CN113019453B - Catalyst for synthesizing diphenyl carbonate, preparation method and application - Google Patents
Catalyst for synthesizing diphenyl carbonate, preparation method and application Download PDFInfo
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- CN113019453B CN113019453B CN201911343350.7A CN201911343350A CN113019453B CN 113019453 B CN113019453 B CN 113019453B CN 201911343350 A CN201911343350 A CN 201911343350A CN 113019453 B CN113019453 B CN 113019453B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 57
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010936 titanium Substances 0.000 claims abstract description 56
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229940049953 phenylacetate Drugs 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims abstract description 25
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 238000005809 transesterification reaction Methods 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 229960002885 histidine Drugs 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 5
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 claims description 5
- 229960003767 alanine Drugs 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims 1
- 229960002449 glycine Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 47
- 150000002148 esters Chemical group 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 2
- ADVORQMAWLEPOI-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxotitanium Chemical compound [Ti]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O ADVORQMAWLEPOI-XHTSQIMGSA-N 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 2
- 229910003872 O—Si Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- BVPWJMCABCPUQY-UHFFFAOYSA-N 4-amino-5-chloro-2-methoxy-N-[1-(phenylmethyl)-4-piperidinyl]benzamide Chemical compound COC1=CC(N)=C(Cl)C=C1C(=O)NC1CCN(CC=2C=CC=CC=2)CC1 BVPWJMCABCPUQY-UHFFFAOYSA-N 0.000 description 1
- HUVAFPHSQFFCID-UHFFFAOYSA-N 5-chlorocyclopenta-1,3-diene titanium(2+) Chemical compound [Ti++].Cl[c-]1cccc1.Cl[c-]1cccc1 HUVAFPHSQFFCID-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 125000003412 L-alanyl group Chemical group [H]N([H])[C@@](C([H])([H])[H])(C(=O)[*])[H] 0.000 description 1
- 125000002066 L-histidyl group Chemical group [H]N1C([H])=NC(C([H])([H])[C@](C(=O)[*])([H])N([H])[H])=C1[H] 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229940109850 royal jelly Drugs 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- -1 titanates Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
-
- B01J35/61—
-
- B01J35/69—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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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
- Y02P20/10—Process efficiency
Abstract
The invention discloses a catalyst for synthesizing diphenyl carbonate, a preparation method and application thereof. The catalyst comprises: the porous carbon carrier is doped with hierarchical porous nitrogen and a titanium active component loaded on the porous carbon carrier; the titanium content is 2-10% by mass of the carrier as 100%. The preparation method comprises the following steps: (1) Preparing a microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier; (2) Adding the complex of titanium into a solvent, and carrying out ultrasonic treatment to completely dissolve the complex of titanium; (3) Adding the microporous and mesoporous composite hierarchical-pore nitrogen-doped porous carbon carrier obtained in the step (1) into the solution obtained in the step (2), and performing ultrasonic treatment; and (4) filtering, washing and drying. The catalyst of the invention has good activity for the ester exchange reaction of dimethyl carbonate and phenyl acetate, the total yield of diphenyl carbonate and methyl phenyl carbonate can reach more than 50 percent, and the ester exchange selectivity can reach more than 90 percent.
Description
Technical Field
The invention relates to the technical field of diphenyl carbonate synthesis, and further relates to a catalyst for synthesizing diphenyl carbonate, a preparation method and application thereof.
Background
Diphenyl carbonate is a chemical intermediate for synthesizing organic chemical products and high molecular materials, wherein the most important purpose is to synthesize Polycarbonate (PC) by a melt transesterification method. At present, the diphenyl carbonate is synthesized mainly by a phosgene method, a phenol oxidative carbonylation method and an ester exchange method. Among them, the transesterification method is the diphenyl carbonate synthesis method with the most industrial application prospect. The traditional technological route for synthesizing DPC by ester exchange method is that phenol and methyl carbonate are used as raw materials and are subjected to reaction and rectification in a Lewis acid catalytic system to prepare DPC products. The equilibrium constant of the reaction is low, and the by-product methanol and excessive dimethyl carbonate generate azeotrope and are difficult to separate. The diphenyl carbonate and phenyl acetate have large equilibrium constant of ester exchange reaction and no azeotrope is generated.
At present, the diphenyl carbonate synthesized by the ester exchange of dimethyl carbonate and phenyl acetate is mostly a homogeneous catalyst, and mainly comprises organic titanium compounds such as titanates, cyclopentadienyl titanium and the like. Caochen et al [ catalytic clast, 2009, 30:65-68] finds that in various organic titanium catalysts, the titanium oxide acetylacetonate has the highest catalytic activity for catalyzing the ester exchange reaction of dimethyl carbonate and phenyl acetate, the reaction time is 8 hours, and the conversion rate of the phenyl acetate is 74 percent; shenrongchun [ petrochemical, 2002, 31: 897-900, reported that the conversion of dimethyl carbonate was 74.9% after 4h of reaction in an autogenous pressure reactor using tetrabutyl titanate as catalyst. However, homogeneous catalysts are difficult to separate from the products and cannot be reused, and titanate compounds are very easy to hydrolyze and deposit sticky precipitates on the inner wall of a reactor. Therefore, it is imperative to develop a heterogeneous titanium catalyst which is highly efficient and has excellent reusability.
However, most of the titanium catalysts commonly used in the reaction adopt SiO2, carbon nanotubes and the like as inert carriers and amorphous TiO 2 As an active component, the catalyst has large using amount, and the active component is easy to dissolve out in the reaction process, so the reusability of the catalyst is poor. Royal jelly et al [ catalytic science, 2009, 30: 853-855]Dissolving tetrabutyl titanate in ethanol solution, and soaking SiO with the solution 2 The carrier is used for obtaining a catalyst precursor, the precursor is roasted at high temperature to obtain the catalyst, and TiO is prepared 2 /SiO 2 A catalyst. After 4 times of catalyst reuse, the DMC conversion was only 35.2% and the transesterification selectivity was only 43.1%. Due to TiO 2 With SiO 2 The Ti-O-Si bond is formed between the two, and the Ti-O-Si bond is unstable and easy to break in the reaction process, so that the catalyst is inactivated.
Disclosure of Invention
The invention provides a catalyst for synthesizing diphenyl carbonate, a preparation method and application, aiming at solving the problems of large dosage and poor reusability of a titanium heterogeneous catalyst in the prior art. Has the characteristics of small catalyst dosage and good reusability.
One of the objects of the present invention is to provide a catalyst for synthesizing diphenyl carbonate.
The method comprises the following steps:
the preparation method comprises the following steps of (1) doping a hierarchical pore nitrogen-doped porous carbon carrier and a titanium active component loaded on the hierarchical pore nitrogen-doped porous carbon carrier;
the titanium content is 2-10%, preferably 3-7% by weight of the carrier as 100%;
the titanium active component is a four-coordinate titanium active component.
The second purpose of the invention is to provide a preparation method of the diphenyl carbonate synthesis catalyst.
The method comprises the following steps:
the catalyst is prepared by taking a titanium complex as a precursor to prepare a four-coordination titanium active component and grafting the four-coordination titanium active component on a microporous and mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier.
The method of the invention comprises the following steps:
(1) Mixing zinc nitrate, a template agent 1 and a template agent 2 in deionized water to obtain a solution A, and mixing 2-methylimidazole and organic amine in deionized water to obtain a solution B; uniformly mixing the solution A and the solution B, and stirring at room temperature; centrifuging, washing and drying the reacted suspension to obtain a microporous-mesoporous composite hierarchical pore precursor, and adding N 2 Roasting in the atmosphere, and treating with inorganic acid to remove metals to obtain a mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier;
(2) Adding the complex of titanium into a solvent, and carrying out ultrasonic treatment to completely dissolve the complex of titanium;
(3) Adding the microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier obtained in the step (1) into the solution obtained in the step (2), and performing ultrasonic treatment;
(4) Filtering, washing and drying.
Among them, it is preferable that,
the preparation method comprises the following steps of (1),
the template agent 1 is one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, tetrapropyl ammonium hydroxide and tetrapropyl ammonium bromide;
the template agent 2 is one of L-histidine, L-alanine and glycine;
the organic amine is one of dopamine, di-n-propylamine, triethylamine and 1,6 hexamethylene diamine;
the inorganic acid is one or a combination of hydrochloric acid, sulfuric acid and hydrofluoric acid.
The molar ratio of the template 1 to the template 2 is 1-1;
the molar ratio of the zinc nitrate to the template 1 is 1.5;
zn in solution A 2+ The concentration range of (A) is 0.02-0.06mol/L;
the concentration range of the 2-methylimidazole in the solution B is 0.1-0.5mol/L;
mixing the solution A and the solution B, and stirring for 1-24h at room temperature;
the roasting temperature is 600-900 ℃, and the roasting time is 2-8h.
The concentration of the inorganic acid solution is 0.1-1mol/L, and the acid treatment time is 24-48h.
A step (2) of carrying out a treatment,
the complex of titanium is one or a combination of titanium tetrachloride, acetylacetonato titanium, dichlorotitanocene, tetrabutyl titanate and tetraisopropyl titanate;
the solvent is at least one of tetrahydrofuran, N-dimethylformamide, acetonitrile, methanol and acetone;
the mass ratio of the solvent to the titanium complex is 10-100.
A step (3) of,
the mass ratio of titanium in the titanium complex to the microporous and mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier is 0.1-0.5, and the ultrasonic treatment time is 1-60min.
The invention also provides the application of the catalyst in the transesterification of dimethyl carbonate and phenyl acetate.
The key point of the invention is to realize in-situ pore expansion of the nitrogen-doped porous carbon carrier derived from ZIF-8 by adopting an organic matter double-template method to obtain the microporous and mesoporous composite hierarchical pore nitrogen-doped carbon carrier. The relative proportion of micropores and mesopores in the carrier, the nitrogen atom content and the existence form can be adjusted. The preparation method of the catalyst carrier effectively improves the mesoporous surface area of the ZIF-8 derived nitrogen-doped porous carbon and improves the mass transfer characteristic of the carrier. The preparation method comprises the steps of preparing a four-coordination titanium compound active component by taking a titanium complex as a precursor, and grafting the four-coordination titanium compound on a microporous mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier in an ultrasonic treatment mode. The dispersity of the four-coordinate titanium active component is improved by screening the titanium source and controlling the reaction process of the titanium source and the nitrogen-containing carrier. The stability of the titanium active component is improved by utilizing the interaction between the nitrogen species with lone pair electrons doped in the porous carbon material and titanium.
The invention has the following characteristics:
1. the catalyst prepared by the invention has high activity. The catalyst prepared by the invention has good activity for the ester exchange reaction of dimethyl carbonate and phenyl acetate, the total yield of diphenyl carbonate and methyl phenyl carbonate can reach more than 50%, and the ester exchange selectivity can reach more than 90%.
2. The catalyst prepared by the invention has good titanium compound active component dispersibility and high titanium atom utilization rate.
3. The catalyst prepared by the method has good reusability, can be reused for 6 times, and still maintains higher activity.
4. The carrier used in the invention is ZIF-8 derived microporous mesoporous composite hierarchical pore nitrogen doped porous carbon, and the stability of the titanium active center of the transesterification catalyst is improved by utilizing the interaction of N and Ti species in the carrier.
5. The catalyst prepared by the method is easy to recover and cannot corrode equipment and pollute the environment.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is only for illustrative purposes and is not intended to limit the scope of the present invention, as those skilled in the art will appreciate numerous insubstantial modifications and variations therefrom.
All materials are commercially available in the examples.
Example 1
0.75g Zn(NO 3 ) 2 ·6H 2 O,0.5g cetyltrimethylammonium bromide (CTAB), 0.84g L-histidine (L-His) was added to 50mL deionized water to dissolve completely to give solution A.2g Triethylamine (TEA) and 1.62g 2-methylimidazole were completely dissolved in 50mL deionized water to give solution B. Solution a was added to solution B and stirred at room temperature for 24h, and the mixture was filtered to give a white solid. The white solid was solvent extracted and the extraction was repeated 3 times to remove the templating agent repeatedly. The specific operation method of the solvent extraction comprises the following steps: the white solid was added to 60mL of ethanol and refluxed at boiling point for 2h in a total reflux apparatus. Filtering, washing and drying to obtain H-ZIF-8
And (3) placing 2g of H-ZIF-8 in a tubular furnace to be roasted in the nitrogen atmosphere at 800 ℃ for 2H to obtain the metal-containing HNC. And placing the mixture into 1mol/L hydrochloric acid solution, stirring for 24 hours, and filtering, washing and drying the mixture to obtain the microporous and mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier HNC.
Adding 1.67g of titanium acetylacetonate into 150g of methanol, carrying out ultrasonic treatment to completely dissolve the titanium acetylacetonate, adding 1g of HNC, carrying out ultrasonic treatment for 60min, filtering, washing and drying the mixture to obtain the catalyst, wherein the titanium content is 8.8 percent based on 100 percent of the mass of the carrier.
Example 2
The transesterification of dimethyl carbonate with phenyl acetate was carried out using the catalyst prepared in example 1.
In a three-necked flask equipped with a thermometer, a rectifying column and a dropping funnel having a constant pressure, 30g of phenyl acetate and 0.6g of the catalyst prepared in example 1 were charged.
When the temperature is heated to 180 ℃, dimethyl carbonate (DMC) is added dropwise, the total amount of the added DMC is 40g, the reaction lasts for 7h, and methyl acetate and DMC are continuously rectified by a rectifying column in the reaction process.
The light components and the bottoms obtained by the distillation of the reaction were analyzed by an Agilent Technologies 7820A gas chromatograph, and quantitative determination was carried out by the calibration normalization method, whereby the conversion of phenyl acetate was 63.97%, the yield of methyl phenyl carbonate was 30.51%, the yield of diphenyl carbonate was 27.34%, and the yield of phenol was 6.12%.
Example 3
The catalyst was prepared in the same manner as in example 1 except that 0.83g of titanyl acetylacetonate was used. The titanium content of the prepared catalyst is 4.5 percent based on 100 percent of the mass of the carrier. Using the obtained catalyst, transesterification of dimethyl carbonate with phenyl acetate was carried out under the same reaction conditions as in example 2. The conversion of PA was 56.42%, yield of DPC 29.34%, yield of MPC 21.07%, and yield of PhOH 6.01%.
Example 4
The procedure of preparation of the catalyst was the same as in example 1 except that the calcination temperature of H-ZIF-8 was 600 ℃ and the amount of titanyl acetylacetonate was 1.11g, and the catalyst obtained had a titanium content of 6.8% based on 100% by mass of the carrier. The transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the obtained catalyst under the same reaction conditions as in example 2. The conversion of PA was 76.24%, yield of DPC was 40.45%, yield of MPC was 29.39%, and yield of PhOH was 6.40%.
Example 5
The catalyst was prepared in the same manner as in example 4 except that L-histidine was replaced with L-alanine and the amount of L-alanine was 0.13g. The titanium content of the prepared catalyst is 7.0 percent based on the mass of the carrier as 100 percent. The transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the obtained catalyst under the same reaction conditions as in example 2. The conversion rate of PA was 65.48%, yield of DPC was 33.75%, yield of MPC was 26.03%, and yield of PhOH was 5.70%.
Example 6
The catalyst was prepared as in example 4 except that cetyltrimethylammonium bromide was replaced by tetrapropylammonium hydroxide and 0.27g of tetrapropylammonium hydroxide was used. A catalyst was prepared having a titanium content of 6.2% based on 100% by mass of the carrier, and the transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the catalyst prepared under the same reaction conditions as in example 2. The conversion of PA was 57.99%, yield of DPC was 29.54%, yield of MPC was 23.07%, and yield of PhOH was 5.38%.
Example 7
The catalyst was prepared as in example 4, but the solution A and solution B were mixed and stirred for 2 hours. The catalyst was prepared with a titanium content of 5.9% based on 100% by mass of the support. Using the obtained catalyst, transesterification of dimethyl carbonate and phenyl acetate was carried out under the same reaction conditions as in example 2. The PA conversion was 56.23%, the DPC yield was 28.59%, the MPC yield was 22.36%, and the PhOH yield was 5.28%.
Example 8
The procedure of preparation of the catalyst was the same as in example 4 except that the calcination time of H-ZIF-8 was 6 hours, and the catalyst was obtained with a titanium content of 5.3% based on 100% by mass of the carrier. The transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the obtained catalyst under the same reaction conditions as in example 2. The PA conversion was 68.82%, the DPC yield was 37.58%, the MPC yield was 25.77%, and the PhOH yield was 5.47%.
Example 9
The procedure for the preparation of the catalyst was the same as in example 4, using acetone as the solvent, to obtain a catalyst having a titanium content of 7.5% based on 100% by mass of the carrier. Using the obtained catalyst, transesterification of dimethyl carbonate and phenyl acetate was carried out under the same reaction conditions as in example 2. The conversion of PA was 73.51%, yield of DPC was 40.31%, yield of MPC was 26.72%, and yield of PhOH was 6.48%.
Example 10
The procedure of the catalyst preparation was the same as in example 4, the titanium source used was titanocene dichloride, and the catalyst was prepared with a titanium content of 6.6% based on 100% by mass of the support. The transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the obtained catalyst under the same reaction conditions as in example 2. The PA conversion was 69.19%, the DPC yield was 37.63%, the MPC yield was 26.29% and the PhOH yield was 5.27%.
Example 11
The preparation procedure of the catalyst was the same as in example 4, and the titanium source used was tetrabutyl titanate, 2g in amount, 20g in amount of methanol, and 10min in the ultrasonic treatment time. A catalyst was prepared having a titanium content of 14.5% by mass based on 100% by mass of the carrier, and the transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the catalyst prepared under the same reaction conditions as in example 2. The conversion of PA was 65.40%, yield of DPC was 33.92%, yield of MPC was 25.15%, and yield of PhOH was 6.33%.
Example 12
The catalyst was prepared as in example 4, except that HF was used instead of HCl, the solution concentration was 0.2mol/L, and the treatment time was 48 hours. A catalyst was prepared having a titanium content of 6.6% by mass based on 100% by mass of the carrier, and the transesterification reaction of dimethyl carbonate and phenyl acetate was carried out using the catalyst prepared under the same reaction conditions as in example 2. The PA conversion was 70.48%, the DPC yield was 39.05%, the MPC yield was 25.04%, and the PhOH yield was 6.39%.
Example 13
The catalyst was prepared as in example 4, except that Zn (NO) was present in solution A 3 ) 2 ·6H 2 O was added in an amount of 0.89g, 2-methylimidazole in an amount of 0.98g, and di-n-propyl was used in place of triethylamine in an amount of 2g. The catalyst was prepared with a titanium content of 6.2% based on 100% by mass of the support. The transesterification of dimethyl carbonate with phenyl acetate was carried out using the obtained catalyst under the same reaction conditions as in example 2. The conversion of PA was 61.80%, yield of DPC was 35.23%, yield of MPC was 20.63%, and yield of PhOH was 5.94%.
Example 14
The catalyst obtained by the reaction of example 4 was washed with dimethyl carbonate 3 times, dried at 120 ℃ and used for the transesterification of phenyl acetate with dimethyl carbonate in the next batch under the same reaction conditions as in example 2. The catalyst was recycled as described above and the reaction results after 1-6 cycles are shown in Table 1.
TABLE 1 evaluation of catalyst Recycling Properties
PA-phenyl acetate, MPC-methyl phenyl carbonate, DPC-diphenyl carbonate, phOH-phenol
Comparative example 1
The preparation of the catalyst was performed as in example 4, but ammonium molybdate was used as the precursor, and the catalyst support obtained after calcination in air atmosphere was MoO 3 The catalyst was used in the transesterification of phenyl acetate with dimethyl carbonate under the same reaction conditions as in example 2, and the catalyst was recycled in the same manner as described above, and the results of the reaction after 1 to 4 times of recycling are shown in Table 2.
TABLE 2 evaluation of catalyst Recycling Properties
PA-phenyl acetate, MPC-methyl phenyl carbonate, DPC-diphenyl carbonate, phOH-phenol
Comparative example 2
The procedure for the preparation of the catalyst was the same as in example 8, except that a commercially available TS-1 molecular sieve as a catalyst carrier was used to carry out the transesterification of dimethyl carbonate and phenyl acetate under the same reaction conditions as in example 2. The conversion of PA was 47.97%, yield of DPC 25.67%, yield of MPC 16.68%, and yield of PhOH 5.62%.
As can be seen from the data in tables 1 and 2, the total yield of diphenyl carbonate and methyl phenyl carbonate of the catalyst prepared by the method can reach more than 50%, the ester exchange selectivity can reach more than 90%, the catalyst is obviously superior to that of the comparative example, and the catalyst still maintains higher activity after being recycled for 6 times.
Claims (10)
1. A catalyst for synthesizing diphenyl carbonate, characterized in that said catalyst comprises:
the microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier comprises a microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier and a titanium active component loaded on the microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier;
the titanium content is 2-10% by taking the mass of the carrier as 100%;
the microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier is prepared by the following steps:
mixing zinc nitrate with template agent 1 and template agent 2 in deionized water to obtain solution A, and deionizing 2-methylimidazole and organic amineMixing in water to obtain solution B; uniformly mixing the solution A and the solution B, and stirring at room temperature; centrifuging, washing and drying the reacted suspension to obtain a microporous-mesoporous composite hierarchical pore precursor, and adding N 2 Roasting in the atmosphere, and treating with inorganic acid to remove metals to obtain a microporous and mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier;
the template 1 is one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, tetrapropyl ammonium hydroxide and tetrapropyl ammonium bromide;
the template agent 2 is one of L-histidine, L-alanine and glycine.
2. A diphenyl carbonate synthesis catalyst according to claim 1 wherein:
the titanium content is 3-7% by mass of the carrier as 100%.
3. A diphenyl carbonate synthesis catalyst according to claim 1 wherein:
the titanium active component is a four-coordinate titanium active component.
4. A method for preparing a catalyst for synthesizing diphenyl carbonate according to any one of claims 1 to 3, characterized by comprising:
(1) Mixing zinc nitrate, a template agent 1 and a template agent 2 in deionized water to obtain a solution A, and mixing 2-methylimidazole and organic amine in deionized water to obtain a solution B; uniformly mixing the solution A and the solution B, and stirring at room temperature; centrifuging, washing and drying the reacted suspension to obtain a microporous-mesoporous composite hierarchical pore precursor, and adding N 2 Roasting in the atmosphere, and treating with inorganic acid to remove metals to obtain a microporous and mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier;
the template agent 1 is one of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, tetrapropyl ammonium hydroxide and tetrapropyl ammonium bromide;
the template agent 2 is one of L-histidine, L-alanine and glycine;
(2) Adding a precursor of titanium into a solvent, and carrying out ultrasonic treatment to completely dissolve the precursor of titanium;
(3) Adding the microporous and mesoporous composite hierarchical pore nitrogen-doped porous carbon carrier obtained in the step (1) into the solution obtained in the step (2), and performing ultrasonic treatment;
(4) Filtering, washing and drying.
5. The method of claim 4, wherein:
the preparation method comprises the following steps of (1),
the organic amine is one of dopamine, di-n-propylamine, triethylamine and 1,6 hexamethylene diamine;
the inorganic acid is one or a combination of hydrochloric acid, sulfuric acid and hydrofluoric acid.
6. The method of claim 4, wherein:
step (1)
The molar ratio of the template 1 to the template 2 is 1-1;
the molar ratio of the zinc nitrate to the template 1 is 1.5;
zn in solution A 2+ The concentration range of (A) is 0.02-0.06mol/L;
the concentration range of the 2-methylimidazole in the solution B is 0.1-0.5mol/L.
7. The method of claim 4, wherein:
step (1) of carrying out a treatment,
mixing the solution A and the solution B, and stirring for 1-24h at room temperature;
the roasting temperature is 600-900 ℃, and the roasting time is 2-8h;
the concentration of the inorganic acid solution is 0.1-1mol/L, and the acid treatment time is 24-48h.
8. The method of claim 4, wherein:
a step (2) of removing the solvent,
the precursor of the titanium is one or a combination of titanium tetrachloride, acetylacetonato-titanium, titanocene dichloride, tetrabutyl titanate and tetraisopropyl titanate;
the solvent is at least one of tetrahydrofuran, N-dimethylformamide, acetonitrile, methanol and acetone;
the mass ratio of the solvent to the precursor of titanium is 10-100.
9. The method of claim 4, wherein:
and (3) the mass ratio of the titanium in the precursor of the titanium to the microporous and mesoporous composite hierarchical porous nitrogen-doped porous carbon carrier is 0.1-0.5, and the ultrasonic treatment time is 1-60min.
10. Use of a catalyst as claimed in any of claims 1 to 3 in an transesterification reaction between dimethyl carbonate and phenyl acetate.
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