CN117586097A - Method for rapidly preparing propargyl alcohol by using fluidized bed reactor - Google Patents
Method for rapidly preparing propargyl alcohol by using fluidized bed reactor Download PDFInfo
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- CN117586097A CN117586097A CN202311591234.3A CN202311591234A CN117586097A CN 117586097 A CN117586097 A CN 117586097A CN 202311591234 A CN202311591234 A CN 202311591234A CN 117586097 A CN117586097 A CN 117586097A
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- catalyst
- fluidized bed
- bed reactor
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- oxide
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- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 36
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005336 cracking Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 29
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 19
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 19
- 230000009471 action Effects 0.000 abstract description 3
- 238000004523 catalytic cracking Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000009718 spray deposition Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007818 Grignard reagent Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- -1 magnesium halide Grignard reagent Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910002708 Au–Cu Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NPKGQBIUYHHPOT-UHFFFAOYSA-N [Cu+2].[C-]#[C-] Chemical compound [Cu+2].[C-]#[C-] NPKGQBIUYHHPOT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000005905 alkynylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- B01J8/001—Controlling catalytic processes
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
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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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of fine chemical industry, and in particular relates to a method for rapidly preparing propargyl alcohol by using a fluidized bed reactor, wherein 1, 4-butynediol is used as a raw material to produce propargyl alcohol and formaldehyde through catalytic cracking reaction under the action of a catalyst by using the fluidized bed reactor, the product is separated and purified to obtain the propargyl alcohol, and an inactivated catalyst is recycled after being regenerated in a catalyst regenerator. The cracking reaction process is safe, the dangerous gas acetylene is not used, the single-pass conversion rate of the 1, 4-butynediol is more than or equal to 65%, and the main reaction selectivity in the product is more than or equal to 85%.
Description
Technical Field
The invention belongs to the field of fine chemical industry, and particularly relates to a method for rapidly preparing propargyl alcohol by using a fluidized bed reactor.
Background
The propargyl alcohol contains two flexible and changeable functional groups, namely alkynyl and hydroxyl, is an important chemical intermediate, is widely applied to medicine, electroplating and resin industries, and is mainly used for preparing electroplating nickel plating brightening agents, rust removers, slow release agents, corrosion inhibitors and the like. The propargyl alcohol has unique performance in inhibiting corrosion of acidic substances such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and the like to metals such as iron, copper, nickel and the like, and is widely used as an acidification corrosion inhibitor in oil and gas wells at high temperature and high pressure under high concentration hydrochloric acid abroad.
At present, the common preparation method of propynyl alcohol is an alkynal method, and the Reppe method process takes acetylene and formaldehyde as raw materials, and carries out catalytic synthesis under the action of a catalyst taking copper acetylide as an active ingredient. Under low pressure, because the solubility of acetylene gas in formaldehyde aqueous solution is low, the formaldehyde concentration on the surface of the catalyst is always far greater than that of acetylene, the reaction of one molecule of acetylene and two molecules of formaldehyde to generate 1, 4-butynediol is extremely easy to occur, the reaction is difficult to stay at the stage of reacting one molecule of acetylene with one molecule of formaldehyde to generate propargyl alcohol, and the yield of the propargyl alcohol is extremely low or even no. Therefore, the yield of the byproduct propynyl alcohol in the process of producing the 1, 4-butynyl diol by the traditional alkynal method is extremely low, and the propynyl alcohol is difficult to separate and purify and cannot be utilized.
In order to improve the yield of the propargyl alcohol, the method of reacting high-pressure acetylene with formaldehyde solution with extremely low concentration is adopted in the current production process in consideration of improving the reaction pressure, so that the ratio of acetylene to formaldehyde is improved, and the purpose of improving the selectivity of the propargyl alcohol is achieved. However, the content of propargyl alcohol in the solution after the reaction is very low, the highest yield of propargyl alcohol with increased acetylene partial pressure is only 37%, and the low yield of propargyl alcohol in the process seriously affects the economic benefit of enterprises. Meanwhile, high-pressure acetylene is dangerous, and the explosion accident is frequent, so that the healthy development of propynyl alcohol and downstream industries is seriously hindered.
GB1232257a discloses that acetylene good solvents tetrahydrofuran, dimethyltetrahydrofuran and the like which are mutually soluble with formaldehyde solution are introduced into a reaction system as reaction mediums, and the solubility of acetylene is improved to improve the yield of propynyl alcohol. The technical proposal disclosed in the patent document of US2712560A directly uses acetone as a reaction medium, and acetylene is dissolved in a liquid phase reaction liquid in the reaction process, thereby improving the selectivity and the yield of propargyl alcohol. Although the acetylene good solvent is beneficial to increasing the yield of propargyl alcohol to a certain extent, the purification difficulty of the product is increased, a large amount of reaction medium needs to be treated in the process of purifying the target product, the purification process is complex, the three wastes are seriously discharged, and the energy consumption is huge.
CN109772353a discloses a catalyst for preparing 1, 4-butynediol and co-producing propargyl alcohol and a preparation method thereof, although the catalyst has the advantages of high activity and high yield of the propargyl alcohol, the selectivity of the propargyl alcohol is only 20.5-28.7% from the published examples, and the yield of the target product is still lower.
CN 113751039A discloses an alkynylation catalyst for synthesizing propargyl alcohol, a preparation method and application thereof, and an anionic auxiliary agent and surface activity are introduced on the basis of a Cu-based catalyst to prepare Au-Cu with interfacial activity 2 C 2 The catalyst can improve the selectivity and the yield of propargyl alcohol to a certain extent, but the catalyst active component uses noble metal Au, and the catalyst cost is high.
CN103896737a provides a method for preparing propargyl alcohol using a micro-structured reactor, which uses grignard reagent, acetylene and aldehyde or ketone as raw materials, and the method adopts the micro-structured reactor to ensure intrinsic safety, but the grignard reagent has high cost.
CN 111747824a discloses a method for continuously and rapidly preparing propargyl alcohol by using a microreactor. Under the anhydrous and anaerobic condition, adding metal magnesium, iodine simple substance and solvent into a reactor, uniformly stirring, then dropwise adding halogenated hydrocarbon, continuously stirring, and reacting to obtain a hydrocarbon-based magnesium halide Grignard reagent; in a microreactor, carrying out Grignard exchange reaction under the continuous flow condition by taking the prepared alkyl magnesium halide and acetylene as raw materials to obtain the ethynyl magnesium halide; then taking ethynyl magnesium halide and formaldehyde as raw materials, and carrying out nucleophilic addition reaction under continuous flow conditions to prepare the propargyl alcohol. However, the Grignard reagent needs to be prepared under anhydrous and anaerobic conditions, so that the preparation method is complex in operation and high in preparation cost.
CN108503505A selects a synthetic catalyst of 1, 4-butynediol as a catalyst, and catalytically cracks the 1, 4-butynediol to prepare propargyl alcohol, but the method has the problems of low yield, slow reaction rate, and difficult separation of the catalyst by adding a reaction solvent and the catalyst, and the whole process needs to operate under the protection of acetylene gas, so that the production cost is high, and potential operation risks exist.
CN109317156a discloses a solid super-alkali catalyst and process conditions for preparing propargyl alcohol by cracking 1, 4-butynediol, which can improve the conversion rate of butynediol to 46.3%, and the selectivity of propargyl alcohol to 57.4%, but has the disadvantages of more byproducts, low feeding airspeed, quick catalyst deactivation, etc.
The existing preparation process of the propargyl alcohol has obvious defects, and whether a simpler and more convenient preparation method of the propargyl alcohol is provided becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for rapidly preparing propargyl alcohol by using a fluidized bed reactor, wherein 1, 4-butynediol is used as a raw material to produce propargyl alcohol and formaldehyde through catalytic cracking reaction under the action of a catalyst by using the fluidized bed reactor, the product is separated and purified to obtain the propargyl alcohol, and the deactivated catalyst is recycled after being regenerated in the catalyst regenerator. The cracking reaction process is safe, the dangerous gas acetylene is not used, the single-pass conversion rate of the 1, 4-butynediol is more than or equal to 65%, and the main reaction selectivity in the product is more than or equal to 85%.
The invention adopts the specific technical scheme that:
a method for rapidly preparing propargyl alcohol by using a fluidized bed reactor comprises the following specific process flows:
preparing 1, 4-butynediol into a solution with the mass fraction of 10% -55%, wherein the adopted solvent is one or more of water, ethanol, methanol and isopropanol;
the solvent is selected to prepare a solution, so that on one hand, 1, 4-butynediol has better fluidity at normal temperature; secondly, the partial pressure of the product is reduced in the reaction process; thirdly, the catalyst is favorable for inhibiting coking and side reactions.
The reaction solution is pressurized by a pump, the raw materials are heated to 120-360 ℃ by a heat exchanger, the materials are fully atomized and uniformly sprayed into a fluidized bed reactor for reaction, and the atomized raw materials are uniformly contacted with a high-temperature cracking catalyst and subjected to cracking reaction.
In the reaction process, the reaction temperature of the fluidized bed reactor is 180-700 ℃, the reaction pressure is 0.1-0.6Mpa, the mass ratio of the catalyst to the raw materials is 0.5-6.0:1, and the reaction time is 0.5s-30.0s;
preferably, the reaction temperature is 300-600 ℃, the reaction pressure is 0.1-0.4Mpa, the mass ratio of the catalyst to the raw materials is 1.0-6.0:1, and the reaction time is 1.5s-20.0s.
Separating the reacted material from the catalyst, separating and purifying the separated reacted material in a coarse separation section, and reactivating the separated catalyst. According to different fluidized bed forms, a separate gas-solid separator and a catalyst reactivating regenerator such as a lifting pipe type reactor and a descending pipe type reactor can be arranged; the gas-solid separator and the catalyst reactivating regenerator, such as a fixed fluidized bed reactor, may not be separately designed.
The catalyst comprises a matrix, active components and auxiliary agents, wherein the active components account for 8-18% of the catalyst in mass percent, the auxiliary agents account for 0.2-3% of the catalyst in mass percent, and the rest is the matrix.
The catalyst matrix is composed of one or more of alumina, silica, activated carbon, magnesia, calcium oxide and silicon-aluminum molecular sieve, preferably one or more of alumina, silica and silicon-aluminum molecular sieve; the active component consists of one or more of nickel oxide, molybdenum oxide, zinc oxide, copper oxide and cobalt oxide; the auxiliary agent consists of one or more of sodium oxide, potassium oxide, bismuth oxide, titanium oxide and zirconium oxide.
The catalyst can be prepared by mixing and pulping matrixes according to the material proportion, preparing matrixes through spray forming, drying and roasting processes, and mixing the matrixes with active components and auxiliary agents; or mixing and pulping the matrix, the active components and the auxiliary agent in proportion by adopting a one-pot method, and preparing the composite material through spray forming, drying and roasting; the inventors exemplify the following:
the catalyst 1 is prepared by the following steps:
(1) the preparation process of the carrier matrix comprises the following steps: weighing 5.2 parts of alumina dry gel, 1 part of hydrochloric acid and 60 parts of water according to parts by weight, uniformly pulping, adding 81.9 parts of silicon dioxide powder, and continuously and uniformly stirring. And (3) performing centrifugal spray forming on the mixed materials in LPG-5, and controlling the average particle size of the carrier matrix to be 55-75 mu m. Roasting the molded carrier in a muffle furnace at the roasting temperature of 350-600 ℃ for 2-12h.
(2) 9.2 parts of copper nitrate, 3.2 parts of cobalt nitrate and 0.5 part of bismuth nitrate are prepared into impregnating solution, 50-90 parts of water and the carrier matrix are uniformly and fully impregnated, then dried for 6-24 hours at 105-180 ℃, and baked for 2-12 hours at 350-580 ℃ to prepare the composite material.
The catalyst 2 is prepared by a one-pot method, and the specific process is as follows:
40 parts of alumina dry glue, 8 parts of hydrochloric acid and 60 parts of water are weighed, uniformly pulped, 55.5 parts of silicon dioxide powder is added, and after uniform stirring, 6.3 parts of copper nitrate, 2.9 parts of cobalt nitrate and 0.3 part of bismuth nitrate are added and fully and uniformly stirred. And (3) performing centrifugal spray forming on the mixed materials in LPG-5, and controlling the average particle size of the carrier matrix to be 55-75 mu m. Roasting the molded carrier in a muffle furnace, and roasting at 350-580 ℃ for 2-12h.
The catalyst can be recycled through a reviving process after being used, the catalyst regenerator adopted during reviving is one of a lifting pipe type regenerator, a dense-phase fluidized bed regenerator, a tank type fluidized bed regenerator and a fixed fluidized bed regenerator, the reviving temperature is 400-700 ℃, the pressure is 0.1-0.6Mpa, compressed air or oxygen is required to be added in the reviving process, fuel or heat taking measures can be also added for guaranteeing the reviving temperature, and the residual carbon of the regenerated catalyst is controlled to be less than 0.1wt% for guaranteeing the reaction effect.
Separating the product and the catalyst after the reaction in a gas-solid separator, and reactivating the catalyst after the separation in a catalyst regenerator, wherein the reactivating catalyst is recycled;
the separated product enters a product separation unit to carry out crude separation of the product, hydrocarbon oxygen substances except propynyl alcohol are used as fuel required by a system, and crude propynyl alcohol enters a rectifying tower to carry out refining separation.
The various devices used in the above reactions are all conventional devices which the inventors have recombined and defined the process parameters.
Compared with the prior art, the invention has the advantages that:
1. the reaction process does not use gas acetylene, so that the preparation method is safer;
2. the fluidized bed reactor is adopted, so that the continuous input and output of the solid catalyst are easy, and the problem of high catalyst deactivation rate is solved; the temperature inside the bed layer is uniform, and side reactions are easy to control;
3. the ratio of the catalyst to the reaction materials is increased, the mass ratio of the catalyst to the materials can reach 1.0-6.0:1, and the conversion rate of the raw materials is further increased, and the single-pass conversion rate of the 1, 4-butynediol is more than or equal to 65%;
4. the special catalyst combination is adopted, so that the selectivity of the target product is better, and the main reaction selectivity in the product is more than or equal to 85 percent.
Drawings
FIG. 1 is a flow chart of a process equipment for the rapid preparation of propargyl alcohol using a fluidized bed reactor in example 1;
FIG. 2 is a flow chart of a process equipment for the rapid preparation of propargyl alcohol using a fluidized bed reactor in example 3;
in the figure: 1 is a regeneration reactor; 2 is a cracking reactor; 3 is a gas-solid separator; 4 is a product separation tower; and 5 is a fixed fluidized bed.
Detailed Description
The foregoing is further described in detail by way of specific embodiments with reference to the accompanying drawings, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples. All the techniques realized based on the above description of the present invention are within the scope of the present invention, and the raw materials used in the following examples are all commercially available products, except for the specific descriptions, and the percentages are all weight percentages. The reactor adopts the existing common device.
Example 1
Catalyst 1 was prepared for experimental evaluation by preparing a support matrix and then impregnating the active components, and the composition of catalyst 1 is shown in table 1.
TABLE 1
The catalyst 1 is prepared by the following steps:
(1) the preparation process of the carrier matrix comprises the following steps: weighing 5.2 parts of alumina dry gel, 1 part of hydrochloric acid and 60 parts of water according to parts by weight, uniformly pulping, adding 81.9 parts of silicon dioxide powder, and continuously and uniformly stirring. And (3) performing centrifugal spray forming on the mixed materials in LPG-5, and controlling the average particle size of the carrier matrix to be 55-75 mu m. Roasting the molded carrier in a muffle furnace at the roasting temperature of 350-600 ℃ for 2-12h.
(2) 9.2 parts by weight of copper nitrate, 3.2 parts by weight of cobalt nitrate and 0.5 part by weight of bismuth nitrate are prepared into impregnating solution, 50-90 parts by weight of aqueous solvent is uniformly and fully impregnated with the carrier matrix, and then the impregnating solution is prepared by drying at 120 ℃ for 12 hours and roasting at 550 ℃ for 6 hours.
The evaluation was performed using the evaluation apparatus shown in fig. 1, and the reaction conditions were as follows:
1, 4-butynediol is prepared into 25% aqueous solution, raw materials are heated to 140-160 ℃, the raw materials are fully atomized and uniformly sprayed into a fluidized bed reactor through a raw material atomizer, the atomized raw materials are uniformly contacted with a high-temperature cracking catalyst and undergo a cracking reaction, the catalyst and the reaction raw materials flow forward and upward to react, the temperature of the catalyst at the inlet of the reactor is controlled to be 400-420 ℃, the temperature of the fed materials is controlled to be 140-160 ℃, the weight ratio of the catalyst to the materials is 5:1, the outlet pressure of the reactor is 0.30-0.35Mpa, and the average reaction time is 2.8s.
The reaction product and the spent catalyst enter a gas-solid separator for separation, and the operation pressure of the separator is 0.26-0.29Mpa, and the adiabatic operation is adopted. The separated catalyst to be regenerated enters a catalyst reactivator for reactivator, the operation temperature of the reactivator is 450-500 ℃, the operation pressure is 0.32-0.35Mpa, air and natural gas are supplemented in the reaction process, the oxygen content in the reactivator tail gas is controlled to be 1.5-2.8% (v/v), and the reactivated catalyst is recycled.
The separated product enters a product separation unit to be refined into propargyl alcohol, hydrocarbon oxygen substances except propargyl alcohol and butynediol are removed to be used as fuel required by a system, and the reaction result is shown in table 3.
Example 2
Catalyst 2 prepared using the one pot method was used for experimental evaluation and the catalyst composition is shown in table 2.
Table 2 experiment uses catalyst composition
The catalyst 2 is prepared by a one-pot method, and the specific process is as follows:
40 parts of alumina dry glue, 8 parts of hydrochloric acid and 60 parts of water are weighed, uniformly pulped, 55.5 parts of silicon dioxide powder is added, and after uniform stirring, 6.3 parts of copper nitrate, 2.9 parts of nickel nitrate and 0.3 part of bismuth nitrate are added and fully and uniformly stirred. And (3) performing centrifugal spray forming on the mixed materials in LPG-5, and controlling the average particle size of the carrier matrix to be 55-75 mu m. And roasting the molded carrier in a muffle furnace for 4 hours at 540 ℃ to prepare the carrier.
The evaluation was performed using the evaluation apparatus shown in fig. 1, and the reaction conditions were as follows:
preparing 35% solution of 1, 4-butynediol, wherein the solvent is water and ethanol, the mass ratio of the water to the ethanol is 1:5, heating the raw materials to 140-160 ℃, fully and uniformly atomizing the raw materials by a raw material atomizer, spraying the atomized raw materials into a fluidized bed reactor, uniformly contacting the atomized raw materials with a high-temperature cracking catalyst and carrying out cracking reaction, controlling the temperature of the catalyst at 450-470 ℃ at the inlet of the reactor, the temperature of the fed materials at 140-160 ℃, the feeding ratio of the catalyst to the materials at 4.7-4.9:1, the outlet pressure of the reactor at 0.22-0.24Mpa, and the average reaction time at 4.2s.
The reaction product and the spent catalyst enter a gas-solid separator for separation, and the operation pressure of the separator is 0.21-0.23Mpa, and the adiabatic operation is adopted.
The separated spent catalyst enters a catalyst reactivator for reactivator, the operation temperature of the reactivator is 450-500 ℃, the operation pressure is 0.28-0.32Mpa, air and natural gas are supplemented in the reaction process, the oxygen content in the reactivator tail gas is controlled to be 1.1-2.3% (v/v), and the reactivated catalyst is recycled. The separated product enters a product separation unit to be refined into propargyl alcohol, hydrocarbon oxygen substances except propargyl alcohol and butynediol are removed to be used as fuel required by a system, and the reaction result is shown in table 3.
Example 3
Catalyst 1 prepared in example 1 was used for experimental evaluation using an evaluation device as in fig. 2 under the following conditions:
the reaction procedure comprises the following steps: 1, 4-butynediol is prepared into 15% solution, a solvent is water, raw materials are heated to 140-160 ℃, the raw materials are fully atomized and uniformly sprayed into a fluidized bed reactor through a raw material atomizer, the atomized raw materials are uniformly contacted with a high-temperature cracking catalyst and subjected to cracking reaction, the reaction temperature of the reactor is controlled to be 320-350 ℃, the feeding ratio of the catalyst to the materials is 4.0-5.0:1, the outlet pressure of the reactor is 0.12-0.15Mpa, and the average reaction time is 19.5s. The reaction product and the reaction catalyst are separated at the top of the fixed fluidized bed reactor, and the separated product enters a product separation unit to be refined into propynyl alcohol, and the reaction result is shown in table 3.
And (3) a regeneration procedure: and (3) along with the reaction time, the catalyst activity is reduced, the reaction feeding is stopped, nitrogen or water vapor purging replacement is carried out, the process is switched to a regeneration process, the temperature in the reactor is increased to 450-520 ℃, air or oxygen is supplemented in the regeneration process, the content of dioxygen carbon in the regenerated tail gas is controlled to be lower than 0.1% (v/v), the catalyst is revived, and the process is carried out after the system cooling replacement, the reaction process is carried out.
Comparative example 1
Catalyst 1 was prepared for experimental evaluation using example 1, using a fixed bed reaction evaluation apparatus. The evaluation conditions were as follows:
the reaction procedure comprises the following steps: 1, 4-butynediol is prepared into 15% solution, the solvent is water, the raw materials are heated to 140-200 ℃, the materials are fully atomized and uniformly sprayed into a reactor through a raw material atomizer, the atomized raw materials are uniformly contacted with a high-temperature cracking catalyst and subjected to cracking reaction, the reaction temperature of the reactor is controlled to be 320-350 ℃, the catalyst is filled with 5g, the feeding amount is 10g/min, the average reaction time is 0.7s, and the outlet pressure of the reactor is normal pressure. The reaction products were analyzed and examined, and the results are shown in Table 3.
TABLE 3 Table 3
As can be seen from the experimental results of examples 1 and 2 in Table 3, the catalyst prepared by the two catalyst preparation methods has excellent performance, the single-pass conversion rate of the raw materials is more than or equal to 65%, the main reaction selectivity in the product is more than or equal to 85%, and the example 2 has higher conversion rate and main reaction selectivity, and is the best example from the comprehensive point of view. As can be seen from the experimental results of examples 1 and 3, example 3 has a higher conversion rate of the raw material, but the selectivity of the target product is poor, presumably due to the secondary reaction of the target product with a longer reaction time.
As can be seen from comparative example 1 and comparative example 1, comparative example 1 employs a fixed bed reactor, which has short reaction time, low catalyst to oil ratio, low conversion of raw materials, and low selectivity of main reaction.
It will be apparent to those skilled in the art that the present invention has been described in detail by way of illustration only, and it is not intended to be limited by the above-described embodiments, as long as various insubstantial modifications of the method concepts and aspects of the invention are employed or the inventive concepts and aspects of the invention are directly applied to other applications without modification, all within the scope of the invention.
Claims (9)
1. A method for rapidly preparing propargyl alcohol by using a fluidized bed reactor, which is characterized in that: the specific process flow is as follows:
1, 4-butynediol is prepared into a solution with the mass fraction of 10% -55%, the reaction solution is pressurized by a pump, the raw materials are heated to 120 ℃ -360 ℃ by a heat exchanger, the materials are fully atomized and uniformly sprayed into a fluidized bed reactor for reaction, and the atomized raw materials are uniformly contacted with a high-temperature cracking catalyst and subjected to cracking reaction.
2. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 1, wherein: when 1, 4-butynediol is prepared as a solution, the solvent used is one or more of water, ethanol, methanol, and isopropanol.
3. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 1, wherein: the fluidized bed reactor is one or more of a lifting pipe reactor, a descending pipe reactor and a fixed fluidized bed reactor.
4. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 1, wherein: the reaction temperature of the fluidized bed reactor is 180-700 ℃, the reaction pressure is 0.1-0.6Mpa, the mass ratio of the catalyst to the raw materials is 0.5-6.0:1, and the reaction time is 0.5s-30.0s.
5. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 4, wherein: the reaction temperature of the fluidized bed reactor is 300-600 ℃, the reaction pressure is 0.1-0.4Mpa, the mass ratio of the catalyst to the raw materials is 1.0-6.0:1, and the reaction time is 1.5s-20.0s.
6. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 1, wherein: the catalyst consists of a matrix, active components and auxiliary agents, wherein the active components account for 8-18% of the catalyst by mass, the auxiliary agents account for 0.2-3% of the catalyst by mass, and the rest is the matrix.
7. The method according to claim 6, wherein: the catalyst matrix is composed of one or more of aluminum oxide, silicon oxide, active carbon, magnesium oxide, calcium oxide and silicon-aluminum molecular sieve, preferably one or more of aluminum oxide, silicon oxide and silicon-aluminum molecular sieve; the active component consists of one or more of nickel oxide, molybdenum oxide, zinc oxide, copper oxide and cobalt oxide; the auxiliary agent consists of one or more of sodium oxide, potassium oxide, bismuth oxide, titanium oxide and zirconium oxide.
8. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 1, wherein: separating the product and the catalyst after the reaction in a gas-solid separator, and reactivating the catalyst after the separation in a catalyst regenerator, wherein the reactivating catalyst is recycled;
the separated product enters a product separation unit to carry out crude separation of the product, hydrocarbon oxygen substances except propynyl alcohol are used as fuel required by a system, and crude propynyl alcohol enters a rectifying tower to carry out refining separation.
9. The method for rapidly preparing propargyl alcohol by using a fluidized bed reactor according to claim 1, wherein: the catalyst regenerator is one of a lifting pipe type regenerator, a dense-phase fluidized bed regenerator, a tank type fluidized bed regenerator and a fixed fluidized bed regenerator, the regeneration temperature is 400-700 ℃, the pressure is 0.1-0.6Mpa, compressed air or oxygen is required to be added in the regeneration process, and the residual carbon of the regenerated catalyst is controlled to be less than 0.1wt% in order to ensure the reaction effect.
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