CN107262135B - The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl - Google Patents
The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl Download PDFInfo
- Publication number
- CN107262135B CN107262135B CN201610212776.9A CN201610212776A CN107262135B CN 107262135 B CN107262135 B CN 107262135B CN 201610212776 A CN201610212776 A CN 201610212776A CN 107262135 B CN107262135 B CN 107262135B
- Authority
- CN
- China
- Prior art keywords
- weight
- composite material
- kaolin
- acid
- containing aluminium
- 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.)
- Active
Links
- 239000004411 aluminium Substances 0.000 title claims abstract description 135
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 135
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 121
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 119
- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000002808 molecular sieve Substances 0.000 claims abstract description 42
- 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 42
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000012065 filter cake Substances 0.000 claims description 32
- 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 26
- 229910002027 silica gel Inorganic materials 0.000 claims description 25
- 239000000741 silica gel Substances 0.000 claims description 25
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000005642 Oleic acid Substances 0.000 claims description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 24
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 24
- 238000001694 spray drying Methods 0.000 claims description 21
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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 17
- 238000000498 ball milling Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000002902 bimodal effect Effects 0.000 claims description 12
- 238000009826 distribution Methods 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
- 150000007522 mineralic acids Chemical class 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
- 239000000243 solution Substances 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 8
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000007974 sodium acetate buffer Substances 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 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 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 238000003756 stirring Methods 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
- -1 isopropyl ester Chemical class 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000000126 substance Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/643—
-
- B01J35/647—
-
- B01J35/69—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Abstract
The present invention relates to catalyst fields, and in particular to it is a kind of spherical shape the mesoporous composite material of kaolin containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl preparation method.Wherein, disclose a kind of spherical mesoporous composite material of kaolin containing aluminium, the preparation method of the spherical shape mesoporous composite material of kaolin containing aluminium, the spherical shape mesoporous composite material of kaolin containing aluminium prepared by this method, loaded catalyst containing the spherical shape mesoporous composite material of kaolin containing aluminium, the preparation method of the loaded catalyst, the loaded catalyst prepared by this method, the application of the loaded catalyst in the esterification reaction.Wherein, the composite material contains kaolin 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 material.The conversion ratio of reaction raw materials can be significantly improved in acid isopropyl preparation process as loaded catalyst made of carrier using composite material provided by the invention.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of spherical shape mesoporous composite material of kaolin containing aluminium, the spherical shape contain
The preparation method of aluminium kaolin mesoporous composite material, the spherical shape mesoporous composite material of kaolin containing aluminium prepared by this method, contains
The loaded catalyst of the spherical shape mesoporous composite material of kaolin containing aluminium, the preparation method of the loaded catalyst, by this method
The loaded catalyst of preparation, the application of the loaded catalyst in the esterification reaction, and use the loaded catalyst system
The method of standby acid isopropyl.
Background technique
Acid isopropyl is transparent oily liquid, can be dissolved each other with animal and vegetable oil, and the coefficient of dispersion is big, and spreadability is good, can be
Thin electrolyte film is formed on skin, and there is skin care effect.With the rapid development of chemical industry, the demand to acid isopropyl is continuous
Increase.Under normal circumstances, acid isopropyl is made by esterification under the effect of the catalyst by oleic acid and isopropanol.It passes
System is liquid organic acid for oleic acid and the catalyst of isopropanol esterification, but because the pair that its corrosiveness is big, causes is anti-
Product separates the defects of complicated and liquid waste processing is difficult and its use is caused to be subject to certain restrictions after Ying Duo, reaction.With
Increase of the whole world to Catalytic processes greenization attention degree, solid acid catalysis technique replace liquid acid Catalytic processes gesture must
Row.
In existing loaded catalyst, meso-porous molecular sieve material is as carrier.Meso-porous molecular sieve material has duct
Orderly, the advantages that aperture is adjustable, specific surface area and hole appearance are larger, so that being made using these meso-porous molecular sieve materials as carrier
Loaded catalyst show lot of advantages in preparation process in organic catalytic reaction, for example, catalytic activity is high, secondary anti-
Should less, post-processing it is simple etc., however, big specific surface area and high hole hold so that these meso-porous molecular sieve materials have it is stronger
Water suction, moisture absorption ability, reunite in catalytic reaction process to will lead to these loaded catalysts, and then reduce oleic acid
The conversion ratio of oleic acid in isopropyl ester preparation process.Therefore, a kind of novel acid isopropyl that is used to prepare further is developed
Catalyst becomes problem in the urgent need to address.
Summary of the invention
The purpose of the invention is to overcome making using loaded catalyst made of existing meso-porous molecular sieve material
The lower defect of reaction raw materials conversion ratio during standby acid isopropyl, provides a kind of spherical shape kaolinite containing aluminium for being suitable as carrier
Native mesoporous composite material, the preparation method of the spherical shape mesoporous composite material of kaolin containing aluminium contain aluminium by the spherical shape of this method preparation
Kaolin mesoporous composite material, the loaded catalyst containing the spherical shape mesoporous composite material of kaolin containing aluminium, the support type are urged
The preparation method of agent, the loaded catalyst prepared by this method, the application of the loaded catalyst in the esterification reaction, with
And the method for using the loaded catalyst preparing acid isopropyl.
In order to achieve the above object, the present inventor is distributed by finding after research with one-dimensional channels diplopore
Kaolin is introduced in the meso-porous molecular sieve material of structure, enters kaolin in the duct of meso-porous molecular sieve material, and should
The spherical shape for being not susceptible to reunite is made in mesoporous composite material, can retain the high-specific surface area, big of meso-porous molecular sieve material in this way
Kong Rong, large aperture and have the characteristics that one-dimensional channels diplopore distributed architecture, and the reunion of meso-porous molecular sieve material can be reduced, increases
Add its mobility；Simultaneously as aluminium element is introduced in meso-porous molecular sieve material, so that sphere intensity increases, as catalyst
Carrier can be repeated as many times and use, and reduce use cost.In addition, being existed using loaded catalyst made of the mesoporous composite material
The conversion ratio of reaction raw materials can be significantly improved when being used to prepare acid isopropyl.
For this purpose, the present invention provides a kind of spherical mesoporous composite materials of kaolin containing aluminium, wherein the spherical shape kaolin containing aluminium
Mesoporous composite material contains kaolin and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the spherical shape contains
The average grain diameter of aluminium kaolin mesoporous composite material is 30-60 microns, and specific surface area is 100-600 meters squared per gram, and pore volume is
0.5-1.5 mls/g, aperture is in bimodal distribution, and bimodal respectively corresponds the first most probable pore size and the second most probable pore size, institute
The first most probable pore size is stated less than second most probable pore size, and first most probable pore size is 1-9 nanometers, described second
Most probable pore size is 40-42 nanometers；The content of aluminium element is 5-30 weight in the spherical shape mesoporous composite material of kaolin containing aluminium
Measure %, preferably 10-29 weight %.
The present invention also provides a kind of methods for preparing the spherical mesoporous composite material of kaolin containing aluminium, and this method includes following
Step:
(1) providing meso-porous molecular sieve material or preparation with one-dimensional channels diplopore distributed architecture has one-dimensional channels double
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and kaolin are subjected to mixing and ball milling in high alumina ceramic ball grinder, and will
Obtained slurry, is then spray-dried by the solid powder obtained after ball milling water slurrying；
Wherein, above-mentioned steps make the average grain diameter of the spherical mesoporous composite material of kaolin containing aluminium be 30-60 microns,
Specific surface area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal right respectively
The first most probable pore size and the second most probable pore size are answered, first most probable pore size is less than second most probable pore size, and
First most probable pore size is 1-9 nanometers, and second most probable pore size is 40-42 nanometers；The spherical shape kaolin containing aluminium
The content of aluminium element is 5-30 weight %, preferably 10-29 weight % in mesoporous composite material.
The present invention also provides the spherical shape mesoporous composite materials of kaolin containing aluminium prepared by the above method.
The present invention also provides a kind of loaded catalyst, which contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein the carrier is the spherical mesoporous composite material of kaolin containing aluminium according to the present invention.
The present invention also provides a kind of methods for preparing loaded catalyst, this method comprises: by carrier, p-methyl benzenesulfonic acid
It is uniformly mixed with water, and obtained mixture is spray-dried, wherein the carrier is the spherical shape according to the present invention
The mesoporous composite material of kaolin containing aluminium.
The present invention also provides the loaded catalysts prepared by the above method.
The present invention also provides the application of above-mentioned loaded catalyst in the esterification reaction.
The present invention also provides a kind of preparation methods of acid isopropyl, this method comprises: in the presence of a catalyst,
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, wherein the catalyst is the present invention
The loaded catalyst.
The spherical shape mesoporous composite material of kaolin containing aluminium according to the present invention, combines and is distributed with one-dimensional channels diplopore
The advantages of meso-porous molecular sieve material of structure, kaolin, aluminium element and ball type carrier, so that the spherical shape kaolin containing aluminium is mesoporous
Composite material is suitable as the carrier of loaded catalyst, is especially suitable as used in the acid isopropyl preparation process
The carrier of loaded catalyst.
In loaded catalyst of the present invention, the spherical shape mesoporous composite material of kaolin containing aluminium as carrier has
The characteristics of porous structure of meso-porous molecular sieve material, and it has been also loaded p-methyl benzenesulfonic acid, so that the loaded catalyst both had
Have the advantages of loaded catalyst such as catalytic activity it is high, side reaction is few, post-processing is simple, and with sour catalytic performance, make
Obtain the loaded catalyst not will lead to equipment corrosion not only when in acid isopropyl preparation process, but also can show
Write the conversion ratio for improving reaction raw materials.
In addition, the loaded catalyst can be with when the method by spray drying prepares the loaded catalyst
It is used repeatedly, and still can obtain higher reaction raw materials conversion ratio during recycling.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of the spherical mesoporous composite material of kaolin containing aluminium according to the present invention；
Fig. 2 is the SEM scanning electricity of the microscopic appearance of the spherical mesoporous composite material of kaolin containing aluminium according to the present invention
Mirror figure；
Fig. 3 is the graph of pore diameter distribution of the spherical mesoporous composite material of kaolin containing aluminium according to the present invention.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of spherical mesoporous composite materials of kaolin containing aluminium, wherein the spherical shape kaolin containing aluminium is mesoporous
Composite material contains kaolin and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and the spherical shape is high containing aluminium
The average grain diameter of ridge soil mesoporous composite material is 30-60 microns, and specific surface area is 100-600 meters squared per gram, pore volume 0.5-
1.5 mls/g, aperture is in bimodal distribution, and it is bimodal respectively correspond the first most probable pore size and the second most probable pore size, described the
One most probable pore size is less than second most probable pore size, and first most probable pore size is 1-9 nanometers, and described second most may be used
Several apertures are 40-42 nanometers；The content of aluminium element is 5-30 weight % in the spherical shape mesoporous composite material of kaolin containing aluminium, excellent
It is selected as 10-29 weight %, more preferably 12-29 weight %, most preferably 15-29 weight %.
The spherical shape mesoporous composite material of kaolin containing aluminium according to the present invention has one-dimensional channels diplopore distributed architecture,
The average grain diameter of particle is measured using laser fineness gage, and specific surface area, pore volume and most probable pore size are according to nitrogen adsorption
Method measures.In the present invention, the average grain diameter is average grain diameter.
The spherical shape mesoporous composite material of kaolin containing aluminium according to the present invention, by the way that spherical kaolin containing aluminium is mesoporous multiple
The particle size of condensation material controls within above range, it can be ensured that the spherical shape mesoporous composite material of kaolin containing aluminium is not easy
Reunite, and is used as loaded catalyst made of carrier and reaction in acid isopropyl preparation process can be improved
Feed stock conversion.When the specific surface area of the spherical mesoporous composite material of kaolin containing aluminium is less than 100 meters squared per grams and/or hole
When volume is less than 0.5 ml/g, the catalytic activity for being used as loaded catalyst made of carrier can be significantly reduced；Work as institute
The specific surface area for stating the spherical mesoporous composite material of kaolin containing aluminium is greater than 600 meters squared per grams and/or pore volume be greater than 1.5 milliliters/
Gram when, be used as loaded catalyst made of carrier and be easy to happen reunion in acid isopropyl preparation process, thus shadow
Ring 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 of kaolin containing aluminium is 45-60 microns, compares table
Area is 100-600 meters squared per gram, and pore volume is 0.9-1.3 mls/g, and first most probable pore size is 2-8 nanometers, institute
Stating the second most probable pore size is 40-42 nanometers.
In the present invention, the aluminium element can carry out ball milling by kaolin and/or in high alumina ceramic ball grinder
Mode introduces.The kaolin can be kaolin commonly used in the art, under preferable case, aluminium element in the kaolin
Content be 10-20 weight %, preferably 15-19 weight %.It is further preferred that the spherical shape kaolin containing aluminium is composite mesoporous
The weight percent of aluminium element is greater than the weight percent of aluminium element in the kaolin in material.
According to the present invention, relative to the mesopore molecular sieve described in 100 parts by weight with one-dimensional channels diplopore distributed architecture
Material, the kaolinic content are 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 of kaolin containing aluminium can also contain the dioxy introduced by silica gel
SiClx." silica introduced by silica gel " refers to the preparation process in the spherical mesoporous composite material of kaolin containing aluminium
In, by silica gel as the silica group for preparing raw material and bringing into the spherical mesoporous composite material of kaolin containing aluminium finally prepared
Point.In the spherical mesoporous composite material of kaolin containing aluminium, relative to described in 100 parts by weight there is one-dimensional channels diplopore to divide
The meso-porous molecular sieve material of cloth structure, the content of the silica introduced by silica gel can be 1-200 parts by weight, preferably
For 50-150 parts by weight, 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 normal for this field
The meso-porous molecular sieve material used is advised, and can be prepared according to the conventional method.
The present invention also provides a kind of methods for preparing the spherical mesoporous composite material of kaolin containing aluminium, and this method includes following
Step:
(1) providing meso-porous molecular sieve material or preparation with one-dimensional channels diplopore distributed architecture has one-dimensional channels double
The filter cake of the meso-porous molecular sieve material of pore size distribution structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and kaolin are subjected to mixing and ball milling in high alumina ceramic ball grinder, and will
Obtained slurry, is then spray-dried by the solid powder obtained after ball milling water slurrying；
Wherein, above-mentioned steps make the average grain diameter of the spherical mesoporous composite material of kaolin containing aluminium be 30-60 microns,
Specific surface area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal right respectively
The first most probable pore size and the second most probable pore size are answered, first most probable pore size is less than second most probable pore size, and
First most probable pore size is 1-9 nanometers, and second most probable pore size is 40-42 nanometers；The spherical shape kaolin containing aluminium
In mesoporous composite material the content of aluminium element be 5-30 weight %, preferably 10-29 weight %, more preferably 12-29 weight %,
Most preferably 15-29 weight %.
In the preferred case, the component a makes the average grain diameter of the spherical mesoporous composite material of kaolin containing aluminium to be
35-55 microns, specific surface area is 100-600 meters squared per gram, and pore volume is 0.8-1.2 mls/g, first most probable hole
Diameter is 1-9 nanometers, and second most probable pore size is 42-44 nanometers.
In step (1), the process with the filter cake of meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture is prepared
It may include: to be contacted tetramethoxy-silicane with sour agent, and will in the presence of template, trimethylpentane and ethyl alcohol
The mixture obtained after contact carries out crystallization and filtering.
The template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane molar ratio can be 1:100-500:200-
500:50-200, preferably 1:180-400:250-400:70-150.
The template can be various templates commonly used in the art.Preferably, the template is three block
Copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, the template can be commercially available (for example, can be purchased from
Aldrich, trade name P123, molecular formula EO20PO70EO20), it can also be prepared by existing various methods
It arrives.When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-
The average molecular weight of polyoxypropylene polyoxyethylene calculates to obtain.
The acid agent can be used for adjusting the substance or mixture (such as solution) of pH value for various routines.The acid agent
It is preferred that using in form of an aqueous solutions, pH value can be 1-6, preferably 3-5.It is highly preferred that it is 1-6 that the acid agent, which is pH value,
The acetic acid and sodium acetate buffer solution of (more preferable 3-5).
The condition that tetramethoxy-silicane is contacted with sour agent may include: that temperature is 10-60 DEG C, and the time is 10-72 hours, pH
Value is 1-7.In order to be more advantageous to the uniform mixing between each substance, the tetramethoxy-silicane is contacted preferably with sour agent in stirring bar
It is carried out under part.The dosage of the acid agent is preferably so that the pH value of tetramethoxy-silicane and the haptoreaction system of sour agent is 1-7.
The condition of the crystallization may include: that temperature is 30-150 DEG C, and the time is 10-72 hours.It is described under preferable case
The condition of crystallization includes: that temperature is 40-100 DEG C, and the time is 10-48 hours.The crystallization is implemented by hydrothermal crystallization method.
During above-mentioned preparation has the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, pass through
Filtering with the process for obtaining filter cake may include: after filtration, wash that (washing times can be 2- repeatedly with deionized water
10) it, is then filtered.
In step (1), " providing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture " be can be directly
The product for weighing or choosing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture is also possible to preparation with one-dimensional
The meso-porous molecular sieve material of duct diplopore distributed architecture.The meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
Preparation method can implement according to the conventional method, for example, preparation method may include: according to the above method preparation have
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture then by gained filtration cakes torrefaction, and will obtain after drying
Product in template removal.The condition of the removed template method may include: that temperature is 300-600 DEG C, time 10-80
Hour.
In step (2), the process for preparing the filter cake of silica gel may include: to carry out waterglass and inorganic acid and glycerine
Contact, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass is contacted with inorganic acid and glycerine, can be according to the routine for preparing silica gel
It is suitably determined in technique.Under preferable case, the condition that waterglass is contacted with inorganic acid and glycerine may include: that temperature is
10-60 DEG C, preferably 20-40 DEG C；Time is 1-5 hours, preferably 1.5-3 hours；PH value is 2-4.
In order to be more advantageous to the uniform mixing between each substance, waterglass and inorganic acid and the catalytic process of glycerine are excellent
Choosing carries out under agitation.
The waterglass is the aqueous solution of sodium metasilicate, and concentration can be 10-50 weight %, preferably 12-30 weight %.
The inorganic acid can be various inorganic acids commonly used in the art, for example, can be sulfuric acid, nitric acid and hydrochloric acid
At least one of.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution.The nothing
The dosage of machine acid is preferably so that the pH value of the haptoreaction system of waterglass and inorganic acid is 2-4.
In step (2), " providing silica gel ", which can be, directly weighs or chooses silica gel product, is also possible to prepare silica gel.
The method for preparing silica gel can be implemented according to the conventional method, such as may include: the filter cake that silica gel is prepared according to the above method,
Then by gained filtration cakes torrefaction.
In step (3), relative to the component a of 100 parts by weight, the dosage of the component b is 1-200 parts by weight,
Preferably 75-150 parts by weight；The kaolinic dosage 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, not destroy or
Substantially carrier structure is not destroyed and enters silica gel subject in carrier duct.Those skilled in the art can select according to mentioned above principle
Various suitable conditions are selected to implement the present invention.In situations where it is preferred, the ball milling can carry out in the ball mill, the ball
The inner wall of ball grinder is high alumina ceramic in grinding machine, and the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball can root
It is reasonably selected according to the size of ball grinder, 1 abrading-ball usually can be used in the ball grinder for being 50-150ml for size；
The material of the abrading-ball is high alumina ceramic.In situations where it is preferred, the content of aluminium element is 30-40 weight in the high alumina ceramic
Measure %.There is no particular limitation in source of the present invention to the high alumina ceramic ball grinder, for example, can be commercially available.Institute
It can be 300-500r/min that the condition for stating ball milling, which may include: the revolving speed of abrading-ball,；Temperature in high alumina ceramic ball grinder can be with
It is 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), by the process of the solid powder water slurrying obtained after ball milling can at 25-60 DEG C into
Row.In pulping process, the weight ratio of the dosage of solid powder and water can be 1:0.1-2, preferably 1:0.3-1, more preferably
For 1:0.5-1.
In step (3), the spray drying can be implemented according to conventional mode, for example, can in atomizer into
Row.The condition of the spray drying may include: that temperature is 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/
min；Under preferable case, the condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-
13000r/min。
In step (3), when the filter that the component a is the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
Cake, when the component b is the filter cake of silica gel, namely when step (1) is that preparation has the mesoporous of one-dimensional channels diplopore distributed architecture
The process of the filter cake of molecular screen material, when step (2) is the process for the filter cake for preparing silica gel, the spherical shape kaolin containing aluminium is mesoporous
The preparation method of composite material can also include: to take off from the product that spray drying obtains after the spray drying of step (3)
Template agent removing.The condition of the removed template method may include: that temperature is 300-600 DEG C, and the time is 10-80 hours；Preferably
In the case of, temperature is 450-550 DEG C, and the time is 15-70 hours.
The present invention also provides the spherical shape mesoporous composite materials of kaolin containing aluminium prepared by the above method.
The present invention also provides a kind of loaded catalyst, which contains pair of carrier and load on the carrier
Toluenesulfonic acid, wherein the carrier is the above-mentioned spherical mesoporous composite material of kaolin containing aluminium provided by the invention.
In the loaded catalyst, there is no particular limitation for the content of the carrier and p-methyl benzenesulfonic acid, Ke Yigen
It is suitably determined according to the loaded catalyst of this field routine, for example, using the total weight of the loaded catalyst as base
Standard, the content of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The content of the carrier is 50-99 weight
Measure %, preferably 50-95 weight %.
In the present invention, the loaded catalyst can be prepared according to various methods commonly used in the art, only be needed
On the carrier by p-methyl benzenesulfonic acid load.
In a preferred embodiment, in order to make the loaded catalyst of preparation may be repeated utilization, and
Higher reaction raw materials conversion ratio still can be obtained during recycling, the method for preparing loaded catalyst include: by
Carrier, p-methyl benzenesulfonic acid and water are uniformly mixed, and obtained mixture is spray-dried, wherein the carrier is this hair
The above-mentioned spherical mesoporous composite material of kaolin containing aluminium of bright offer.
It is above-mentioned prepare loaded catalyst during, on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid,
The dosage of p-methyl benzenesulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The dosage of the carrier can be 50-99 weight
Measure %, preferably 50-95 weight %.
The spray drying can be implemented according to conventional mode, such as can carry out in atomizer.It is described spraying dry
Dry condition may include: that temperature is 100-300 DEG C, and the revolving speed of rotation can be 10000-15000r/min；Under preferable case,
The condition of the spray drying includes: that temperature is 150-250 DEG C, and the revolving speed of rotation is 11000-13000r/min.
The present invention also provides the loaded catalysts prepared by above-mentioned spray drying process.
The present invention also provides the application of above-mentioned loaded catalyst in the esterification reaction.
The present invention also provides a kind of preparation methods of acid isopropyl, this method comprises: in the presence of a catalyst,
Under conditions of esterification, contact oleic acid and isopropanol, to obtain acid isopropyl, which is characterized in that the catalyst is
Loaded catalyst of the present invention.
In the preparation method of the acid isopropyl, there is no particular limitation for the dosage of oleic acid and isopropanol, as long as energy
Enough reactions obtain acid isopropyl, but in order to improve the utilization rate of raw material, under preferable case, mole of oleic acid and isopropanol
Than for 1:0.5-10, preferably 1:1-5.
Also there is no particular limitation for the dosage of the catalyst, can be carried out according to conventional acid isopropyl preparation process
Suitably determine.Under preferable case, relative to the oleic acid of 100 parts by weight, the dosage of the catalyst is 1-15 parts by weight, more excellent
It is selected as 2-14 parts by weight.
In the acid isopropyl preparation process, in order to be more advantageous to the progress of esterification, the reaction preferably exists
It is carried out in there-necked flask, that is, 25~100 DEG C of the reaction temperature.Reaction time can be 1-20 hours, preferably 2-15 hours.
After the preparation method of the acid isopropyl can also be included in esterification, to final reaction mixture
Suction filtration separation is carried out, and isolated solid product will be filtered and be dried in vacuo 1-24 hours at 25-200 DEG C；It is preferred that in 50-
It is dried in vacuo 6-10 hours at 150 DEG C, to recycle catalyst.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula EO20PO70EO20, the substance for being 9003-11-6 in the registration number of U.S. chemical abstract, average molecular weight
Mn is 5800.
In following embodiment and comparative example, X-ray diffraction analysis is in the model for being purchased from Bruker AXS company, Germany
It is carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co., the U.S.
It is carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from U.S. Kang Ta company
It is carried out on attached instrument, wherein before being tested, sample is deaerated 4 hours at 200 DEG C；The analysis of reaction product liquid phase ingredient exists
Purchased from being carried out on Agilent company, Britain 7890A/5973N gas chromatograph-mass spectrometer.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 are according to following
Formula is calculated.
The conversion ratio (%) of oleic acid=(content of oleic acid in dosage-reaction product of oleic acid) ÷ oleic acid dosage ×
The theoretical yield of selectivity (%)=acid isopropyl actual production ÷ acid isopropyl of 100% acid isopropyl ×
100%
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment be used to illustrate spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst of the invention and
Their preparation method.
(1) the spherical mesoporous composite material of kaolin containing aluminium is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.69g (0.037mol) ethyl alcohol is added
Into 28ml, the acetic acid and sodium acetate buffer that pH value is 4, stirring is completely dissolved to P123 at 15 DEG C, obtain backward
6g (0.053mol) trimethylpentane is added in solution, 8h is stirred at 15 DEG C, then 2.13g (0.014mol) four is added thereto
Methoxy silane stirs 20h under conditions of 15 DEG C, pH value are 4.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, at 60 DEG C crystallization for 24 hours, be then filtered and and be washed with deionized 4 times, then filter and had
There is the filter cake A1 of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
5:1:1 carries out mixing and haptoreaction 2 hours at 30 DEG C, then adjusts pH value to 3, so with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered afterwards, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B1.
(wherein, 10g filter cake A1,10g filter cake B1 and 10g kaolin of above-mentioned preparation is put into togerther in 100ml ball grinder
The material of ball grinder and abrading-ball is high alumina ceramic, and the content of aluminium element is 35 weight %, the diameter of abrading-ball in the high alumina ceramic
For 3mm, quantity is 1, revolving speed 400r/min).Ball grinder is closed, temperature is to obtain ball milling 1 hour at 60 DEG C in ball grinder
To 30g solid powder；The solid powder is dissolved in 30 grams of deionized waters, at 200 DEG C in the case where revolving speed is 12000r/min
Spray drying；The product obtained after spray drying is calcined 24 hours at 500 DEG C in Muffle furnace, removed template method obtains
The 28 grams of spherical shape mesoporous composite material of kaolin containing aluminium C1 with one-dimensional channels diplopore distributed architecture.According to XPS Analysis
As a result, in C1 aluminium content be 22 weight %.
(2) loaded catalyst is prepared
At 25 DEG C, by 30g spherical shape kaolin containing the aluminium mesoporous composite material C1 prepared in above-mentioned steps (1) and to toluene
Sulfonic acid is put into togerther in deionized water, stirring to dissolution, and the spherical shape mesoporous composite material C1 of kaolin containing aluminium and p-methyl benzenesulfonic acid
Weight ratio be 50:50, the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, in revolving speed is 12000r/ at 200 DEG C
It is spray-dried under min, obtains loaded catalyst Cat-1.
With XRD, scanning electron microscope and U.S.'s Kang Ta company Atsorb-1 type instrument come to the support type Catalyzed by p-Toluenesulfonic Acid
Agent is characterized.
Fig. 1 is X-ray diffracting spectrum, for the XRD spectra of the spherical mesoporous composite material of kaolin containing aluminium C1, abscissa 2
θ, ordinate are intensity.By the low-angle spectral peak that occurs in XRD spectra it is found that the spherical shape mesoporous composite material C1 of kaolin containing aluminium has
There is one-dimensional channels diplopore distributed architecture specific to mesoporous material.
Fig. 2 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical mesoporous composite material of kaolin containing aluminium C1.As seen from the figure,
The microscopic appearance of the spherical shape mesoporous composite material of kaolin containing aluminium C1 is the Mesoporous Spheres that particle diameter is 30-60 μm.
Fig. 3 is the pore size distribution curve of the spherical mesoporous composite material of kaolin containing aluminium C1.
Pore structure parameter such as the following table 1 institute of spherical shape kaolin containing aluminium mesoporous composite material C1 and loaded catalyst Cat-1
Show.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Composite material C1 | 160 | 1.0 | 7,41 | 50 |
| Catalyst Cat-1 | 110 | 0.7 | 3,38 | 50 |
*: the 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.
The spherical mesoporous composite material of kaolin containing aluminium is after loading p-methyl benzenesulfonic acid it can be seen from the data of upper table 1,
Specific surface area and pore volume are reduced, this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical kaolinite containing aluminium
The inside of native mesoporous composite material.
Comparative example 1
The spherical mesoporous composite material of kaolin containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is different
, it is added without kaolin during preparation is used as the mesoporous composite material of carrier, so that mesoporous composite material be made respectively
D1 and loaded catalyst Cat-D-1.According to XPS Analysis as a result, the content of aluminium is 14 weight % in D1.
Comparative example 2
The spherical mesoporous composite material of kaolin containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is different
, during preparing loaded catalyst, (Jilin University is purchased from the rodlike mesoporous silicon oxide SBA-15 of identical weight
High-tech limited liability company) the filter cake A1 with the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture is replaced, thus
Mesoporous composite material D2 and loaded catalyst Cat-D-2 is made respectively.According to XPS Analysis as a result, aluminium in D2
Content is 10 weight %.
Comparative example 3
The spherical mesoporous composite material of kaolin containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is different
, the material of ball grinder is polytetrafluoroethylene (PTFE) during preparation is used as the mesoporous composite material of carrier, and Material quality of grinding balls is
Agate.To which mesoporous composite material D3 and loaded catalyst Cat-D-3 be made respectively.According to the knot of XPS Analysis
Fruit, the content of aluminium is 12 weight % in D3.
Comparative example 4
The spherical mesoporous composite material of kaolin containing aluminium and loaded catalyst are prepared according to the method for embodiment 1, institute is different
, the step of spray drying during preparing loaded catalyst, and only will be to toluene sulphur by the method for dipping
Acid is supported on the spherical mesoporous composite material of kaolin containing aluminium, so that loaded catalyst Cat-D-4 be made.
Embodiment 2
The present embodiment be used to illustrate spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst of the invention and
Their preparation method.
(1) the spherical mesoporous composite material of kaolin containing aluminium is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 1.84g (0.04mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 5, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
9.12g (0.08mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 3.04g (0.02mol) four is added thereto
Methoxy silane stirs 15h under conditions of 25 DEG C, pH value are 5.5, then obtained solution is transferred in polytetrafluoroethylene (PTFE)
In the reaction kettle of lining, the crystallization 10h at 100 DEG C, be then filtered and and be washed with deionized 4 times, then filter and obtain
The filter cake A2 of meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
4:1:1 carries out mixing and haptoreaction 1.5 hours at 40 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %,
Then obtained reaction mass is filtered, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B2.
(wherein, 20g filter cake A2,15g filter cake B2 and 15g kaolin of above-mentioned preparation is put into togerther in 100ml ball grinder
The material of ball grinder and abrading-ball is high alumina ceramic, and the content of aluminium element is 35 weight %, the diameter of abrading-ball in the high alumina ceramic
For 3mm, quantity is 1, revolving speed 300r/min).Close ball grinder, in ball grinder temperature be 80 DEG C at ball milling 0.5 hour,
Obtain 50g solid powder；The solid powder is dissolved in 36 grams of deionized waters, at 250 DEG C revolving speed be 11000r/min
Lower spray drying；The product obtained after spray drying is calcined 15 hours at 550 DEG C in Muffle furnace, removed template method obtains
To 30 grams of spherical shapes mesoporous composite material of kaolin containing aluminium C2.According to XPS Analysis as a result, the content of aluminium is 10 in C2
Weight %.
(2) loaded catalyst is prepared
At 25 DEG C, by 20g spherical shape kaolin containing the aluminium mesoporous composite material C2 prepared in above-mentioned steps (1) and to toluene
Sulfonic acid is put into togerther in deionized water, stirring to dissolution, and the spherical shape mesoporous composite material C2 of kaolin containing aluminium and p-methyl benzenesulfonic acid
Weight ratio be 95:5, the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, in revolving speed is 13000r/min at 150 DEG C
Lower spray drying, obtains loaded catalyst Cat-2.
Pore structure parameter such as the following table 2 institute of spherical shape kaolin containing aluminium mesoporous composite material C2 and loaded catalyst Cat-2
Show.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Composite material C2 | 236 | 1.3 | 8,42 | 59 |
| Catalyst Cat-2 | 218 | 1.1 | 2.5,23 | 48 |
*: the 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.
The spherical mesoporous composite material of kaolin containing aluminium is after loading p-methyl benzenesulfonic acid it can be seen from the data of upper table 2,
Specific surface area and pore volume are reduced, this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical kaolinite containing aluminium
The inside of native mesoporous composite material.
Embodiment 3
The present embodiment be used to illustrate spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst of the invention and
Their preparation method.
(1) the spherical mesoporous composite material of kaolin containing aluminium is prepared
1.0g (0.0002mol) triblock copolymer surfactant P123 and 3.68g (0.08mol) ethyl alcohol is added to
In 28ml, the acetic acid and sodium acetate buffer that pH value is 3, stirring is completely dissolved to P123 at 15 DEG C, obtain backward it is molten
5.7g (0.05mol) trimethylpentane is added in liquid, 8h is stirred at 15 DEG C, then 4.56g (0.03mol) tetramethyl is added thereto
Oxysilane stirs 10h under conditions of 40 DEG C, pH value are 3.5, obtained solution is then transferred to polytetrafluoroethyllining lining
Reaction kettle in, the crystallization 48h at 40 DEG C, be then filtered and and be washed with deionized 4 times, then filtering is had
The filter cake A3 of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture.
By waterglass and concentration that concentration is 15 weight % be 12 weight % sulfuric acid solution and glycerine with weight ratio be
6:1:1 carries out mixing and haptoreaction 3 hours at 20 DEG C, then adjusts pH value to 4, so with the sulfuric acid that concentration is 98 weight %
Obtained reaction mass is filtered afterwards, and being washed with distilled water to sodium ions content is 0.02 weight %, obtains silica gel
Filter cake B3.
(wherein, 20g filter cake A3,30g filter cake B3 and 5g kaolin of above-mentioned preparation is put into togerther in 100ml ball grinder
The material of ball grinder and abrading-ball is high alumina ceramic, and the content of aluminium element is 35 weight %, the diameter of abrading-ball in the high alumina ceramic
For 3mm, quantity is 1, revolving speed 500r/min).Close ball grinder, in ball grinder temperature be 40 DEG C at ball milling 10 hours,
Obtain 55g solid powder；The solid powder is dissolved in 30 grams of deionized waters, at 150 DEG C revolving speed be 13000r/min
Lower spray drying；The product obtained after spray drying is calcined 70 hours at 450 DEG C in Muffle furnace, removed template method obtains
To 33 grams of spherical shapes mesoporous composite material of kaolin containing aluminium C3.According to XPS Analysis as a result, the content of aluminium is 29 in C3
Weight %.
(2) loaded catalyst is prepared
At 25 DEG C, by 20g spherical shape kaolin containing the aluminium mesoporous composite material C3 prepared in above-mentioned steps (1) and to toluene
Sulfonic acid is put into togerther in deionized water, stirring to dissolution, and the spherical shape mesoporous composite material C3 of kaolin containing aluminium and p-methyl benzenesulfonic acid
Weight ratio be 85:15, the molar ratio of deionized water and p-methyl benzenesulfonic acid is 25:1, in revolving speed is 11000r/ at 250 DEG C
It is spray-dried under min, obtains loaded catalyst Cat-3.
Pore structure parameter such as the following table 3 institute of spherical shape kaolin containing aluminium mesoporous composite material C3 and loaded catalyst Cat-3
Show.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size*(nm) | Partial size (μm) |
| Composite material C3 | 185 | 0.9 | 8,42 | 45 |
| Catalyst Cat-3 | 150 | 0.6 | 7,31 | 59 |
*: the 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.
The spherical mesoporous composite material of kaolin containing aluminium is after loading p-methyl benzenesulfonic acid it can be seen from the data of upper table 3,
Specific surface area and pore volume are reduced, this explanation p-methyl benzenesulfonic acid during load-reaction enters spherical kaolinite containing aluminium
The inside of native mesoporous composite material.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used to illustrate the application and the system of acid isopropyl of the loaded catalyst provided by the invention
Preparation Method.
Loaded catalyst Cat-1 prepared by embodiment 1 is dried in vacuo 6 hours at 150 DEG C, after being cooled to room temperature,
0.5 gram is weighed, oleic acid 6g, isopropanol 2.8g, Cat-10.5g are sequentially added in there-necked flask, is heated to 75 DEG C, reacts half an hour
Afterwards, it is centrifugated, utilizes gas chromatographic analysis reaction product liquid ingredient, oleic acid conversion 100%, acid isopropyl selectivity
100%, yield 74%, solid catalyst Cat-1 is dried in vacuo 6 hours at 150 DEG C, sharp again after recycling after being cooled to room temperature
With.
EXPERIMENTAL EXAMPLE 2-3 and Experimental comparison's example 1-4
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, the difference is that using embodiment 2-3 and comparison respectively
The loaded catalyst of example 1-4 preparation replaces the loaded catalyst Cat-1.As a result, the oleic acid being respectively calculated turns
Rate and acid isopropyl selective data are as shown in table 4 below.
Table 4
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 100% | 100% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 99% | 100% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 98% | 100% |
| Experimental comparison's example 1 | Cat-D-1 | 98% | 99% |
| Experimental comparison's example 2 | Cat-D-2 | 97% | 99% |
| Experimental comparison's example 3 | Cat-D-3 | 77% | 99% |
| Experimental comparison's example 4 | Cat-D-4 | 60% | 99% |
EXPERIMENTAL EXAMPLE 4-6 and Experimental comparison's example 5-8
Acid isopropyl is prepared according to the method for EXPERIMENTAL EXAMPLE 1, the difference is that respectively with from EXPERIMENTAL EXAMPLE 1-3
The loaded catalyst Cat-1 is replaced with the catalyst of Experimental comparison's example 1-4 recycling.As a result, the oleic acid being respectively calculated
Conversion ratio and acid isopropyl selective data it is as shown in table 5 below.
Table 5
| Catalyst | The conversion ratio of oleic acid | Acid isopropyl selectivity | |
| EXPERIMENTAL EXAMPLE 4 | The Cat-1 of recycling | 95% | 100% |
| EXPERIMENTAL EXAMPLE 5 | The Cat-2 of recycling | 73% | 100% |
| EXPERIMENTAL EXAMPLE 6 | The Cat-3 of recycling | 69% | 100% |
| Experimental comparison's example 5 | The Cat-D-1 of recycling | 66% | 99% |
| Experimental comparison's example 6 | The Cat-D-2 of recycling | 66% | 99% |
| Experimental comparison's example 7 | The Cat-D-3 of recycling | 60% | 99% |
| Experimental comparison's example 8 | The Cat-D-4 of recycling | 55% | 99% |
Using the spherical mesoporous composite material of kaolin containing aluminium of the invention it can be seen from the data of above-mentioned table 4 and 5
The conversion ratio of reaction raw materials can be significantly improved in acid isopropyl preparation process as loaded catalyst made of carrier.
Moreover, the loaded catalyst may be repeated when the method by spray drying prepares the loaded catalyst
It utilizes, and still can obtain higher reaction raw materials conversion ratio during recycling.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of spherical shape mesoporous composite material of kaolin containing aluminium, which is characterized in that the spherical shape mesoporous composite material of kaolin containing aluminium
Meso-porous molecular sieve material containing kaolin and with one-dimensional channels diplopore distributed architecture, and the spherical shape kaolin containing aluminium is mesoporous
The average grain diameter of composite material be 30-60 micron, specific surface area be 100-600 meters squared per gram, pore volume for 0.5-1.5 milliliters/
Gram, aperture is in bimodal distribution, and bimodal respectively corresponds the first most probable pore size and the second most probable pore size, first most probable
Aperture is less than second most probable pore size, and first most probable pore size is 1-9 nanometers, and second most probable pore size is
40-42 nanometers；It is described relative to the meso-porous molecular sieve material described in 100 parts by weight with one-dimensional channels diplopore distributed architecture
Kaolinic content is 1-100 parts by weight；
Wherein, the content of aluminium element is 5-30 weight % in the spherical mesoporous composite material of kaolin containing aluminium, and the spherical shape
The weight percent of aluminium element is greater than the weight percent of aluminium element in the kaolin in the mesoporous composite material of kaolin containing aluminium.
2. composite material according to claim 1, wherein aluminium element in the spherical shape mesoporous composite material of kaolin containing aluminium
Content be 10-29 weight %.
3. composite material according to claim 1 or 2, wherein relative to double with one-dimensional channels described in 100 parts by weight
The meso-porous molecular sieve material of pore size distribution structure, the kaolinic content are 25-100 parts by weight.
4. composite material according to claim 1 or 2, wherein the content of aluminium element is 10-20 weight in the kaolin
Measure %.
5. composite material according to claim 1 or 2, wherein the content of aluminium element is 15-19 weight in the kaolin
Measure %.
6. a kind of method for preparing spherical shape kaolin containing aluminium mesoporous composite material described in any one of claim 1-5, should
Method the following steps are included:
(1) providing meso-porous molecular sieve material or preparation with one-dimensional channels diplopore distributed architecture has one-dimensional channels diplopore point
The filter cake of the meso-porous molecular sieve material of cloth structure, as component a；
(2) it provides silica gel or prepares the filter cake of silica gel, as component b；
(3) the component a, the component b and kaolin are subjected to mixing and ball milling in high alumina ceramic ball grinder, and by ball milling
Obtained slurry, is then spray-dried by the solid powder obtained afterwards water slurrying, described group relative to 100 parts by weight
Divide a, the dosage of the component b is 1-200 parts by weight；The kaolinic dosage is 1-100 parts by weight；
Wherein, above-mentioned steps make the average grain diameter of the spherical mesoporous composite material of kaolin containing aluminium be 30-60 microns, compare table
Area is 100-600 meters squared per gram, and pore volume is 0.5-1.5 mls/g, and aperture is in bimodal distribution, and bimodal respectively corresponds the
One most probable pore size and the second most probable pore size, first most probable pore size are less than second most probable pore size, and described
First most probable pore size is 1-9 nanometers, and second most probable pore size is 40-42 nanometers；The spherical shape kaolin containing aluminium is mesoporous
The content of aluminium element is 5-30 weight % in composite material, and aluminium element in the spherical mesoporous composite material of kaolin containing aluminium
Weight percent is greater than the weight percent of aluminium element in the kaolin.
7. according to the method described in claim 6, wherein, above-mentioned steps make the spherical mesoporous composite material of kaolin containing aluminium
The content of middle aluminium element is 10-29 weight %.
8. method according to claim 6 or 7, wherein in step (3), relative to the component a of 100 parts by weight,
The dosage of the component b is 75-150 parts by weight；The kaolinic dosage is 25-100 parts by weight.
9. method according to claim 6 or 7, wherein in step (1), preparation has one-dimensional channels diplopore distribution knot
The process of the filter cake of the meso-porous molecular sieve material of structure includes: in the presence of template, trimethylpentane and ethyl alcohol, by four methoxies
Base silane is contacted with sour agent, and the mixture obtained after contact is carried out crystallization and filtering.
10. according to the method described in claim 9, wherein, template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane rub
You are than being 1:100-500:200-500:50-200.
11. according to the method described in claim 9, wherein, template, ethyl alcohol, trimethylpentane and tetramethoxy-silicane rub
You are than being 1:180-400:250-400:70-150.
12. according to the method described in claim 9, wherein, the template is triblock copolymer polyoxyethylene-polyoxy third
Alkene-polyoxyethylene；The acid agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6；Tetramethoxy-silicane is contacted with sour agent
Condition include: temperature be 10-60 DEG C, the time be 10-72 hours, pH value 1-7；The condition of the crystallization includes: that temperature is
30-150 DEG C, the time is 10-72 hours.
13. method according to claim 6 or 7, wherein in step (2), the process for preparing the filter cake of silica gel includes:
Waterglass is contacted with inorganic acid and glycerine, and the mixture obtained after contact is filtered.
14. according to the method for claim 13, wherein the condition that waterglass is contacted with inorganic acid and glycerine includes: temperature
Degree is 10-60 DEG C, and the time is 1-5 hours, pH value 2-4；The inorganic acid is one of sulfuric acid, nitric acid and hydrochloric acid or more
Kind.
15. method according to claim 6 or 7, wherein in step (3), the condition of the ball milling includes: high alumina pottery
The revolving speed of porcelain media is 300-500r/min, and the temperature in high alumina ceramic ball grinder 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, revolving speed 10000-15000r/min.
16. method according to claim 6 or 7, wherein the component a is with one-dimensional channels diplopore distributed architecture
The filter cake of meso-porous molecular sieve material, the component b are the filter cake of silica gel, the method also includes: the spray drying in step (3)
After process, the removed template method from the product that spray drying obtains.
17. according to the method for claim 16, wherein the condition of the removed template method includes: that temperature is 300-600
DEG C, the time is 10-80 hours.
18. a kind of loaded catalyst, which contains the p-methyl benzenesulfonic acid of carrier and load on the carrier, feature
It is, the carrier is the spherical shape mesoporous composite material of kaolin containing aluminium described in any one of claim 1-5.
19. catalyst according to claim 18, wherein on the basis of the total weight of the loaded catalyst, to first
The content of benzene sulfonic acid is 1-50 weight %；The content of the carrier is 50-99 weight %.
20. catalyst according to claim 18, wherein on the basis of the total weight of the loaded catalyst, to first
The content of benzene sulfonic acid is 5-50 weight %；The content of the carrier is 50-95 weight %.
21. a kind of method for preparing loaded catalyst described in any one of claim 18-20, this method comprises: will
Carrier, p-methyl benzenesulfonic acid and water are uniformly mixed, and obtained mixture is spray-dried, wherein the carrier is right
It is required that spherical shape kaolin containing aluminium mesoporous composite material described in any one of 1-5.
22. according to the method for claim 21, wherein right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 1-50 weight %；The dosage of the carrier is 50-99 weight %.
23. according to the method for claim 21, wherein right on the basis of total dosage of the carrier and p-methyl benzenesulfonic acid
The dosage of toluenesulfonic acid is 5-50 weight %；The dosage of the carrier is 50-95 weight %.
24. the application of loaded catalyst in the esterification reaction described in any one of claim 18-20.
25. a kind of preparation method of acid isopropyl, wherein this method comprises: in the presence of a catalyst, in esterification
Under the conditions of, contact oleic acid and isopropanol, to obtain acid isopropyl, which is characterized in that the catalyst is claim 18-
Loaded catalyst described in any one of 20.
26. preparation method according to claim 25, wherein the molar ratio of oleic acid and isopropanol is 1:0.5-10.
27. preparation method according to claim 25, wherein relative to the oleic acid of 100 parts by weight, the use of the catalyst
Amount is 1-15 parts by weight.
28. preparation method according to claim 25, wherein relative to the oleic acid of 100 parts by weight, the use of the catalyst
Amount is 2-14 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610212776.9A CN107262135B (en) | 2016-04-07 | 2016-04-07 | The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610212776.9A CN107262135B (en) | 2016-04-07 | 2016-04-07 | The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107262135A CN107262135A (en) | 2017-10-20 |
| CN107262135B true CN107262135B (en) | 2019-07-19 |
Family
ID=60052376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610212776.9A Active CN107262135B (en) | 2016-04-07 | 2016-04-07 | The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107262135B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614108B (en) * | 2018-06-20 | 2022-07-12 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with carrier being mesoporous molecular sieve with three-dimensional cage-shaped pore channel distribution structure, preparation method and application |
| CN108483458B (en) * | 2018-06-22 | 2021-02-19 | 中国高岭土有限公司 | Method for improving specific surface area of kaolin by wet method |
| CN110732339A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with spherical double-mesoporous diatomite composite material as carrier and preparation method and application thereof |
| CN114515601B (en) * | 2020-11-19 | 2023-07-21 | 中国石油化工股份有限公司 | Modified polymeric mesoporous material catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN104248985A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method |
| CN104415795A (en) * | 2013-09-11 | 2015-03-18 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and supported catalyst, and preparation methods and application of spherical zeolite mesoporous composite material and supported catalyst, and preparation method of ethyl acetate |
| 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 CN201610212776.9A patent/CN107262135B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| CN104248985A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite carrier, supported catalyst and preparation method and application thereof, and ethyl acetate preparation method |
| CN104415795A (en) * | 2013-09-11 | 2015-03-18 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and supported catalyst, and preparation methods and application of spherical zeolite mesoporous composite material and supported catalyst, and preparation method of ethyl acetate |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107262135A (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| 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 | |
| CN105149011B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| 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 | |
| CN104248992B (en) | The preparation method of spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN107457005B (en) | Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method | |
| CN107262135B (en) | The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl | |
| CN104248987B (en) | The preparation method of spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and ethyl acetate | |
| CN104248986B (en) | The preparation method of the composite mesoporous carrier of spherical attapulgite 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 | |
| CN105214734B (en) | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN104248993A (en) | Spherical diatomite mesoporous composite and supported catalyst, preparation method thereof and application thereof, and ethyl acetate preparation method | |
| CN109745977A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109746029A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN106622378B (en) | It is a kind of spherical shape mesoporous composite material containing aluminium and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketal method | |
| CN107456992B (en) | Spherical zeolite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method | |
| CN107262157B (en) | The preparation method of spherical shape mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl | |
| CN107262136B (en) | The preparation method of spherical shape illite containing aluminium mesoporous composite material 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 | |
| CN108855201B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN105435854B (en) | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN109382129B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN107262159B (en) | The preparation method of spherical shape 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 | |
| CN109746031A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
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 |