CN107952484B - Preparation method and application of Nafion film loaded rare earth metal catalyst - Google Patents
Preparation method and application of Nafion film loaded rare earth metal catalyst Download PDFInfo
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- CN107952484B CN107952484B CN201711193424.4A CN201711193424A CN107952484B CN 107952484 B CN107952484 B CN 107952484B CN 201711193424 A CN201711193424 A CN 201711193424A CN 107952484 B CN107952484 B CN 107952484B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 229920000557 Nafion® Polymers 0.000 title claims abstract description 83
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 383
- 235000011187 glycerol Nutrition 0.000 claims abstract description 135
- 238000006243 chemical reaction Methods 0.000 claims abstract description 123
- 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 93
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 93
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 12
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- VCPPTNDHEILJHD-UHFFFAOYSA-N lithium;prop-1-ene Chemical compound [Li+].[CH2-]C=C VCPPTNDHEILJHD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 230000003197 catalytic effect Effects 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 11
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 230000008016 vaporization Effects 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000011345 viscous material Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 63
- 230000000694 effects Effects 0.000 description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000003225 biodiesel Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 230000002277 temperature effect Effects 0.000 description 6
- 230000018044 dehydration Effects 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-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- DQZWMOWSTWWMPP-UHFFFAOYSA-N 3-diphenylphosphanylpropan-1-amine Chemical compound C=1C=CC=CC=1P(CCCN)C1=CC=CC=C1 DQZWMOWSTWWMPP-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000004458 analytical method Methods 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
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000005507 spraying Methods 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
- 238000005809 transesterification reaction Methods 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000010523 cascade reaction Methods 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration 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
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of acrylic acid preparation, and particularly relates to a preparation method and application of a Nafion film loaded rare earth metal catalyst. The method for preparing the Nafion film loaded rare earth metal catalyst comprises the following steps: the Nafion film loaded rare earth metal catalyst is prepared under certain conditions by taking anhydrous rare earth metal chloride, tetrahydrofuran suspension, allyl lithium-containing tetrahydrofuran-diethyl ether solution and loaded phosphine-containing ligand as raw materials. In addition, the acrylic acid is prepared by applying catalysis to a Nafion film loaded rare earth metal catalyst, biomass glycerol is used as a raw material, the Nafion film loaded rare earth metal catalyst is used as a catalyst, and the reaction is carried out under a certain catalysis condition to obtain the acrylic acid; the conversion rate of glycerin reaches 100%, and the yield of acrylic acid reaches 80.0%. The preparation method provided by the invention has the advantages of high glycerol conversion rate, high acrylic acid yield, simple post-treatment, high continuous service performance of the catalyst, simple preparation process, safety, environmental protection and good industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of acrylic acid preparation, and particularly relates to a preparation method and application of a Nafion film loaded rare earth metal catalyst.
Background
Acrylic acid (Acrylic acid) is one of the very important chemical raw materials, and is widely used in rubber synthesis, plastics and coating industries; the main preparation method at present is to prepare propylene or propane by a two-step oxidation industrial process in air. However, as biodiesel (biodiesel) is increasingly used as a fuel in recent years for diesel engines, the global demand for biodiesel is increasing, and the yield of biodiesel is expected to reach 4.0 × 10 in 202310And L. Transesterification method is mostly used for producing biodieselAccording to statistics, about 0.1 ton of glycerin is generated in each 1 ton of biodiesel production by-product, and in addition, the glycerin can be obtained through microbial starch fermentation, enzyme-catalyzed starch conversion, sorbitol hydrogenolysis, lignocellulose catalytic decomposition and other ways, and how to effectively utilize the glycerin becomes a problem which is very troublesome at the moment of limiting the development of the biodiesel industry. Glycerol exists as one of bio-based chemicals and platform compounds in animal and plant bodies in the form of triglyceride building blocks. In industry, the processes of saponification soap making, hydrolysis fatty acid making, and transesterification biodiesel production, which use triglyceride as a raw material, all produce glycerol as a by-product. In the last two decades, researchers have actively explored the conversion processes for producing high value-added chemicals by glycerol conversion, such as acrolein production by glycerol dehydration, hydrogen production by steam reforming, dihydroxyacetone production by oxidation, and the like. However, most of the existing reactions have the defects of complex process flow, harsh reaction conditions and the like. Scientists assume that if a mild glycerol dehydration oxidation cascade reaction process is successfully developed to produce acrylic acid, the reliance of the acrylic acid production industry on petroleum-based propylene or propane raw materials is significantly reduced, and the energy consumption and CO are significantly reduced2And the emission of acid gas effectively solves the problem of limiting the development of the biodiesel industry due to the excess of glycerin. This is just in response to the global green chemical call in recent years, and the development of green catalytic new chemical industrial processes for producing chemicals and clean energy from biomass or bio-based chemicals as raw materials will significantly reduce fossil fuel consumption and impact on the environment. In recent years, the catalytic dehydration and oxidation of glycerol to produce acrylic acid in series has become a new focus of attention. However, whether a feasible catalytic system and a catalyst with high activity, high yield and high stability can be developed is the key to the realization of industrialization of acrylic acid preparation by dehydration and oxidation of glycerol.
The patent CN200580002350.0 discloses a method for preparing acrylic acid by two-step gas phase dehydration, which takes glycerin as a raw material, the concentration of a glycerin water solution is 10-50 wt%, the reaction temperature is 200-370 ℃, dehydration reaction and gas phase oxidation reaction are carried out in a single reactor to prepare acrylic acid, and the yield of the acrylic acid is 55-65%. The technology adopts a single reactor, a large amount of energy is needed for gasification, a large amount of cost is needed for water drainage, the technology cannot be applied industrially, the yield of the acrylic acid is low, and the continuous use performance is not disclosed.
Disclosure of Invention
Aiming at the problems of low glycerol concentration, high reaction temperature, low acrylic acid yield, high production process and post-treatment cost, difficult continuous use and the like in the prior art, the invention provides a catalyst which uses a Nafion film to load rare earth metal, has higher activity for catalyzing glycerol to prepare acrylic acid, and has good continuous use characteristics.
The invention also provides a preparation method of the catalyst with the Nafion film loaded with the rare earth metal, which adopts the following technical scheme:
(1) pretreatment of the Nafion 115 membrane material:
the Nafion 115 membrane material adopted by the invention is produced by Dupont company in the United states, and the membrane material needs to be subjected to certain pretreatment before each use, and the process is as follows: first, a Nafion 115 membrane was placed at 75 ℃ in a 50mL2mol/L H environment2O2Soaking in the solution for 1.5h to remove organic impurities; then 50mL of 2mol/L H at 75 DEG C2SO4Soaking in the solution for 1h to remove metal impurities; finally, the membrane is boiled and rinsed in secondary distilled water for several times to obtain the colorless transparent sulfonyl fluoride type Nafion-F resin membrane.
(2) Preparing rare earth metal chloride:
20mL each of concentrated hydrochloric acid and distilled water was added to the round-bottom flask, followed by 10g M2O3(M is rare earth elements La, Ce, Pr, Nd, Sm and Y), and stirring with magneton2O3Dissolving the solid to obtain a reaction solution A; adding 15g of ammonium chloride solid into the reaction liquid A, and stirring to dissolve the ammonium chloride solid to obtain reaction liquid B; transferring the concentrated reaction solution B into an evaporating dish, parching for 1h on an electric furnace, and stirring with a glass rod until the solid becomes dry and white; cooling at 30 ℃, grinding the obtained white solid, transferring the white solid into another round-bottom flask, putting the flask into a sublimation device with dry ice refrigeration, heating by a sand bath, setting a temperature automatic controller to control the reaction temperature to 460 ℃, slowly subliming ammonium chloride, keeping the whole process for 10-12 hours, and reactingAfter the reaction is finished, the reaction product is cooled down under the protection of argon, and then the reaction product is transferred into a vacuum drier for storage to prepare the rare earth metal chloride.
(3) Preparing a catalyst with a Nafion film loaded with rare earth metal:
ice-bath a certain amount of anhydrous rare earth metal chloride (lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm or yttrium Y) and tetrahydrofuran suspension, and adding a certain amount of allyl lithium-containing tetrahydrofuran-diethyl ether solution under the stirring of magnetons. Adjusting the reaction temperature to 0 ℃, continuously stirring for a period of time, concentrating the reaction solution to be viscous, extracting the rare earth elements in the viscous substance by using diethyl ether, and then carrying out coordination reaction with the loaded phosphine-containing ligand (the preparation method is that 3- (diphenylphosphino) -1-propylamine and sulfonyl fluoride type Nafion-F resin film (the mass ratio of the two is 1-4: 100) under the promotion of microwave with the wavelength of 100mm to obtain the loaded phosphine-containing ligand) to obtain the rare earth metal catalyst loaded on the Nafion film.
In the step (3), the dosage ratio of the rare earth metal chloride to the tetrahydrofuran is 5-10 mmol: 20-30 mL; the dosage ratio of the allyl lithium, the tetrahydrofuran-diethyl ether solution and the loaded phosphine-containing ligand is 50 mmol: 20mL of: 1-10 g; the dosage ratio of tetrahydrofuran to diethyl ether in the tetrahydrofuran-diethyl ether solution is 1: 1; the time for continuing stirring is 2 hours; the coordination reaction is 1 h.
The invention also provides a method for preparing acrylic acid by using the catalyst of Nafion film loaded rare earth metal, which adopts the following technical scheme:
(1) preparing a glycerol aqueous solution with a certain concentration by taking glycerol as a raw material for later use;
(2) loading a certain amount of Nafion film loaded rare earth metal catalyst into a miniature fixed bed reactor; heating and vaporizing glycerin and gas at a certain ratio and a certain temperature, mixing the glycerin and the gas at a certain total gas space velocity, feeding the mixture into a fixed bed reactor, reacting the mixture for a certain time at a certain temperature, and connecting a chilled water spray device at an outlet to absorb reaction products; and after the reaction is finished, collecting a product, namely the acrylic acid.
In the method for preparing acrylic acid by catalysis, in the step (1), the concentration of the glycerol aqueous solution is 5-25 wt%;
in the step (2), the addition amount of the Nafion film loaded rare earth metal catalyst is 4-5 g; the gas comprises Xe, CO2、N2Or water vapor; the water vapor is obtained by vaporizing water in the glycerin water solution; the volume ratio of the glycerol to the gas is 1: 2-1: 30; the vaporization temperature is 300 ℃; the total space velocity of the gas is 100-30000 h-1(ii) a The reaction temperature of the miniature fixed bed reactor is 200-300 ℃; the reaction time is 7-9 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the invention, a Nafion film loaded rare earth metal catalyst is adopted for the first time, which reduces the reaction temperature of preparing acrylic acid from glycerol, improves the concentration of reactant glycerol, has simple post-treatment and improves the yield of acrylic acid. More importantly, the catalyst has good continuous use characteristics, the catalyst continuously reacts for 240 hours, and the calculated yield of the obtained product is not lower than 78.4%.
(2) According to the invention, acrylic acid is obtained through a rearrangement reaction of an intermediate product obtained by catalyzing glycerol in a miniature fixed bed reactor by nitrogen in a catalytic way; the method realizes the conversion of the glycerol to the acrylic acid in a dehydrogenation and oxidation mode in a miniature fixed bed reactor with high yield, the yield of the acrylic acid can reach 80.0 percent, and the glycerol is completely converted; the method can realize the completion of the reaction at 200-300 ℃ without excessively high reaction temperature, thereby greatly reducing the required reaction energy; the method of the invention reacts under the condition of inert gas flow, has low corrosion to equipment and small investment; the method has simple and convenient process and is easy for industrialization.
(3) The method has the advantages of high glycerol conversion rate, high target product yield, simple post-treatment, high continuous service performance of the catalyst, simple, safe and environment-friendly process and the like, and has good industrial prospect.
Drawings
FIG. 1 shows the principal reaction scheme for the conversion of glycerol to acrylic acid.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention, and the data presented are not intended to limit the scope of the invention.
Example 1:
the preparation method of the catalyst with the Nafion film loaded with the rare earth metal comprises the following steps:
(1) pretreatment of the Nafion 115 membrane material:
the Nafion 115 membrane was placed at 75 ℃ in 50mL of 2mol/L H2O2Soaking in the solution for 1.5h to remove organic impurities, and then soaking at 75 ℃ for 50mL of 2mol/L H2SO4Soaking in the solution for 1h to remove metal impurities, and finally boiling and rinsing the film in secondary distilled water for several times to obtain the colorless transparent sulfonyl fluoride type Nafion-F resin film.
(2) Preparing rare earth metal chloride:
20mL of concentrated hydrochloric acid and 15mL of distilled water were placed in a 50mL round-bottom flask, followed by 10g of La2O3Stirring La with magneton2O3The solid dissolved until the solution was clear. 15g of ammonium chloride solid was weighed and added to the reaction solution, and the ammonium chloride solid was dissolved by stirring. The concentrated solution was transferred to an evaporating dish when it was about 25mL, stir-fried on a hotplate, and stirred with a glass rod until the solid dried to a white color. After cooling at room temperature, the resulting white solid was ground and transferred to another 250mL round bottom flask. The flask was placed in a sublimation apparatus with dry ice freezing, heated with a sand bath and set up with an automatic temperature controller to control the reaction temperature. Regulating the temperature to 460 ℃ to slowly sublimate the ammonium chloride, and completely reacting for 10-12 h. After the reaction is finished, the reaction product is cooled down under the protection of argon, and then the reaction product is transferred into a vacuum drier for storage to prepare lanthanum chloride.
(3) Preparing a catalyst with a Nafion film loaded with rare earth metal:
a suspension of 10mmol of lanthanum chloride and 30mL of tetrahydrofuran was ice-cooled, and 20mL of a tetrahydrofuran-diethyl ether solution (tetrahydrofuran-diethyl ether ratio 1:1) containing 50mmol of allyllithium was added with stirring. Adjusting the reaction temperature to 0 ℃, continuously stirring for 2h, concentrating the reaction solution to be viscous, extracting lanthanum element in the viscous substance by using 80mL of diethyl ether, filtering insoluble substances, and performing coordination reaction for 1h with 1g of supported phosphine-containing ligand (the preparation method is that 3- (diphenylphosphino) -1-propylamine and sulfonyl fluoride type Nafion-F resin film (the mass ratio of the two is 1-4: 100) under the promotion of microwave to obtain the supported phosphine-containing ligand), so as to obtain the lanthanum catalyst loaded on the Nafion film.
The method for preparing the acrylic acid by the catalysis of the catalyst of Nafion film loaded rare earth metal comprises the following steps:
5g of a Nafion film loaded with a rare earth metal catalyst was loaded into a micro fixed bed reactor having an outer diameter of 12mm and an inner diameter of 8 mm. The glycerol and the gas are vaporized and mixed into a fixed bed reactor at 300 ℃ according to a certain proportion, and the total space velocity of the gas is 100-30000 h-1The reaction temperature is 200-300 ℃, the reaction time is 8 hours, and the specific reaction parameters are shown in table 1; the outlet of the reaction vessel was connected to a chilled water spray apparatus to absorb the reaction product, and after the reaction was completed, 1mL of the reaction solution was removed by a pipette and 20. mu.L of isopropanol was added to the reaction solution for gas chromatography.
The catalytic activity of the Nafion film loaded lanthanum catalyst on the preparation of acrylic acid by catalytic conversion of glycerol is shown in Table 1:
TABLE 1 influence of different reaction parameters on the catalytic conversion of glycerol to acrylic acid by Nafion film supported lanthanum catalyst
Table 1 shows the influence of water content, temperature, volume ratio of vaporized glycerol to gas, total gas space velocity and reaction time in glycerol on the preparation of acrylic acid by catalyzing glycerol with a Nafion film loaded lanthanum catalyst.
Water content in glycerol effects: wherein, under the condition of keeping other conditions unchanged and only changing the water content in the glycerol, as the water content in the glycerol is increased from 5 wt% to 25 wt%, the conversion rate of the glycerol is increased from 96.8% to 100%, and the yield of the acrylic acid is reduced from 80.0% to 71.8%. This shows that the Nafion film loaded lanthanum catalyst has good catalytic effect.
Reaction temperature effects: the glycerol conversion rate increased from 96.8% to 100% as the temperature increased from 200 ℃ to 300 ℃ with only temperature changes, otherwise unchanged. The yield of acrylic acid was about 75.0%.
Vaporized glycerol to gas volume ratio effects: as other conditions remain unchanged, as the ratio is varied from 1:2 to 1:30, the conversion rate of the glycerol is 100 percent, and the yield of the acrylic acid is about 75.0 percent.
Gas total space velocity effect: only the total space velocity of the gas is changed, and other conditions are not changed when the total space velocity of the gas is 100h-1Increased to 30000h-1When the conversion of glycerol is increased from 96.8% to 100%, the yield of acrylic acid is 5000h at a total gas space velocity-1A maximum of 80.0% is obtained. This indicates that an increase in the total gas space velocity contributes to the glycerol conversion, but too high an acrylic acid starts to decompose.
Example 2:
the catalyst preparation and reaction conditions were the same as in example 1 except that the type of catalyst was changed to a cerium catalyst supported on a Nafion membrane, the amount of cerium chloride used in step (3) was 5mmol, the volume of tetrahydrofuran was 20mL, the volume of tetrahydrofuran-diethyl ether solution containing 50mmol of allyllithium was 18mL, and the amount of phosphine-containing ligand supported was 10 g.
The conditions for preparing acrylic acid were the same as in example 1 except that the type of catalyst was changed to a cerium catalyst supported on a Nafion film, the amount of the cerium catalyst supported on a Nafion film was 4g, and the reaction time was 7 hours.
The catalytic activity of the cerium catalyst supported on the Nafion film for preparing acrylic acid by catalytic conversion of glycerol is shown in Table 2:
TABLE 2 influence of different reaction parameters of Nafion film loaded cerium catalyst on catalytic conversion of glycerol to acrylic acid
Table 2 shows the effect of water content, temperature, vaporized glycerol to gas volume ratio, total gas space velocity, and reaction time in glycerol on the catalysis of glycerol to acrylic acid by a cerium catalyst supported on a Nafion film.
Water content in glycerol effects: wherein, under the condition of keeping other conditions unchanged and only changing the water content in the glycerol, the conversion rate of the glycerol is increased from 86.1 percent to 97.7 percent as the water content in the glycerol is increased from 5 percent to 25 percent by weight, and the yield of the acrylic acid is reduced from 51.4 percent to 43.3 percent. This shows that the cerium catalyst supported by Nafion film has good catalytic effect.
Reaction temperature effects: the glycerol conversion rate increased from 86.1% to 97.7% as the temperature increased from 200 ℃ to 300 ℃ with only temperature changes and other conditions unchanged. The yield of acrylic acid was about 47.0%.
Vaporized glycerol to gas volume ratio effects: as other conditions remain unchanged, as the ratio is varied from 1:2 to 1:30, the conversion rate of the glycerol is improved to 97.7 percent from 86.1 percent, and the yield of the acrylic acid is about 45.0 percent.
Gas total space velocity effect: only the total space velocity of the gas is changed, and other conditions are not changed when the total space velocity of the gas is 100h-1Increased to 30000h-1When the conversion rate of glycerin is increased from 86.1% to 97.7%, the yield of acrylic acid is 5000h at the total gas space velocity-1A maximum of 51.4% is obtained. This indicates that an increase in the total gas space velocity contributes to the glycerol conversion, but too high an acrylic acid starts to decompose.
Example 3:
the preparation of the catalyst and the reaction conditions were the same as in example 1; the conditions for preparing acrylic acid were the same as in example 1 except that the kind of the catalyst was changed to Nafion film supported praseodymium catalyst.
The catalytic activity of the Nafion film supported praseodymium catalyst on the preparation of acrylic acid by catalytic conversion of glycerol is shown in table 3:
TABLE 3 influence of different reaction parameters Nafion film loaded praseodymium catalyst on preparation of acrylic acid by catalytic conversion of glycerol
Table 3 shows the influence of water content, temperature, volume ratio of vaporized glycerol to gas, total gas space velocity and reaction time in glycerol on the preparation of acrylic acid by catalyzing glycerol with a Nafion film supported praseodymium catalyst.
Water content in glycerol effects: wherein, under the condition of keeping other conditions unchanged and only changing the water content in the glycerol, as the water content in the glycerol is increased from 5 wt% to 25 wt%, the conversion rate of the glycerol is increased from 93.5% to 100%, and the yield of the acrylic acid is reduced from 77.2% to 64.7%. This shows that the cerium catalyst supported by Nafion film has good catalytic effect.
Reaction temperature effects: the glycerol conversion rate increased from 93.5% to 100% as the temperature increased from 200 ℃ to 300 ℃ with only temperature changes, otherwise unchanged. While the yield of acrylic acid is about 70.0%.
Vaporized glycerol to gas volume ratio effects: as other conditions remain unchanged, as the ratio is varied from 1:2 to 1:30, the conversion rate of the glycerol is improved to 100 percent from 93.5 percent, and the yield of the acrylic acid is about 75.0 percent.
Gas total space velocity effect: only the total space velocity of the gas is changed, and other conditions are not changed when the total space velocity of the gas is 100h-1Increased to 30000h-1When the conversion rate of glycerin is increased from 93.5% to 100%, the yield of acrylic acid is 5000h at the total gas space velocity-1A maximum of 77.2% is obtained. This indicates that an increase in the total gas space velocity contributes to the glycerol conversion, but too high an acrylic acid starts to decompose.
Example 4:
the preparation and reaction conditions of the catalyst are the same as those of example 1, except that the type of the catalyst is changed into a Nafion film loaded neodymium catalyst, the dosage of the neodymium chloride in the step (3) is 7mmol, the volume of the tetrahydrofuran is 25mL, the volume of the tetrahydrofuran-diethyl ether solution containing 50mmol of allyl lithium is 19mL, and the loaded phosphine-containing ligand is 7 g; the conditions for preparing acrylic acid were the same as in example 1 except that the type of catalyst was changed to Nafion membrane-supported neodymium catalyst, the amount of Nafion membrane-supported neodymium catalyst was 4.5g, and the reaction time was 9 hours.
The catalytic activity of the neodymium catalyst loaded on the Nafion film for preparing acrylic acid by catalyzing and converting glycerol is shown in Table 4:
TABLE 4 influence of different reaction parameters of Nafion film loaded neodymium catalyst on catalytic conversion of glycerol to acrylic acid
Table 4 shows the influence of water content, temperature, volume ratio of vaporized glycerin to gas, total gas space velocity and reaction time in the glycerol on the catalysis of the Nafion film loaded neodymium catalyst to prepare acrylic acid.
Water content in glycerol effects: wherein, under the condition of keeping other conditions unchanged and only changing the water content in the glycerol, as the water content in the glycerol is increased from 5 wt% to 25 wt%, the conversion rate of the glycerol is increased from 86.1% to 100%, and the yield of the acrylic acid is reduced from 60.5% to 53.3%. This shows that the Nafion film loaded neodymium catalyst has good catalytic effect.
Reaction temperature effects: the glycerol conversion rate increased from 86.1% to 100% as the temperature increased from 200 ℃ to 300 ℃ with only temperature changes, otherwise unchanged. The yield of acrylic acid was about 55.0%.
Vaporized glycerol to gas volume ratio effects: as other conditions remain unchanged, as the ratio is varied from 1:2 to 1:30, the conversion rate of the glycerol is improved to 100 percent from 86.1 percent, and the yield of the acrylic acid is about 55.0 percent.
Gas total space velocity effect: only the total space velocity of the gas is changed, and other conditions are not changed when the total space velocity of the gas is 100h-1Increased to 30000h-1When the conversion rate of glycerin is increased from 86.1% to 100%, the yield of acrylic acid is 5000h at the total gas space velocity-1A maximum of 60.5% is obtained. This indicates that an increase in the total gas space velocity contributes to the glycerol conversion, but too high an acrylic acid starts to decompose.
Example 5:
the preparation of the catalyst and the reaction conditions were the same as in example 1; the conditions for preparing acrylic acid were the same as in example 1 except that the type of catalyst was changed to a Nafion film supported samarium catalyst.
The catalytic activity of the Nafion film supported samarium catalyst on the catalytic conversion of glycerol to acrylic acid is shown in table 5:
TABLE 5 influence of different reaction parameters Nafion film loaded samarium catalyst on catalytic conversion of glycerol to acrylic acid
Table 5 shows the influence of water content, temperature, volume ratio of vaporized glycerol to gas, total gas space velocity and reaction time in glycerol on the preparation of acrylic acid by catalyzing glycerol with Nafion film supported samarium catalyst.
Water content in glycerol effects: wherein, under the condition of keeping other conditions unchanged and only changing the water content in the glycerol, as the water content in the glycerol is increased from 5 wt% to 25 wt%, the conversion rate of the glycerol is increased from 95.5% to 100%, and the yield of the acrylic acid is reduced from 69.4% to 63.2%. This shows that the Nafion film supported samarium catalyst has good catalytic effect.
Reaction temperature effects: the glycerol conversion rate increased from 95.5% to 100% as the temperature increased from 200 ℃ to 300 ℃ only by changing the temperature, otherwise unchanged. The yield of acrylic acid was about 65.0%.
Vaporized glycerol to gas volume ratio effects: as other conditions remain unchanged, as the ratio is varied from 1:2 to 1:30, the conversion rate of the glycerol is improved to 100 percent from 95.5 percent, and the yield of the acrylic acid is about 65.0 percent.
Gas total space velocity effect: only the total space velocity of the gas is changed, and other conditions are not changed when the total space velocity of the gas is 100h-1Increased to 30000h-1When the conversion rate of glycerin is increased from 95.5% to 100%, and the yield of acrylic acid is 5000h at the total gas space velocity-1A maximum of 69.4% is obtained. This indicates that an increase in the total gas space velocity contributes to the glycerol conversion, but too high an acrylic acid starts to decompose.
Example 6:
the preparation of the catalyst and the reaction conditions were the same as in example 1; the conditions for preparing acrylic acid were the same as in example 1 except that the type of catalyst was changed to Nafion film supported yttrium catalyst.
The catalytic activity of the Nafion film supported yttrium catalyst on the preparation of acrylic acid by catalytic conversion of glycerol is shown in Table 6:
TABLE 6 influence of Nafion film loaded yttrium catalyst with different reaction parameters on the catalytic conversion of glycerol to acrylic acid
Table 6 shows the effect of water content, temperature, vaporized glycerol to gas volume ratio, total gas space velocity, and reaction time in glycerol on the preparation of acrylic acid from glycerol catalyzed by Nafion film supported yttrium catalyst.
Water content in glycerol effects: wherein, under the condition of keeping other conditions unchanged and only changing the water content in the glycerol, as the water content in the glycerol is increased from 5 wt% to 25 wt%, the conversion rate of the glycerol is increased from 96.1% to 100%, and the yield of the acrylic acid is reduced from 70.1% to 63.3%. This shows that the Nafion film loaded yttrium catalyst has good catalytic effect.
Reaction temperature effects: the glycerol conversion rate increased from 96.1% to 100% as the temperature increased from 200 ℃ to 300 ℃ with only temperature changes, otherwise unchanged. The yield of acrylic acid was about 65.0%.
Vaporized glycerol to gas volume ratio effects: as other conditions remain unchanged, as the ratio is varied from 1:2 to 1:30, the conversion rate of the glycerol is improved to 100 percent from 96.1 percent, and the yield of the acrylic acid is about 65.0 percent.
Gas total space velocity effect: only the total space velocity of the gas is changed, and other conditions are not changed when the total space velocity of the gas is 100h-1Increased to 30000h-1When the conversion rate of glycerin is increased from 96.1% to 100%, and the yield of acrylic acid is 5000h at the total gas space velocity-1A maximum of 70.1% is obtained. This indicates that an increase in the total gas space velocity contributes to the glycerol conversion, but too high an acrylic acid starts to decompose.
Example 7:
the preparation of the catalyst and the reaction conditions were the same as in example 1; the conditions for preparing acrylic acid are the same as example 1, except that the type of the catalyst is changed to be lanthanum loaded by a Nafion film, cerium loaded by the Nafion film, praseodymium loaded by the Nafion film, neodymium loaded by the Nafion film, samarium loaded by the Nafion film and yttrium loaded by the Nafion film, and the reaction time is 120 or 240 hours.
The catalytic activity of the Nafion film-supported rare earth metal catalyst on the preparation of acrylic acid by catalytic conversion of glycerol is shown in table 7:
TABLE 7 continuous catalysis effect of Nafion film loaded rare earth metal catalyst
Table 7 shows that the catalyst has a constant conversion rate of 100% in 240h of continuous catalysis of glycerol, while the yield of acrylic acid is slightly reduced to 78.4%, and the quality of the dried catalyst is about 0.1g due to operation and reaction, so it can be seen that the Nafion film supported rare earth metal catalyst has a very good continuous catalytic potential.
Comparative example:
5g of a sulfonyl fluoride type Nafion-F resin film was charged into a micro fixed bed reactor having an outer diameter of 12mm and an inner diameter of 8 mm. Glycerol, water and nitrogen were mixed at a ratio of 1: 0.8: 10 are vaporized and mixed to enter a fixed bed reactor, and the total space velocity of the gas is 5000h-1The reaction temperature is 250 ℃ C; connecting a freezing water spraying device at the outlet to absorb the reaction product, transferring 1mL of reaction solution by using a pipette after the reaction is finished, and adding 20 mu L of isopropanol into the reaction solution to perform gas chromatography analysis; the results were: the glycerol conversion after 8h of reaction was 0%.
5g of rare earth chloride is loaded into a miniature fixed bed reactor with an outer diameter of 12mm and an inner diameter of 8 mm. Glycerol, water and nitrogen were mixed at a ratio of 1: 0.8: 10 are vaporized and mixed to enter a fixed bed reactor, and the total space velocity of the gas is 5000h-1The reaction temperature is 250 ℃ C; connecting a freezing water spraying device at the outlet to absorb the reaction product, transferring 1mL of reaction solution by using a pipette after the reaction is finished, and adding 20 mu L of isopropanol into the reaction solution to perform gas chromatography analysis; the results were: after 8 hours of reaction, the conversion of glycerol was only 12.8%, the yield of acrylic acid was 9.9%, and the yield of carbon oxide was 2.0%.
The embodiment can show that the Nafion film loaded rare earth metal catalyst has good effect on preparing acrylic acid by catalytic conversion of glycerol by a fixed bed, the catalytic effect generated by different rare earth metals is very different, and the catalytic result shows that the Nafion film loaded lanthanum has the best catalytic effect and good continuous catalytic performance.
As can be seen from example 5 and comparative example, the rare earth chloride supported on the Nafion film with the conventional sulfonyl fluoride Nafion-F resin film has much inferior catalytic effect to that of the Nafion film supported on the rare earth metal catalyst, and under the same conditions, the conversion rate of glycerin and the yield of acrylic acid are substantially improved when the Nafion film supported on the rare earth metal catalyst is used.
As can be seen from the examples, under the same experimental conditions, 5g of Nafion film loaded lanthanum is used as a catalyst to catalyze glycerol to prepare acrylic acid, the water content in the glycerol is 5 wt%, the temperature is 250oC, the volume ratio of vaporized glycerol to gas is 1:2, and the total gas space velocity is 5000h-1When the reaction time was 8 hours, the optimum reaction results were obtained, and at this time, the conversion of glycerin was 100% and the yield of acrylic acid was 80.0%.
Claims (7)
1. A preparation method of a catalyst with a Nafion film loaded with rare earth metal is characterized by comprising the following steps:
(1) pretreatment of the Nafion 115 membrane material: separately placing Nafion 115 membranes in H2O2Solution and H2SO4Soaking in the solution to remove organic impurities and metal impurities, and then boiling and rinsing the membrane in secondary distilled water to obtain a colorless transparent sulfonyl fluoride type Nafion-F resin membrane;
(2) preparing rare earth metal chloride;
(3) preparing a catalyst with a Nafion film loaded with rare earth metal:
ice-bath anhydrous rare earth metal chloride and tetrahydrofuran suspension, and adding a tetrahydrofuran-diethyl ether solution containing allyl lithium under magneton stirring; adjusting the reaction temperature to 0 ℃, continuously stirring for 2h, concentrating the reaction solution to be viscous, extracting the rare earth elements in the viscous substance by using diethyl ether, and then performing coordination reaction with the loaded phosphine-containing ligand to obtain the rare earth metal catalyst loaded on the Nafion film;
the preparation method of the supported phosphine-containing ligand comprises the following steps: under the promotion of microwave with the wavelength of 100mm, 3- (diphenylphosphine) -1-propylamine reacts with a sulfonyl fluoride type Nafion-F resin film to obtain a loaded phosphine-containing ligand; the mass ratio of the 3- (diphenylphosphine) -1-propylamine to the sulfonyl fluoride type Nafion-F resin film is 1-4: 100, respectively;
the dosage ratio of the rare earth metal chloride to the tetrahydrofuran is 5-10 mmol: 20-30 mL;
the dosage ratio of the allyl lithium, the tetrahydrofuran-diethyl ether solution and the loaded phosphine-containing ligand is 50 mmol: 20mL of: 1-10 g; the dosage ratio of tetrahydrofuran to diethyl ether in the tetrahydrofuran-diethyl ether solution is 1: 1; the coordination reaction time is 1 h.
2. The method for preparing a catalyst with a Nafion film supporting rare earth metal as claimed in claim 1, wherein in the step (2), the rare earth metal in the rare earth metal chloride comprises lanthanum, cerium, praseodymium, neodymium, samarium or yttrium.
3. The method for preparing acrylic acid by catalysis of the catalyst prepared by the preparation method of claim 1 and loaded with the rare earth metal through the Nafion film is characterized by comprising the following steps:
(1) preparing a glycerol aqueous solution with a certain concentration by taking glycerol as a raw material for later use;
(2) loading a Nafion film loaded rare earth metal catalyst into a miniature fixed bed reactor; heating and vaporizing glycerin and gas at a certain ratio and a certain temperature, mixing the glycerin and the gas at a certain total gas space velocity, feeding the mixture into a fixed bed reactor, reacting the mixture for a certain time at a certain temperature, and connecting a chilled water spray device at an outlet to absorb reaction products; and after the reaction is finished, collecting a product, namely the acrylic acid.
4. The catalytic production process for acrylic acid according to claim 3, wherein in the step (1), the concentration of the aqueous glycerol solution is 5 to 25 wt%.
5. The method for preparing acrylic acid under catalysis of claim 3, wherein in the step (2), the addition amount of the Nafion film loaded rare earth metal catalyst is 4-5 g.
6. The catalytic production method of acrylic acid according to claim 3, wherein in the step (2), the volume ratio of glycerin to gas is 1:2 to 1: 30; the vaporization temperature is 300 ℃; the gas comprises Xe, CO2、N2Or water vapor; the water vapor is obtained by vaporizing water in the glycerin water solution.
7. The catalytic production method of acrylic acid according to claim 3, wherein in the step (2), the total gas space velocity is 100 to 30000h-1(ii) a The reaction temperature of the miniature fixed bed reactor is 200-300 ℃; the reaction time is 7-9 h.
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