CN116832850A - Esterification catalyst, preparation method thereof and application of esterification catalyst in methyl oleate synthesis reaction - Google Patents
Esterification catalyst, preparation method thereof and application of esterification catalyst in methyl oleate synthesis reaction Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 114
- 230000032050 esterification Effects 0.000 title claims abstract description 95
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 title claims abstract description 39
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 title claims abstract description 39
- 229940073769 methyl oleate Drugs 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 38
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 37
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 37
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000005642 Oleic acid Substances 0.000 claims abstract description 37
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims description 51
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 51
- 239000011148 porous material Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 150000002505 iron Chemical class 0.000 claims description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 239000008188 pellet Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 230000002902 bimodal effect Effects 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002390 adhesive tape Substances 0.000 claims description 2
- 229940024546 aluminum hydroxide gel Drugs 0.000 claims description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 19
- 239000000047 product Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 238000007493 shaping process Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229940049964 oleate Drugs 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- -1 oleic acid ester Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101100442269 Shewanella piezotolerans (strain WP3 / JCM 13877) dapB gene Proteins 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of fine chemical engineering, and discloses an esterification catalyst, a preparation method thereof and application thereof in methyl oleate synthesis reaction. The esterification catalyst comprises a spherical carrier and ferric salt loaded on the spherical carrier, wherein the spherical carrier is a spherical alumina-MCM-48 composite carrier, the content of the spherical carrier is 50-90 wt% and the content of the ferric salt is 10-50 wt% based on the total weight of the esterification catalyst. The esterification catalyst is used for the synthesis reaction of methyl oleate, and can obtain higher oleic acid conversion rate and methyl oleate selectivity.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to an esterification catalyst, a preparation method thereof and application thereof in methyl oleate synthesis reaction.
Background
Methyl oleate is an important organic chemical product, is mainly used as a surface active basic raw material, leather and rubber softener, fluorescent-free slurry lubricant for petroleum exploration, plastic plasticizer, water repellent agent and toughening agent of resin, and is also commonly used for organic synthesis. In addition, methyl oleate may be used as an intermediate for detergents, emulsifiers, wetting agents and stabilizers, and is widely used in various emulsified products, as well as a solvent for fragrances and as a lubricant for spray products. At present, the traditional process for industrially producing methyl oleate uses inorganic acid or organic acid (for example, concentrated sulfuric acid, concentrated hydrochloric acid or p-toluenesulfonic acid) as a catalyst to catalyze the esterification reaction of oleic acid and methanol to produce methyl oleate. The inorganic acid or organic acid catalyst has the advantages of low price, but has the defects of serious environmental pollution, high requirements on equipment materials, more side reactions, more byproducts, difficult separation and purification of the obtained products, and the like. In recent years, the production process of the oleic acid ester in China is continuously developed, the production capacity of the oleic acid ester is continuously improved, the solid acid or the cation exchange resin is used as a catalyst for synthesizing the methyl oleate, the process is greatly developed, and the process is widely applied to industrial production. The solid catalyst has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, such catalysts have a relatively slow reaction rate and a relatively low ester yield. The cation exchange resin has the advantages of good stability, high selectivity, low cost, easy separation and the like in the esterification reaction. However, the cation exchange resin itself has poor heat resistance (generally suitable for esterification reactions at temperatures below 150 ℃), small specific surface area and pore volume, and is susceptible to swelling, poor in reactivity as an esterification catalyst, and low in ester yield.
Compared with the resin catalyst, the hydrogen zeolite molecular sieve has a certain pore channel structure and surface acidity, and is suitable for catalyzing esterification reaction of small molecules. However, the zeolite molecular sieve has small pore size (0.5-0.7 nm), and can inhibit the diffusion of macromolecular products in the reaction; and the zeolite molecular sieve has less acid sites on the surface and lower catalytic esterification efficiency.
Along with the increasing demand of the oleate, the green and environment-friendly process for synthesizing the oleate has wide prospect. For researchers, developing an oleate synthesis reaction catalyst with excellent performance, improving the reaction efficiency and inhibiting the generation of byproducts is an important working direction in the future.
Disclosure of Invention
The invention aims to solve the problems of excessive side reactions and serious environmental pollution of a homogeneous acid catalyst used in the existing methyl oleate production process, and the problems of poor catalytic activity, low ester selectivity and the like of a solid acid catalyst and an acidic cation exchange resin catalyst. Provides an esterification catalyst, a preparation method thereof and application thereof in methyl oleate synthesis reaction. The esterification catalyst is used for the synthesis reaction of methyl oleate, and can obtain higher oleic acid conversion rate and methyl oleate selectivity.
In order to achieve the above object, a first aspect of the present invention provides an esterification catalyst, wherein the esterification catalyst comprises a spherical support and an iron salt supported on the spherical support, the spherical support is a spherical alumina-MCM-48 composite support, and the content of the spherical support is 50 to 90 wt% and the content of the iron salt is 10 to 50 wt% based on the total weight of the esterification catalyst.
The second aspect of the invention provides a preparation method of an esterification catalyst, wherein the preparation method comprises the following steps: and (3) contacting the spherical alumina-MCM-48 composite carrier with an iron salt solution for reaction, separating to obtain a solid product, and drying and roasting the solid product to obtain the esterification catalyst.
In a third aspect, the present invention provides an esterification catalyst prepared by the method described above.
In a fourth aspect, the invention provides the use of an esterification catalyst as hereinbefore described in a methyl oleate synthesis reaction.
Through the technical scheme, compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) The esterification catalyst provided by the invention is spherical, uniform in size, smooth in surface, high in mechanical strength, stable in structure, good in high temperature resistance, and free from deformation and swelling in the reaction process.
(2) The esterification catalyst provided by the invention has the advantages of easily available raw materials, simple preparation method and process, easily controlled conditions and good product repeatability.
(3) The esterification catalyst provided by the invention is used for the synthetic reaction of the oleic acid ester, has mild process conditions and has low requirements on a reaction device; the oleic acid conversion rate is high, and the oleic acid ester selectivity is high.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a photograph of a spherical alumina-MCM-48 composite carrier A prepared in example 1 of the present invention;
FIG. 2 is a small angle XRD spectrum of spherical alumina-MCM-48 composite carrier A prepared in example 1 of the invention;
FIG. 3 is a wide-angle XRD spectrum of spherical alumina-MCM-48 composite carrier A prepared in example 1 of the invention;
FIG. 4 is a graph showing pore size distribution of spherical alumina-MCM-48 composite carrier A prepared in example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides an esterification catalyst, wherein the esterification catalyst comprises a spherical support and an iron salt supported on the spherical support, the spherical support is a spherical alumina-MCM-48 composite support, and the content of the spherical support is 50 to 90 wt% and the content of the iron salt is 10 to 50 wt% based on the total weight of the esterification catalyst.
The inventors of the present invention found that: in the prior art, esterification catalysts used to produce methyl oleate are divided into two classes, homogeneous catalysts and heterogeneous catalysts. Wherein, the homogeneous catalyst mainly comprises inorganic acid solution and organic acid, and the heterogeneous catalyst mainly comprises solid acid and cation exchange resin. The homogeneous catalyst has the advantages of low cost and good catalytic activity, but the defects of difficult separation of products and the catalyst, more side reactions, easy corrosion to equipment and the like are eliminated. Although the solid acid esterification catalyst solves the problems of difficult product separation and serious equipment corrosion, the catalyst is rarely applied to industrial production due to the defects of poor catalytic activity, higher reaction temperature, lower product selectivity and the like. Compared with the catalyst, the resin catalyst has the advantages of high selectivity, low cost, easy separation and the like, but has low ester yield and poor high temperature resistance in the process of synthesizing methyl oleate. The resin is an organic polymer material, is easy to swell in an organic solvent, is easy to deform and even decompose in a high-temperature environment, and is a main reason for poor temperature resistance of the resin catalyst. Based on this, the inventors of the present invention developed a novel solid catalyst system to compensate for the performance defect of the resin catalyst, well solving the problem.
Further, the inventors of the present invention have found that: ferric trichloride, ferric sulfate and ferrous sulfate are all Lewis acids, and the catalyst has high activity, good selectivity and mild reaction conditions when used as an esterification catalyst, and is a very promising green esterification catalyst. However, such catalysts may be partially soluble in organic solvents, resulting in difficult separation of the reaction products. If a proper carrier can be selected to disperse the ferric salt catalyst well, the problems can be solved, and the efficiency of the catalyst can be improved. If the above-mentioned problems are to be solved, the catalytic performance of the esterification catalyst is improved, first a novel material having excellent structural characteristics is selected. The MCM-48 mesoporous molecular sieve has the structural characteristics of long-range ordered pore canal structure, large specific surface area and large pore volume, and is beneficial to the diffusion of macromolecular reaction raw materials and products in the esterification reaction. Although the MCM-48 mesoporous molecular sieve is suitable for being used as a carrier of an esterification catalyst, the MCM-48 mesoporous molecular sieve has poor viscosity and is not easy to form. In industrial production, the solid-phase esterification catalyst is shaped to be applicable, for example: the resin catalyst is generally spherical. The spherical catalyst has the advantages of high bulk density, large loading and processing capacity, low abrasion, small dust during loading, fast mass transfer, high adsorption efficiency or reaction efficiency and the like.
Furthermore, the inventor of the invention discovers that if the MCM-48 mesoporous molecular sieve and the aluminum-containing material with better viscosity are mixed and acidified into sol according to a certain proportion in the development process of the esterification catalyst, the spherical alumina-MCM-48 composite carrier is prepared by a specific molding method. The carrier belongs to an inorganic structure, can not be swelled and deformed in an organic solvent, and has good temperature resistance. The esterification catalyst with better mechanical strength can be obtained after ferric salt is loaded on the spherical alumina-MCM-48 composite carrier in situ. The catalyst can show good catalytic activity and oleate selectivity when being used for oleic acid esterification reaction.
According to the present invention, preferably, the spherical support is contained in an amount of 60 to 80 wt% and the iron salt is contained in an amount of 20 to 40 wt% based on the total weight of the esterification catalyst; more preferably, the spherical carrier is present in an amount of 63 to 73 wt% and the iron salt is present in an amount of 27 to 37 wt% based on the total weight of the esterification catalyst; still more preferably, the spherical support is present in an amount of 63.3 to 72.9 weight percent and the iron salt is present in an amount of 27.1 to 36.7 weight percent, based on the total weight of the esterification catalyst. In the invention, the prepared catalyst has better catalytic activity and ester selectivity when being used for oleic acid esterification reaction by adopting the content of the specific spherical carrier and the content of ferric salt.
According to the invention, the iron salt is Fe-containing 3+ Or/or Fe 2+ Is a salt of (2); preferably, the iron salt is selected from one or more of ferric trichloride, ferric sulfate and ferrous sulfate.
According to the invention, the spherical alumina-MCM-48 composite carrier comprises alumina and MCM-48 all-silicon mesoporous molecular sieve; and the content of the alumina is 45-75 wt% based on the total weight of the spherical alumina-MCM-48 composite carrier, and the content of the MCM-48 all-silicon mesoporous molecular sieve is 25-55 wt%; preferably, the content of the alumina is 55-66 wt% based on the total weight of the spherical composite carrier, and the content of the MCM-48 all-silicon mesoporous molecular sieve is 34-45 wt%; more preferably, the content of the alumina is 55.6 to 65.2 weight percent and the content of the MCM-48 all-silicon mesoporous molecular sieve is 34.8 to 44.4 weight percent based on the total weight of the spherical composite carrier.
According to the invention, the specific surface area of the spherical alumina-MCM-48 composite carrier is 400-900m 2 The pore volume is 0.5-1.2mL/g, the pore size distribution is bimodal, the most probable pore diameters corresponding to the bimodal are 2-4nm and 12-18nm respectively, the average particle diameter is 1.0-3.0mm, and the average particle strength is 20-70N; preferably, the specific surface area of the spherical alumina-MCM-48 composite carrier is 550-700m 2 The pore volume is 0.6-0.9mL/g, the pore size distribution is bimodal, the most probable pore diameters corresponding to the bimodal are 2-3nm and 13-16nm respectively, the average particle diameter is 1.2-2.7mm, and the average particle strength is 25-60N; more preferably, the specific surface area of the spherical alumina-MCM-48 composite carrier is 603-654m 2 And/g, wherein the pore volume is 0.67-0.75mL/g, the pore size distribution is in bimodal distribution, the most probable pore diameters corresponding to the two peaks are 2.3-2.5nm and 13.7-14.8nm respectively, the average particle diameter is 1.74-2.44mm, and the average particle strength is 26.8-35.4N. In the invention, the spherical carrier with the specific parameters is adopted, so that the prepared catalyst has better catalytic activity and ester selectivity when being used for the esterification reaction of oleic acid.
According to the invention, the preparation method of the spherical alumina-MCM-48 composite carrier comprises the following steps:
(1) The alumina precursor, the MCM-48 all-silicon mesoporous molecular sieve, the acidic aqueous solution and the extrusion aid are contacted and mixed, and the obtained mixture is subjected to pellet processing to obtain a spherical alumina-MCM-48 precursor;
(2) And drying and roasting the spherical alumina-MCM-48 precursor to obtain the spherical alumina-MCM-48 composite carrier.
According to the present invention, in step (1), the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite, and boehmite; in the present invention, the alumina precursor may be commercially available or prepared, and in the present invention, specifically, the alumina precursor includes: boehmite powder (available from Shandong Zigbbai chemical Co., ltd., specific surface area: 269 m) having a model BD-BS03 2 Per gram, pore volume of 0.41cm 3 Per g), model SB, german original imported pseudo-boehmite powder (available from Tatai-O Hua chemical auxiliary Co., ltd., beijing, specific surface area 241m 2 Per gram, pore volume of 0.53cm 3 /g) and pseudo-boehmite powder (produced by Shandong aluminum Co., ltd., specific surface area of 286 m) having a type of P-DF-09-LSi 2 Per gram, pore volume of 1.08cm 3 /g).
According to the invention, the specific surface area of the MCM-48 all-silicon mesoporous molecular sieve is 800-1200m 2 Per gram, pore volume of 0.5-0.8cm 3 /g, pore diameter is 2-3nm; preferably, the specific surface area of the MCM-48 all-silicon mesoporous molecular sieve is 1000-1150m 2 Per gram, pore volume of 0.6-0.7cm 3 /g, pore diameter of 2.2-2.8nm; more preferably, the specific surface area of the MCM-48 all-silicon mesoporous molecular sieve is 1089-1132m 2 Per gram, pore volume of 0.68-0.72cm 3 And/g, the pore diameter is 2.3-2.5nm. In the invention, the MCM-48 all-silicon mesoporous molecular sieve with the specific parameters is adopted, so that the prepared esterification catalyst can show good catalytic activity and oleate selectivity when being used for oleic acid esterification reaction.
According to the invention, the MCM-48 mesoporous molecular sieve can be a commercial product or a self-made sample. In the invention, the preparation method of the MCM-48 mesoporous molecular sieve preferably comprises the following steps:
(S1) hydrolyzing a template agent, a silicon source and sodium hydroxide under the condition of preparing an adhesive tape piece by hydrolysis to obtain a gel mixture;
(S2) crystallizing the gel mixture under crystallization conditions, and separating solid phases from liquid phases to obtain a solid product;
and (S3) washing, drying and removing the template agent from the solid product to obtain the MCM-48 mesoporous molecular sieve.
According to the invention, the silicon source preferably has the general formula (RO) 4 Orthosilicate of Si, wherein R is C 1 -C 4 Straight or branched alkyl of (a).
According to the invention, the template agent is a mixture of a quaternary ammonium cationic surfactant and a neutral amine surfactant; and the molar ratio of the quaternary ammonium cationic surfactant to the neutral amine surfactant is 1: (0.03-0.07).
According to the invention, the silicon source: template agent: sodium hydroxide: the molar ratio of the water usage is 1: (0.1-0.2): (0.4-0.6): (50-90), preferably 1: (0.12-0.18): (0.45-0.55): (60-80).
According to the invention, the hydrolysis strip comprises: the temperature is 10-60 ℃ and the time is 0.5-10h.
According to the present invention, the crystallization conditions include: the temperature is 100-130 ℃ and the time is 12-96h.
According to the present invention, the drying conditions include: the temperature is 70-150 ℃ and the time is 3-10h.
According to the invention, the method for removing the template agent is not particularly required, and can be various existing methods, such as a roasting method or an extraction method.
According to the present invention, the acidic aqueous solution may be an aqueous organic acid solution or an aqueous inorganic acid solution, preferably, the acidic aqueous solution is one or more selected from an aqueous formic acid solution, an aqueous acetic acid solution, an aqueous citric acid solution, an aqueous nitric acid solution and an aqueous hydrochloric acid solution, more preferably, the acidic aqueous solution is an aqueous nitric acid solution or an aqueous citric acid solution; in the present invention, the mass concentration of the acidic aqueous solution is 1 to 20%, preferably 2 to 15%.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, polyethylene glycol, polyvinyl alcohol, polyacrylamide and cellulose; preferably, the auxiliary agent is sesbania powder.
According to the invention, the weight ratio of the alumina precursor, the MCM-48 mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.3-0.8): (0.02-0.5): (0.2-5); preferably, the weight ratio of the alumina precursor, the MCM-48 mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.4-0.6): (0.05-0.2): (0.4-2).
According to the invention, in step (1), an alumina precursor, an MCM-48 all-silica mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid are contacted and mixed, and the mixing conditions comprise: the stirring speed is 50-300r/min, the temperature is 20-60 ℃ and the time is 0.5-6h; preferably, the stirring speed is 150-200r/min, the temperature is 20-35 ℃ and the time is 0.5-1h.
According to the present invention, in step (2), the drying conditions include: the temperature is 70-150 ℃ and the time is 3-24 hours; preferably, the temperature is 110-120 ℃ and the time is 8-12h.
According to the present invention, in step (2), the conditions of the firing include: the temperature is 400-700 ℃ and the time is 2-30h; preferably, the temperature is 550-700 ℃ and the time is 6-15h.
According to the present invention, in step (1), the method of pelleting the pellets comprises:
(1-1) extruding the mixture into a strip, and then cutting and extruding into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
(1-3) screening the standard spheres to obtain spherical precursors.
According to a preferred embodiment of the present invention, the method for preparing pellets comprises: uniformly mixing an alumina precursor, an MCM-48 mesoporous molecular sieve, an acidic aqueous solution and an extrusion assisting agent in a kneader, transferring the mixture into a miniature ball making machine, extruding a strip with a circular section, and extruding the strip into raw material balls after cutting; and (3) putting the raw material balls into a pellet shaper for shaping to form standard spherical shapes, and putting the obtained product into a pellet screening machine for screening spherical precursors with proper sizes.
According to the invention, in the step (1-1), after uniformly mixing an alumina precursor, an MCM-48 mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, transferring the obtained mixture into a miniature ball making machine to extrude a strip with a circular section, and then extruding the strip into raw material balls after cutting; wherein the conditions of extrusion into a strip include: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.0-3.0mm; the conditions of the cutting include: the cutting speed is 100-3500 grains/min.
According to the invention, in the step (1-2), the raw material balls are put into a pellet shaper for shaping, so that the raw material balls become standard spherical balls; wherein the shaping conditions include: the rounding time is 0.5-10 min/time, the number of times of rounding is 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min.
According to the invention, in step (1-3), the standard spheres are placed in a pellet screening machine to screen out spherical precursors of suitable size.
The second aspect of the invention provides a preparation method of an esterification catalyst, wherein the preparation method comprises the following steps: and (3) contacting the spherical alumina-MCM-48 composite carrier with an iron salt solution for reaction, separating to obtain a solid product, and drying and roasting the solid product to obtain the esterification catalyst.
According to the invention, the ferric salt solution is one or more of an aqueous solution, an ethanol solution, a methanol solution, a toluene solution and an acetone solution of ferric salt; preferably an aqueous or ethanol solution.
According to the invention, the weight ratio of the spherical alumina-MCM-48 composite carrier to the ferric salt solution is 1: (1-200), preferably 1: (2-50).
According to the invention, the concentration of the iron salt solution is 0.1-20%, preferably 2.0-15.0%.
According to the invention, the contact reaction conditions of the spherical alumina-MCM-48 composite carrier and the ferric salt solution comprise: the reaction temperature may be 20-100 ℃, preferably 30-80 ℃; the time may be 0.5 to 20 hours, preferably 1 to 10 hours.
According to the invention, in order to achieve better mixing effect, the reaction efficiency can be improved by rapid stirring or by means of ultrasonic means in the process of the contact reaction of the spherical alumina-MCM-48 composite carrier and the ferric salt solution.
The separation method according to the present invention is not particularly limited and may be a method known in the art, for example: the water is removed using a rotary evaporator or by evaporation with heating during stirring.
According to the invention, the drying conditions include: the drying temperature is 70-150 ℃ and the drying time is 2-20 hours; preferably, the drying temperature is 90-130 ℃ and the drying time is 4-12 hours.
According to the invention, the firing conditions include: roasting at 200-400 deg.c for 2-10 hr; preferably, the calcination temperature is 250-360 ℃ and the calcination time is 5-8 hours.
In a third aspect, the present invention provides an esterification catalyst prepared by the method described above.
In a fourth aspect, the invention provides the use of an esterification catalyst as hereinbefore described in a methyl oleate synthesis reaction.
According to the invention, the application comprises: oleic acid and methanol are simultaneously contacted with an esterification catalyst.
In the invention, the contact conditions of the oleic acid and the methanol with the catalyst comprise: the temperature of contact may be 40-100deg.C, preferably 50-80deg.C; catalyst: oleic acid: the weight ratio of the methanol is 1: (2-50): (1-10), preferably 1: (5-20): (2-5); the reaction time may be 1 to 12 hours, preferably 2 to 8 hours.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
wide angle XRD testing of the samples was performed on an X' Pert MPD X-ray powder diffractometer, philips company, netherlands, cu ka target, scan range 2θ=5-90 °.
Small angle XRD testing of the samples was performed on a high power, rotary target X-ray diffractometer, D8 ADVANCE, BRUKER AXS, germany, scan range: 0.5-10 deg..
The pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model.
Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The rotary evaporator is manufactured by IKA corporation of Germany and has the model RV10 digital.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The kneader is an FN-NH2 kneader manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the miniature ball making machine is a HWJ-100 miniature ball making machine manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the pellet shaper is an FN-XZXJ pellet shaper manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the micropill screening machine is SWP-1200 micropill screening machine produced by Tianshuihua round pharmaceutical equipment science and technology Co.
The reagents used in examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
(1) Preparation of spherical alumina-MCM-48 composite carrier
23.2g of cetyltrimethylammonium bromide, 0.6g of dodecylamine were mixed with 8.1g of sodium hydroxide and 500ml of deionized water, and stirred at 45℃for 1 hour; 82.9g of ethyl orthosilicate is added dropwise to the solution and stirred for 1 hour; the mixture was transferred to a hydrothermal kettle and hydrothermally crystallized at 100 ℃ for 72 hours. After the hydrothermal crystallization is finished, separating a solid product from a mother solution, washing the solid product to be neutral by deionized water, and drying the solid product in air at 110 ℃ for 10 hours; and then roasting for 20 hours at 550 ℃ to obtain the MCM-48 mesoporous molecular sieve.
The specific surface area of the MCM-48 mesoporous molecular sieve is 1109m 2 Per gram, pore volume of 0.7cm 3 And/g, pore diameter of 2.4nm.
100g of pseudo-boehmite powder with the model of P-DF-09-LSi, 50g of MCM-48 mesoporous molecular sieve, 78g of dilute nitric acid with the concentration of 5.0 percent and 10g of sesbania powder are mixed, transferred into a kneader and stirred and mixed uniformly. The kneading temperature was 30℃and the main shaft rotation speed of the kneader was 200r/min, and the kneading time was 1h. Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 1.8mm, adjusting the strip extruding speed to be 1.5m/min and the cutting speed to be 900 grains/min, extruding the raw materials into strips, and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 2 minutes/time, the number of times of rounding is 4, and the rotating speed of the sample cavity is 300r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 1.8 mm. Drying the spherical precursor at 110 ℃ for 10 hours, and roasting at 600 ℃ for 12 hours to obtain the spherical alumina-MCM-48 composite carrier A.
The content of alumina in the spherical alumina-MCM-48 composite carrier A is 58.3 weight percent, and the content of the MCM-48 all-silicon mesoporous molecular sieve is 41.7 weight percent.
The structural parameters of the spherical alumina-MCM-48 composite support A are set forth in Table 1.
FIG. 1 is a photograph of a spherical alumina-MCM-48 composite carrier A prepared in example 1 of the present invention. It can be seen that the carrier has the appearance of white sphere, good sphericity, smooth sphere and uniform particle size.
FIG. 2 is a small angle XRD spectrum of spherical alumina-MCM-48 composite carrier A prepared in example 1 of the present invention. As can be seen from fig. 2, the sample exhibits a sharp strong diffraction peak and a weaker but clearly discernable diffraction peak between 2θ=2.5° and 3.5 °, the two signals corresponding to the (211) and (220) crystal planes, respectively. In addition, there is also a set of diffraction signals at 2θ=4.0° to 6.0 °, including diffraction peaks corresponding to (420) and (332) crystal planes. The diffraction signal is a characteristic diffraction peak of the MCM-48 mesoporous molecular sieve. The spherical composite carrier A is shown to have no obvious change of the crystalline phase of the MCM-48 mesoporous molecular sieve after being roasted at 600 ℃, and still maintains a typical three-dimensional cubic phase mesoporous structure.
FIG. 3 is a wide-angle XRD spectrum of spherical alumina-MCM-48 composite carrier A prepared in example 1 of the invention. XRD wide-angle diffraction pattern and oxidation of spherical alumina-MCM-48 composite carrierThe wide angle diffraction pattern of aluminum is identical because the structure of MCM-48 mesoporous molecular sieve has no diffraction signal at the wide angle portion. The x-ray diffraction angles are mainly: 2θ=37.1 °, 39.3 °, 46.1 °, 60.7 °, and 66.6 °, these five diffraction signals are associated with γ -Al 2 O 3 The diffraction patterns are identical, which shows that the spherical composite carrier A shows typical gamma-Al after being dehydrated by pseudo-boehmite with the model of P-DF-09-LSi after being roasted at 600 DEG C 2 O 3 A crystalline phase. In addition, the XRD signal of the spherical composite carrier is not shown in one figure, nor is it detected by the same characterization means. The XRD pattern given here is two, a wide angle and a small angle.
FIG. 4 is a graph showing pore size distribution of spherical alumina-MCM-48 composite carrier A prepared according to the present invention. As can be seen from fig. 4, the pore size of the sample is in bimodal distribution, and the first most probable pore size is 2.4nm, which is mainly contributed by the mesoporous molecular sieve; the second most probable pore size is 14.0nm, contributed mainly by alumina.
(2) Preparation of esterification catalyst
100g of spherical alumina-MCM-48 composite carrier A and 800g of ferric trichloride aqueous solution with the mass concentration of 6.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst A.
Based on the total weight of the esterification catalyst A, the content of the spherical alumina-MCM-48 composite carrier A is 67.5 weight percent, and the content of ferric trichloride is 32.5 weight percent.
(3) Evaluation of catalyst reactivity
1 g of esterification catalyst A is weighed, 14.1 g of oleic acid and 3.2 g of methanol are weighed and put into a 100ml three-neck flask, a condenser tube is added, stirring is carried out for 6 hours under the condition of heating reflux at 60 ℃, after cooling to room temperature, products are centrifugally separated and analyzed by Agilent 7890A gas chromatograph equipped with FFAP capillary chromatographic column and hydrogen flame detector (FID), and temperature programming and quantitative analysis are carried out by using correction factors. The oleic acid conversion was 98.2% and the methyl oleate selectivity was 99.4%.
Example 2
(1) Preparation of spherical alumina-MCM-48 composite carrier
An MCM-48 mesoporous molecular sieve was prepared in the same manner as in step (1) of example 1.
100g of boehmite powder with the model BD-BS03, 40g of MCM-48 mesoporous molecular sieve, 62g of 10% acetic acid aqueous solution and 5g of polyethylene glycol are mixed, and the mixture is transferred to a kneader for stirring and mixing uniformly. The kneading temperature was 35℃and the main shaft rotation speed of the kneader was 150r/min, and the kneading time was 1h. Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 2.5mm, adjusting the strip extruding speed to be 5m/min and the cutting speed to be 2000 grains/min, extruding the raw materials into strips and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 0.5 min/time, the number of times of rounding is 2, and the rotating speed of the sample cavity is 500r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 2.5 mm. Drying the spherical precursor at 120 ℃ for 8 hours, and roasting at 700 ℃ for 6 hours to obtain the spherical alumina-MCM-48 composite carrier B.
The content of alumina in the spherical alumina-MCM-48 composite carrier B is 65.2 weight percent, and the content of the MCM-48 all-silicon mesoporous molecular sieve is 34.8 weight percent.
The spherical alumina-MCM-48 composite carrier B was characterized and its structural parameters are shown in Table 1.
(2) Preparation of esterification catalyst
100g of spherical alumina-MCM-48 composite carrier B and 1860g of ferric sulfate ethanol solution with the mass concentration of 2.0% are mixed and stirred at 30 ℃ for reaction for 16h. After the reaction, stirring is stopped, and the solvent ethanol is removed by using a rotary evaporator, so that a solid product is obtained. The solid product is dried at 90 ℃ for 8 hours and baked at 250 ℃ for 8 hours, so that the esterification catalyst B is obtained.
The content of the spherical alumina-MCM-48 composite carrier B was 72.9 wt% and the content of the ferric sulfate was 27.1 wt% based on the total weight of the esterification catalyst B.
(3) Evaluation of catalyst reactivity
The esterification reaction performance test of catalyst B was conducted in the same manner as in step (3) of example 1. The oleic acid conversion was 98.0% and the methyl oleate selectivity was 99.2%.
Example 3
(1) Preparation of spherical alumina-MCM-48 composite carrier
An MCM-48 mesoporous molecular sieve was prepared in the same manner as in step (1) of example 1.
100g of German original-package imported pseudo-boehmite powder with the model SB, 60g of MCM-48 mesoporous molecular sieve, 80g of citric acid aqueous solution with the concentration of 15.0 percent and 18g of cellulose are mixed, transferred into a kneader and stirred and mixed uniformly. The kneading temperature was 20℃and the main shaft rotation speed of the kneader was 200r/min, and the kneading time was 0.5h. Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 2.0mm, adjusting the strip extruding speed to be 1m/min and the cutting speed to be 500 grains/min, extruding the raw materials into strips and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 2 minutes/time, the number of times of rounding is 4, and the rotating speed of the sample cavity is 200r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 2.0 mm. Drying the spherical precursor at 110 ℃ for 12 hours, and roasting at 550 ℃ for 15 hours to obtain the spherical alumina-MCM-48 composite carrier C.
The content of alumina in the spherical alumina-MCM-48 composite carrier C is 55.6 weight percent, and the content of the MCM-48 all-silicon mesoporous molecular sieve is 44.4 weight percent.
The spherical alumina-MCM-48 composite carrier C was characterized and its structural parameters are shown in Table 1.
(2) Preparation of esterification catalyst
100g of spherical alumina-MCM-48 composite carrier C and 385g of ferrous sulfate aqueous solution with the mass concentration of 15.0% are mixed and stirred at 80 ℃ for reaction for 1.5h. After the reaction, the stirring was stopped, and the solvent water was removed by using a rotary evaporator to obtain a solid product. The solid product was dried at 130℃for 4 hours and calcined at 360℃for 5 hours to give esterification catalyst C.
The content of the spherical alumina-MCM-48 composite carrier C was 63.3 wt% and the content of ferrous sulfate was 36.7 wt% based on the total weight of the esterification catalyst C.
(3) Evaluation of catalyst reactivity
The esterification reaction performance test of catalyst C was conducted in the same manner as in step (3) of example 1. The oleic acid conversion was 98.4% and the methyl oleate selectivity was 99.1%.
TABLE 1
Example 4
An esterification catalyst was prepared in the same manner as in example 1 except that: the preparation conditions of the catalyst of step (2) in example 1 were changed, specifically:
100g of spherical alumina-MCM-48 composite carrier A and 525g of ferric trichloride aqueous solution with the mass concentration of 6.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst D.
Based on the total weight of the esterification catalyst D, the content of the spherical alumina-MCM-48 composite carrier A is 76.1 weight percent, and the content of ferric trichloride is 23.9 weight percent.
Catalyst D was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 96.0% and the methyl oleate selectivity was 98.5%.
Example 5
An esterification catalyst was prepared in the same manner as in example 1 except that: the preparation conditions of the catalyst of step (2) in example 1 were changed, specifically:
100g of spherical alumina-MCM-48 composite carrier A and 833g of ferric trichloride aqueous solution with the mass concentration of 8.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst E.
The content of the spherical alumina-MCM-48 composite carrier A is 60 weight percent and the content of the ferric trichloride is 40 weight percent based on the total weight of the esterification catalyst E.
Catalyst E was tested for its catalytic performance according to the esterification performance evaluation method of step (3) in example 1. The oleic acid conversion was 95.7% and the methyl oleate selectivity was 98.2%.
Example 6
An esterification catalyst was prepared in the same manner as in example 1 except that: the preparation conditions of the catalyst of step (2) in example 1 were changed, specifically:
100g of spherical alumina-MCM-48 composite carrier A and 214g of ferric trichloride aqueous solution with the mass concentration of 6.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst F.
The content of the spherical alumina-MCM-48 composite carrier A was 88.6 wt% and the content of ferric trichloride was 11.4 wt% based on the total weight of the esterification catalyst F.
Catalyst F was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 94.0% and the methyl oleate selectivity was 97.5%.
Example 7
An esterification catalyst was prepared in the same manner as in example 1 except that: the preparation conditions of the catalyst of step (2) in example 1 were changed, specifically:
100g of spherical alumina-MCM-48 composite carrier A and 1000g of ferric trichloride aqueous solution with the mass concentration of 10.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst G.
The content of the spherical alumina-MCM-48 composite carrier A is 50 weight percent and the content of the ferric trichloride is 50 weight percent based on the total weight of the esterification catalyst G.
Catalyst G was tested for its catalytic performance according to the esterification performance evaluation method of step (3) in example 1. The oleic acid conversion was 94.4% and the methyl oleate selectivity was 97.6%.
Comparative example 1
An esterification catalyst was prepared in the same manner as in example 1 except that: the preparation conditions of the catalyst of step (2) in example 1 were changed, specifically:
100g of spherical alumina-MCM-48 composite carrier A and 130g of ferric trichloride aqueous solution with the mass concentration of 6.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst D1.
The content of the spherical alumina-MCM-48 composite carrier A was 92.7 wt% and the content of ferric trichloride was 7.3 wt% based on the total weight of the esterification catalyst D1.
Catalyst D1 was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 70.8% and the methyl oleate selectivity was 92.0%.
Comparative example 2
An esterification catalyst was prepared in the same manner as in example 1 except that: the preparation conditions of the catalyst of step (2) in example 1 were changed, specifically:
100g of spherical alumina-MCM-48 composite carrier A and 1087g of ferric trichloride aqueous solution with the mass concentration of 15.0% are mixed and stirred at 60 ℃ for 8 hours. Solvent water in the system is removed by using a rotary evaporator, the solid product is dried for 12 hours at 100 ℃, and then baked for 6 hours at 320 ℃ to obtain an esterification catalyst D2.
The content of the spherical alumina-MCM-48 composite carrier A was 38% by weight and the content of ferric trichloride was 62% by weight, based on the total weight of the esterification catalyst D2.
Catalyst D2 was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 75.3% and the methyl oleate selectivity was 93.7%.
Comparative example 3
Preparation of esters according to the same procedure as in example 1A catalyst, the difference being that: step (1) of example 1 was omitted, and spherical alumina-MCM-48 composite support A of step (2) of example 1 was replaced with commercially available silica (from Qingdao sea wave silica gel desiccant plant, specific surface area 329 m) 2 /g, average particle diameter 1.5 mm) to give catalyst D3.
The commercially available silica content was 67.5% by weight and the ferric trichloride content was 32.5% by weight, based on the total weight of catalyst D3.
Catalyst D3 was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 89.1% and the methyl oleate selectivity was 95.5%.
Comparative example 4
An esterification catalyst was prepared in the same manner as in example 1 except that: step (1) in example 1 was omitted, and 100g of spherical alumina-MCM-48 composite carrier A in step (2) in example 1 was replaced with 143g of pseudo-boehmite of model P-DF-09-LSi to obtain catalyst D4.
The content of alumina was 67.5% by weight and the content of ferric trichloride was 32.5% by weight, based on the total weight of catalyst D4.
Catalyst D4 was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 90.8% and the methyl oleate selectivity was 96.0%.
Comparative example 5
An esterification catalyst was prepared in the same manner as in example 1 except that: in the step (1), 70g of pseudo-boehmite powder with the model of P-DF-09-LSi and 98g of MCM-48 mesoporous molecular sieve are used to obtain a catalyst D5; namely, the content of the alumina is 41.7 weight percent and the content of the MCM-48 all-silicon mesoporous molecular sieve is 58.3 weight percent based on the total weight of the spherical alumina-MCM-48 composite carrier;
The content of the spherical carrier was 67.5% by weight and the content of ferric trichloride was 32.5% by weight, based on the total weight of the catalyst D5.
Catalyst D5 was tested for its catalytic performance according to the method for evaluating the performance of esterification reaction in step (3) of example 1. The oleic acid conversion was 92.7% and the methyl oleate selectivity was 96.5%.
From the results, the esterification catalyst provided by the invention can directly convert oleic acid and methanol to generate methyl oleate, so that higher oleic acid conversion rate and methyl oleate selectivity are obtained.
In comparative example 1, too high content of spherical alumina-MCM-48 composite carrier A, low oleic acid conversion rate and low selectivity of methyl oleate are caused by too low content of active component ferric salt on the catalyst and insufficient active site in the reaction process.
In comparative example 2, the content of the spherical alumina-MCM-48 composite carrier A is too low, and the active component iron salt content on the catalyst is too high, so that the active component is unevenly dispersed on the carrier, and part of active centers cannot play a catalytic role in the reaction process, so that the oleic acid conversion rate is low and the selectivity of methyl oleate is low.
In comparative example 3, the spherical support specifically defined in the present invention was not employed, but commercially available silica was employed, and the oleic acid conversion rate was low and the selectivity of methyl oleate was low due to irregular pore structure of commercially available silica and uneven dispersion of the active ingredient on the surface of the support.
In comparative example 4, the spherical support specifically defined by the present invention was not used, but a single alumina support was used, and the dispersion of the active component on the surface of the support was not facilitated due to the non-uniform size distribution of alumina channels, and the diffusion of the raw materials and the products during the reaction was also not facilitated, resulting in low oleic acid conversion and low selectivity of methyl oleate.
In comparative example 5, the weight ratio of the contents of alumina and MCM-48 mesoporous molecular sieve in the spherical carrier is 1:2, the content of the MCM-48 mesoporous molecular sieve is too high, and the proportion of the MCM-48 mesoporous molecular sieve in the spherical carrier is not in the scope of the claims, so that the prepared catalyst has poor strength, uneven surface and poor dispersion of active components, thereby having low oleic acid conversion rate and low selectivity of methyl oleate.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. The esterification catalyst is characterized by comprising a spherical carrier and ferric salt supported on the spherical carrier, wherein the spherical carrier is a spherical alumina-MCM-48 composite carrier, the content of the spherical carrier is 50-90 wt% and the content of the ferric salt is 10-50 wt% based on the total weight of the esterification catalyst.
2. The esterification catalyst according to claim 1, wherein the content of the spherical carrier is 60 to 80 wt% and the content of the iron salt is 20 to 40 wt%, based on the total weight of the esterification catalyst;
preferably, the spherical carrier is present in an amount of 63 to 73 wt% and the iron salt is present in an amount of 27 to 37 wt% based on the total weight of the esterification catalyst.
3. The esterification catalyst according to claim 1 or 2, wherein the iron salt is a catalyst comprising Fe 3+ Or/or Fe 2+ Is a salt of (2);
preferably, the iron salt is selected from one or more of ferric trichloride, ferric sulfate and ferrous sulfate.
4. The esterification catalyst according to claim 1 or 2, wherein the spherical alumina-MCM-48 composite carrier comprises alumina and MCM-48 all-silicon mesoporous molecular sieve;
and/or, based on the total weight of the spherical alumina-MCM-48 composite carrier, the content of the alumina is 45-75 wt%, and the content of the MCM-48 all-silicon mesoporous molecular sieve is 25-55 wt%;
Preferably, the content of the alumina is 55-66 wt% and the content of the MCM-48 all-silicon mesoporous molecular sieve is 34-45 wt% based on the total weight of the spherical composite carrier.
5. The esterification catalyst according to claim 1 or 4, wherein the specific surface area of the spherical alumina-MCM-48 composite carrier is 400-900m 2 And/g, wherein the pore volume is 0.5-1.2mL/g, the pore size distribution is in bimodal distribution, the most probable pore diameters corresponding to the two peaks are 2-4nm and 12-18nm respectively, the average particle diameter is 1.0-3.0mm, and the average particle strength is 20-70N.
6. The esterification catalyst according to claim 1 or 4, wherein the preparation method of the spherical alumina-MCM-48 composite carrier comprises the following steps:
(1) The alumina precursor, the MCM-48 all-silicon mesoporous molecular sieve, the acidic aqueous solution and the extrusion aid are contacted and mixed, and the obtained mixture is subjected to pellet processing to obtain a spherical alumina-MCM-48 precursor;
(2) And drying and roasting the spherical alumina-MCM-48 precursor to obtain the spherical alumina-MCM-48 composite carrier.
7. The esterification catalyst of claim 6, wherein in step (1), the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, aluminum sol, gibbsite, and boehmite;
And/or the specific surface area of the MCM-48 all-silicon mesoporous molecular sieve is 800-1200m 2 Per gram, pore volume of 0.5-0.8cm 3 /g, pore diameter is 2-3nm;
and/or the weight ratio of the alumina precursor, the MCM-48 mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.3-0.8): (0.02-0.5): (0.2-5).
8. The esterification catalyst according to claim 6 or 7, wherein the preparation method of the MCM-48 all-silicon mesoporous molecular sieve comprises the following steps:
(S1) hydrolyzing a template agent, a silicon source and sodium hydroxide under the condition of preparing an adhesive tape piece by hydrolysis to obtain a gel mixture;
(S2) crystallizing the gel mixture under crystallization conditions, and separating solid phases from liquid phases to obtain a solid product;
and (S3) washing, drying and removing the template agent from the solid product to obtain the MCM-48 mesoporous molecular sieve.
9. The esterification catalyst of claim 8, wherein the templating agent is a mixture of a quaternary ammonium cationic surfactant and a neutral amine surfactant; and the molar ratio of the amount of the quaternary ammonium cationic surfactant to the amount of the neutral amine surfactant is 1: (0.03-0.07);
and/or the molar ratio of the silicon source, the template agent, sodium hydroxide and water is 1: (0.1-0.2): (0.4-0.6): (50-90);
And/or, the hydrolysis glue strip manufacturing piece comprises: the temperature is 10-60 ℃ and the time is 0.5-10h.
10. A method for preparing an esterification catalyst, which is characterized by comprising the following steps: and (3) contacting the spherical alumina-MCM-48 composite carrier with an iron salt solution for reaction, separating to obtain a solid product, and drying and roasting the solid product to obtain the esterification catalyst.
11. The method of claim 10, wherein the iron salt solution is one or more of an aqueous solution of an iron salt, an ethanol solution, a methanol solution, a toluene solution, and an acetone solution;
and/or, the weight ratio of the spherical alumina-MCM-48 composite carrier to the ferric salt solution is 1: (1-200);
and/or the concentration of the ferric salt solution is 0.1-20%;
and/or, the reaction conditions include: the temperature is 20-100 ℃ and the time is 0.5-20h;
and/or, the roasting conditions include: the temperature is 200-400 ℃ and the time is 2-10h.
12. An esterification catalyst prepared by the process of claim 10 or 11.
13. Use of an esterification catalyst according to any one of claims 1 to 9 and 12 in a methyl oleate synthesis reaction.
14. The application of claim 13, wherein the application comprises: contacting oleic acid, methanol, and an esterification catalyst;
and/or, the contacting comprises: the temperature is 40-100 ℃ and the time is 1-12h;
and/or the weight ratio of the amount of the esterification catalyst, the oleic acid and the methanol is 1: (2-50): (1-10).
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