CN110240577A - A kind of production method of N- crassitude - Google Patents
A kind of production method of N- crassitude Download PDFInfo
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- CN110240577A CN110240577A CN201910574091.2A CN201910574091A CN110240577A CN 110240577 A CN110240577 A CN 110240577A CN 201910574091 A CN201910574091 A CN 201910574091A CN 110240577 A CN110240577 A CN 110240577A
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- Prior art keywords
- crassitude
- catalyst
- hydrogen
- production method
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 129
- 239000001257 hydrogen Substances 0.000 claims abstract description 100
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 100
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000047 product Substances 0.000 claims abstract description 48
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 31
- 230000000694 effects Effects 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000008187 granular material Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 34
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 31
- 239000008103 glucose Substances 0.000 claims description 28
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 24
- 230000009467 reduction Effects 0.000 claims description 23
- 239000008246 gaseous mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052594 sapphire Inorganic materials 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 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 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 235000009754 Vitis X bourquina Nutrition 0.000 claims 1
- 235000012333 Vitis X labruscana Nutrition 0.000 claims 1
- 240000006365 Vitis vinifera Species 0.000 claims 1
- 235000014787 Vitis vinifera Nutrition 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims 1
- 239000003863 metallic catalyst Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 15
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 15
- 229940043237 diethanolamine Drugs 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- -1 heterocycle secondary amine Chemical class 0.000 description 7
- 150000003235 pyrrolidines Chemical class 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- LOTYADDQWWVBDJ-UHFFFAOYSA-N 2-methyl-2-nitropropane-1,3-diol Chemical compound OCC(C)(CO)[N+]([O-])=O LOTYADDQWWVBDJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007036 catalytic synthesis reaction Methods 0.000 description 2
- 238000006210 cyclodehydration reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- PFCBHFDNVFQUJI-UHFFFAOYSA-N 3-methylbut-2-en-1-amine Chemical compound CC(C)=CCN PFCBHFDNVFQUJI-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HVFLCNVBZFFHBT-ZKDACBOMSA-N cefepime Chemical compound S([C@@H]1[C@@H](C(N1C=1C([O-])=O)=O)NC(=O)\C(=N/OC)C=2N=C(N)SC=2)CC=1C[N+]1(C)CCCC1 HVFLCNVBZFFHBT-ZKDACBOMSA-N 0.000 description 1
- 229960002100 cefepime Drugs 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 208000010877 cognitive disease Diseases 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004904 shortening 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
-
- 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
- B01J23/84—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
-
- B01J35/617—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- 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
Abstract
The invention discloses a kind of production methods of N- crassitude, the following steps are included: using N-Methyl pyrrolidone as raw material, using N methyldiethanol amine as solvent, under the effect of the catalyst, N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen occur isomery and add hydrogen cyclization, further purification, obtains target product N- crassitude.Production method mild condition of the present invention, non-environmental-pollution, and also the processing capacity of catalyst is strong, conversion ratio >=99% of N-Methyl pyrrolidone, N methyldiethanol amine almost all participate in reaction, and by-product is few, the selectivity of N- crassitude may be up to 99.2%, be suitble to industrialized production.
Description
Technical field
The invention belongs to fine chemical product preparation fields, and in particular to a kind of production method of N- crassitude.
Background technique
N- crassitude is a kind of organic base for being widely used in medicine, chemical industry, anti-mainly for the preparation of wide spectrum
Raw element Cefepime and Tolmentin Sodium, can also be used as dye stabilizers, preservative etc..
N- crassitude (NMPD), molecular formula: C5H11N, molecular weight 85.15,80.8 DEG C of boiling point, relative density (water=
1): 0.8190 (25 DEG C), the N- crassitude newly distilled are colourless transparent liquid, are gathered in storage process vulnerable to the effect of light
Merging switchs to band yellow liquid, is for a long time brown, and NMPD is a kind of organic base, is heterocycle secondary amine, with general amine
Property has certain genotoxic potential to human body.N- crassitude structure formula are as follows:
The preparation method of existing N- crassitude is relatively more, wherein more representational mainly have: one, the U.S. is special
The N-Methyl pyrrolidone Hydrogenation method of sharp US4892959 report, this method is in copper-chromium or chromium-Al catalysts
Under, N-Methyl pyrrolidone and hydrogen synthesize N- crassitude under 150~300 DEG C, the condition of high voltage of 6.9~34.5MPa,
Wherein N-Methyl pyrrolidone conversion ratio is 85%, and selectivity is 85%.This method carries out at high temperature under high pressure, wants to equipment
Ask higher, risk is larger, so that this method industrialization difficulty increases.Two, " chemical intermediate ", in 2008,08 (19~21)
The pyrrolidines and methanol of introduction catalytic synthesis of N-methylpyrrolidine on H-13X molecular sieve, this method are the pyrrolidines at 300 DEG C:
When methanol=1:3, pyrrolidinomethyl obtains N- crassitude, and this method report document is relatively more, and yield is probably 83
~91% or so, it is relatively high that this method synthesizes N- crassitude yield, but is limited to raw material pyrrolidines higher cost, hardly
It is likely to be breached industrialized production, also the industrialization of this method is not reported so far.Three, " finely and specialty chemicals ",
2004,12 (10): the methylation reaction of pyrrolidines and formaldehyde in the presence of the formic acid reported in 24~25, this method be normal pressure,
80~90 DEG C, carry out under Catalyzed by Formic Acid；Thick N- methylpyrrole is obtained after hydrochloric acid acidification, distillation removal of impurities and alkali neutralization after reaction
Alkane, yield is 54~92%.The method expensive starting materials are not easy to obtain, and more formic acid, hydrochloric acid and hydrogen-oxygen are consumed in reaction process
Change sodium, virtually increases cost, while also resulting in biggish environmental pollution.Four, the Chinese invention of publication number CN1810787A is special
Nucleophilic substitution occurs under a certain pressure by 1,4- dichloroetane and methylamine disclosed in benefit application to be cyclized to obtain N- methyl pyrrole
Alkane is coughed up, this method is that liquid phase reactor, yield 85.5% occur under 50~200 DEG C, 0.4~4.0MPa pressure.The method by-product
Object is hydrochloric acid, and amount is not easily recycled greatly, to aggravate environmental pollution, simultaneous reactions post-processing needs in a large amount of sodium hydroxide
With increased costs.Five, United States Patent (USP) US5136053 is disclosed with cyclic ester and NH2R amination under alumino-silicate catalyst obtains
The pyrrolidines that nitrogen replaces, but reaction needs to carry out under a certain pressure, and ammonia is bigger in reaction, between 5~20, ammonia ratio
Increase not only increase production cost, while also shortening catalyst life.Six, The Journal of Organic
Chemistry, 1994,59 (14): studying 5~6 atom heterocycle compound synthesis in 3998~4000, Cr-ZSM-59 (30) is urged
Agent can be catalyzed tetrahydrofuran and synthesize N- crassitude with methylamine amination, but in the technical process, catalyst effect is not
The yield of height, target product only maintains 48% or less.Seven, " Qufu Normal University's journal ", 2009,35 (1): 79~81 intermediaries
Continued the reacting of solid superacid as catalyst tetrahydrofuran and synthetic methylamine N- crassitude, under optimum process condition, N- methyl
The yield of pyrrolidines is 81.5%, but the acidity of solid super-strong acid is too strong, causes carbon deposition quantity in reaction process to increase, catalyst is urged
Change performance and the service life is affected to some extent.Eight, Chinese patent application CN105753768A discloses a kind of containing single azepine cyclisation
The production method for closing object is reacted using the method for pyrrolidones plus hydrogen production pyrrolidine ring compound in continuous tubular reactor
Middle progress, 200~280 DEG C of temperature, 0.2~3.0MPa of pressure, liquid hourly space velocity (LHSV) is 0.03~0.5h-1, hydrogen and pyrrolidones
Molar ratio is 8~10, and 95% or more yield, reaction temperature is higher, and catalyst effect is general.
Summary of the invention
To overcome drawbacks described above, the purpose of the present invention is to provide a kind of production methods of N- crassitude.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Add hydrogen cyclization, further purifies, obtain target product N- crassitude；The catalyst is load type metal catalysis
Agent, the reaction temperature are 120~180 DEG C, and reaction pressure is 0.1~0.2MPa, and liquid hourly space velocity (LHSV) is 0.6~1.2h-1。
Preferably, the N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:0.5~1:4~
9。
Preferably, the specific surface area of the catalyst is 600~800m2/ g, compression strength >=150N/cm.
Preferably, the catalyst preparation method the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to 1~2mol/L (copper nitrate and zinc nitrate total concentration)
Mixed solution, then be added α-Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, then 400~
5~7h is roasted at 500 DEG C under nitrogen atmosphere, obtains crude product, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol
In, it is configured to the mixed solution of 1~2mol/L, α-Al is then added2O3, incipient impregnation is carried out, is filtered, it is dry, then exist
6~8h is roasted at 350~450 DEG C under nitrogen atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:20-30mL, the presoma that step (1) obtains then is added
Particle I and II are mixed, and it is 7~9 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, are obtained slurry, are then warming up at 80~90 DEG C and are aged
3~5h is filtered, washed, dries, and 6~8h is finally roasted at 400~600 DEG C, obtains catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Restore 36~72h, 160~230 DEG C of reduction temperature, until reactor outlet do not have vapor.
Preferably, the mass concentration of glucose solution described in step (1) is 40~60%.
Preferably, the granularity of granular precursor described in step (1) is 200~300 mesh.
Preferably, catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 20~35%, ZnO 15
~30%, α-Al2O38~15%, Bi2O33~6%, surplus is carrier.
Preferably, the carrier is one or more of silica, boron oxide, nickel oxide and titanium dioxide.
Preferably, drying condition described in step (1) or step (2) are as follows: 120~200 DEG C of dry 10~20h.
Preferably, nitrogen and hydrogen molar ratio are 1:2~4 in nitrogen-hydrogen gaseous mixture described in step (3).
A kind of production method of N- crassitude, reaction formula are as follows:
R1For methyl.
Isomery of the present invention adds hydrogen cyclization to carry out in shell and tube reactor, the shell and tube reactor include it is upper,
Lower two sections, it is respectively provided with more tubulations in two reactor, material is after the feed distributor of upper section reactor, and from upper section
The hydrogen that the bottom of reactor enters is sufficiently mixed contact, reacts in tubulation；Then the material warp come out from upper section reactor
It crosses liquid collecting distributer and enters lower section reactor, be sufficiently mixed and connect again with the hydrogen entered from the bottom of lower section reactor
Touching, reacts in tubulation；The material come out from lower section reactor enters upper section reactor again, walks the shell of upper section reactor tubulation
Journey is discharged by upper section reactor discharge port.
The purification step are as follows: reaction mass first passes around after reactor outlet outflow with ethylene glycol as cooling matchmaker
The heat exchanger of Jie is cooled to 25 DEG C and speeds to put tank, lightness-removing column and rectifying column purification, N- methyl hereinafter, then continuing through two gases
Pyrrolidines is by the top of the distillation column side take-off, and gained N- crassitude water content≤200ppm, water content is low, the rectifying
The reflux ratio of tower is 0.5~10, the number of plates 18~22.
In the production history of entire N- crassitude, because the characteristics of organic base itself, and be heterocycle secondary amine, tool
There is the property of general amine, person of ordinary skill in the field thinks, high temperature and pressure is the necessary condition of the production product, such as
U.S.'s US4892959 patent document of application in 1988, the US5136053 patent document of nineteen ninety application, 2008,08 (19~
21) " chemical intermediate ", 2009, " Qufu Normal University's journal ", 2009,35 (1): 79~81,2016 years
A document of CN105753768A etc. more than 60 is all that the condition of high temperature and pressure achieves relatively good effect.But because high temperature
The obvious technical problem of high pressure bring, safety increasingly become the problem of enterprise production and management is paid attention to.
With the development of the times, many research institutions and enterprise all break through original technique in research, from the nineties in last century
Start, various countries technical staff attempts to the production for carrying out N- crassitude under cryogenic, still, in the mistake of actual production
In journey or cost is odd high, other harm occurs, or even be unable to industrialization, or pollution is too serious, and catalyst is urged
It is bad or the service life is too short or recovery rate is low to change effect, such as The Journal of Organic Chemistry,
1994,59 (14): " finely and specialty chemicals " of 3998~4000, CN1810787A, 2004 year, 2004,12 (10): 24~
25 equal more than 20 a documents, and polluting overweight is not permitted in current Environmental Protection Situation.So all the time, technical field
Technical staff all think that this is one group of contradiction that cannot be reconciled, even one cares for the multiple-choice question or hold that this necessarily loses that
Born that pollution is high, at high cost, consequence that yield is low by the danger or go of high temperature and pressure, the two always has faulty place, on
Stating is to be divided to two classifications greatly, in the case where segmenting in fact, can study and obtain relatively sharp argument and more targeted right
Data are answered, as without Lu Kehang.According in applicant company generally acknowledge the big coffee expert introduction of industry, now it is both domestic and external very much
Relevant large enterprises, inventor Hitoshi Sugiyama, the Tomoyuki Mori including the more well-known field in the U.S.,
Donald H.Champion, John F.Knifton, Wei-Yang Su have abandoned the research of this respect, it is believed that in this way
Research be not to be worth and effect.
The beginning of the nineties in last century starts to propose sustainable development till now in fact, in nearly 30 years or so time, facing to more
Carry out the pressure of severeer Environmental Protection Situation and safety in production, does not also occur which company or which research institution always
Record or the report of the normal industrialization of N- crassitude are realized under low-temperature atmosphere-pressure about the product.Present invention applicant from
Begin one's study N- crassitude for 2006, and under the urgent need of many years market, research team is by prolonged research
Experiment repeatedly is compared, and realizes the production work that the N- crassitude of high recovery rate is produced under mild environment finally
Skill, specifically, technical solution of the present invention also realize following technology effect on the basis of effectively solving industry cognitive disorder
Fruit:
Positive beneficial effect of the invention:
1. the addition of Cu, Zn element in catalyst of the present invention can make catalyst form two peak structure, effectively inhibit
The quantity of fine pore avoids liquefaction condensation of the reaction mass in fine pore；The addition of Bi element effectively inhibits
Carbon distribution；Al element increases catalyst activity position；Carrier increases the contact area of catalyst and reaction mass, being capable of steady load
Each active constituent.The specific surface area of gained catalyst of the invention is 600~800m2/ g, compression strength >=150N/cm, specific surface
Product is big, and compression strength is high, improves catalyst backbone structure and cellular structure, the shrinking percentage in reduction process is low, effectively prevents
The leakage current of reaction mass, bias current in catalyst bed are stopped, and have enhanced the mechanical strength and thermal stability of catalyst, has reduced
To the corrosion of equipment and the pollution of environment, it is more suitable catalytic synthesis of N-methylpyrrolidine in industrialization shell and tube reactor,
It is effective to improve N- crassitude production efficiency.When each chemical composition content in the change catalyst of comparative example 1 and 2, urge
The specific surface area and compression strength of agent are decreased obviously, and directly affect N- crassitude production efficiency.
2. the present invention, under the catalytic action of catalyst, the N methyldiethanol amine as solvent participates in N- crassitude
The isomery of ketone adds hydrogen cyclization to obtain N- crassitude, process conditions are as follows: and 120~180 DEG C of reaction temperature, reaction pressure
0.1~0.2MPa, reaction pressure is close to normal pressure, 0.6~1.2h of liquid hourly space velocity (LHSV)-1, the application catalyst is in Solvents N-methyl diethyl
Directly facilitated under the auxiliary of alcohol the open loop of N-Methyl pyrrolidone, isomerization, C=O's plus hydrogen dehydration, then in catalyst and life
Under the action of Cheng Shui, energy barrier Δ E value is reduced, allows to the closed loop under lower temperature, pressure and generates N- crassitude,
Production method mild condition, non-environmental-pollution, raw material sources are extensive, cheap, and the processing capacity of catalyst is strong, are suitble to
Industrialized production.
3. N-Methyl pyrrolidone of the present invention is under the catalytic action of catalyst, in the participation of Solvents N-methyl diethanol amine
Under, generation open loop first, then the hydroxyl on N methyldiethanol amine and the N-Methyl pyrrolidone intermediate product after open loop are sent out
Raw isomery hydrogenation reaction, isomery add the product after hydrogen to occur that hydrogen cyclization is added to generate N- crassitude again with hydrogen, simultaneously
The intermediate product for sloughing the N methyldiethanol amine after hydroxyl can also occur recirculation reaction and generate N- crassitude,
Conversion ratio >=99% of N-Methyl pyrrolidone of the present invention, N methyldiethanol amine almost all participate in reaction, and by-product is few, N-
The selectivity of crassitude may be up to 99.2%, when comparative example 3 and 4 changes the dosage of N methyldiethanol amine, gained
The conversion ratio and selectivity of product are decreased obviously；In addition N methyldiethanol amine can be N- alkyldiethanolamine, and product is it
The N- alkyl pyrrolidine and N- crassitude mixture of corresponding alkyl pass through isolated two different products, the present invention
Process conditions have biggish versatility, are suitble to industrial diversification production, meet the requirement in market.
4. isomery of the present invention adds hydrogen cyclization to carry out in shell and tube reactor, shell and tube reactor includes upper and lower two
Section occurs open loop, isomery plus hydrogen, cyclodehydration reaction in upper section reactor and lower section reactor, carries out in upper section reactor
Open loop, isomery, hydrogenation reaction are more, and lower section reactor carries out cyclodehydration and reacts more, and entire reactor reaction is thorough；And
Only lower section reactor needs extraneous heating agent to provide heat to maintain to react required temperature, heat required for upper section reacts by
The heat for the material institute band that lower section reactor comes out provides, and the design of Dual heat exchange system avoids reaction temperature gradient problem,
It realizes that the heat of upper and lower two-stage reaction is complementary, reaches energy-efficient effect.
Specific embodiment
Below with reference to some specific embodiments, the present invention is further described.
Embodiment 1
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Add hydrogen cyclization, conversion ratio 99.2%, selectivity 99% further purifies, obtains target product N- crassitude, pure
Degree 99.5%, moisture 150ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:0.5:
4；The isomery adds hydrogen cyclization temperature to be 160 DEG C, reaction pressure 0.1MPa, liquid hourly space velocity (LHSV) 0.8h-1。
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 602m2/ g, pressure resistance
Spend 161N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 2mol/L, α-Al is then added2O3,
Incipient impregnation is carried out in glucose solution, is filtered, it is dry, 5h then is roasted under nitrogen atmosphere at 450 DEG C, so that grape
Sugar charcoal obtains crude product, and grinding obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, the mixed of 2mol/L is configured to
Solution is closed, α-Al is then added2O3, incipient impregnation is carried out, is filtered, it is dry, 7h then is roasted under nitrogen atmosphere at 450 DEG C,
Crude product is obtained, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:20mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 9 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 5h, mistake are aged under the conditions of being then warming up to 80 DEG C
Filter, washing, drying, finally roast 8h at 500 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 50h, 200 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 50%.
The granularity of granular precursor described in step (1) is 250 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 25%, ZnO 28%, α-Al2O3
12%, Bi2O33%, surplus is carrier.
The carrier is silica.
Drying condition described in step (1) or step (2) are as follows: 180 DEG C of dry 16h.
Nitrogen and hydrogen molar ratio are 1:3 in nitrogen described in step (3)-hydrogen gaseous mixture.
Embodiment 2
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 99.5%, selectivity 98.9% further purifies, obtains target product N- crassitude,
Purity 99.7%, moisture 173ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:
0.6:5；The isomery adds hydrogen cyclization temperature to be 150 DEG C, reaction pressure 0.11MPa, liquid hourly space velocity (LHSV) 1h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 619m2/ g, pressure resistance
Spend 155N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.2mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 400 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, is configured to
Then α-Al is added in the mixed solution of 1.2mol/L2O3, incipient impregnation is carried out, filtering is dry, then the nitrogen at 400 DEG C
8h is roasted under atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:25mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and uses sodium carbonate liquor to adjust pH value as 7, obtains slurry, 4h, mistake are aged under the conditions of being then warming up to 85 DEG C
Filter, washing, drying, finally roast 8h at 400 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to urging
Agent carries out reduction 45h, and 180 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 60%.
The granularity of granular precursor described in step (1) is 200 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 30%, ZnO 15%, α-Al2O3
8%, Bi2O36%, surplus is carrier.
The carrier is titanium dioxide.
Drying condition described in step (1) or step (2) are as follows: 120 DEG C of dry 20h.
Nitrogen and hydrogen molar ratio are 1:2 in nitrogen-hydrogen gaseous mixture described in step (3).
Embodiment 3
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, reaction mixture material uses gas chromatographic detection, conversion ratio 99%, and selectivity 98.6% further purifies,
Obtain target product N- crassitude, purity 99.6%, moisture 112ppm；The N-Methyl pyrrolidone, N- methyl
Diethanol amine, hydrogen molar ratio be 1:0.8:6；The isomery adds hydrogen cyclization temperature to be 130 DEG C, and reaction pressure is
0.1MPa, liquid hourly space velocity (LHSV) 0.6h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 660m2/ g, pressure resistance
Spend 163N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1mol/L, α-Al is then added2O3,
Incipient impregnation is carried out in glucose solution, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 500 DEG C, so that grape
Sugar charcoal obtains crude product, and grinding obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, the mixed of 1mol/L is configured to
Solution is closed, α-Al is then added2O3, incipient impregnation is carried out, is filtered, it is dry, then roasted under nitrogen atmosphere at 380 DEG C
6.5h obtains crude product, and grinding obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:30mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 8 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 4h, mistake are aged under the conditions of being then warming up to 90 DEG C
Filter, washing, drying, finally roast 7h at 500 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 52h, 200 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 50%.
The granularity of granular precursor described in step (1) is 300 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 30%, ZnO 20%, α-Al2O3
10%, Bi2O35%, surplus is carrier.
The carrier is silica and nickel oxide, and the two weight ratio is 1:1.
Drying condition described in step (1) or step (2) are as follows: 200 DEG C of dry 10h.
Nitrogen and hydrogen molar ratio are 1:3 in nitrogen-hydrogen gaseous mixture described in step (3).
Embodiment 4
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 99.3%, selectivity 99.2% further purifies, obtains target product N- crassitude,
Purity 99.7%, moisture 88ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:0.6:
5；The isomery adds hydrogen cyclization temperature to be 120 DEG C, reaction pressure 0.12MPa, liquid hourly space velocity (LHSV) 1h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 780m2/ g, pressure resistance
Spend 167N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.6mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 7h then is roasted under nitrogen atmosphere at 400 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, is configured to
Then α-Al is added in the mixed solution of 1.6mol/L2O3, incipient impregnation is carried out, filtering is dry, then the nitrogen at 350 DEG C
8h is roasted under atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:20mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 8 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 3h, mistake are aged under the conditions of being then warming up to 85 DEG C
Filter, washing, drying, finally roast 6h at 600 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to urging
Agent carries out reduction 64h, and 210 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 45%.
The granularity of granular precursor described in step (1) is 240 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 30%, ZnO 20%, α-Al2O3
12%, Bi2O34%, surplus is carrier.
The carrier is silica, nickel oxide and titanium dioxide, three's weight ratio 1:0.8:1.
Drying condition described in step (1) or step (2) are as follows: 150 DEG C of dry 20h.
Nitrogen and hydrogen molar ratio are 1:4 in nitrogen-hydrogen gaseous mixture described in step (3).
Embodiment 5
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 99.6%, selectivity 99.1% further purifies, obtains target product N- crassitude,
Purity 99.8%, moisture 96ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:0.8:
6；The isomery adds hydrogen cyclization temperature to be 130 DEG C, reaction pressure 0.1MPa, liquid hourly space velocity (LHSV) 1.2h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 794m2/ g, pressure resistance
Spend 168N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.5mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 500 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, is configured to
Then α-Al is added in the mixed solution of 1.5mol/L2O3, incipient impregnation is carried out, filtering is dry, then the nitrogen at 400 DEG C
6.5h is roasted under atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:25mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 8 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 5h, mistake are aged under the conditions of being then warming up to 85 DEG C
Filter, washing, drying, finally roast 8h at 500 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 48h, 200 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 50%.
The granularity of granular precursor described in step (1) is 300 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 25%, ZnO 25%, α-Al2O3
15%, Bi2O35%, surplus is carrier.
The carrier is silica and nickel oxide, and the two weight ratio is 1:0.9.
Drying condition described in step (1) or step (2) are as follows: 160 DEG C of dry 15h.
Nitrogen and hydrogen molar ratio are 1:3 in nitrogen-hydrogen gaseous mixture described in step (3).
Embodiment 6
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 99.4%, selectivity 98.3% further purifies, obtains target product N- crassitude,
Purity 99.8%, moisture 103ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:1:
9；The isomery adds hydrogen cyclization temperature to be 120 DEG C, reaction pressure 0.2MPa, liquid hourly space velocity (LHSV) 1h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 643m2/ g, pressure resistance
Spend 156N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.5mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 7h then is roasted under nitrogen atmosphere at 400 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, is configured to
Then α-Al is added in the mixed solution of 1.5mol/L2O3, incipient impregnation is carried out, filtering is dry, then the nitrogen at 400 DEG C
6h is roasted under atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:30mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 9 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 3h, mistake are aged under the conditions of being then warming up to 90 DEG C
Filter, washing, drying, finally roast 7h at 400 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 36h, 230 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 40%.
The granularity of granular precursor described in step (1) is 200 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 20%, ZnO 30%, α-Al2O3
10%, Bi2O36%, surplus is carrier.
The carrier is nickel oxide.
Drying condition described in step (1) or step (2) are as follows: 200 DEG C of dry 10h.
Nitrogen and hydrogen molar ratio are 1:2 in nitrogen-hydrogen gaseous mixture described in step (3).
Embodiment 7
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Add hydrogen cyclization, reaction mixture material uses gas chromatographic detection, conversion ratio 99.5%, and selectivity 98.8% further mentions
It is pure, obtain target product N- crassitude, purity 99.7%, moisture 129ppm；The N-Methyl pyrrolidone, N- first
Base diethanol amine, hydrogen molar ratio be 1:1:4；The isomery adds hydrogen cyclization temperature to be 180 DEG C, and reaction pressure is
0.16MPa, liquid hourly space velocity (LHSV) 1h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 708m2/ g, pressure resistance
Spend 166N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.8mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 5h then is roasted under nitrogen atmosphere at 500 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Copper nitrate, zinc nitrate, bismuth nitrate are dissolved in ethylene glycol
In, it is configured to the mixed solution of 1.8mol/L, α-Al is then added2O3, incipient impregnation is carried out, is filtered, it is dry, then 380
7.5h is roasted under nitrogen atmosphere at DEG C, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:20mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 7 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 5h, mistake are aged under the conditions of being then warming up to 80 DEG C
Filter, washing, drying, finally roast 6h at 500 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 72h, 160 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 50%.
The granularity of granular precursor described in step (1) is 300 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 25%, ZnO 25%, α-Al2O3
12%, Bi2O35%, surplus is carrier.
The carrier is boron oxide, nickel oxide and titanium dioxide, and three's weight ratio is 0.5:0.9:1.
Drying condition described in step (1) or step (2) are as follows: 160 DEG C of dry 12h.
Nitrogen and hydrogen molar ratio are 1:3 in nitrogen-hydrogen gaseous mixture described in step (3).
Embodiment 8
A kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Add hydrogen cyclization, reaction mixture material uses gas chromatographic detection, conversion ratio 99.2%, and selectivity 99.1% further mentions
It is pure, obtain target product N- crassitude, purity 99.8%, moisture 192ppm；The N-Methyl pyrrolidone, N- first
Base diethanol amine, hydrogen molar ratio be 1:0.8:8；The isomery adds hydrogen cyclization temperature to be 130 DEG C, and reaction pressure is
0.1MPa, liquid hourly space velocity (LHSV) 1h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 730m2/ g, pressure resistance
Spend 159N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 2mol/L, α-Al is then added2O3,
Incipient impregnation is carried out in glucose solution, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 500 DEG C, so that grape
Sugar charcoal obtains crude product, and grinding obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, the mixed of 2mol/L is configured to
Solution is closed, α-Al is then added2O3, incipient impregnation is carried out, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 390 DEG C,
Crude product is obtained, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:30mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 8 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 3h, mistake are aged under the conditions of being then warming up to 90 DEG C
Filter, washing, drying, finally roast 6h at 600 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 40h, 220 DEG C of reduction temperature, until reactor outlet does not have vapor.
The mass concentration of glucose solution described in step (1) is 50%.
The granularity of granular precursor described in step (1) is 200 mesh.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 35%, ZnO 20%, α-Al2O3
10%, Bi2O34%, surplus is carrier.
The carrier is silica and boron oxide, and the two weight ratio is 1:0.6.
Drying condition described in step (1) or step (2) are as follows: 200 DEG C of dry 10h.
Nitrogen and hydrogen molar ratio are 1:3 in nitrogen-hydrogen gaseous mixture described in step (3).
Comparative example 1
The production method of the present embodiment N- crassitude is substantially the same manner as Example 5, and the same thing is not repeated, some are not
With: a kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 96.3%, selectivity 92.7% further purifies, obtains target product N- crassitude,
Purity 99.5%, moisture 143ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:
0.8:6；The isomery adds hydrogen cyclization temperature to be 130 DEG C, reaction pressure 0.2MPa, liquid hourly space velocity (LHSV) 0.5h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 519m2/ g, pressure resistance
Spend 133N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.5mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 500 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, is configured to
Then α-Al is added in the mixed solution of 1.5mol/L2O3, incipient impregnation is carried out, filtering is dry, then the nitrogen at 400 DEG C
6.5h is roasted under atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:25mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 8 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 5h, mistake are aged under the conditions of being then warming up to 85 DEG C
Filter, washing, drying, finally roast 8h at 500 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 48h, 200 DEG C of reduction temperature, until reactor outlet does not have vapor.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 39%, ZnO 15%, α-Al2O3
20%, Bi2O35%, surplus is carrier.
Comparative example 2
The production method of the present embodiment N- crassitude is substantially the same manner as Example 5, and the same thing is not repeated, some are not
With: a kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 91.5%, selectivity 89.2% further purifies, obtains target product N- crassitude,
Purity 98.5%, moisture 171ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:
0.8:6；The isomery adds hydrogen cyclization temperature to be 130 DEG C, reaction pressure 0.2MPa, liquid hourly space velocity (LHSV) 0.4h-1；
The catalyst is load type metal catalyst, and the specific surface area of the catalyst is 502m2/ g, pressure resistance
Spend 142N/cm.
The preparation method of the catalyst the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1.5mol/L, α-is then added
Al2O3, incipient impregnation is carried out in glucose solution, is filtered, it is dry, 6h then is roasted under nitrogen atmosphere at 500 DEG C, is made
Glucose charing is obtained, crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, is configured to
Then α-Al is added in the mixed solution of 1.5mol/L2O3, incipient impregnation is carried out, filtering is dry, then the nitrogen at 400 DEG C
6.5h is roasted under atmosphere, obtains crude product, grinds, obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:25mL, the presoma that step (1) obtains then is added
Grain I and II, mixes, and it is 8 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, 5h, mistake are aged under the conditions of being then warming up to 85 DEG C
Filter, washing, drying, finally roast 8h at 500 DEG C, obtain catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst
Carry out reduction 48h, 200 DEG C of reduction temperature, until reactor outlet does not have vapor.
Catalyst granules finished weight percentage composition described in step (2) are as follows: CuO 16%, ZnO 32%, α-Al2O3
16%, Bi2O34%, surplus is carrier.
Comparative example 3
The production method of the present embodiment N- crassitude is substantially the same manner as Example 5, and the same thing is not repeated, some are not
With: a kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 83.2%, selectivity 90.4% further purifies, obtains target product N- crassitude,
Purity 99.1%, moisture 125ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:
0.4:6；The isomery adds hydrogen cyclization temperature to be 130 DEG C, reaction pressure 0.12MPa, liquid hourly space velocity (LHSV) 1.2h-1。
Comparative example 4
The production method of the present embodiment N- crassitude is substantially the same manner as Example 5, and the same thing is not repeated, some are not
With: a kind of production method of N- crassitude, comprising the following steps: using N-Methyl pyrrolidone as raw material, with N- first
Base diethanol amine is solvent, and under the effect of the catalyst, isomery occurs for N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Adding hydrogen cyclization, conversion ratio 94.6%, selectivity 88.7% further purifies, obtains target product N- crassitude,
Purity 98%, moisture 162ppm；The N-Methyl pyrrolidone, N methyldiethanol amine, hydrogen molar ratio be 1:1.1:
6；The isomery adds hydrogen cyclization temperature to be 130 DEG C, reaction pressure 0.1MPa, liquid hourly space velocity (LHSV) 1.2h-1。
Claims (10)
1. a kind of production method of N- crassitude, which comprises the following steps: with N-Methyl pyrrolidone be original
Material, using N methyldiethanol amine as solvent, under the effect of the catalyst, N-Methyl pyrrolidone, N methyldiethanol amine and hydrogen
Gas occurs isomery and adds hydrogen cyclization, further purifies, obtains target product N- crassitude；The catalyst is load
Type metallic catalyst, the reaction temperature be 120~180 DEG C, reaction pressure be 0.1~0.2MPa, liquid hourly space velocity (LHSV) be 0.6~
1.2h-1。
2. the production method of N- crassitude according to claim 1, which is characterized in that the N- crassitude
Ketone, N methyldiethanol amine, hydrogen molar ratio be 1:0.5~1:4~9.
3. the production method of N- crassitude according to claim 1, which is characterized in that the ratio table of the catalyst
Area is 600~800m2/ g, compression strength >=150N/cm.
4. the production method of N- crassitude according to claim 1, which is characterized in that the preparation of the catalyst
Method the following steps are included:
(1) in ethanol by copper nitrate, zinc nitrate dissolution, it is configured to the mixed solution of 1~2mol/L, α-Al is then added2O3,
Incipient impregnation is carried out in glucose solution, is filtered, it is dry, 5~7h is then roasted under nitrogen atmosphere at 400~500 DEG C,
Crude product is obtained, grinds, obtains granular precursor I；Bismuth nitrate is dissolved in ethylene glycol, the mixing for being configured to 1~2mol/L is molten
Then α-Al is added in liquid2O3, incipient impregnation is carried out, is filtered, it is dry, then 6 are roasted under nitrogen atmosphere at 350~450 DEG C
~8h obtains crude product, and grinding obtains granular precursor II；
(2) carrier is mixed with deionized water by amount ratio 1g:20-30mL, the granular precursor that step (1) obtains then is added
I and II is mixed, and it is 7~9 that sodium carbonate liquor, which is added dropwise, and adjusts pH value, obtains slurry, be then warming up at 80~90 DEG C ageing 3~
5h is filtered, washed, dries, and 6~8h is finally roasted at 400~600 DEG C, obtains catalyst granules finished product；
(3) the resulting catalyst granules finished product of step (2) is placed in reactor, using nitrogen-hydrogen gaseous mixture to catalyst reduction
36~72h, 160~230 DEG C of reduction temperature, until reactor outlet does not have vapor.
5. the production method of N- crassitude according to claim 4, which is characterized in that grape described in step (1)
The mass concentration of sugar juice is 40~60%.
6. the production method of N- crassitude according to claim 4, which is characterized in that forerunner described in step (1)
The granularity of body particle is 200~300 mesh.
7. the production method of N- crassitude according to claim 4, which is characterized in that catalysis described in step (2)
Agent finished granule weight percent composition are as follows: CuO 20~35%, ZnO 15~30%, α-Al2O38~15%, Bi2O33~
6%, surplus is carrier.
8. the production method of N- crassitude according to claim 4, which is characterized in that the carrier is titanium dioxide
One or more of silicon, boron oxide, nickel oxide and titanium dioxide.
9. the production method of N- crassitude according to claim 4, which is characterized in that step (1) or step (2) institute
The drying condition stated are as follows: 120~200 DEG C of dry 10~20h.
10. the production method of N- crassitude according to claim 4, which is characterized in that nitrogen-described in step (3)
Nitrogen and hydrogen molar ratio are 1:2~4 in hydrogen gaseous mixture.
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| CN115710237A (en) * | 2022-11-08 | 2023-02-24 | 河南中汇电子新材料有限公司 | Preparation process for synthesizing N-methylpyrrolidine by continuous catalytic hydrogenation of NMP |
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