CN107952484A - A kind of preparation method and applications with Nafion film supported rare earth metallic catalysts - Google Patents
A kind of preparation method and applications with Nafion film supported rare earth metallic catalysts Download PDFInfo
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- CN107952484A CN107952484A CN201711193424.4A CN201711193424A CN107952484A CN 107952484 A CN107952484 A CN 107952484A CN 201711193424 A CN201711193424 A CN 201711193424A CN 107952484 A CN107952484 A CN 107952484A
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- China
- Prior art keywords
- acrylic acid
- nafion
- rare earth
- glycerine
- catalyst
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- 229920000557 Nafion® Polymers 0.000 title claims abstract description 84
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 53
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003863 metallic catalyst Substances 0.000 title claims abstract description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 287
- 238000006243 chemical reaction Methods 0.000 claims abstract description 110
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 92
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 12
- -1 rare-earth metal chloride Chemical class 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 235000011187 glycerol Nutrition 0.000 claims description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 230000008016 vaporization Effects 0.000 claims description 14
- 229910052779 Neodymium Inorganic materials 0.000 claims description 11
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 9
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010668 complexation reaction Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 8
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 239000002028 Biomass Substances 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 64
- 230000008859 change Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 10
- 239000003225 biodiesel Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940120503 dihydroxyacetone Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101000892220 Geobacillus thermodenitrificans (strain NG80-2) Long-chain-alcohol dehydrogenase 1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ATMLPEJAVWINOF-UHFFFAOYSA-N acrylic acid acrylic acid Chemical compound OC(=O)C=C.OC(=O)C=C ATMLPEJAVWINOF-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 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
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to acrylic acid preparing technical field, and in particular to a kind of preparation method and applications with Nafion film supported rare earth metallic catalysts.The present invention prepares as follows in the method for Nafion film supported rare earth metallic catalysts：Using anhydrous rare-earth metal chloride, the suspension of tetrahydrofuran, the lithium containing pi-allyl tetrahydrofuran diethyl ether solution, load containing Phosphine ligands as raw material, be prepared under certain condition with Nafion film supported rare earth metallic catalysts.In addition, the present invention will be supported on prepares acrylic acid with Nafion film supported rare earth metallic catalyst applied catalysis, using biomass glycerol as raw material, reacted using Nafion film supported rare earth metallic catalysts as catalyst, under certain catalytic condition and obtain acrylic acid；Glycerol conversion yield is up to 100%, and acrylic acid yield is up to 80.0%.Preparation method provided by the invention, glycerol conversion yield is high, acrylic acid high income, and post processing is simple, and catalyst continuous use performance is high, and preparation process is simple, safety and environmental protection, has good industrial prospect.
Description
Technical field
The invention belongs to acrylic acid preparing technical field, and in particular to one kind is with Nafion film supported rare earth metal catalytics
The preparation method and applications of agent.
Background technology
Acrylic acid (Acrylic acid) is very important one of industrial chemicals, it is widely used in rubber synthesis, modeling
Material and coating industry；Main preparation methods are produced in atmosphere through two-step oxidation industrial process by propylene or propane at present.But
It is that the whole world is to biodiesel as diesel engine begins to use biodiesel (biodiesel) to be used as fuel gradually in recent years
Demand increasingly increase, it is contemplated that yield of biodiesel will be up to 4.0 × 10 in 202310L.The production of biodiesel is mostly used
Ester-interchange method, often produces 1 ton of biodiesel byproduct just about 0.1 ton of glycerine, in addition, glycerine can also be sent out by microorganism according to statistics
The approach such as ferment starch, enzymatic Starch Conversion, carrying out hydrogenolysis on sorbierite and catalytic decomposition lignocellulosic obtain, and how to efficiently use this
A little glycerine become limitation biodiesel industrial development now very thorny problem.Glycerine is as biological-based chemicals and platform chemical combination
One of thing, there are in animal and plant body in the form of triglyceride construction unit.Industrially, the saponification system using triglycerides as raw material
The processes such as soap, hydrolysis aliphatic acid processed and ester exchange production biodiesel can produce glycerin by-products.In the latest 20 years, people is studied
Member tries to explore the conversion process of glycerine conversion production high valuable chemicals, such as preparing acrolein by dehydrating glycerin, steam reforming system
Hydrogen and oxidation dihydroxyacetone (DHA) etc..But these reactions are mostly complicated there are technological process at present, and severe reaction conditions etc. lack
Point.If scientist contemplates the gentle dehydrating glycerin oxidation consecutive reaction production acrylic acid process flow of success exploit condition, will
The dependence of whole world acrylic acid production industry on petroleum base propylene or propane feed can be significantly reduced, substantially reduces energy consumption and CO2
Deng the discharge of sour gas, effectively solve because glycerol overstock limits biodiesel industrial development problem.This has been responded in recent years just
Carry out the global call for Green Chemistry, using biomass or biological-based chemicals as raw material, develop the new chemical industry of green catalysis
Process production of chemicals and clean energy resource, it will significantly reduce Fossil fuel consumption and the influence to environment.In contrast, it is near
Dehydrating glycerin with catalyst oxidation consecutive reaction acrylic acid becomes the new focus of attention over year.But a kind of feasible catalysis can be developed
System and high activity, the in high yield catalyst with high stability, be dehydrating glycerin aoxidize acrylic acid processed can realize it is industrialized
It is crucial.
Patent CN200580002350.0 discloses a kind of two step gas-phase dehydrations and prepares acrylic acid, using glycerine as original
Material, the concentration of glycerine water solution be 10~50wt%, 200~370 DEG C of reaction temperature, carried out in single reactor dehydration with
Gas phase oxidation acrylic acid, can obtain acrylic acid yield 55~65%.The technology uses single reactor, and gasification needs a large amount of
Energy, draining are also required to a large amount of expenses, it is impossible to industrial applications, and also acrylic acid yield is low, and performance is also not publicly used continuously.
The content of the invention
For glycerol concentration existing in the prior art is low, reaction temperature is high, acrylic acid yield is low, production process and after
The problems such as processing cost is high, and continuous use is difficult, the present invention propose a kind of catalyst with Nafion film supported rare earth metals,
There is the catalyst higher catalyzing glycerol to prepare propylene acid activity, and have good continuous use characteristic.
The present invention also provides a kind of preparation method of the catalyst with Nafion film supported rare earth metals, the technology of use
Scheme is specific as follows：
(1) 115 membrane materials of Nafion are pre-processed：
115 membrane materials of Nafion that the present invention uses originate in Dupont companies of the U.S., which all needs before every time
To pass through certain pretreatment, process is as follows：115 films of Nafion are placed on 75 DEG C of 50mL2mol/L H first2O2Soaked in solution
1.5h is steeped to remove organic impurities；Then in 75 DEG C of 50mL 2mol/L H2SO41h is soaked in solution, to remove metal impurities；Most
Afterwards by film as boiled in redistilled water rinsing for several times after can obtain water white transparency sulphonyl fluorine-type Nafion-F resin films.
(2) rare-earth metal chloride is prepared：
Concentrated hydrochloric acid and each 20mL of distilled water are added in round-bottomed flask, then adds 10g M2O3(M is rare-earth elements of lanthanum La, cerium
Ce, praseodymium Pr, neodymium Nd, samarium Sm and yttrium Y), make M with magneton stirring2O3Solid dissolves, and obtains reaction solution A；15g chloride solids are added
Enter in reaction solution A, stirring dissolves chloride solid, obtains reaction solution B；Concentration of reaction solution B is transferred in evaporating dish, on electric furnace
Parch 1h, is stirred white to solid exsiccation with glass bar；It is after 30 DEG C of coolings, gained white solid is finely ground, it is transferred to another circle
In the flask of bottom, flask is put into the sublimation apparatus with dry ice freezing, is heated with sand-bath and sets up Automatic Temperature Control control
Reaction temperature processed is 460 DEG C, ammonium chloride is slowly distilled, and whole process continues 10~12h, after reaction, is protected in argon gas
Under reaction product is cooled down, be then transferred to storage in vacuum desiccator, rare-earth metal chloride be made.
(3) prepare with the catalyst of Nafion film supported rare earth metals：
A certain amount of anhydrous rare-earth metal chloride (lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm or yttrium Y) of ice bath and tetrahydrochysene furan
The suspension muttered, adds tetrahydrofuran-diethyl ether solution of a certain amount of lithium containing pi-allyl under magneton stirring.By reaction temperature tune
To 0 DEG C, continue stirring a period of time, then reaction solution is concentrated into thick, the rare earth element in dope is extracted with ether
Take, then containing Phosphine ligands, (preparation method is by 3- (diphenylphosphine) -1- third under the microwave assisted that wavelength is 100mm with load
(both mass ratioes are 1-4 to amine with sulphonyl fluorine-type Nafion-F resin films：100) what reaction was loaded contains Phosphine ligands) carry out
Complexation reaction obtains the rare-earth metal catalyst being supported on Nafion films.
In step (3), the rare-earth metal chloride, the amount ratio of tetrahydrofuran are 5-10mmol：20-30mL；Allyl
Base lithium, tetrahydrofuran-diethyl ether solution, the amount ratio containing Phosphine ligands of load are 50mmol：20mL：1-10g；The tetrahydrochysene furan
Mutter-diethyl ether solution in the amount ratio of tetrahydrofuran and ether be 1：1；The time for continuing stirring is 2h；Complexation reaction is 1h.
The present invention also provides a kind of catalyst with Nafion film supported rare earth metals to prepare acrylic acid,
The technical solution of use is specific as follows：
(1) using glycerine as raw material, certain density glycerine water solution is prepared, it is spare；
(2) a certain amount of Nafion films supported rare earth metallic catalyst is fitted into micro fixed-bed reactor；Will be sweet
Oil and gas are vaporized with being heated under certain proportion certain temperature, and it is anti-with certain gas gross space speed to be mixed into fixed bed
Device is answered, reacts certain time under certain temperature, freezing water spray system absorbing reaction product is connect in exit；After reaction,
The product of collection is acrylic acid.
In above-mentioned catalysis prepares acrylic acid, in step (1), the concentration of the glycerine water solution for 5~
25wt%；
In step (2), the additive amount of the Nafion films supported rare earth metallic catalyst is 4~5g；The gas bag
Include Xe, CO2、N2Or one kind in vapor；The vapor is that the water vapor in glycerine water solution obtains；The glycerine
With gas volume than 1:2~1:30；The vapourizing temperature is 300 DEG C；The gas gross space speed is 100~30000h-1；Institute
The reaction temperature for stating micro fixed-bed reactor is 200~300 DEG C；The reaction time is 7~9h.
Compared with prior art, beneficial effects of the present invention embody as follows：
(1) use first in the present invention a kind of with Nafion film supported rare earth metallic catalysts, its reduction glycerine system
The reaction temperature of standby acrylic acid, while the concentration of reactant glycerine is improved, post processing is simple, and improves the receipts of acrylic acid
Rate.Particular, it is important that catalyst has good continuous use characteristic, catalyst successive reaction 240h, products therefrom calculates
Yield is not less than 78.4%.
(2) present invention is by catalytic route, in micro fixed-bed reactor, using nitrogen, in miniature fixed bed reaction
The rearrangement reaction for obtaining intermediate product in device by catalyzing glycerol obtains acrylic acid；The method of the present invention is in micro fixed-bed reactor
In, realize glycerol dehydrogenase mode of oxidizing and converted in high yield to acrylic acid, up to 80.0%, glycerine turns acrylic acid yield completely
Change；The completion of reaction can be achieved at 200~300 DEG C, greatly reduce institute without excessive reaction temperature for the method for the present invention
The reaction energy needed；The method of the present invention is reacted under the conditions of inert gas, low to equipment corrosion, and investment is small；The method of the present invention mistake
Journey is simple and convenient to be easy to industrialize.
(3) the method for the present invention has glycerol conversion yield is high, target product yield is high, post-processes simple, catalyst continuously to make
With the advantages that performance is high, process is simple and safe environmentally friendly, there is good industrial prospect.
Brief description of the drawings
Fig. 1 is converted into acrylic acid key reaction route for glycerine.
Embodiment
With reference to specific embodiment, the present invention will be further described, but the embodiment of the present invention not limited to this, at the same time
Its shown data does not represent the limitation to feature of present invention scope.
Embodiment 1：
It is as follows with the preparation method of the catalyst of Nafion film supported rare earth metals：
(1) 115 membrane materials of Nafion are pre-processed：
115 films of Nafion are placed on 75 DEG C of 50mL 2mol/L H2O21.5h is soaked in solution to remove organic impurities, so
Afterwards in 75 DEG C of 50mL 2mol/L H2SO41h is soaked in solution, to remove metal impurities, finally by film as in redistilled water
In boil rinsing for several times after can obtain water white transparency sulphonyl fluorine-type Nafion-F resin films.
(2) rare-earth metal chloride is prepared：
20mL concentrated hydrochloric acids and 15mL distilled water are added in 50mL round-bottomed flasks, then adds 10g La2O3, stirred with magneton
Mixing makes La2O3Solid dissolves, until solution is clarified.Weigh 15g chloride solids to add in reaction solution, stirring makes chloride solid
Dissolving.It is transferred in evaporating dish, the parch on electric furnace, is stirred with glass rod white to solid exsiccation when concentrate solution is to about 25mL.
It is after room temperature cooling, gained white solid is finely ground, it is transferred in another 250mL round-bottomed flask.Flask is put into cold with dry ice
In the sublimation apparatus of jelly, heated with sand-bath and set up Automatic Temperature Control controlling reaction temperature.Adjusting the temperature to 460 DEG C makes chlorine
Change ammonium slowly to distil, the reaction was complete by 10~12h.After reaction, reaction product is made to cool down under argon gas protection, Ran Houzhuan
Enter storage in vacuum desiccator, lanthanum chloride is made.
(3) prepare with the catalyst of Nafion film supported rare earth metals：
The suspension of ice bath 10mmol lanthanum chlorides and 30mL tetrahydrofurans, pi-allyl containing 50mmol is added under magneton stirring
Tetrahydrofuran-diethyl ether solution (tetrahydrofuran, the proportions of ether 1 of lithium:1)20mL.Reaction temperature is adjusted to 0 DEG C, continues to stir
Reaction solution, is then concentrated into thick, the lanthanum element 80mL ether extraction in dope, elimination insoluble matter by 2h, then with
(preparation method is by 3- (diphenylphosphine) -1- propylamine and sulphonyl fluorine-type under microwave assisted to the Phosphine ligands that contain of 1g loads
(both mass ratioes are 1-4 to Nafion-F resin films：100) what reaction was loaded contains Phosphine ligands) complexation reaction 1h is carried out,
Obtain the lanthanum catalyst being supported on Nafion films.
It is as follows that acrylic acid is prepared with the catalyst of Nafion film supported rare earth metals：
By supported rare earth metallic catalyst on 5g Nafion films load outside diameter 12mm, internal diameter 8mm miniature fixed bed it is anti-
Answer in device.Glycerine and gas are vaporized with 300 DEG C of certain proportion and are mixed into fixed bed reactors, gas gross space speed is
100~30000h-1, reaction temperature is 200~300 DEG C, and reaction time 8h, specific response parameter is shown in Table 1；Connect in exit cold
Freeze water spray system absorbing reaction product, after reaction, pipette 1mL reaction solutions with pipette and add 20 μ L isopropanols into promoting the circulation of qi
Analysis of hplc.
Nafion films load lanthanum catalyst prepares catalyzed conversion glycerine in the catalytic activity such as table 1 of acrylic acid：
1 differential responses parameter of table prepares Nafion films lanthanum-carried catalyst glycerine converting the influence of acrylic acid
When table 1 reflects water content in glycerine, temperature, vaporization glycerine and gas volume ratio, gas gross space speed, reaction
Between the influence of acrylic acid is prepared to the lanthanum-carried catalyst glycerine of Nafion films.
Water content influences in glycerine：Wherein keeping other conditions constant, only changing in glycerine in the case of water content, with
Water content in glycerine and be increased to 25wt% from 5wt%, glycerol conversion yield brings up to 100% from 96.8%, and acrylic acid yield is in
Downward trend, 71.8% is dropped to from 80.0%.This explanation Nafion film load lanthanum catalyst has good catalytic effect.
Reaction temperatures affect：Only change temperature when other conditions are constant, it is sweet as temperature is increased to 300 DEG C from 200 DEG C
Oily conversion ratio lifting, 100% is brought up to from 96.8%.And acrylic acid yield is 75.0% or so.
Vaporizing glycerine and gas volume ratio influences：When other conditions remain unchanged, as ratio is from 1：2 are increased to 1：30,
Glycerol conversion yield is 100%, and acrylic acid yield is 75.0% or so.
Gas gross space speed influences：Only change gas gross space speed, other conditions are constant, when gas gross space speed
From 100h-1Bring up to 30000h-1When, glycerol conversion yield is increased to 100% from 96.8%, and acrylic acid yield is always empty in gas
Between speed be 5000h-1When obtain maximum 80.0%.This shows that the rise of gas gross space speed contributes to glycerine to convert, but mistake
High acrylic acid can start to decompose.
Embodiment 2：
The species of catalyst is simply changed to the load of Nafion films by the preparation of catalyst and reaction condition with embodiment 1
Cerium catalyst, the dosage of cerium chloride is 5mmol in step (3), and the volume of tetrahydrofuran is 20mL, the lithium of pi-allyl containing 50mmol
Tetrahydrofuran-diethyl ether solution 18mL, load is 10g containing Phosphine ligands.
The condition of acrylic acid is prepared with embodiment 1, the species of catalyst is simply changed to the catalysis of Nafion films cerium-carrying
Agent, the dosage of Nafion films load cerium catalyst is 4g, reaction time 7h.
Nafion films load cerium catalyst prepares catalyzed conversion glycerine in the catalytic activity such as table 2 of acrylic acid：
2 differential responses parameter Nafion film cerium-carrying catalyst glycerine convertings of table prepare the influence of acrylic acid
When table 2 reflects water content in glycerine, temperature, vaporization glycerine and gas volume ratio, gas gross space speed, reaction
Between the influence of acrylic acid is prepared to Nafion film cerium-carrying catalyst glycerine.
Water content influences in glycerine：Wherein keeping other conditions constant, only changing in glycerine in the case of water content, with
Water content in glycerine and be increased to 25wt% from 5wt%, glycerol conversion yield brings up to 97.7% from 86.1%, and acrylic acid yield is in
Downward trend, 43.3% is dropped to from 51.4%.This explanation Nafion film load cerium catalyst has good catalytic effect.
Reaction temperatures affect：Only change temperature when other conditions are constant, it is sweet as temperature is increased to 300 DEG C from 200 DEG C
Oily conversion ratio lifting, 97.7% is brought up to from 86.1%.And acrylic acid yield 47.0% or so.
Vaporizing glycerine and gas volume ratio influences：When other conditions remain unchanged, as ratio is from 1：2 are increased to 1：30,
Glycerol conversion yield brings up to 97.7% from 86.1%, acrylic acid yield 45.0% or so.
Gas gross space speed influences：Only change gas gross space speed, other conditions are constant, when gas gross space speed
From 100h-1Bring up to 30000h-1When, glycerol conversion yield brings up to 97.7% from 86.1%, and acrylic acid yield is always empty in gas
Between speed be 5000h-1When obtain maximum 51.4%.This shows that the rise of gas gross space speed contributes to glycerine to convert, but mistake
High acrylic acid can start to decompose.
Embodiment 3：
The preparation of catalyst and reaction condition are the same as embodiment 1；The condition of acrylic acid is prepared with embodiment 1, simply will catalysis
The species of agent is changed to Nafion films load praseodymium catalyst.
Nafion films load praseodymium catalyst prepares catalyzed conversion glycerine in the catalytic activity such as table 3 of acrylic acid：
3 differential responses parameter Nafion films of table load praseodymium catalyst glycerine converting prepares the influence of acrylic acid
When table 3 reflects water content in glycerine, temperature, vaporization glycerine and gas volume ratio, gas gross space speed, reaction
Between prepared by the influence of acrylic acid to Nafion films load praseodymium catalyst glycerine.
Water content influences in glycerine：Wherein keeping other conditions constant, only changing in glycerine in the case of water content, with
Water content in glycerine and be increased to 25wt% from 5wt%, glycerol conversion yield brings up to 100% from 93.5%, and acrylic acid yield is in
Downward trend, 64.7% is dropped to from 77.2%.This explanation Nafion film load cerium catalyst has good catalytic effect.
Reaction temperatures affect：Only change temperature when other conditions are constant, it is sweet as temperature is increased to 300 DEG C from 200 DEG C
Oily conversion ratio lifting, 100% is brought up to from 93.5%.And acrylic acid yield 70.0% or so.
Vaporizing glycerine and gas volume ratio influences：When other conditions remain unchanged, as ratio is from 1：2 are increased to 1：30,
Glycerol conversion yield brings up to 100% from 93.5%, acrylic acid yield 75.0% or so.
Gas gross space speed influences：Only change gas gross space speed, other conditions are constant, when gas gross space speed
From 100h-1Bring up to 30000h-1When, glycerol conversion yield brings up to 100% from 93.5%, and acrylic acid yield is always empty in gas
Between speed be 5000h-1When obtain maximum 77.2%.This shows that the rise of gas gross space speed contributes to glycerine to convert, but mistake
High acrylic acid can start to decompose.
Embodiment 4：
The species of catalyst is simply changed to the load of Nafion films by the preparation of catalyst and reaction condition with embodiment 1
Neodymium catalyst, the dosage of neodymium chloride is 7mmol in step (3), and the volume of tetrahydrofuran is 25mL, the lithium of pi-allyl containing 50mmol
Tetrahydrofuran-diethyl ether solution 19mL, load is 7g containing Phosphine ligands；The condition of acrylic acid is prepared with embodiment 1, simply will catalysis
The species of agent is changed to Nafion films load neodymium catalyst, and the dosage of Nafion films load neodymium catalyst is 4.5g, during reaction
Between be 9h.
Nafion films load neodymium catalyst prepares catalyzed conversion glycerine in the catalytic activity such as table 4 of acrylic acid：
4 differential responses parameter Nafion films of table load neodymium catalyst catalyzed conversion glycerine prepares the influence of acrylic acid
When table 4 reflects water content in glycerine, temperature, vaporization glycerine and gas volume ratio, gas gross space speed, reaction
Between prepared by the influence of acrylic acid to Nafion films load neodymium catalyst catalyzing glycerol.
Water content influences in glycerine：Wherein keeping other conditions constant, only changing in glycerine in the case of water content, with
Water content in glycerine and be increased to 25wt% from 5wt%, glycerol conversion yield brings up to 100% from 86.1%, and acrylic acid yield is in
Downward trend, 53.3% is dropped to from 60.5%.This explanation Nafion film load neodymium catalyst has good catalytic effect.
Reaction temperatures affect：Only change temperature when other conditions are constant, it is sweet as temperature is increased to 300 DEG C from 200 DEG C
Oily conversion ratio lifting, 100% is brought up to from 86.1%.And acrylic acid yield 55.0% or so.
Vaporizing glycerine and gas volume ratio influences：When other conditions remain unchanged, as ratio is from 1：2 are increased to 1：30,
Glycerol conversion yield brings up to 100% from 86.1%, acrylic acid yield 55.0% or so.
Gas gross space speed influences：Only change gas gross space speed, other conditions are constant, when gas gross space speed
From 100h-1Bring up to 30000h-1When, glycerol conversion yield brings up to 100% from 86.1%, and acrylic acid yield is always empty in gas
Between speed be 5000h-1When obtain maximum 60.5%.This shows that the rise of gas gross space speed contributes to glycerine to convert, but mistake
High acrylic acid can start to decompose.
Embodiment 5：
The preparation of catalyst and reaction condition are the same as embodiment 1；The condition of acrylic acid is prepared with embodiment 1, simply will catalysis
The species of agent is changed to Nafion films load samarium catalyst.
Nafion films load samarium catalyst prepares catalyzed conversion glycerine in the catalytic activity such as table 5 of acrylic acid：
5 differential responses parameter Nafion films of table load samarium catalyst glycerine converting prepares the influence of acrylic acid
When table 5 reflects water content in glycerine, temperature, vaporization glycerine and gas volume ratio, gas gross space speed, reaction
Between prepared by the influence of acrylic acid to Nafion films load samarium catalyst glycerine.
Water content influences in glycerine：Wherein keeping other conditions constant, only changing in glycerine in the case of water content, with
Water content in glycerine and be increased to 25wt% from 5wt%, glycerol conversion yield brings up to 100% from 95.5%, and acrylic acid yield is in
Downward trend, 63.2% is dropped to from 69.4%.This explanation Nafion film load samarium catalyst has good catalytic effect.
Reaction temperatures affect：Only change temperature when other conditions are constant, it is sweet as temperature is increased to 300 DEG C from 200 DEG C
Oily conversion ratio lifting, 100% is brought up to from 95.5%.And acrylic acid yield 65.0% or so.
Vaporizing glycerine and gas volume ratio influences：When other conditions remain unchanged, as ratio is from 1：2 are increased to 1：30,
Glycerol conversion yield brings up to 100% from 95.5%, acrylic acid yield 65.0% or so.
Gas gross space speed influences：Only change gas gross space speed, other conditions are constant, when gas gross space speed
From 100h-1Bring up to 30000h-1When, glycerol conversion yield brings up to 100% from 95.5%, and acrylic acid yield is always empty in gas
Between speed be 5000h-1When obtain maximum 69.4%.This shows that the rise of gas gross space speed contributes to glycerine to convert, but mistake
High acrylic acid can start to decompose.
Embodiment 6：
The preparation of catalyst and reaction condition are the same as embodiment 1；The condition of acrylic acid is prepared with embodiment 1, simply will catalysis
The species of agent is changed to Nafion films load yttrium catalyst.
Nafion films load yttrium catalyst prepares catalyzed conversion glycerine in the catalytic activity such as table 6 of acrylic acid：
6 differential responses parameter Nafion films of table load yttrium catalyst glycerine converting prepares the influence of acrylic acid
When table 6 reflects water content in glycerine, temperature, vaporization glycerine and gas volume ratio, gas gross space speed, reaction
Between prepared by the influence of acrylic acid to Nafion films load yttrium catalyst glycerine.
Water content influences in glycerine：Wherein keeping other conditions constant, only changing in glycerine in the case of water content, with
Water content in glycerine and be increased to 25wt% from 5wt%, glycerol conversion yield brings up to 100% from 96.1%, and acrylic acid yield is in
Downward trend, 63.3% is dropped to from 70.1%.This explanation Nafion film load yttrium catalyst has good catalytic effect.
Reaction temperatures affect：Only change temperature when other conditions are constant, it is sweet as temperature is increased to 300 DEG C from 200 DEG C
Oily conversion ratio lifting, 100% is brought up to from 96.1%.And acrylic acid yield 65.0% or so.
Vaporizing glycerine and gas volume ratio influences：When other conditions remain unchanged, as ratio is from 1：2 are increased to 1：30,
Glycerol conversion yield brings up to 100% from 96.1%, acrylic acid yield 65.0% or so.
Gas gross space speed influences：Only change gas gross space speed, other conditions are constant, when gas gross space speed
From 100h-1Bring up to 30000h-1When, glycerol conversion yield brings up to 100% from 96.1%, and acrylic acid yield is always empty in gas
Between speed be 5000h-1When obtain maximum 70.1%.This shows that the rise of gas gross space speed contributes to glycerine to convert, but mistake
High acrylic acid can start to decompose.
Embodiment 7：
The preparation of catalyst and reaction condition are the same as embodiment 1；The condition of acrylic acid is prepared with embodiment 1, simply will catalysis
The species of agent is changed to lanthanum-carried Nafion films, Nafion films cerium-carrying, Nafion films load praseodymium, the load of Nafion films
Neodymium, Nafion films load samarium and Nafion films load yttrium, the reaction time is 120 or 240h.
Nafion film supported rare earth metallic catalysts prepare catalyzed conversion glycerine in the catalytic activity such as table 7 of acrylic acid：
Table 7Nafion film supported rare earth metallic catalyst continuous catalysis effect tables
Table 7Nafion film supported rare earth metallic catalyst continuous catalysis glycerine prepares the catalytic effect of acrylic acid, therefrom
It can be seen that catalyst continuous catalysis 240h glycerol conversion yields are constant, remain as 100%, and acrylic acid yield somewhat under
Drop, drops to 78.4%, and dries rear catalyst quality also because the reason loss about 0.1g such as operating and reacting, it can be seen that
Nafion film supported rare earth metallic catalysts have good continuous catalysis potential.
Comparative example：
5g sulphonyl fluorine-type Nafion-F resin films are loaded to the micro fixed-bed reactor of outside diameter 12mm, internal diameter 8mm
In.By glycerine, water and nitrogen with 1：0.8：10 vaporize and are mixed into fixed bed reactors, and gas gross space speed is 5000h-1, reaction temperature 250oC；Freezing water spray system absorbing reaction product is connect in exit, after reaction, is moved with pipette
Take 1mL reaction solutions to add 20 μ L isopropanols and carry out gas chromatographic analysis；The result is that：Glycerol conversion yield is 0% after reacting 8h.
5g rare earth-iron-borons are fitted into the micro fixed-bed reactor of outside diameter 12mm, internal diameter 8mm.By glycerine, water and nitrogen
Gas is with 1：0.8：10 vaporize and are mixed into fixed bed reactors, and gas gross space speed is 5000h-1, reaction temperature is
250oC；Freezing water spray system absorbing reaction product is connect in exit, after reaction, 1mL reaction solutions is pipetted with pipette and adds
Enter 20 μ L isopropanols and carry out gas chromatographic analysis；The result is that：React 8 it is small when after glycerol conversion yield only 12.8%, acrylic acid yield
9.9%, aoxidize carbon yield 2.0%.
It can show that Nafion film supported rare earth metallic catalysts prepare fixed-bed catalytic glycerine converting by embodiment
Acrylic acid has a good effect, and the catalytic effect that different rare earth metals produces also has very big difference, its comprehensive catalytic result can be with
Find out that the lanthanum-carried catalytic effect of Nafion films is optimal, and have good continuous catalysis performance.
It can be drawn by embodiment 5 and comparative example, with common sulphonyl fluorine-type Nafion-F resin films, rare earth-iron-boron
Compared with Nafion film supported rare earth metallic catalysts, common sulphonyl fluorine-type Nafion-F resin films and rare-earth chlorination
Thing catalytic effect is inferior very much, and under the same conditions, either glycerol conversion yield or acrylic acid yield are thin using Nafion
There is qualitative leap during film supported rare earth metallic catalyst.
It can be seen from embodiment under identical experiment condition, catalyst is used as using 5g Nafion films are lanthanum-carried
Catalyzing glycerol prepares acrylic acid, and water content is 5wt% in glycerine, temperature 250oC, vaporization glycerine and gas volume is than 1:2nd, gas
Gross space speed 5000h-1, the reaction time can obtain optimal reaction result when being 8h, glycerol conversion yield 100% at this time, propylene
Sour yield 80.0%.
Claims (10)
1. the preparation method of a kind of catalyst with Nafion film supported rare earth metals, it is characterised in that comprise the following steps：
（1）Pre-process 115 membrane materials of Nafion：115 films of Nafion are individually placed to H2O2Solution and H2SO4Soaked in solution,
After removing organic impurities and metal impurities, by film as rinsing is boiled in redistilled water, water white transparency sulphonyl fluorine-type is obtained
Nafion-F resin films；
（2）Prepare rare-earth metal chloride；
（3）Prepare with the catalyst of Nafion film supported rare earth metals：
The suspension of the anhydrous rare-earth metal chloride of ice bath and tetrahydrofuran, adds the tetrahydrochysene of the lithium containing pi-allyl under magneton stirring
Furans-diethyl ether solution；Reaction temperature is adjusted to certain temperature, continues after stirring a period of time, reaction solution is concentrated into sticky
Shape, the rare earth element in dope are extracted with ether, then carry out complexation reaction containing Phosphine ligands with load, are supported on
Rare-earth metal catalyst on Nafion films.
2. the preparation method of the catalyst according to claim 1 with Nafion film supported rare earth metals, its feature exist
In step（2）In, the rare earth metal in the rare-earth metal chloride includes lanthanum, cerium, praseodymium, neodymium, samarium or yttrium.
3. the preparation method of the catalyst according to claim 1 with Nafion film supported rare earth metals, its feature exist
In step（3）In, the rare-earth metal chloride, the amount ratio of tetrahydrofuran are 5-10mmol：20-30 mL.
4. the preparation method of the catalyst according to claim 1 with Nafion film supported rare earth metals, its feature exist
In step（3）In, pi-allyl lithium, tetrahydrofuran-diethyl ether solution, the amount ratio containing Phosphine ligands of load are 50 mmol：20
mL：1-10g；The amount ratio of tetrahydrofuran and ether is 1 in the tetrahydrofuran-diethyl ether solution：1；Reaction temperature is adjusted to 0 DEG C,
The time for continuing stirring is 2h；The complexation reaction time is 1h.
5. the preparation method of the catalyst according to claim 1 with Nafion film supported rare earth metals, its feature exist
In step（3）In, the preparation method containing Phosphine ligands of load：In the case where wavelength is the microwave assisted of 100mm by 3- (diphenyl
Phosphine) -1- propylamine and sulphonyl fluorine-type Nafion-F resin films react, and what is loaded contains Phosphine ligands；3- (the diphenyl
Phosphine) mass ratio of -1- propylamine and sulphonyl fluorine-type Nafion-F resin films is 1-4：100.
6. the catalyst system with Nafion film supported rare earth metals for using the preparation method described in claim 1 to prepare
Standby acrylic acid, it is characterised in that comprise the following steps：
（1）Using glycerine as raw material, certain density glycerine water solution is prepared, it is spare；
（2）Nafion film supported rare earth metallic catalysts are fitted into micro fixed-bed reactor；By glycerine and gas with one
Vaporization is heated under certainty ratio certain temperature, and fixed bed reactors, a constant temperature are mixed into certain gas gross space speed
Degree lower reaction certain time, freezing water spray system absorbing reaction product is connect in exit；After reaction, the product of collection is
For acrylic acid.
7. catalysis according to claim 6 prepares acrylic acid, it is characterised in that step（1）In, the glycerine
The concentration of aqueous solution is 5 ~ 25 wt%.
8. catalysis according to claim 6 prepares acrylic acid, it is characterised in that step（2）In, it is described
The additive amount of Nafion film supported rare earth metallic catalysts is 4 ~ 5 g.
9. catalysis according to claim 6 prepares acrylic acid, it is characterised in that step（2）In, the glycerine with
Gas volume is than 1:2~1:30；The vapourizing temperature is 300 DEG C；The gas includes Xe, CO2、N2Or one in vapor
Kind；The vapor is that the water vapor in glycerine water solution obtains.
10. catalysis according to claim 6 prepares acrylic acid, it is characterised in that step（2）In, the gas
Gross space speed is 100 ~ 30000 h-1；The reaction temperature of the micro fixed-bed reactor is 200 ~ 300 DEG C；During the reaction
Between be 7 ~ 9 h.
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| CN109369366A (en) * | 2018-11-13 | 2019-02-22 | 广东省石油与精细化工研究院 | A kind of method that glycerine catalytic dehydrogenation prepares lactic acid |
| CN111342094A (en) * | 2020-04-02 | 2020-06-26 | 陈婧 | Preparation method of rare earth doped perfluorosulfonic acid membrane |
| CN114316120A (en) * | 2022-01-13 | 2022-04-12 | 陕西科技大学 | Coated supporting tracer containing rare earth metal elements and preparation method and application thereof |
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| CN111342094B (en) * | 2020-04-02 | 2021-07-27 | 罗仙花 | Preparation method of rare earth doped perfluorosulfonic acid membrane |
| CN114316120A (en) * | 2022-01-13 | 2022-04-12 | 陕西科技大学 | Coated supporting tracer containing rare earth metal elements and preparation method and application thereof |
| CN114316120B (en) * | 2022-01-13 | 2022-12-09 | 陕西科技大学 | Coated propping tracer containing rare earth metal elements and preparation method and application thereof |
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| CN107952484B (en) | 2019-12-31 |
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