CN117548101A - Catalyst for preparing 3, 4-dihydro-2H-pyran and method for preparing 3, 4-dihydro-2H-pyran - Google Patents
Catalyst for preparing 3, 4-dihydro-2H-pyran and method for preparing 3, 4-dihydro-2H-pyran Download PDFInfo
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- CN117548101A CN117548101A CN202311480349.5A CN202311480349A CN117548101A CN 117548101 A CN117548101 A CN 117548101A CN 202311480349 A CN202311480349 A CN 202311480349A CN 117548101 A CN117548101 A CN 117548101A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000012298 atmosphere Substances 0.000 claims abstract description 68
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims abstract description 37
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 239000000047 product Substances 0.000 claims description 66
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006462 rearrangement reaction Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 230000008707 rearrangement Effects 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000007867 post-reaction treatment Methods 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract description 34
- 239000006227 byproduct Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 tetrahydropyran Chemical compound 0.000 description 1
Classifications
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/18—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member containing only hydrogen and carbon atoms in addition to the ring hetero atom
Abstract
The present application relates to a catalyst for preparing 3, 4-dihydro-2H-pyran, a method for preparing the same, and a method for preparing 3, 4-dihydro-2H-pyran using the same. The catalyst comprises a carrier, an active component and a cocatalyst component, and is prepared as follows: immersing the carrier into an active component precursor aqueous solution, uniformly stirring, standing, and drying; roasting in air atmosphere; reducing in a hydrogen atmosphere; immersing in the precursor aqueous solution of the cocatalyst component, uniformly stirring, standing, and drying; roasting in air atmosphere; and reducing in a hydrogen atmosphere. The catalyst is applied to the process of preparing 3, 4-dihydro-2H-pyrane by taking tetrahydrofurfuryl alcohol as a raw material, and improves the selectivity of 3, 4-dihydro-2H-pyrane and reduces the difficulty of separation by reducing the generation of tetrahydropyran byproducts. The method for preparing the 3, 4-dihydro-2H-pyran has the advantages of easily available raw materials, more green route, simple process, high efficiency and continuous production.
Description
Technical Field
The present application relates to the field of chemical synthesis, and in particular to a catalyst for preparing 3, 4-dihydro-2H-pyran from tetrahydrofurfuryl alcohol by dehydration rearrangement and a method for preparing 3, 4-dihydro-2H-pyran using the catalyst.
Background
3, 4-dihydro-2H-pyran, CAS no: 110-87-2, DHP for short, colorless liquid, solidifying point-70 ℃, boiling point 86-87 ℃, relative density 0.9221 (19/15 ℃), refractive index 1.4402 (19 ℃), flash point-15 ℃, which is widely used for hydroxy protecting reagent, can prepare tetrahydropyran, pentanediol, glutaric acid, valerolactone, pentadiene and resin products through polymerization, hydrogenation, oxidation and other reactions, and can be used as medical intermediate; can also be used as solvent and organic synthesis intermediate. When 3, 4-dihydro-2H-pyran is used for protecting hydroxyl, the 3, 4-dihydro-2H-pyran is generally not reacted with nucleophilic reagents and organic metal reagents, is resistant to strong alkali and is easy to change under the condition of low pH value or Lewis acid.
There are many reports of the synthesis of 3, 4-dihydro-2H-pyran by the dehydration rearrangement of Guan Siqing furfuryl alcohol (as shown above), such as Schniepp and Geller (J.Am. Chem. Soc.68 (1946) 1646-1648), in 1946, it was reported that tetrahydrofurfuryl alcohol can be used as a raw material for the synthesis of 3, 4-dihydro-2H-pyran by the dehydration rearrangement. Sato (Applied Catalysis A: general 453 (2013) 213-218) and Huber (literature source: doi.org/10.1016/j.apcatb.2018.12.039) each studied the above-mentioned dehydration rearrangement reaction in detail, and found that it was difficult to reduce the formation of tetrahydropyran as a by-product while ensuring a high 3, 4-dihydro-2H-pyran selectivity (> 90%) during the reaction. The quality standard of the commercial 3, 4-dihydro-2H-pyran is that the purity is more than 98.5%, and the tetrahydropyran content is less than 1.5%. Because the 3, 4-dihydro-2H-pyran and the tetrahydropyran have similar molecular structures and similar properties, the boiling points are only different by 2 ℃ (the boiling point of the 3, 4-dihydro-2H-pyran is 86 ℃ and the boiling point of the tetrahydropyran is 88 ℃), a great deal of energy is required for separating the two materials, and the production cost is increased.
In the prior art, gamma-Al is often adopted 2 O 3 Or the molecular sieve directly catalyzes tetrahydrofurfuryl alcohol to dehydrate and rearrange to synthesize 3, 4-dihydro-2H-pyrane. Huber et Al (doi.org/10.1016/j.apcatab.2018.12.039) vs. gamma-Al 2 O 3 Comparing the reaction results of the tetrahydrofurfuryl alcohol dehydration rearrangement reaction with the various molecular sieve catalysts to synthesize the 3, 4-dihydro-2H-pyrane, the gamma-Al under the same condition is found compared with the molecular sieve (HY, H-Beta, H-ZSM 5) 2 O 3 Has higher reactivity and product selectivity. From the cost aspect, gamma-Al 2 O 3 Is a relatively suitable catalyst support. The main problem of the present reaction is that the selectivity of 3, 4-dihydro-2H-pyran in the product is not high enough, and the content of the by-product tetrahydropyran is difficult to reduce, which brings great disadvantages to the subsequent separation of the two.
Therefore, the content of the byproduct tetrahydropyran is reduced as much as possible while the yield of the target product 3, 4-dihydro-2H-pyran is ensured, and the operation difficulty and the energy consumption of the production process are greatly reduced, so that the method becomes a key problem of the reaction.
Disclosure of Invention
Technical problem
It is an object of the present application to provide a catalyst for preparing 3, 4-dihydro-2H-pyran, which is used for preparing 3, 4-dihydro-2H-pyran from tetrahydrofurfuryl alcohol as a raw material by a continuous selective dehydration rearrangement reaction. The catalyst for preparing the 3, 4-dihydro-2H-pyran has extremely excellent catalytic activity and target selectivity, can catalyze the dehydration rearrangement of tetrahydrofurfuryl alcohol to prepare the target product 3, 4-dihydro-2H-pyran, and has the selectivity of more than 92 percent, and meanwhile, the selectivity of the byproduct tetrahydropyran is only about 0.2 percent, so that the difficulty of subsequent separation is greatly reduced while the yield of the target product is ensured, and the high-purity 3, 4-dihydro-2H-pyran can be obtained without complex rectification operation.
It is another object of the present application to provide a process for preparing the above catalyst.
It is a further object of the present application to provide a process for preparing 3, 4-dihydro-2H-pyran using the catalyst.
Technical proposal
According to one aspect of the present application, there is provided a catalyst for the preparation of 3, 4-dihydro-2H-pyran, the catalyst comprising a carrier, an active component and a co-catalyst component, wherein:
the carrier comprises a material selected from gamma-Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 One or more of HZSM5, SAPO-34, HY, hβ and HMOR;
the active component comprises one or more metal elements selected from platinum (Pt), palladium (Pd), ruthenium (Ru) and rhodium (Rh);
the promoter component comprises one or more metal elements selected from potassium (K), sodium (Na), lithium (Li), magnesium (Mg) and calcium (Ca).
According to one embodiment of the present application, in the catalyst, the mass ratio of the metal element in the active component to the carrier is (0.01-2): 100. When the content is lower than the range, the selectivity of the byproduct tetrahydropyran in the product is improved, so that the purification difficulty of the target product 3, 4-dihydro-2H-pyran is increased; whereas above this range, a large amount of light component by-products are formed by the reaction, so that the material balance of the reaction is deteriorated.
According to one embodiment of the present application, in the catalyst, the mass ratio of the metal element in the promoter component to the metal element in the active component is (0.05-2): 1. Below this range, the reaction produces a large amount of light component byproducts, deteriorating the material balance of the reaction; and above this range, the conversion of the target product 3, 4-dihydro-2H-pyran in the reaction is greatly reduced.
Preferably, the active component includes one or more metal elements selected from platinum (Pt), palladium (Pd) and ruthenium (Ru).
Preferably, the promoter component includes one or more metal elements selected from potassium (K), sodium (Na) and lithium (Li).
According to another aspect of the present application, there is provided a method for preparing the catalyst, the method comprising the steps of:
(1) Soaking the carrier in an equal volume of an active component precursor aqueous solution, standing, and drying;
(2) Roasting the product obtained in the step (1) for 2-5 hours in the air atmosphere at the temperature of 250-300 ℃;
(3) Reducing the product obtained in the step (2) for 2 to 4 hours in a hydrogen atmosphere at the temperature of 250 to 350 ℃;
(4) Soaking the product obtained in the step (3) in an isovolumetric mode into a promoter component precursor aqueous solution, standing, and drying;
(5) Roasting the product obtained in the step (4) for 2-5 hours in the air atmosphere at the temperature of 250-300 ℃; and
(6) And (3) reducing the product obtained in the step (5) for 2-4 hours in a hydrogen atmosphere at the temperature of 250-350 ℃.
According to one embodiment of the present application, the active component precursor includes one or more selected from the group consisting of nitrate, chloride (chlorine coordination salt) and acetate of Pt, pd, ru and Rh.
According to one embodiment of the present application, the promoter component precursor comprises one or more selected from the group consisting of carbonates, sulfates and hydroxides of potassium, sodium, lithium, magnesium and calcium.
According to one embodiment of the present application, in step (1), the concentration of the active component precursor aqueous solution is 0.005mol/L to 0.05mol/L.
According to one embodiment of the present application, in step (1), the standing time is 2 to 5 hours.
According to one embodiment of the present application, in step (1), the drying temperature is 110 to 150 ℃ and the drying time is 5 to 10 hours.
According to one embodiment of the present application, in step (4), the concentration of the aqueous solution of the promoter component precursor is from 0.05mol/L to 0.2mol/L.
According to one embodiment of the present application, in step (4), the standing time is 2 to 5 hours.
According to one embodiment of the present application, in step (4), the drying temperature is 110 to 150 ℃ and the drying time is 5 to 10 hours.
According to one embodiment of the present application, the method of preparing a catalyst further comprises a pretreatment of the support. Specifically, before step (1), the carrier is baked for 2 to 5 hours in an air atmosphere at a temperature of 200 to 400 ℃.
According to still another aspect of the present application, there is provided a method for preparing 3, 4-dihydro-2H-pyran using the above-described catalyst, comprising:
in the presence of the catalyst, the tetrahydrofurfuryl alcohol is subjected to dehydration rearrangement reaction in a reactor at 200-500 ℃.
According to one embodiment of the present application, the reactor in the process for preparing 3, 4-dihydro-2H-pyran is selected from any one of a batch reactor, a semi-batch reactor, a continuous stirred tank reactor, a plug flow reactor, a stationary phase reactor and a fluidized bed reactor or may be a connected mixed reactor of two or more of these reactors. Preferably a fixed bed reactor.
The catalyst may be in the form of a strip, column or sheet.
According to one embodiment of the present application, the dehydration rearrangement reaction temperature may preferably be 250 to 400 ℃.
According to one embodiment of the present application, the dehydration rearrangement reaction may be performed under one or more of a nitrogen atmosphere, a helium atmosphere, an argon atmosphere, and a hydrogen atmosphere.
According to one embodiment of the present application, the process for preparing 3, 4-dihydro-2H-pyran may be carried out at a reaction pressure of 0.1MPa (or normal pressure) to 4MPa, preferably 0.1MPa (or normal pressure) to 2 MPa.
According to one embodiment of the present application, the tetrahydrofurfuryl alcohol may be reacted in the absence of a solvent or in the presence of a solvent, which is one or more selected from tetrahydrofuran, acetonitrile and 1, 4-dioxane, preferably tetrahydrofuran or acetonitrile.
According to one embodiment of the present application, the method for preparing 3, 4-dihydro-2H-pyran may be performed at 0.05H -1 ～5h -1 Preferably 0.03h -1 ～3h -1 Is carried out at a reaction space velocity.
According to one embodiment of the present application, the method for preparing 3, 4-dihydro-2H-pyran further comprises activating the catalyst prior to the reaction. Specifically, before the reaction, the catalyst is heated to an activation temperature of 300-500 ℃ and maintained for 1-6 hours. Preferably, the activation temperature may be 300 ℃ to 400 ℃.
According to one embodiment of the present application, the method for preparing 3, 4-dihydro-2H-pyran further comprises a post-reaction treatment. Specifically, the reaction product is rectified after condensation and gas-liquid separation. The condensation, gas-liquid separation and rectification are methods and conditions for separating 3, 4-dihydro-2H-pyrane and byproducts including tetrahydropyran, which are conventional in the art, and are not described herein.
Advantageous effects
The catalyst for synthesizing 3, 4-dihydro-2H-pyran can catalyze tetrahydrofurfuryl alcohol reaction with higher conversion rate, has very high 3, 4-dihydro-2H-pyran selectivity (up to 92 percent or more) and extremely low by-product tetrahydropyran selectivity (only about 0.2 percent), can greatly reduce the amount of tetrahydropyran in the product, fundamentally solves the difficult problem of separating the tetrahydropyran from the 3, 4-dihydro-2H-pyran in the product, further reduces production energy consumption, reduces production cost and is easy to realize industrial production.
Drawings
Fig. 1 is a schematic view of a 3, 4-dihydro-2H-pyran synthesis reaction apparatus according to one embodiment of the present application.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the catalyst prepared in preparation example 1 according to one embodiment of the present application.
FIG. 3 is a physical adsorption test result of the catalyst prepared in preparation example 1 according to one embodiment of the present application.
Fig. 4 is an ammonia temperature programmed desorption result of the catalyst prepared in preparation example 1 and comparative preparation example 1 according to one embodiment of the present application.
FIG. 5 is a gas chromatogram of the reaction product of reaction example 1 according to one embodiment of the present application.
FIG. 6 is a gas chromatogram of the reaction product of comparative reaction example 1 according to one embodiment of the present application.
Detailed Description
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description herein is for the purpose of illustrating preferred examples only and is not intended to limit the scope of the invention, as it will be understood that other equivalent implementations and modifications may be made without departing from the spirit and scope of the invention.
The following examples are merely illustrative of embodiments of the present application and do not constitute any limitation to the present application, and those skilled in the art will appreciate modifications within the scope of the spirit and concept of the present application.
Preparation of 3, 4-dihydro-2H-pyran
In the method for preparing 3, 4-dihydro-2H-pyran according to the present application, tetrahydrofurfuryl alcohol is used as a raw material, and enol is obtained through a dehydration rearrangement reaction. The product obtained after the post-treatment was filtered through a 0.22 μm filter and analyzed by Gas Chromatography (GC). Qualitative analysis of the low boiling products by gas chromatography-mass spectrometry (GC-MS) and standard GC retention time control determined that the reaction product was predominantly tetrahydrofurfuryl alcohol. The low boiling point substances were quantitatively determined by gas chromatography using Shimadzu-GC 2020, and quantitatively analyzed by comparison with the standard retention time and peak area size. The correlation calculation formula is as follows:
wherein the flow unit of tetrahydrofurfuryl alcohol is g/min, and the unit of the dosage of the catalyst is g.
As shown in fig. 1, which is a schematic diagram of a synthesis reaction apparatus of 3, 4-dihydro-2H-pyran according to one embodiment of the present application. Wherein the reaction tube is filled with a catalyst for preparing 3, 4-dihydro-2H-pyran according to the present application. First, a carrier gas is introduced into the reaction tube by controlling a flow rate through a mass flow meter to create a carrier gas atmosphere, after which a heating furnace may be heated to activate the catalyst. Then, maintaining the temperature of the reaction tube, feeding tetrahydrofurfuryl alcohol into the reaction tube through a feed pump, and reacting to generate a product containing 3, 4-dihydro-2H-pyrane under the condition of carrier gas atmosphere and catalyst catalysis. Then condensing and separating gas from liquid to obtain the 3, 4-dihydro-2H-pyran.
According to the application, the catalyst is applied to the process of preparing 3, 4-dihydro-2H-pyrane by taking tetrahydrofurfuryl alcohol as a raw material. By reducing the formation of tetrahydropyran byproducts, the selectivity of 3, 4-dihydro-2H-pyran is improved, and the difficulty of separation is reduced. The method for preparing the 3, 4-dihydro-2H-pyran has the advantages of easily available raw materials, more green route, simple process, high efficiency and continuous production.
The starting materials used in this application are commercially available and the methods and apparatus used are conventional in the art, except as specifically described herein.
In the following examples, tetrahydrofurfuryl alcohol, potassium carbonate, potassium sulphate, sodium carbonate, magnesium nitrate were purchased from the national pharmaceutical chemicals company, ltd; chloroplatinic acid, palladium nitrate and ruthenium chloride were purchased from the new materials limited of sienna kii, high purity nitrogen, high purity helium and air from the science and technology limited of the Qingdao de sea.
Preparation of the catalyst
Preparation example 1
The catalyst for preparing 3, 4-dihydro-2H-pyran is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: 50g of gamma-Al are added at 300 ℃ 2 O 3 Roasting for 5 hours in an air atmosphere;
(ii) Immersing the pretreated carrier obtained in the step (i) in an aqueous solution of chloroplatinic acid with the concentration of 0.01mol/L in an equal volume, standing for 5h, and drying at 120 ℃ for 10h;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product obtained in step (iii) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min;
(v) Soaking the product obtained in the step (iv) in an isovolumetric potassium carbonate aqueous solution with the concentration of 0.03mol/L for 5 hours, and then drying the product at 120 ℃ for 10 hours;
(vi) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours; and
(vii) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby producing a catalyst 1.
Fig. 2 is a Transmission Electron Microscope (TEM) image of the catalyst prepared in preparation example 1 according to one embodiment of the present application. From fig. 2, it can be seen that the active component metal Pt is uniformly distributed on the surface of the catalyst support in the particle size of about 3nm to 4 nm.
Fig. 3 is a physical adsorption test (specific surface area) result of the catalyst prepared in preparation example 1 according to one embodiment of the present application. Specifically, the specific surface area and pore structure of the catalyst are measured on an Autosorb iQ full-automatic rapid specific surface area and mesopore/micropore analyzer of Quantachrome company. The sample is firstly vacuumized at 150 ℃ for 3 hours, then the weight of the sample is accurately weighed, then the adsorption quantity of nitrogen is measured at the temperature of liquid nitrogen, and the specific surface area of the sample is calculated according to the adsorption quantity. The specific surface area of the sample is calculated by a BET method, and the pore size distribution is calculated by a DFT method.
Fig. 4 is an ammonia temperature programmed desorption result of the catalyst prepared in preparation example 1 and comparative preparation example 1 (shown below) according to one embodiment of the present application. In particular, NH of the catalyst 3 TPR characterization was performed on an AutoChem 2920 chemisorber from Micromeritics. The specific experimental steps are as follows: taking 0.1g sample, placing into a U-shaped quartz tube, purging at 150deg.C in Ar gas atmosphere for 2 hr, cooling to 100deg.C, and adsorbing 5wt% NH at 100deg.C 3 and/Ar gas mixture for 2h. Then switching to purging the physically adsorbed ammonia gas for 1h under Ar atmosphere, leveling the base line, and then heating to 800 ℃ at a heating rate of 10 ℃/min. NH3 signals were recorded using a TCD detector. From NH 3 The TPD comparison shows that catalyst 1 and comparative catalyst 1 both have an acidic site in the range of 130℃to 220℃with the difference that the amount of the acidic site is different for both catalysts and that catalyst 1 is significantly lower than comparative catalyst 1 (the mass of catalyst added during the test is the same, so that the peak area represents the amount of acidic site). Thus, the catalyst surface can be controlled by controlling the addition of the promoter componentThe amount of acid sites.
Preparation example 2
The catalyst for preparing 3, 4-dihydro-2H-pyran is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: roasting 50g of HY in air atmosphere at 300 ℃ for 5 hours;
(ii) Immersing the pretreated carrier obtained in the step (i) in an aqueous solution of chloroplatinic acid with the concentration of 0.01mol/L in an equal volume, standing for 5h, and drying at 120 ℃ for 10h;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product obtained in step (iii) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min;
(v) Soaking the product obtained in the step (iv) into 0.03mol/L potassium sulfate aqueous solution in an equal volume mode, standing for 5 hours, and drying at 110 ℃ for 10 hours;
(vi) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours; and
(vii) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby producing catalyst 2.
Preparation example 3
The catalyst for preparing 3, 4-dihydro-2H-pyran is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: roasting 50g of H beta in an air atmosphere at 300 ℃ for 5 hours; roasting 50g H beta in an air atmosphere at 300 ℃ for 5 hours;
(ii) Immersing the pretreated carrier obtained in the step (i) in an aqueous solution of chloroplatinic acid with the concentration of 0.01mol/L in an equal volume, standing for 5h, and drying at 120 ℃ for 10h;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product obtained in step (iii) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min;
(v) Soaking the product obtained in the step (iv) into 0.03mol/L potassium sulfate aqueous solution in an equal volume mode, standing for 5 hours, and drying at 110 ℃ for 10 hours;
(vi) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours; and
(vii) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby producing a catalyst 3.
Preparation example 4
The catalyst for preparing 3, 4-dihydro-2H-pyran is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: 50g of gamma-Al are added at 300 ℃ 2 O 3 Roasting for 5 hours in an air atmosphere;
(ii) Immersing the pretreated carrier obtained in the step (i) in an equal volume of a palladium nitrate aqueous solution with the concentration of 0.01mol/L, standing for 5 hours, and then drying for 10 hours at 120 ℃;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product obtained in step (iii) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min;
(v) Soaking the product obtained in the step (iv) into 0.03mol/L potassium sulfate aqueous solution in an equal volume mode, standing for 5 hours, and drying at 110 ℃ for 10 hours;
(vi) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours; and
(vii) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby producing a catalyst 4.
Preparation example 5
The catalyst for preparing 3, 4-dihydro-2H-pyran is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: 50g of SiO are introduced at 300 ℃ 2 Roasting for 5 hours in an air atmosphere;
(ii) Immersing the pretreated carrier obtained in the step (i) in an aqueous solution of chloroplatinic acid with the concentration of 0.01mol/L in an equal volume, standing for 5h, and drying at 120 ℃ for 10h;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product obtained in step (iii) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min;
(v) Soaking the sodium carbonate aqueous solution with the equal volume of the product obtained in the step (iv) and the concentration of 0.03mol/L for 5 hours, and then drying the solution at 110 ℃ for 10 hours;
(vi) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours; and
(vii) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby producing a catalyst 5.
Preparation example 6
The catalyst for preparing 3, 4-dihydro-2H-pyran is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: 50g of gamma-Al are added at 300 ℃ 2 O 3 Roasting for 5 hours in an air atmosphere;
(ii) Immersing the pretreated carrier obtained in the step (i) into a ruthenium chloride aqueous solution with the concentration of 0.01mol/L in an equal volume manner, standing for 5 hours, and then drying for 10 hours at 120 ℃;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product obtained in step (iii) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min;
(v) Soaking the lithium hydroxide aqueous solution with the equal volume of the product obtained in the step (iv) and the concentration of 0.03mol/L for 5 hours, and then drying the solution at 110 ℃ for 10 hours;
(vi) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours; and
(vii) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby producing a catalyst 6.
Comparative preparation example 1
The catalyst is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: 50g of gamma-Al are added at 300 ℃ 2 O 3 Roasting for 5 hours in an air atmosphere;
(ii) Immersing the pretreated carrier obtained in the step (i) in an aqueous solution of chloroplatinic acid with the concentration of 0.01mol/L in an equal volume, standing for 5h, and drying at 120 ℃ for 10h;
(iii) Roasting the product obtained in the step (ii) in an air atmosphere at 300 ℃ for 5 hours;
(iv) The product obtained in step (iii) was reduced at 350℃for 4 hours in a hydrogen atmosphere at a hydrogen flow rate of 50mL/min, whereby comparative catalyst 1 was produced.
The ammonia temperature programmed desorption result of the comparative catalyst 1 is shown in fig. 4.
Comparative preparation example 2
The catalyst is prepared by a process comprising the steps of:
(i) Pretreatment of the carrier: 50g of gamma-Al are added at 300 ℃ 2 O 3 Roasting for 5 hours in an air atmosphere;
(ii) Soaking the pretreated carrier obtained in the step (i) in an aqueous solution of potassium hydroxide with the concentration of 0.5mol/L in an equal volume, standing for 5h, and then drying at 110 ℃ for 10h;
(iii) Roasting the product obtained in the step (v) in an air atmosphere at 300 ℃ for 5 hours;
(iv) Reducing the product of step (vi) in a hydrogen atmosphere at 350 ℃ for 4 hours, wherein the hydrogen flow is 50mL/min, thereby preparing comparative catalyst 2.
Reaction example 1
The 3, 4-dihydro-2H-pyran is prepared by the following steps:
(a) 2g of the shaped catalyst 1 from preparation example 1 were introduced into a fixed-bed reactor, in N 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours for activation, and then cooling to 350 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at a temperature of 350℃and at atmospheric pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.3%, the selectivity of 3, 4-dihydro-2H-pyrane is 92.4%, the selectivity of tetrahydropyran is 0.2%, and the material balance of the reactor is 97%.
As shown in FIG. 5, a gas chromatogram of the reaction product of reaction example 1 was obtained. As can be seen from FIG. 5, the 3, 4-dihydro-2H-pyran content ratio in the reactants was very high, while the tetrahydropyran content was very low, demonstrating the higher 3, 4-dihydro-2H-pyran selectivity and very low tetrahydropyran selectivity of the catalyst according to the present application.
Reaction example 2
The 3, 4-dihydro-2H-pyran is prepared by the following steps:
(a) 2g of the shaped catalyst 2 of preparation example 2, N, were introduced into a fixed-bed reactor 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 1.0h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 87.2%, the selectivity of 3, 4-dihydro-2H-pyrane is 95.2%, the selectivity of tetrahydropyran is 0.1%, and the material balance of the reactor is 98%.
Reaction example 3
The process for the preparation of 3, 4-dihydro-2H-pyran according to the present application is carried out by the following steps:
(a) 2g of the catalyst 3 of preparation example 3 shaped in N were introduced into a fixed-bed reactor 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.4%, the selectivity of 3, 4-dihydro-2H-pyrane is 94.6%, the selectivity of tetrahydropyran is 0.1%, and the material balance of the reactor is 95%.
Reaction example 4
A process for preparing 3, 4-dihydro-2H-pyran by the steps of:
(a) 2g of the catalyst 4 of preparation example 4 shaped in N were introduced into a fixed-bed reactor 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 280 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at a temperature of 280℃and at atmospheric pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.3%, the selectivity of 3, 4-dihydro-2H-pyrane is 94.1%, the selectivity of tetrahydropyran is 0.1%, and the material balance of the reactor is 97%.
Reaction example 5
A process for preparing 3, 4-dihydro-2H-pyran by the steps of:
(a) 2g of the catalyst 5 of preparation example 5 shaped in N were introduced into a fixed-bed reactor 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 0.3h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.0%, the selectivity of 3, 4-dihydro-2H-pyrane is 93.9%, the selectivity of tetrahydropyran is 0.3%, and the material balance of the reactor is 96%.
Reaction example 6
A process for preparing 3, 4-dihydro-2H-pyran by the steps of:
(a) 2g of the catalyst 6 of preparation example 6 shaped in N were introduced into a fixed-bed reactor 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.0%, the selectivity of 3, 4-dihydro-2H-pyrane is 93.7%, the selectivity of tetrahydropyran is 0.1%, and the material balance of the reactor is 97%.
Comparative reaction example 1
A process for preparing 3, 4-dihydro-2H-pyran by the steps of:
(a) 2g of shaped comparative catalyst 1 were introduced into a fixed bed reactor, in N 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.7%, the selectivity of 3, 4-dihydro-2H-pyrane is 61.3%, the selectivity of tetrahydropyran is 0.1%, and the material balance of the reactor is 72%.
As shown in FIG. 6, a gas chromatogram of the reaction product of comparative reaction example 1 was obtained. As can be seen from FIG. 6, there is a distinct peak in the content of tetrahydropyran in the reaction product, demonstrating that the ratio of tetrahydropyran to 3, 4-dihydro-2H-pyran in the reaction product is very substantial.
Comparative reaction example 2
A process for preparing 3, 4-dihydro-2H-pyran by the steps of:
(a) 2g of shaped comparative catalyst 2 were introduced into a fixed bed reactor, in N 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 85.2%, the selectivity of 3, 4-dihydro-2H-pyrane is 80.2%, the selectivity of tetrahydropyran is 10.7%, and the material balance of the reactor is 96%.
Comparative reaction example 3
A process for preparing 3, 4-dihydro-2H-pyran by the steps of:
(a) 2g of shaped gamma-Al are introduced into a fixed bed reactor 2 O 3 At N 2 Heating to 400 ℃ under the atmosphere, maintaining for 3 hours to activate, and then cooling to 300 ℃; and
(b) Tetrahydrofurfuryl alcohol is reacted at 300℃under normal pressure for 0.6h -1 Is introduced into the reactor for reaction.
GC detection is carried out on the reaction product after condensation and gas-liquid separation, and the result shows that the conversion rate of tetrahydrofurfuryl alcohol is 99.1%, the selectivity of 3, 4-dihydro-2H-pyrane is 83.9%, the selectivity of tetrahydropyran is 8.7%, and the material balance of the reactor is 96%.
From the reaction results according to the above reaction examples 1 to 6 and comparative reaction examples 1 to 3, in comparative reaction example 1, the comparative catalyst 1 used contained only the active component and no co-catalyst component, so that the content of tetrahydropyran in the obtained product was significantly reduced, to only 0.1%, which means that the addition of the active component to the catalyst did significantly reduce the formation of tetrahydropyran, but no co-catalyst component was added, so that the selectivity of the objective 3, 4-dihydro-2H-pyran was significantly reduced, to only 61.3%, and it was found from the reaction mass balance that the reaction produced a light component product which was more difficult to condense when using the comparative catalyst 1. From the analysis of the NH3-TPD characterization results shown in fig. 4, the absence of the promoter component may significantly increase the acidity of the catalyst surface, resulting in a decrease in catalyst selectivity. In comparative reaction example 2, comparative catalyst 2 used contained only the cocatalyst component and no active component, so that the conversion of the reaction was significantly reduced, and the selectivity of tetrahydropyran in the product reached more than 10%. It can be seen that in the case of the inclusion of no active component but only of the cocatalyst component, only the acidity of the support is reduced, which only allows the conversion of the starting material to be reduced, but does not increase the selectivity of the product. In comparative reaction example 3, gamma-Al was used 2 O 3 When the catalyst is used, the selectivity of the tetrahydropyran in the tetrahydrofurfuryl alcohol dehydration rearrangement reaction product is as high as 8.7 percent. In contrast, when the catalysts prepared according to preparation examples 1 to 6 of the present application were used, the production of tetrahydropyran could be reducedMeanwhile, the generation of light component products is obviously reduced, the selectivity of the target product 3, 4-dihydro-2H-pyran is improved to more than 92%, and the selectivity of the tetrahydropyran in the reaction product is only about 0.2%, so that the difficulty of subsequent separation is greatly reduced while the yield of the target product is ensured, and the high-purity 3, 4-dihydro-2H-pyran can be obtained without complex rectification operation.
The above-described embodiments of the present application are intended to be illustrative of the preferred embodiments of the present application and not to be limiting of the present application, and modifications, equivalents, improvements, etc. that do not constitute an inventive contribution to the art may, however, be within the scope of the protection of the present application, are intended to be included within the spirit and principles of the present application, as desired.
Claims (10)
1. A catalyst for the preparation of 3, 4-dihydro-2H-pyran, characterized in that the catalyst comprises a support, an active component and a cocatalyst component, wherein:
the carrier comprises a material selected from gamma-Al 2 O 3 、SiO 2 、ZrO 2 、TiO 2 One or more of HZSM5, SAPO-34, HY, hβ and HMOR;
the active component comprises one or more metal elements selected from platinum, palladium, ruthenium and rhodium, preferably one or more metal elements selected from platinum, palladium and ruthenium;
the promoter component comprises one or more metal elements selected from potassium, sodium, lithium, magnesium and calcium, preferably comprises one or more metal elements selected from potassium, sodium and lithium.
2. The catalyst of claim 1, wherein the catalyst is,
the mass ratio of the metal element in the active component to the carrier is (0.01-2) 100; and/or
The mass ratio of the metal element in the promoter component to the metal element in the active component is (0.05-2): 1.
3. A method of preparing a catalyst according to claim 1 or 2, characterized in that the method of preparation comprises the steps of:
(1) Soaking the carrier in an equal volume of an active component precursor aqueous solution, standing, and drying;
(2) Roasting the product obtained in the step (1) for 2-5 hours in the air atmosphere at the temperature of 250-300 ℃;
(3) Reducing the product obtained in the step (2) for 2 to 4 hours in a hydrogen atmosphere at the temperature of 250 to 350 ℃;
(4) Soaking the product obtained in the step (3) in an isovolumetric mode into a promoter component precursor aqueous solution, standing, and drying;
(5) Roasting the product obtained in the step (4) for 2-5 hours in the air atmosphere at the temperature of 250-300 ℃; and
(6) And (3) reducing the product obtained in the step (5) for 2-4 hours in a hydrogen atmosphere at the temperature of 250-350 ℃.
4. A process according to claim 3, wherein,
the active component precursor comprises one or more of nitrate, chloride and acetate selected from Pt, pd, ru and Rh; and/or
According to one embodiment of the present application, the promoter component precursor comprises one or more selected from the group consisting of carbonates, sulfates and hydroxides of potassium, sodium, lithium, magnesium and calcium.
5. A process according to claim 3, wherein, in step (1),
preferably, the concentration of the active component precursor aqueous solution is 0.005mol/L to 0.05mol/L;
preferably, the standing time is 2-5 hours; and
preferably, the drying temperature is 110-150 ℃ and the drying time is 5-10 h.
6. A process according to claim 3, wherein, in step (4),
preferably, the concentration of the promoter component precursor aqueous solution is 0.05mol/L to 0.2mol/L;
preferably, the standing time is 2-5 hours; and
preferably, the drying temperature is 110-150 ℃ and the drying time is 5-10 h.
7. The method according to claim 3, further comprising pretreatment of the carrier: before the step (1), roasting the carrier for 2-5 hours in an air atmosphere at 200-400 ℃.
8. A process for preparing 3, 4-dihydro-2H-pyran, the process comprising:
a process for the dehydration rearrangement of tetrahydrofurfuryl alcohol in the presence of a catalyst according to claim 1 or 2 or a catalyst obtainable by a process according to any of claims 3 to 7, in a reactor at 200 ℃ to 500 ℃.
9. The method according to claim 8, characterized in that it comprises at least one of the following features (a) - (g):
(a) The reactor used in the process is selected from any one of a batch reactor, a semi-batch reactor, a continuous stirred tank reactor, a plug flow reactor, a stationary phase reactor and a fluidized bed reactor or a mixed reactor of more than two of these reactors connected, preferably a fixed bed reactor;
(b) The catalyst is in a strip shape, a column shape or a sheet shape;
(c) The dehydration rearrangement reaction temperature is preferably 250-400 ℃;
(d) The dehydration rearrangement reaction is carried out under one or more of nitrogen atmosphere, helium atmosphere, argon atmosphere and hydrogen atmosphere;
(e) The method for preparing 3, 4-dihydro-2H-pyran is carried out under the reaction pressure of 0.1-4 MPa, preferably 0.1-2 MPa, or under the reaction pressure of normal pressure-4 MPa, preferably normal pressure-2 MPa;
(f) The tetrahydrofurfuryl alcohol is reacted in the presence of no solvent or a solvent, wherein the solvent is one or more selected from tetrahydrofuran, acetonitrile and 1, 4-dioxane, preferably tetrahydrofuran or acetonitrile; and
(g) The method is carried out for 0.05h -1 ～5h -1 Preferably 0.03h -1 ～3h -1 Is carried out at a reaction space velocity.
10. The method of claim 4, comprising at least one of the following features (a) and (b):
(a) The method further comprises activating the catalyst prior to the reacting: heating the catalyst to an activation temperature of 300-500 ℃ and maintaining for 1-6 hours, preferably, the activation temperature is 300-400 ℃; and
(b) The method further comprises post-reaction treatment: and (3) rectifying the reaction product after condensation and gas-liquid separation.
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| CN202311480349.5A CN117548101A (en) | 2023-11-08 | 2023-11-08 | Catalyst for preparing 3, 4-dihydro-2H-pyran and method for preparing 3, 4-dihydro-2H-pyran |
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| CN202311480349.5A CN117548101A (en) | 2023-11-08 | 2023-11-08 | Catalyst for preparing 3, 4-dihydro-2H-pyran and method for preparing 3, 4-dihydro-2H-pyran |
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