 DEG C, is then 98 weights with concentration
The sulfuric acid for measuring % adjusts pH value to 4, then carries out suction filtration to obtained reaction mass, and use distilled water
Washing to sodium ions content is 0.02 weight %, obtains the filter cake B3 of silica gel.
20g filter cake A3,30g filter cake B3 and 5g sepiolites of above-mentioned preparation are put into 100ml together
(wherein, the material of ball grinder and abrading-ball is high alumina ceramic, aluminium element in the high alumina ceramic in ball grinder
Content be 35 weight %, a diameter of 3mm of abrading-ball, quantity be 1, rotating speed is 500r/min).
Ball grinder is closed, temperature is ball milling 10 hours at 40 DEG C in ball grinder, obtains 55g solid powders；
The solid powder is dissolved in 30 grams of deionized waters, at 150 DEG C in the case where rotating speed is 13000r/min
Spray drying；By the product obtained after spray drying in Muffle furnace at 450 DEG C calcine 70 hours, take off
Template agent removing, obtains 33 grams of spherical C3 of mesoporous composite material containing meerschalminite.According to photoelectron spectroscopy point
The content of aluminium is 29 weight % in the result of analysis, C3.
(2) loaded catalyst is prepared
At 25 DEG C, the spherical composite mesoporous materials containing meerschalminite of 20g that will be prepared in above-mentioned steps (1)
Material C3 is put into deionized water together with p-methyl benzenesulfonic acid, stirring to dissolving, and spherical containing meerschalminite
The weight ratio of mesoporous composite material C3 and p-methyl benzenesulfonic acid is 85:15, deionized water and p-methyl benzenesulfonic acid
Mol ratio is 25:1, it is spray-dried at 250 DEG C in the case where rotating speed is 11000r/min, obtains support type and urge
Agent Cat-3.
The spherical C3 of mesoporous composite material containing meerschalminite and loaded catalyst Cat-3 pore structure parameter
It is as shown in table 3 below.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Particle diameter (μm) |
| Composite C3 | 185 | 0.9 | 9.5,42 | 45 |
| Catalyst Cat-3 | 136 | 0.61 | 7,31 | 53 |
*：First most probable pore size and the second most probable pore size are separated with comma：It is the first most probable pore size before comma,
It is the second most probable pore size after comma.
Spherical mesoporous composite material containing meerschalminite is being loaded to toluene it can be seen from the data of upper table 3
After sulfonic acid, specific surface area and pore volume have reduced, and this explanation is during load-reaction to toluene
Sulfonic acid enters the inside of the spherical mesoporous composite material containing meerschalminite.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for the application for illustrating the loaded catalyst that the present invention is provided and oleic acid is different
The preparation method of propyl ester.
Loaded catalyst Cat-1 prepared by embodiment 1 is dried in vacuo 6 hours at 150 DEG C, cold
But to after room temperature, 0.5 gram is weighed, oleic acid 6g, isopropanol 2.8g are sequentially added in there-necked flask,
Cat-10.5g, is heated to after 75 DEG C, reaction half an hour, centrifuges, reacted using gas chromatographic analysis
Product liquid composition, oleic acid conversion 100%, acid isopropyl selectivity 100%, yield 76%, solid
Catalyst Cat-1 is dried in vacuo 6 hours at 150 DEG C, is cooled to after room temperature, is recycled after recovery.
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, embodiment is used respectively
Loaded catalyst prepared by 2-3 and comparative example 1-4 replaces the loaded catalyst Cat-1.As a result,
The conversion ratio and acid isopropyl selective data for each calculating obtained oleic acid are as shown in table 4 below.
Table 4
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 100% | 100% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 99% | 100% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 99% | 100% |
| Experimental comparison's example 1 | Cat-D-1 | 98% | 99% |
| Experimental comparison's example 2 | Cat-D-2 | 98% | 99% |
| Experimental comparison's example 3 | Cat-D-3 | 60% | 95% |
| Experimental comparison's example 4 | Cat-D-4 | 50% | 90% |
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 experiment
The catalyst that embodiment 1-3 and Experimental comparison's example 1-4 are reclaimed replaces the loaded catalyst Cat-1.Knot
Really, the conversion ratio and acid isopropyl selective data for each calculating obtained oleic acid are 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 | 85% | 100% |
| EXPERIMENTAL EXAMPLE 5 | The Cat-2 of recovery | 70% | 100% |
| EXPERIMENTAL EXAMPLE 6 | The Cat-3 of recovery | 65% | 100% |
| Experimental comparison's example 5 | The Cat-D-1 of recovery | 63% | 99% |
| Experimental comparison's example 6 | The Cat-D-2 of recovery | 60% | 99% |
| Experimental comparison's example 7 | The Cat-D-3 of recovery | 55% | 90% |
| Experimental comparison's example 8 | The Cat-D-4 of recovery | 50% | 80% |
Using the described spherical containing meerschalminite Jie of the present invention it can be seen from the data of above-mentioned table 4 and 5
The loaded catalyst that hole composite material is made as carrier can show in acid isopropyl preparation process
Write the conversion ratio for improving reaction raw materials.Moreover, being urged when the method by being spray-dried prepares the support type
During agent, the loaded catalyst may be repeated utilization, and during recycling still
Higher reaction raw materials conversion ratio can be obtained.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of spherical mesoporous composite material containing meerschalminite, it is characterised in that the spherical Hai Pao containing aluminium
Stone mesoporous composite material contains sepiolite and the mesopore molecular sieve material with one-dimensional channels diplopore distributed architecture
Material, and the average grain diameter of the spherical mesoporous composite material containing meerschalminite is 30-60 microns, compares surface
Product is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and double
Peak corresponds to the first most probable pore size and the second most probable pore size respectively, and first most probable pore size is 1-10
Nanometer, second most probable pore size is 40-42 nanometers；
Wherein, the content of aluminium element is 5-30 weights in the spherical mesoporous composite material containing meerschalminite
Measure %, preferably 10-29 weight %.
2. composite according to claim 1, wherein, relative to described in 100 parts by weight
Meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, the content of the sepiolite is 1-100
Parts by weight, preferably 25-100 parts by weight；
Preferably, the content of aluminium element is 1-10 weight %, more preferably 2-8 weights in the sepiolite
Measure %；It is further preferred that in the spherical mesoporous composite material containing meerschalminite aluminium element weight hundred
Divide than the percentage by weight more than aluminium element in the sepiolite.
3. a kind of method for preparing the spherical mesoporous composite material containing meerschalminite, this method includes following step
Suddenly：
(1) providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, is used as component a；
(2) provide silica gel or prepare the filter cake of silica gel, be used as component b；
(3) the component a, the component b and sepiolite are mixed in high alumina ceramic ball grinder
And ball milling, and by the solid powder obtained after ball milling water slurrying, then obtained slurry is sprayed
Dry；
Wherein, above-mentioned steps make it that the average grain diameter of the spherical mesoporous composite material containing meerschalminite is
30-60 microns, specific surface area is 100-600 meters squared per grams, and pore volume is 0.5-1.5 mls/g, hole
Footpath is in bimodal distribution, and it is bimodal correspond to the first most probable pore size and the second most probable pore size respectively, described the
One most probable pore size is 1-10 nanometers, and second most probable pore size is 40-42 nanometers；It is described spherical to contain
The content of aluminium element is 5-30 weight %, preferably 10-29 weight % in meerschalminite mesoporous composite material.
4. method according to claim 3, wherein, in step (3), relative to 100 weights
The component a of part is measured, the consumption of the component b is 1-200 parts by weight, preferably 75-150 weight
Part；The consumption of the sepiolite is 1-100 parts by weight, preferably 25-100 parts by weight.
5. method according to claim 3, wherein, in step (1), prepare with one-dimensional
The process of the filter cake of the meso-porous molecular sieve material of duct diplopore distributed architecture includes：In template, trimethyl
In the presence of pentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and will be obtained after contact
Mixture carries out crystallization and filtering.
6. method according to claim 5, wherein, template, ethanol, trimethylpentane and
The mol ratio of tetramethoxy-silicane is 1：100-500：200-500：50-200, preferably 1：180-400：
250-400：70-150.
7. the method according to claim 5 or 6, wherein, the template is triblock copolymer
Thing polyoxyethylene-poly-oxypropylene polyoxyethylene；The sour agent is that the acetic acid and sodium acetate that pH value is 1-6 delay
Rush solution；The condition that tetramethoxy-silicane is contacted with sour agent includes：Temperature is 10-60 DEG C, and the time is 10-72
Hour, pH value is 1-7；The condition of the crystallization includes：Temperature is 30-150 DEG C, and the time is 10-72
Hour.
8. method according to claim 3, wherein, in step (2), prepare the filter of silica gel
The process of cake includes：Waterglass is contacted with inorganic acid and glycerine, and it is mixed by what is obtained after contact
Compound is filtered.
9. method according to claim 8, wherein, waterglass is contacted with inorganic acid and glycerine
Condition include：Temperature is 10-60 DEG C, and the time is 1-5 hours, and pH value is 2-4；The inorganic acid
For the one or more in sulfuric acid, nitric acid and hydrochloric acid.
10. the method according to claim 3 or 4, wherein, in step (3), the ball
The condition of mill includes：The rotating speed of high alumina ceramic abrading-ball is in 300-500r/min, high alumina ceramic ball grinder
Temperature is 15-100 DEG C, and the time of ball milling is 0.1-100 hours；The condition of the spray drying includes：
100-300 DEG C of temperature, rotating speed is 10000-15000r/min.
11. the method according to claim 3 or 4, wherein, the component a is with one-dimensional hole
The filter cake of the meso-porous molecular sieve material of road diplopore distributed architecture, the component b is the filter cake of silica gel, described
Method also includes：After the spray-drying process of step (3), in the product obtained from spray drying
Removed template method；Preferably, the condition of the removed template method includes：Temperature is 300-600 DEG C, when
Between be 10-80 hours.
12. what is prepared as the method described in any one in claim 3-11 is spherical containing meerschalminite Jie
Hole composite material.
13. a kind of loaded catalyst, the catalyst contain carrier and load on the carrier to first
Benzene sulfonic acid, it is characterised in that the carrier is the ball described in any one in claim 1-2 and 12
Shape mesoporous composite material containing meerschalminite.
14. catalyst according to claim 13, wherein, with the total of the loaded catalyst
On the basis of weight, the content of p-methyl benzenesulfonic acid is 1-50 weight %, preferably 5-50 weight %；It is described
The content of carrier is 50-99 weight %, preferably 50-95 weight %.
15. 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 will for right
Seek the spherical mesoporous composite material containing meerschalminite described in any one in 1-2 and 12.
16. method according to claim 15, wherein, with the carrier and p-methyl benzenesulfonic acid
On the basis of total consumption, the consumption of p-methyl benzenesulfonic acid is 1-50 weight %, preferably 5-50 weight %；Institute
The consumption for stating carrier is 50-99 weight %, preferably 50-95 weight %.
17. the loaded catalyst prepared as the method described in claim 15 or 16.
18. the loaded catalyst in claim 13-14 and 17 described in any one is in esterification
In application.
19. a kind of preparation method of acid isopropyl, wherein, this method includes：In the presence of catalyst
Under, under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, it is special
Levy and be, the catalyst is the supported catalyst described in any one in claim 13-14 and 17
Agent.
20. preparation method according to claim 19, wherein, the mol ratio of oleic acid and isopropanol
For 1：0.5-10；Preferably, relative to the oleic acid of 100 parts by weight, the consumption of the catalyst is 1-15
Parts by weight, more preferably 2-14 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610213169.4A CN107262157B (en) | 2016-04-07 | 2016-04-07 | The preparation method of spherical shape mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610213169.4A CN107262157B (en) | 2016-04-07 | 2016-04-07 | The preparation method of spherical shape mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107262157A true CN107262157A (en) | 2017-10-20 |
| CN107262157B CN107262157B (en) | 2019-07-19 |
Family
ID=60051811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610213169.4A Active CN107262157B (en) | 2016-04-07 | 2016-04-07 | The preparation method of spherical shape mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107262157B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614095A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical double-mesoporous sepiolite composite material as carrier and preparation method and application thereof |
| CN114426486A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248988A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| CN104248992A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| 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 |
| CN104248980A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248986A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| 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 |
| CN105149011A (en) * | 2014-06-09 | 2015-12-16 | 中国石油化工股份有限公司 | Chlorite mesoporous composite material, supported catalyst, preparation method thereof, application and preparation method of cyclohexanone glycerol ketal |
-
2016
- 2016-04-07 CN CN201610213169.4A patent/CN107262157B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248988A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical mesoporous sepiolite composite carrier, catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| CN104248992A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| 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 |
| CN104248980A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method |
| CN104248986A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate |
| 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 |
| CN105149011A (en) * | 2014-06-09 | 2015-12-16 | 中国石油化工股份有限公司 | Chlorite mesoporous composite material, supported catalyst, preparation method thereof, application and preparation method of cyclohexanone glycerol ketal |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614095A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical double-mesoporous sepiolite composite material as carrier and preparation method and application thereof |
| CN114426486A (en) * | 2020-09-23 | 2022-05-03 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
| CN114426486B (en) * | 2020-09-23 | 2024-02-13 | 中国石油化工股份有限公司 | Method for preparing methyl methacrylate and supported catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107262157B (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105149011B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN104415795B (en) | Spherical zeolite mesoporous composite material and loaded catalyst and its preparation method and application and the preparation method of ethyl acetate | |
| CN104248980B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248992B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248987B (en) | The preparation method of spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248991B (en) | The preparation method of the composite mesoporous carrier of spherical montmorillonite and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248993B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN105435853B (en) | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN104248981B (en) | The spherical complex carrier in three-dimensional cubic duct and catalyst and its preparation method and application and the preparation method of ethyl acetate | |
| CN106622377B (en) | It is a kind of spherical shape mesoporous composite material containing aluminium and loaded catalyst and its preparation method and application and ethyl acetate preparation method | |
| CN107457005B (en) | Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method | |
| CN104248986A (en) | Spherical attapulgite mesoporous composite carrier, supported catalyst and preparation method and application thereof and preparation method of ethyl acetate | |
| CN107262135A (en) | The preparation method of the spherical mesoporous composite material of kaolin containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl | |
| CN104248984B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN105435854B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN106622378A (en) | Spherical aluminium-containing mesoporous composite material, supported catalyst, preparation method and applications of spherical aluminium-containing mesoporous composite material and supported catalyst, and method used for preparing cyclohexanone glyceryl | |
| CN107456992B (en) | Spherical zeolite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method | |
| CN107262157A (en) | The preparation method of spherical mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl | |
| CN107262136A (en) | The preparation method of the spherical mesoporous composite material of illite containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl | |
| CN105435852B (en) | The preparation method of mesoporous composite material and catalyst and its preparation method and application and the dioxolanes of 2,2 dimethyl, 4 methyl 1,3 | |
| CN105435850B (en) | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN107262159A (en) | The preparation method of spherical mesoporous composite material containing mackensite and loaded catalyst and its preparation method and application and acid isopropyl | |
| CN107262158B (en) | The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl preparation method | |
| CN105214735B (en) | The preparation method of mesoporous composite material and catalyst and its preparation method and application and the dioxolanes of 2,2 dimethyl, 4 methyl 1,3 | |
| CN107457004B (en) | Spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |