CN111530472A - Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal panel - Google Patents
Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal panel Download PDFInfo
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- CN111530472A CN111530472A CN202010383330.9A CN202010383330A CN111530472A CN 111530472 A CN111530472 A CN 111530472A CN 202010383330 A CN202010383330 A CN 202010383330A CN 111530472 A CN111530472 A CN 111530472A
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- methylpyrrolidone
- temperature
- methyl pyrrolidone
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000005576 amination reaction Methods 0.000 title claims abstract description 66
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 59
- 239000010936 titanium Substances 0.000 title claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 238000000746 purification Methods 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 29
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 8
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 88
- 239000007788 liquid Substances 0.000 claims description 74
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 70
- 239000000945 filler Substances 0.000 claims description 62
- 239000000047 product Substances 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 49
- 229910021645 metal ion Inorganic materials 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- 238000012856 packing Methods 0.000 claims description 30
- 239000008139 complexing agent Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 19
- 239000012065 filter cake Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 7
- 238000010668 complexation reaction Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000012264 purified product Substances 0.000 claims description 5
- 239000011226 reinforced ceramic Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims 1
- 239000012045 crude solution Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 230000009286 beneficial effect Effects 0.000 description 13
- 239000012535 impurity Substances 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 238000000605 extraction Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 238000006210 cyclodehydration reaction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000010944 silver (metal) Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- ALZLTHLQMAFAPA-UHFFFAOYSA-N 3-Methylbutyrolactone Chemical compound CC1COC(=O)C1 ALZLTHLQMAFAPA-UHFFFAOYSA-N 0.000 description 1
- DLKOPXVSDZXMRM-UHFFFAOYSA-N 4-hydroxy-n-methylbutanamide Chemical compound CNC(=O)CCCO DLKOPXVSDZXMRM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- 240000002836 Ipomoea tricolor Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 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 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention discloses a titanium-based heterogeneous amination composite catalyst which comprises, by mass, 25-35% of Ti, 5-10% of Si, 2-10% of Co, 2-5% of Mn, 1-3% of Mo, 0.5-1.0% of Mg, 0.2-0.5% of Ag and the balance of a carrier; the catalyst is used for producing the N-methyl pyrrolidone for the liquid crystal panel, and comprises a reaction section, an intermittent purification section, a gas stripping purification section and a secondary rectification purification section, wherein the N-methyl pyrrolidone product reaches the standard of SEMI C8 without traditional fiber filtration and completely through innovation of reaction raw materials, a reaction process and a purification process and strict control of process parameters, and the quality of the product after pressure adsorption filtration can basically reach the standard of SEMI C12.
Description
Technical Field
The invention relates to the technical field of preparation of fine chemical products, in particular to a titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for a liquid crystal panel.
Background
N-methyl pyrrolidone is a fine chemical with excellent performance, has strong dissolving capacity for polar or non-polar substances due to the strong dissolving capacity, is called as a universal solvent, and is widely used in the industrial fields of coatings, printing ink, electronic chemicals, high-grade cleaning agents, power lithium ion batteries and the like as a solvent or an organic raw material.
The problems of N-methylpyrrolidone dehydration and metal ion removal are widely concerned, and for the problem of N-methylpyrrolidone dehydration, CN101696182A is that N-methylpyrrolidone to be purified is adsorbed by a molecular sieve column to remove water, the limitation of adsorption speed and adsorption capacity is limited, and the treatment capacity is only 0.4-0.8 liter/hour; CN200910064504.9 discloses a purification method of N-methyl pyrrolidone, wherein a water-blocking agent is added into raw material N-methyl pyrrolidone, and then the raw material N-methyl pyrrolidone enters a three-tower component rectification system for continuous vacuum distillation, so that the purity of the prepared product is more than 99.9%, and the water content is less than 0.01%.
For removing impurity metal ions in N-methylpyrrolidone, U.S. Pat. No. 4,982,370 removes the impurity metal ions by adding alkali metal or alkali metal salt, and then obtains high-purity NMP by continuous fractional rectification; CN110551051A discloses a method for removing metal ion content and granularity, which is a technology for preparing N-methylpyrrolidone by aminating monomethylamine and gamma-butyrolactone (GBL), wherein the most critical metal ion particle removal is in the control stage of filtration and demagnetization in the last step, but the requirements of updating or reactivating the fiber after the substitution filtration are not met; CN108299266A high-purity N-methyl pyrrolidone preparation method discloses a method for removing water in raw material liquid by using a permeating gas sliding membrane component, and then filtering metal ions or particles by strong acid styrene cation exchange resin or weak acid acrylic cation exchange resin; in the production method of CN102399179B ultrapure N-methyl pyrrolidone, industrial grade N-methyl pyrrolidone is used as a raw material, the raw material is pretreated, adsorbed and dehydrated by a 4A molecular sieve, membrane filtration is respectively carried out twice through a beta-cyclodextrin composite membrane and a 18-crown-6-composite membrane, the filtrate is subjected to reduced pressure rectification, the collected fraction is condensed, and then, tertiary membrane filtration is carried out through a microporous membrane, so that a target product is obtained; the disclosures of CN102190611 and CN102001986A show that resin treatment and filtration are performed, but the resin needs regeneration and material replacement, so that industrial sewage treatment and material waste are large, the metal ion content in the product is trace impurities, and the regeneration liquid such as hydrochloric acid used in the resin regeneration link needs high-purity reagents, so that it is difficult to ensure the metal impurity content, which indirectly increases the production and environmental treatment cost, and is not suitable for industrial production and purification. However, in general, the above methods have the disadvantages of complex operation process, difficult operation control, high energy consumption and low efficiency.
In addition, at present, the purity of domestic N-methyl pyrrolidone is between 99.5% and 99.9%, the content of metal particles is basically between 20 ppb and 30ppb, the national standard does not put forward the control requirement on the granularity of the N-methyl pyrrolidone, but domestic liquid crystal panel enterprises generally have the requirement on the content of metal ions in the N-methyl pyrrolidone of less than or equal to 5ppb, and the content of the particles is less than or equal to 5/ml (0.5 mu m).
Therefore, how to provide a method for producing N-methylpyrrolidone with simple operation process and high cleanliness is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a titanium-based heterogeneous amination composite catalyst and an application thereof in the production of N-methylpyrrolidone, which not only effectively control the content of metal ion impurities in the N-methylpyrrolidone product, but also greatly improve the product purity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the titanium-based heterogeneous amination composite catalyst comprises, by mass, 25-35% of Ti, 5-10% of Si, 2-10% of Co, 2-5% of Mn, 1-3% of Mo, 0.5-1.0% of Mg, 0.2-0.5% of Ag, and the balance of a carrier.
The titanium-based heterogeneous amination composite catalyst prepared by the invention has large specific surface area which can reach 600-800 m2The catalyst has the advantages of improving the framework structure and the pore structure of the catalyst, effectively preventing the leakage and the bias flow of reaction materials in a catalyst bed layer, enhancing the mechanical strength and the thermal stability of the catalyst, reducing the corrosion to equipment and the environmental pollution, being more suitable for industrialization, effectively improving the production efficiency of N-methyl pyrrolidone, having no metal ions in the catalyst separated out in the amine synthesis process, and effectively controlling the content of metal ions from the source when the catalyst is used for synthesizing the N-methyl pyrrolidone, along with high compressive strength which is more than 150N/cm, low shrinkage rate in the reduction process, and effectively preventing the leakage and the bias flow of the reaction materials in the catalyst bed layer.
The invention also discloses a preparation method of the titanium-based heterogeneous amination composite catalyst, which comprises the following steps:
(1) mixing Al (NO)3)3·9H2O、Mo(NO3)3·5H2O、Ni(NO3)2·6H2O、H2PtCl6·6H2Dissolving two or three of O in deionized water to prepare a solution of 0.5-1 mol/L, heating to 60-80 ℃, adding a carrier, fully and uniformly stirring, gradually dropwise adding 0.02-0.5 mol/L dilute nitric acid or dilute sulfuric acid in the stirring process, fully mixing, controlling the pH value to be 5-6, and gradually reducing to room temperature to obtain a mixed solution A;
(2) c is to be16H36O4Si (n-butyl silicate) is dissolved in 0.02mol/L dilute nitric acid or dilute sulfuric acid, the temperature is controlled to be 20-30 ℃, and C is dripped16H36O4Ti (tetrabutyl titanate), stirring and drippingAmmonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 10-15 h, transferring to a hydration heat reaction kettle, reacting for 24-36 h at 160-200 ℃, cooling to room temperature, performing suction filtration and washing, placing a filter cake in a drying oven at 120-160 ℃, drying for 10-20 h, then roasting for 1-2 h at 500-600 ℃, and grinding to obtain a catalyst carrier C;
(3) gradually heating the solution A to 55-70 ℃, refluxing for 30-90 min while stirring, cooling to room temperature, slowly dropwise adding a precipitator for neutralization until the pH value is 8-9, aging for 12-18 h at room temperature, performing suction filtration and washing, placing a filter cake in a drying oven at 120-160 ℃, drying for 5-8 h, then roasting for 3-4 h at 600-800 ℃, and grinding to obtain a catalyst carrier D;
(4) from Co (NO)3)2.6H2O、Mn(NO3)2·4H2O、Mg(NO3)2.6H2O、AgNO3Preparing an isovolumetric impregnation liquid B containing active components of Co, Mn, Mg and Ag, impregnating the catalyst carrier C and the catalyst carrier D in the impregnation liquid B, uniformly stirring, ultrasonically oscillating, standing for a period of time, filtering, placing a filter cake in a drying oven, drying for 5-8 h at 120-160 ℃, roasting for 3-4 h at 600-800 ℃, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Preferably, in the above preparation method of a titanium-based heterogeneous amination complex catalyst, step (1) is Al (NO)3)3·9H2O、Mo(NO3)3·5H2O、Ni(NO3)2·6H2O、H2PtCl6·6H2The mol ratio of Al, Mo, Ni and Pt in O is 1: 0.5-1.5: 0-0.8: 0 to 0.05.
The beneficial effects of the above technical scheme are: the activity of the catalyst is an important parameter for evaluating the commercialization of a process, and the active components and the composition ratio thereof are important control indexes in the preparation process of the catalyst. Taking the active component nickel in the catalyst as an example, the grain size of the metal rapidly grows and is sintered along with the temperature rise, and NiO and some elements in the carrier generate strong interaction to generate NiAl which is difficult to reduce2O4Spinel, etc., and a method for producing the same,the conversion activity is reduced by more than 30 percent, so the addition amount of the substances is strictly controlled in the preparation process of the catalyst, when the molar ratio of Ni to Al element is more than 0.8, the specific surface area reduction rate of the catalyst under the condition that the molar ratio of Ni to Al element is 0-0.8: 1 under the same condition is more than 20 percent, which shows that after the Ni content is increased, the crystal grain size of the metal is rapidly increased along with the temperature rise, the absolute value of sintering is increased, the influence on the catalyst activity is large, and the speed is high.
Preferably, in the above preparation method of the titanium-based heterogeneous amination composite catalyst, the precipitant in step (3) is ammonia water or NaHCO3、NaOH、K2CO3And KHCO3One or a mixture of several of them.
In the preparation process of the catalyst, the high relevance of the carbon deposition inactivation of the catalyst and the pore diameter of the catalyst is found, which is the reason of the serious capillary condensation phenomenon of an intermediate, Si, a pore-expanding agent and the like are introduced in the preparation of the catalyst, the average pore diameter of the catalyst is improved to 28nm, and the catalyst has a bimodal structure; it was also found that if the Si content in the catalyst exceeds 10%, the compressive strength of the catalyst decreases by about 10% per 1% increase, which is caused by the increase in Si content, the pore diameter becomes large, the toughness decreases, and the catalyst tends to collapse.
The heterogeneous titanium-based heterogeneous amination composite catalyst comprises the following components in percentage by weight of oxides, wherein magnesium oxide, manganese oxide, aluminum oxide and the like effectively enhance the strength of the catalyst. For example, the promoter Ag can inhibit the generation of by-products such as N-methylpiperidine, and the like, the addition amount of the promoter Ag is too small, the inhibition effect is not obvious, and the activity of the catalyst is reduced when the addition amount is too large.
It is further noted that: the optimization of each active component, the content of the components and the preparation process thereof in the invention enables the performance of the catalyst to be fully exerted in the process technology, under the condition of the required amount of the catalyst, the activity of the catalyst can be greatly improved, the service life of the catalyst can be longer, the process conditions such as pressure, temperature and the like of the invention are greatly optimized compared with the prior art (pure monomethylamine and GBL amination for preparing NMP), the operation process is safer, and the energy-saving effect is more obvious.
The invention also discloses a production method of the N-methylpyrrolidone for the liquid crystal panel, which comprises a reaction section, wherein the amination reaction step of the reaction section is as follows:
(1) respectively pumping monomethylamine and gamma-butyrolactone into a mixing and stirring tank by a feed pump, controlling the stirring and preheating temperature to be 30-40 ℃, and stirring for 5-10 min to obtain a mixed solution;
(2) pumping the mixed solution into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst according to claim 1 through a metering pump to carry out amination reaction to obtain N-methylpyrrolidone crude liquid with the pH value of 9-11;
(3) the N-methyl pyrrolidone crude liquid is discharged from a material outlet of the fixed bed reactor, and the content of gamma-butyrolactone in the N-methyl pyrrolidone crude liquid discharged from the material outlet is controlled to be less than or equal to 0.01 percent.
The traditional N-methyl pyrrolidone is prepared by reacting monomethylamine with gamma-butyrolactone in a reactor, firstly producing an intermediate product 4-hydroxy-N-methyl butyramide, and carrying out cyclodehydration on the intermediate product to produce the N-methyl pyrrolidone, wherein the cyclodehydration step is slow in reaction, is a control step of the reaction and needs to be carried out at high temperature and high pressure; the traditional theory that monomethylamine and gamma-butyrolactone react in a reactor to prepare N-methyl pyrrolidone is that water in a 40% monomethylamine aqueous solution can promote the cyclodehydration of the second step, the delta E value of the reaction is reduced, and the smooth progress of the cyclodehydration of the second step is promoted, even under favorable conditions, the reaction generally needs to control the reaction temperature to be 265-270 ℃ and the pressure to be 7-9 MPa.
The amination reaction of the invention can obtain N-methyl pyrrolidone at relatively low temperature and pressure under the action of the specially screened titanium-based heterogeneous amination composite catalyst, the GBL conversion rate is high and can reach 99.5%, the content of gamma-butyrolactone in a crude liquid discharged from a monitoring discharge port is less than or equal to 0.01%, and the primary reaction yield of the N-methyl pyrrolidone can reach 99%, which both embody the superior performance of the catalyst of the invention.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in step (1), the total content by mass of dimethylamine, trimethylamine and amine in the monomethylamine is not more than 0.05%, and the total content by mass of 3-methyl- γ -butyrolactone, 4-methyl- γ -butyrolactone and 5-methyl- γ -butyrolactone in the γ -butyrolactone is not more than 0.05%.
The beneficial effects of the above technical scheme are: the amination reaction of the invention optimizes the reaction process of preparing N-methyl pyrrolidone by traditional amination in the specially screened titanium-based heterogeneous amination composite catalyst, so that the pure monomethylamine is mainly adopted to be more beneficial to the control of metal ions, and the influence of softened water in monomethylamine aqueous solution on the metal ions is reduced, thereby meeting the application requirements of the N-methyl pyrrolidone in the liquid crystal panel industry or the semiconductor industry.
Specifically, even if a small amount of water is beneficial to the reaction of the subsequent dehydration and cyclization step, the catalyst activity is reduced when the water content at the outlet of the reactor is too high, and the water forms an azeotrope with low-boiling-point substances in the N-methylpyrrolidone, so that the water is difficult to remove cleanly in the subsequent refining process, and the metal ions and the granularity are relatively large.
Meanwhile, the process of preparing NMP by amination of monomethylamine and GBL is also the process of generating water, the generated water not only promotes the reaction with the titanium-based catalyst of the invention, but also forms an aqueous solution with monomethylamine (with lower boiling point) in the subsequent deaminizing and refining process, thus greatly avoiding the drift of monomethylamine with low boiling point; in addition, in order to match the characteristics of the synthesis process in the invention, the subsequent refining process, the design of the rectifying tower, the selection of the filler of the rectifying tower, the design of the stripping section and the rectifying section of the rectifying tower, the position of the feeding plate, the position of the discharging plate and the like are designed and developed aiming at the low water content in the N-methyl pyrrolidone crude product, so that better effect is obtained, and the produced N-methyl pyrrolidone product can meet the requirements of liquid crystal panel enterprises.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (1), the molar ratio of monomethylamine to γ -butyrolactone is 1.2 to 1.5: 1; the temperature of the amination reaction is 200 toThe reaction pressure is 5-6 MPa at 260 ℃, and the liquid hourly space velocity is 0.5-10 h-1。
The beneficial effects of the above technical scheme are: because the subsequent complex reaction needs to be carried out in an alkaline environment, the molar ratio of the monomethylamine to the gamma-butyrolactone is controlled to be 1.2-1.5: 1, and the amount of the monomethylamine exceeds a theoretical value required by the reaction; in addition, excessive monomethylamine is required to be separated in the intermittent purification process, but the monomethylamine has a low boiling point and is easy to float in the air to cause air pollution, so that the phenomenon of white smoke is caused, so that water and monomethylamine generated in the amination reaction process do not necessarily form an azeotropic point, but can be separated together in the purification process to form monomethylamine aqueous solution, the phenomenon of white smoke is avoided, the amine is well and thoroughly separated in the intermittent purification process, the pressure of subsequent purification is reduced, the quality of a final product is guaranteed, and meanwhile, the recovered monomethylamine aqueous solution can be continuously used as a raw material for producing low-quality N-methylpyrrolidone.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the mixed solution is preheated again before being injected into the fixed bed reactor, and the preheating temperature is 120 to 200 ℃.
The beneficial effects of the above technical scheme are: the process for preparing NMP by amination of GBL and monomethylamine mainly comprises two steps, wherein the first step of ring opening reaction is a violent exothermic process (delta H-104 KJ/mol), the activation energy is 12KJ/mol, the reaction belongs to a rapid reaction, the second step of dehydration reaction is an endothermic process (delta H-18 KJ/mol), the activation energy is 127KJ/mol, and the reaction belongs to a speed-determining step. Therefore, after the crude product discharged from the reactor exchanges heat with the raw material, the beneficial effects on the reaction process are mainly shown as follows: firstly, heat exchange is carried out between a crude product at 200-260 ℃ from a reactor and a raw material, so that waste of heat is avoided; secondly, the temperature gradient problem of the reaction is solved, the preheated mixture of GBL and monomethylamine reaches the temperature point for triggering the reaction in a short time, the waste of the load of the reactor is avoided, the phase change increases the processing capacity of the reactor, the flow speed of the raw materials is indirectly improved, the heat transfer coefficient is increased, the heat exchange area is enlarged, and the ring-opening reaction heat is timely removed, the dehydration stage is compressed to the bottom of the reactor as much as possible due to the selection of a high-efficiency catalyst and a raw material preheating technology, the dehydration reaction activity is reduced to 44KJ/mol under the action of the high-efficiency catalyst, the selectivity of NMP is improved to be more than or equal to 99.0 percent under the same condition, and the GBL content of the aminated crude product is reduced to be less than 100 ppm. The heat exchange system avoids the problem of reaction temperature gradient, improves the liquid hourly space velocity and increases the productivity of the reactor.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the reaction section further comprises a complexation reaction, and the steps are as follows:
(A) preparing a metal ion complexing agent solution with the concentration of 0.5-1.0 mol/L;
(B) continuously and uniformly adding the metal ion complexing agent solution into the N-methyl pyrrolidone crude liquid through a dosing device, controlling the reaction temperature to be 80-100 ℃, and reacting for 10-25 min;
(C) and (3) sending the N-methyl pyrrolidone crude liquid subjected to the complexation reaction to an intermittent purification section.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the reaction section further comprises a complexation reaction, and the steps are as follows:
(A) preparing a metal ion complexing agent solution with the concentration of 0.5-1.0 mol/L;
(B) adding the metal ion complexing agent solution into raw material gamma-butyrolactone before feeding in the amination reaction, and pumping the raw material gamma-butyrolactone into a mixing and stirring tank along with the gamma-butyrolactone through a feeding pump;
or continuously and uniformly adding the metal ion complexing agent solution into a mixing and stirring tank for amination reaction through a dosing device.
The beneficial effects of the above technical scheme are: the metal ion complexing agent (which is used in an alkaline environment) is added in the purification process, the complex can be finally retained to the tower kettle as a high-boiling point substance to be discharged, the content of metal ions in the NMP product can be effectively reduced through the treatment of the step, and the requirements of SEMI C8 can be met without using a demagnetizing device to filter the metal ions in the product in the final packaging process.
In addition, the metal ion complexing agent can be directly added into the N-methyl pyrrolidone crude liquid, or added before/during the amination reaction process, the effect of the two adding modes is the same, but the adding amount of the metal ion complexing agent in the former method is less.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the metal ion complexing agent solution in step (a) is a solution of any one or a mixture of several of hydroxyethylidene diphosphonic acid, hydroxyethylethylene diamine triacetic acid, triethylenetetramine hexaacetic acid and ethylene glycol bistetraacetic acid dissolved in ethanol.
The beneficial effects of the above technical scheme are: the complexing agent selected by the invention can ensure that almost all metal ions in the crude liquid are complexed and deposited at the lower part of the kettle in an alkaline environment, and other impurity ions (mainly light molecular weight) introduced by adding the complexing agent can be almost completely removed by the stripping tower.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the volume ratio of the mass of N-methylpyrrolidone to the metal ion complexing agent solution in step (a) is 10000 kg: (2-3) L.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the ratio of the mass of γ -butyrolactone to the volume of metal ion complexing agent solution in step (a) is 10000 kg: (2-3) L.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the method further comprises a subsequent purification of the crude N-methylpyrrolidone liquid, and the specific steps are as follows:
(S1) batch purification section
Conveying the N-methyl pyrrolidone crude liquid into an intermittent purification tower to remove monomethylamine, water and light components to obtain an N-methyl pyrrolidone primary product with the purity of more than 99.8%;
(S2) a stripping purification section
Feeding the N-methyl pyrrolidone primary product from the top of a stripping tower, uniformly dispersing the N-methyl pyrrolidone primary product by a distributor, and removing light components and partial particles in the N-methyl pyrrolidone primary product by convection and dispersion with nitrogen which enters from the bottom of the tower in a countercurrent manner on the surface of a filler, discharging the purified product from the bottom of a tower kettle, and entering the next procedure;
(S3) two-stage continuous rectification section
Purified N-methyl pyrrolidone discharged from the bottom of the stripping tower enters a first-stage rectifying tower to remove substances with a boiling point close to or forming an azeotropic point with the N-methyl pyrrolidone; one part of tower bottoms discharged from the first-stage rectifying tower is used as a raw material of the second-stage rectifying tower, and the other part of tower bottoms returns to a feed inlet of the first-stage rectifying tower;
and the raw material of the second-stage rectifying tower is bubble point feeding, part of the tower top extract is treated by a condenser and then flows back to the second-stage rectifying tower, part of the tower top extract is used as feeding material and is sent into the second-stage rectifying tower again, and the rest part of the tower top extract is used as a product to be extracted, so that the N-methyl pyrrolidone meeting the quality requirement is obtained.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the operation of the batch purification column in step (S1) mainly has three stages:
in the first stage, water and monomethylamine are mainly removed, the pressure is controlled to be-80 to-75 KPa, the top temperature is less than or equal to 60 ℃, the kettle temperature is less than or equal to 90 ℃, after most of water and monomethylamine are extracted, the pressure is gradually controlled to be-90 to-85 KPa, the top temperature is controlled to be less than or equal to 110 ℃, and the kettle temperature is controlled to be less than or equal to 120 ℃;
the second stage mainly removes middle fractions, and controls the pressure to be-95 to-85 KPa, the top temperature to be 115 to 120 ℃ and the kettle temperature to be 135 to 130 ℃;
and (3) the primary product is collected in the third stage, the pressure is controlled to be-95 to-85 KPa, the top temperature is controlled to be 120 to 125 ℃, and the kettle temperature is controlled to be 135 to 140 ℃.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the ratio of N-methylpyrrolidone primary product to nitrogen gas in step (S2) is 1 t: (5 to 9) m3And controlling the temperature of the nitrogen to be 80-120 ℃, and carrying out heat exchange on the nitrogen and the hot materials discharged after the reaction to reach the required temperature.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, ultrapure water in an amount of 0.05% by mass of the total amount of the raw materials is added to the stripping column before the N-methylpyrrolidone is fed to the stripping column.
The beneficial effects of the above technical scheme are: if the content of free amine after the treatment of the gas purification section is slightly high, a small amount of ultrapure water is added before the feeding of the stripping tower to prevent incomplete removal in the case of secondary continuous rectification, the adding amount of the ultrapure water is controlled to be 0.05 percent of the total mass of the feeding, the free amine can be almost completely removed, and the quality safety of the subsequent section is ensured, which is an accidental result of the invention.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S2), the filler is one of a light porcelain filler, a intalox saddle filler and a pall ring filler; further preference is given to pall ring packings;
if the light porcelain filler is selected, the specification requirements are as follows: the packing weight is 280-350 kg/m3The stacking porosity is more than or equal to 72 percent, the apparent porosity is more than or equal to 15 percent, and the total porosity is more than 85 percent; the ceramic filler has strong adhesion and adsorption capacity on impurities and good purification effect, and is preferably one of a ceramic multi-tooth ring, a ceramic grating ring and a ceramic flying saucer ring;
if the rectangular saddle filler is selected, the specification requirements are as follows: the specific surface area is more than or equal to 80m2/m3The void ratio is more than or equal to 0.7m3/m3The stacking weight is more than or equal to 480kg/m3The stacking number is more than or equal to 5500; the smooth arc side surface of the rectangular saddle filler is changed into a sawtooth or convex side surface, so that the contact gap between the fillers is increased in the packed bed layer, the flowing and the dispersion of gas and liquid in the filler layer are facilitated, and the rectangular saddle filler has the characteristics of pressure reduction and high mass transfer efficiency.
If the pall ring packing is selected, the specification requirements are as follows: the specific surface area is more than or equal to 120m2/m3, and the void ratio is more than or equal to 0.7m3/m 3. Taking the Bohr ring with the specification of 25X25 as an example, the specific surface area is about 350m2/m3A porosity of about 0.7m3/m3About 42000 piled up, and about the piled up weight600kg/m3The packing ring wall is provided with the holes, so that the distribution performance of gas and liquid is greatly improved, and particularly, the inner surface area of the ring can be fully utilized.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the pressure in the first-stage rectification tower is-98 to-96 KPa, the top temperature is 95 to 100 ℃, the intermediate temperature is 108 to 112 ℃, the kettle temperature is 116 to 121 ℃, and the feeding amount is less than or equal to 2500L/h.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the number of plates in the first-stage rectification column in the step (S3) is 45 to 50, and the feed inlet of purified N-methylpyrrolidone is at 15 th to 20 th plates.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the column packing of the first-stage rectifying column is filled in four sections, wherein the two sections of equal-height stripping section packing are grid plate packing or perforated corrugated packing, and the two sections of equal-height rectifying section packing are pulse packing; the height ratio of the stripping section to the rectifying section is 1:1.9 to 2.3, and more preferably 1: 2.1.
the beneficial effects of the above technical scheme are: the filler can form a porous rhombic channel with a locking neck, the longitudinal surface flow channel of the porous rhombic channel alternately shrinks and expands, a gas-liquid two-phase generates strong turbulence when passing through, the gas velocity is highest and violent at the necking position, so that the mass transfer is enhanced, the gas velocity is minimized at the expanding section, and the high-efficiency separation of the two phases is realized, so that the designed process flow, the selected filler material and the designed filler filling mode change the azeotropic point of a gamma-butyrolactone and N-methyl pyrrolidone azeotropic system, and the separation difficulty is reduced.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the first-stage rectification tower is provided with an internal condenser and an external condenser, a part of the overhead product treated by the external condenser is refluxed into the tower, and the other part of the overhead product is extracted as a light component, and the reflux ratio is controlled to be 1: 0.5-0.8, and more preferably 0.6.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the ratio of the bottoms discharged from the first stage rectification column in the step (S3) as the raw material for the second stage rectification column to the feed inlet returning to the first stage rectification column is 0.2-0.5: 1, and the feed inlet returning to the first stage rectification column is at the 13 th-18 th plate.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the pressure in the second-stage rectification tower is-98 KPa to-96 KPa, the top temperature is 96KPa to 101 ℃, the middle temperature is 106 KPa to 111 ℃, the kettle temperature is 113 KPa to 118 ℃, and the feeding amount is less than or equal to 3000L/h.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the number of plates of the second-stage rectification column is 50 to 55, and the feed inlet of the bottom liquid discharged from the first-stage rectification column into the second-stage rectification column is at the 18 th to 22 th plates.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the column packing of the second-stage rectification column is filled in six sections, namely, three sections of equally high stripping sections and three sections of equally high rectification sections, and the column packing is ceramic plate corrugated; the specification requirements of the ceramic plate corrugated packing are as follows: the specific surface area is 350-700 m2/m3A porosity of 72 to 78m3/m3A bulk density of 470 to 650kg/m3The angle of inclination is 30 or 45 degrees on the filler sheet
Regularly opening holes with the distance of 10 mm; therefore, the gas and liquid between adjacent meshes are distributed more uniformly, and almost no amplification effect exists. Taking the specific surface area 350 as an example, the specific surface area is 350m2/m3Porosity of 78m3/m3The pressure drop is 2.5mmHg/m, and the bulk density is 470kg/m3An inclination angle of 45 °; the preferred ceramic corrugated packing has a specific surface area of 400m2/m3Porosity of 75m3/m3The pressure is reduced by 3mmHg/m, and the bulk density is 500kg/m3The angle of inclination is 45 degrees, which is just suitable for the structure and the load of the designed tower, and the separation effect is optimal.
The height ratio of the packing of the stripping section to the packing of the rectifying section is 1:1.8 to 2.5, and more preferably 1: 2.3.
the beneficial effects of the above technical scheme are: the turbulence of an extremely thin liquid film and the inclined and zigzag channel of the air flow can be formed on the surface of the ceramic filler, so that the air flow can be promoted but not blocked, the ceramic filler can be comparable to the metal filler, the surface structure has good wetting performance, the liquid can flow quickly, the liquid stagnation of the filler is reduced to the minimum, and the chances of overheating, polymerization and coking are reduced; and the corrosion resistance, high temperature resistance and cleaning property (introducing impurity metal ions) of the composite material are incomparable with those of the metal wire mesh filler.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the ratio of the overhead product in the second-stage rectification column which is refluxed into the second-stage rectification column, fed into the second-stage rectification column again as a feed, and withdrawn as a product is 0.8 to 1: 0.2-0.5: 1.
preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (S3), the second-stage rectification column further includes a side draw-out port located at the 48 th to 53 th plates and located between the uppermost first-layer filler and the second-layer filler or between the uppermost second-layer filler and the third-layer filler, and the ratio of the draw-out amount to the reflux amount of the overhead material is 1: 0.8 to 1.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the fillers of the batch purification tower, the stripping tower, the first-stage rectification tower and the second-stage rectification tower are all high-silicon ceramic fillers, the silicon content is required to be not less than 70%, and the processing cost and the filling difficulty are preferably 75-80%.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the packing support devices of the batch purification tower, the gas stripping tower, the first-stage rectification tower and the second-stage rectification tower are all pore tube type packing support devices with polytetrafluoroethylene or polyperfluoroethylpropylene wrapped on the outer layer.
The beneficial effects of the above technical scheme are: the hole tube type packing supporting device has the characteristics of high flux and low pressure drop, different channels are provided for gas and liquid, gas and liquid in the plate type support are prevented from flowing through the same hole groove in a reverse flow mode, accumulation of the liquid on the plate is avoided, and therefore uniform redistribution of the liquid is facilitated.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, defoamers are disposed in the batch purification tower, the first-stage rectification tower and the second-stage rectification tower, and all are polyperfluoroethylene propylene wire mesh defoamers.
The refining and purifying process flow of the intermittent purifying section, the gas stripping purifying section and the secondary continuous rectifying section designed by the invention can better realize the purpose that the product quality to be realized by the invention reaches the SEMI C8 standard.
Firstly, the N-methyl pyrrolidone crude product after the complex reaction enters an intermittent purification section, and the temperature of the top of the tower and the temperature of the bottom of the tower are controlled by controlling the negative pressure vacuum degree of a rectifying tower in different time periods, so that light components in the crude product can be better removed in the stage, and the obtained monomethylamine aqueous solution and the middle distillate with higher purity can be respectively collected and can be respectively used as raw materials after being concentrated by a certain amount; the N-methyl pyrrolidone product obtained in this stage has the indexes of purity, free amine, moisture, pH value and the like meeting the requirements except that the indexes of granularity and metal ions can not meet the requirements of the liquid crystal panel industry;
the gas stripping purification section can further remove light particles and free amine in the obtained N-methyl pyrrolidone, and the step is also a key step for realizing the product quality required by the invention;
the other important key point of the invention is that a secondary continuous rectification section is designed, particularly the selection of the packing of the rectification tower, the design of the stripping section, the rectification section, the feeding plate position and the discharging plate position of the rectification tower can completely separate impurities with the boiling point close to that of N-methyl pyrrolidone, the boiling point difference between GBL and NMP is only 2 ℃, if the impurities are difficult to separate by conventional rectification and purification, the invention designs that a first-stage rectification tower is provided with an internal condenser and an external condenser; a side draw is arranged in the second-stage rectification, and a side draw outlet is positioned on the 48 th to 53 th plates and is positioned between the uppermost first-layer filler and the second-layer filler or between the uppermost second-layer filler and the third-layer filler;
and the technological parameters of the optimized design are also the key points of the success of the invention, the azeotropic point of the azeotropic system formed by the N-methyl pyrrolidone is broken through the treatment of the step, the separation difficulty is reduced, and the separation efficiency is improved by adopting the proper number and height of the tower plates in consideration of the manufacturing cost.
Preferably, the method for producing N-methylpyrrolidone for liquid crystal panels further comprises a pressure adsorption filtration operation, and the specific steps are as follows:
conveying the rectified and purified N-methyl pyrrolidone to a dust-free workshop through a pipeline, and filling a reinforced ceramic fiber filter material with the aperture of 0.05-0.10 mu m into a pressure filter tank lined with polytetrafluoroethylene or fluorinated ethylene propylene;
then, replacing and maintaining the pressure of the pressure filter tank by using dry hot nitrogen;
under the control of a feeding pressure control device, the pressure is alternatively changed into the processed pressure filter tank at intervals of 5-10 seconds, and the pressure is controlled to be 0.2-0.4 MPa and 0.6-0.8 MPa respectively.
It is further preferred that the pressure is changed alternately every 8 seconds to feed the treated pressure filtration tank at pressures controlled to 0.3MPa and 0.7MPa, respectively.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the filter material is heated and activated at a temperature of 100 to 120 ℃ before feeding of N-methylpyrrolidone obtained by rectification and purification.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, the pressure adsorption filtration may be replaced by pressure swing vacuum filtration adsorption, and both effects are the same and have no effect on product quality.
The invention also discloses N-methyl pyrrolidone for the liquid crystal panel produced by the method, if the operation of pressure adsorption and filtration is not carried out, the comprehensive yield of the N-methyl pyrrolidone is more than or equal to 98 percent, the purity is more than or equal to 99.95 percent, the metal ions are less than or equal to 0.5ppm, and the granularity is more than 0.5 mu m and less than or equal to 5 particles/ml, which is superior to the standard of SEMI C8.
The invention also discloses N-methyl pyrrolidone for the liquid crystal panel produced by the method, after the operation of pressure adsorption and filtration, the purity of the N-methyl pyrrolidone is more than or equal to 99.95 percent, the metal ions are less than or equal to 0.1ppm, the granularity is more than 0.2 mu m and less than or equal to 3 particles/ml, the N-methyl pyrrolidone basically reaches the standard of SEMI C12, and the requirements of the semiconductor industry are met.
And an application of N-methyl pyrrolidone for liquid crystal panels, wherein the N-methyl pyrrolidone is used as an electronic component cleaning agent or a stripping liquid.
According to the technical scheme, compared with the prior art, the invention discloses a titanium-based heterogeneous amination composite catalyst and application thereof in N-methylpyrrolidone production, and the obtained N-methylpyrrolidone product has the following advantages:
(1) the invention does not need traditional fiber filtration, and realizes that the N-methyl pyrrolidone product reaches the standards of SEMI C8 and SEMI C12 by innovating reaction raw materials, a reaction process and a purification process and strictly controlling process parameters;
(2) the invention provides a method for producing N-methyl pyrrolidone by combining a titanium-based heterogeneous amination composite catalyst, the purity of the obtained high-purity N-methyl pyrrolidone can reach more than 99.95 percent, even 99.99 percent, the content of particles in the obtained N-methyl pyrrolidone is less than or equal to 5/ml when the particle size of impurity particles is more than 0.5 mu m, the content of metal ions in the N-methyl pyrrolidone is less than or equal to 1ppb, the content of the metal ions is effectively reduced, and a product with low granularity is obtained while the purity is met;
(3) the electronic grade or high-purity N-methyl pyrrolidone prepared by the invention is used as cleaning solution or stripping solution in the manufacturing process of a liquid crystal panel display, and is used as cleaning solution in the manufacturing step of a semiconductor, and the N-methyl pyrrolidone is used as an environment-friendly electronic element cleaning agent, thereby providing a strong support for the development of liquid crystal televisions and liquid crystal displays.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment 1 of the invention discloses a titanium-based heterogeneous amination composite catalyst, which is prepared by the following method:
(1) mixing Al (NO)3)3·9H2O、Mo(NO3)3·5H2O、Ni(NO3)2·6H2Dissolving O in deionized water to prepare a 0.5mol/L solution, heating to 60 ℃, adding a carrier, fully and uniformly stirring, gradually dropwise adding 0.02mol/L dilute nitric acid or dilute sulfuric acid in the stirring process, fully mixing, controlling the pH value to be 5-6, and gradually reducing to room temperature to obtain a mixed solution A; al (NO)3)3·9H2O、Mo(NO3)3·5H2O、Ni(NO3)2·6H2The molar ratio of Al, Mo and Ni in O is 1: 1.2: 0.5;
(2) c is to be16H36O4Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dropwise adding C16H36O4Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 10h, transferring to a hydration thermal reaction kettle, reacting for 36h at 160 ℃, cooling to room temperature, performing suction filtration and washing, placing a filter cake in a drying oven, drying for 20h at 120 ℃, then roasting for 2h at 500 ℃, and grinding to obtain a catalyst carrier C;
(3) gradually heating the solution A to 55-70 ℃, refluxing for 30min while stirring, cooling to room temperature, slowly dropwise adding a precipitator for neutralization until the pH value is 8-9, aging for 12h at room temperature, performing suction filtration and washing, placing a filter cake in a drying oven at 120 ℃ for drying for 8h, then roasting for 4h at 600 ℃, and grinding to obtain a catalyst carrier D;
(4) preparing an isovolumetric impregnation liquid B containing active components of Co, Mn, Mg and Ag, impregnating the catalyst carrier C and the catalyst carrier D in the impregnation liquid B, uniformly stirring, ultrasonically oscillating, standing for a period of time, filtering, placing a filter cake in a drying oven, drying for 8 hours at 120 ℃, then roasting for 4 hours at 600 ℃, and molding to obtain the titanium-based heterogeneous amination composite catalyst.
Example 2
The embodiment 2 of the invention discloses a titanium-based heterogeneous amination composite catalyst, which is prepared by the following method:
(1) mixing Al (NO)3)3·9H2O、Mo(NO3)3·5H2Dissolving O in deionized water to prepare a 1mol/L solution, heating to 60-80 ℃, adding a carrier, fully and uniformly stirring, gradually dropwise adding 0.5mol/L dilute nitric acid or dilute sulfuric acid in the stirring process, fully mixing, controlling the pH value to be 5-6, and gradually reducing to room temperature to obtain a mixed solution A; al (NO)3)3·9H2O、Mo(NO3)3·5H2The molar ratio of Al and Mo in O is 1: 0.9;
(2) c is to be16H36O4Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dropwise adding C16H36O4Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 15h, transferring to a hydration thermal reaction kettle, reacting at 200 ℃ for 24h, cooling to room temperature, performing suction filtration and washing, placing a filter cake in a drying oven at 160 ℃ for drying for 10h, then roasting at 600 ℃ for 1h, and grinding to obtain a catalyst carrier C;
(3) gradually heating the solution A to 55-70 ℃, refluxing for 90min while stirring, cooling to room temperature, slowly dropwise adding a precipitator for neutralization until the pH value is 8-9, aging at room temperature for 18h, performing suction filtration and washing, placing a filter cake in a drying oven at 160 ℃ for drying for 5h, then roasting at 800 ℃ for 3h, and grinding to obtain a catalyst carrier D;
(4) preparing an isovolumetric impregnation liquid B containing active components of Co, Mn, Mg and Ag, impregnating the catalyst carrier C and the catalyst carrier D in the impregnation liquid B, uniformly stirring, ultrasonically oscillating, standing for a period of time, filtering, placing a filter cake in a drying oven, drying for 5 hours at 160 ℃, then roasting for 3 hours at 800 ℃, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Example 3
The embodiment 3 of the invention discloses a titanium-based heterogeneous amination composite catalyst, which is prepared by the following method:
(1) mixing Al (NO)3)3·9H2O、Mo(NO3)3·5H2O、H2PtCl6·6H2Dissolving O in deionized water to prepare a 0.8mol/L solution, heating to 70 ℃, adding a carrier, fully and uniformly stirring, gradually dropwise adding 0.3mol/L dilute nitric acid or dilute sulfuric acid in the stirring process, fully mixing, controlling the pH value to be 5-6, and gradually reducing to room temperature to obtain a mixed solution A; al (NO)3)3·9H2O、Mo(NO3)3·5H2O、H2PtCl6·6H2The mol ratio of Al, Mo and Pt in O is 1: 1.1: 0.05;
(2) c is to be16H36O4Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dropwise adding C16H36O4Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 12h, transferring to a hydration thermal reaction kettle, reacting at 180 ℃ for 30h, cooling to room temperature, performing suction filtration and washing, placing a filter cake in a drying oven, drying at 14 ℃ for 15h, then roasting at 550 ℃ for 1.5h, and grinding to obtain a catalyst carrier C;
(3) gradually heating the solution A to 55-70 ℃, refluxing for 60min while stirring, cooling to room temperature, slowly dropwise adding a precipitator for neutralization until the pH value is 8-9, aging for 5h at room temperature, performing suction filtration and washing, placing a filter cake in a drying oven at 140 ℃ for drying for 6.5h, then roasting for 3.5h at 700 ℃, and grinding to obtain a catalyst carrier D;
(4) preparing an isovolumetric impregnation liquid B containing active components of Co, Mn, Mg and Ag, impregnating the catalyst carrier C and the catalyst carrier D in the impregnation liquid B, uniformly stirring, ultrasonically oscillating, standing for a period of time, filtering, placing a filter cake in a drying oven, drying for 6.5h at 140 ℃, then roasting for 3.5h at 700 ℃, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Example 4
Example 4 is the same as the preparation method of example 1, and only differs in the content of each component of the catalyst, see table 1 specifically.
Example 5
Example 5 is prepared identically to example 3, except for the different amounts of the catalyst components, as shown in table 1.
Comparative example 1
The comparative example 1 is the same as the preparation method of the example 3, and is different only in the content of each component of the catalyst, and the content of Si in the comparative example 1 is 11% which is beyond the proportion range of 5-10% of the mass percentage of Si in the invention.
Comparative example 2
Comparative example 2 is the same as the preparation method of example 3 except that Al (NO) is added in step (1)3)3·9H2O、Mo(NO3)3·5H2O and Ni (NO)3)2·6H2O is dissolved in deionized water, wherein the molar ratio of Al to Ni is 1: 0.9.
Comparative example 3
Comparative example 3 is the same as the preparation method of example 3 except that Al (NO) is added in step (1)3)3·9H2O、Mo(NO3)3·5H2O and H2PtCl6·6H2O is dissolved in deionized water, wherein the molar ratio of Al to Pt is 1: 0.1.
In the above catalyst preparation process, the contents of the respective components in the catalyst and the molar ratio of the respective components added in step (1) have an important influence on the performance of the catalyst, and thus examples 1 to 5 and comparative examples 1 to 3 were obtained by changing the contents of the respective components in the catalyst and the molar ratio of the respective components in step (1), and the contents of the respective components in the catalyst were changed specifically as shown in table 1.
TABLE 1
The performance of the catalysts obtained in examples 1 to 5 and comparative examples 1 to 3 was measured, and the results are shown in Table 2.
TABLE 2 test results
The titanium-based heterogeneous amination composite catalysts obtained in examples 1 to 5 and comparative examples 1 to 3 were used to synthesize N-methylpyrrolidone for liquid crystal panels, and the synthesis method was as follows:
example 6
1. A reaction section: comprises two steps of reaction.
The first amination reaction: firstly, respectively pumping monomethylamine and gamma-butyrolactone with a molar ratio of 1.2:1 into a mixing and stirring tank by a feed pump, controlling the stirring preheating temperature to be 30 ℃, stirring for 5min, preheating again, wherein the preheating temperature is 120 ℃, and then pumping into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst obtained in the embodiment 1 by a metering pump to carry out amination reaction, wherein the reaction temperature is 200 ℃, and the reaction pressure is 5 MPa; liquid hourly space velocity of 0.5h-1Obtaining N-methyl pyrrolidone crude liquid, discharging the crude liquid through a material outlet of the reactor, and controlling the content of gamma-butyrolactone in the crude liquid discharged through a discharge port to be less than or equal to 0.01%;
the second step of complex reaction: the pH value of the crude liquid containing the N-methyl pyrrolidone obtained through the steps is 9-11, then 0.5mol/L complexing agent solution prepared by the metal ion complexing agent obtained through screening is continuously and uniformly added with 2L complexing agent solution per 10 tons of crude liquid containing the N-methyl pyrrolidone through a dosing device; controlling the reaction temperature to be 80 ℃ and the reaction time to be 10 min; sending the crude liquid containing the N-methyl pyrrolidone after the complexation reaction to a gap purification section;
2. an intermittent purification section: the crude liquid containing N-methyl pyrrolidone obtained in the reaction stage is sent to an intermittent purification tower to obtain a primary product, and the intermittent purification tower mainly removes monomethylamine, water and light components (middle distillate). The operation of the intermittent purification tower mainly comprises three stages, wherein the first stage is mainly to remove water and monomethylamine, the pressure is controlled to be between 80 and 75KPa below zero, the top temperature is less than or equal to 60 ℃, the kettle temperature is less than or equal to 90 ℃, after most of water and monomethylamine are extracted, the pressure is gradually controlled to be between 90 and 85KPa below zero, the top temperature is controlled to be less than or equal to 110 ℃, and the kettle temperature is controlled to be less than or equal to 120 ℃; the second stage mainly removes middle fractions, and controls the pressure to be-95 to-85 KPa, the top temperature to be 115 to 120 ℃ and the kettle temperature to be 135 to 130 ℃; in the third stage, primary products are collected, the pressure is controlled to be-95 to-85 KPa, the top temperature is controlled to be 120 to 125 ℃, and the kettle temperature is controlled to be 135 to 140 ℃; after being treated by an intermittent purification tower, a qualified N-methyl pyrrolidone primary product is obtained;
3. a gas stripping purification section: the primary N-methyl pyrrolidone product obtained by the intermittent purification tower is sent to a gas stripping tower, and the gas tower is mainly used for removing light components and partial particles which are not removed by intermittent rectification. The primary product of the N-methyl pyrrolidone obtained in the previous step is sent to a stripping tower, the N-methyl pyrrolidone is fed from the top of the stripping tower, after being uniformly dispersed by a distributor, the N-methyl pyrrolidone and nitrogen which enters from the bottom of the stripping tower in a countercurrent manner are subjected to convection and dispersion between the surface of the filler and the N-methyl pyrrolidone, light components such as free amine and partial particles in the N-methyl pyrrolidone are removed, and the purified product is discharged from the bottom of a tower kettle and enters the next procedure; controlling the ratio of N-methyl pyrrolidone to nitrogen to be 1t/5m3Controlling the temperature of nitrogen (stripping temperature) to be 80 ℃; the nitrogen exchanges heat with hot materials discharged after the reaction and then reaches the required temperature.
4. A second-stage continuous rectification section: the first stage of rectification is mainly to remove substances which have boiling points close to or form azeotropic points with the N-methyl pyrrolidone. Controlling the pressure to be-98 to-96 KPa, the top temperature to be 95 to 100 ℃, the middle temperature to be 108 to 112 ℃, the kettle temperature to be 116 to 121 ℃, and the feeding amount to be less than or equal to 2500L/h; the number of the plates of the primary rectifying tower is 45, and a feed inlet is arranged on a 15 th plate; the tower body filler is filled in four sections, the stripping section filler is a grating plate filler or a perforated corrugated filler, and the rectifying section filler is a pulse filler; the height ratio of the stripping section to the rectifying section is 1: 1.9; the first-stage rectifying tower is provided with an internal condenser and an external condenser, a part of the tower top extract treated by the external condenser flows back to the tower, a part of the tower top extract is extracted as a light component, and the reflux ratio (namely the ratio of reflux amount to the extracted amount) is controlled to be 1: 0.5; part of the tower bottom effluent is used as a raw material for the second-stage rectification, part of the tower bottom effluent returns to the feeding of the first rectification tower again, the feeding hole of the tower bottom effluent is arranged on the 13 th plate, and the ratio of the feeding of the tower bottom effluent returning to the first-stage rectification tower to the amount of the tower bottom effluent withdrawn and entering the second-stage rectification tower is controlled to be 0.2: 1;
the second stage of rectification is a rectifying tower with top extraction and side extraction to obtain qualified products meeting the quality requirements. Controlling the pressure to be-98 to-96 KPa, the top temperature to be 96-101 ℃, the middle temperature to be 106-111 ℃, the kettle temperature to be 113-118 ℃ and the feeding amount to be less than or equal to 3000L/h; the number of the second-stage rectifying tower plates is 50, and the feed inlet is arranged on 18 plates; the tower body filler is filled in six sections, and the filler is ceramic plate corrugation; the stripping section comprises: the height ratio of the rectifying section is 1: 1.8; the raw material of the second-stage rectifying tower comes from tower bottom liquid discharged by the first-stage rectifying tower to realize bubble point feeding of the second-stage rectifying tower; and the tower top produced material of the second-stage rectifying tower is treated by a condenser, and then flows back to the tower in parts, one part of the tower top produced material is used as the feeding material of the second-stage rectifying tower and is sent to the tower again, the other part of the tower top produced material is used as a product and is extracted, and the proportion of the three is controlled to be 0.8: 0.2: 1; and a side line extraction outlet of the second-stage rectification tower is positioned on a 49 th theoretical plate and between the uppermost first layer of packing and the second layer of packing, the extracted material is a qualified product meeting the quality standard, and the ratio of the extracted amount to the reflux amount of the top extracted material is controlled to be 1: 0.8.
5. pressure (pressure swing) adsorption filtration, to obtain SEMI C8Conveying the standard N-methyl pyrrolidone to a dust-free workshop through a pipeline; filling a reinforced ceramic fiber filter material with the aperture of 0.05-0.10 mu m in a pressure tank lined with polytetrafluoroethylene or fluorinated ethylene propylene; before N-methyl pyrrolidone begins to be fed, heating and activating the filter material at the temperature of 100-120 ℃; then, replacing and maintaining the pressure of the pressure filter tank by using dry hot nitrogen; staggered every 5-10 seconds under the control of a feeding pressure control deviceAnd (3) feeding (N-methyl pyrrolidone) into the treated pressure filter tank by changing the pressure, wherein the pressure is controlled to be 0.2-0.4 MPa and 0.6-0.8 MPa respectively.
Example 7
1. A reaction section: comprises two steps of reaction.
The first amination reaction: firstly, respectively pumping monomethylamine and gamma-butyrolactone with a molar ratio of 1.3:1 into a mixing and stirring tank by a feed pump, controlling the stirring preheating temperature to be 35 ℃, stirring for 8min, preheating again, wherein the preheating temperature is 160 ℃, and then pumping into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst obtained in the embodiment 2 by a metering pump to carry out amination reaction, wherein the reaction temperature is 230 ℃, and the reaction pressure is 5.5 MPa; liquid hourly space velocity of 5h-1Obtaining N-methyl pyrrolidone crude liquid, discharging the crude liquid through a material outlet of the reactor, and controlling the content of gamma-butyrolactone in the crude liquid discharged through a discharge port to be less than or equal to 0.01%;
the second step of complex reaction: the pH value of the crude liquid containing the N-methyl pyrrolidone obtained through the steps is 9-11, then 0.8mol/L complexing agent solution prepared by the metal ion complexing agent obtained through screening is continuously and uniformly added with 2.5L complexing agent solution per 10 tons of crude liquid containing the N-methyl pyrrolidone through a dosing device; controlling the reaction temperature to be 90 ℃ and the reaction time to be 18 min; sending the crude liquid containing the N-methyl pyrrolidone after the complexation reaction to a gap purification section;
2. an intermittent purification section: the crude liquid containing N-methyl pyrrolidone obtained in the reaction stage is sent to an intermittent purification tower to obtain a primary product, and the intermittent purification tower mainly removes monomethylamine, water and light components (middle distillate). The operation of the intermittent purification tower mainly comprises three stages, wherein the first stage is mainly to remove water and monomethylamine, the pressure is controlled to be between 80 and 75KPa below zero, the top temperature is less than or equal to 60 ℃, the kettle temperature is less than or equal to 90 ℃, after most of water and monomethylamine are extracted, the pressure is gradually controlled to be between 90 and 85KPa below zero, the top temperature is controlled to be less than or equal to 110 ℃, and the kettle temperature is controlled to be less than or equal to 120 ℃; the second stage mainly removes middle fractions, and controls the pressure to be-95 to-85 KPa, the top temperature to be 115 to 120 ℃ and the kettle temperature to be 135 to 130 ℃; in the third stage, primary products are collected, the pressure is controlled to be-95 to-85 KPa, the top temperature is controlled to be 120 to 125 ℃, and the kettle temperature is controlled to be 135 to 140 ℃; after being treated by an intermittent purification tower, a qualified N-methyl pyrrolidone primary product is obtained;
3. a gas stripping purification section: the primary N-methyl pyrrolidone product obtained by the intermittent purification tower is sent to a gas stripping tower, and the gas tower is mainly used for removing light components and partial particles which are not removed by intermittent rectification. The primary product of the N-methyl pyrrolidone obtained in the previous step is sent to a stripping tower, the N-methyl pyrrolidone is fed from the top of the stripping tower, after being uniformly dispersed by a distributor, the N-methyl pyrrolidone and nitrogen which enters from the bottom of the stripping tower in a countercurrent manner are subjected to convection and dispersion between the surface of the filler and the N-methyl pyrrolidone, light components such as free amine and partial particles in the N-methyl pyrrolidone are removed, and the purified product is discharged from the bottom of a tower kettle and enters the next procedure; controlling the ratio of N-methyl pyrrolidone to nitrogen to be 1t/7m3Controlling the temperature of nitrogen (stripping temperature) to be 100 ℃; the nitrogen exchanges heat with hot materials discharged after the reaction and then reaches the required temperature.
4. A second-stage continuous rectification section: the first stage of rectification is mainly to remove substances which have boiling points close to or form azeotropic points with the N-methyl pyrrolidone. Controlling the pressure to be-98 to-96 KPa, the top temperature to be 95 to 100 ℃, the middle temperature to be 108 to 112 ℃, the kettle temperature to be 116 to 121 ℃, and the feeding amount to be less than or equal to 2500L/h; the number of the plates of the primary rectifying tower is 48, and a feed inlet is arranged on the 18 th plate; the tower body filler is filled in four sections, the stripping section filler is a grating plate filler or a perforated corrugated filler, and the rectifying section filler is a pulse filler; the height ratio of the stripping section to the rectifying section is 1: 2.1; the first-stage rectifying tower is provided with an internal condenser and an external condenser, a part of the tower top extract treated by the external condenser flows back to the tower, a part of the tower top extract is extracted as a light component, and the reflux ratio (namely the ratio of reflux amount to the extracted amount) is controlled to be 1: 0.6; part of the tower bottom effluent is used as a raw material for the second-stage rectification, part of the tower bottom effluent returns to the feeding of the first rectification tower again, the feeding hole of the tower bottom effluent is arranged on the 15 th plate, and the ratio of the feeding of the tower bottom effluent returning to the first-stage rectification tower to the amount of the tower bottom effluent withdrawn and entering the second-stage rectification tower is controlled to be 0.3: 1;
the second stage of rectification is a rectifying tower with top extraction and side extraction to obtain qualified products meeting the quality requirements. Controlling the pressure to be-98 to-96 KPa, the top temperature to be 96-101 ℃, the middle temperature to be 106-111 ℃, the kettle temperature to be 113-118 ℃ and the feeding amount to be less than or equal to 3000L/h; the number of the second-stage rectifying tower plates is 53, and the feed inlet is arranged on 20 plates; the tower body filler is filled in six sections, and the filler is ceramic plate corrugation; the stripping section comprises: the height ratio of the rectifying section is 1: 2.3; the raw material of the second-stage rectifying tower comes from tower bottom liquid discharged by the first-stage rectifying tower to realize bubble point feeding of the second-stage rectifying tower; and the tower top produced material of the second-stage rectifying tower is treated by a condenser, and then flows back to the tower in parts, one part of the tower top produced material is used as the feeding material of the second-stage rectifying tower and is sent to the tower again, the other part of the tower top produced material is used as a product and is extracted, and the proportion of the three is controlled to be 0.9: 0.3: 1; and a side line extraction outlet of the second-stage rectification tower is positioned on the 51 th theoretical plate and between the uppermost second-layer filler and the third-layer filler, the extracted material is a qualified product meeting the quality standard, and the ratio of the extracted amount to the reflux amount of the top extracted material is controlled to be 1: 0.9.
5. pressure (pressure swing) adsorption filtration, to obtain SEMI C8Conveying the standard N-methyl pyrrolidone to a dust-free workshop through a pipeline; filling a reinforced ceramic fiber filter material with the aperture of 0.05-0.10 mu m in a pressure tank lined with polytetrafluoroethylene or fluorinated ethylene propylene; before N-methyl pyrrolidone begins to be fed, heating and activating the filter material at the temperature of 100-120 ℃; then, replacing and maintaining the pressure of the pressure filter tank by using dry hot nitrogen; under the control of a feeding pressure control device, the pressure (N-methyl pyrrolidone) is alternately changed every 5 to 10 seconds to feed into the treated pressure filter tank, and the pressure is controlled to be 0.2 to 0.4MPa and 0.6 to 0.8MPa respectively.
Example 8
1. A reaction section: comprises two steps of reaction.
The first amination reaction: firstly, monomethylamine and gamma-butyrolactone with a molar ratio of 1.5:1 are respectively pumped into a mixing and stirring tank by a feed pump, the stirring preheating temperature is controlled at 40 ℃, the stirring is carried out for 10min, the preheating is carried out again, the preheating temperature is 200 ℃, and then the monomethylamine and the gamma-butyrolactone are pumped into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst obtained in the embodiment 3 for amination reaction by a metering pump,the reaction temperature is 260 ℃, and the reaction pressure is 6 MPa; liquid hourly space velocity of 10h-1Obtaining N-methyl pyrrolidone crude liquid, discharging the crude liquid through a material outlet of the reactor, and controlling the content of gamma-butyrolactone in the crude liquid discharged through a discharge port to be less than or equal to 0.01%;
the second step of complex reaction: the pH value of the crude liquid containing the N-methyl pyrrolidone obtained through the steps is 9-11, then 1.0mol/L complexing agent solution prepared by the metal ion complexing agent obtained through screening is continuously and uniformly added into per 10 tons of crude liquid containing the N-methyl pyrrolidone through a dosing device, and 3L of complexing agent solution is added into the crude liquid; controlling the reaction temperature to be 100 ℃ and the reaction time to be 25 min; sending the crude liquid containing the N-methyl pyrrolidone after the complexation reaction to a gap purification section;
2. an intermittent purification section: the crude liquid containing N-methyl pyrrolidone obtained in the reaction stage is sent to an intermittent purification tower to obtain a primary product, and the intermittent purification tower mainly removes monomethylamine, water and light components (middle distillate). The operation of the intermittent purification tower mainly comprises three stages, wherein the first stage is mainly to remove water and monomethylamine, the pressure is controlled to be between 80 and 75KPa below zero, the top temperature is less than or equal to 60 ℃, the kettle temperature is less than or equal to 90 ℃, after most of water and monomethylamine are extracted, the pressure is gradually controlled to be between 90 and 85KPa below zero, the top temperature is controlled to be less than or equal to 110 ℃, and the kettle temperature is controlled to be less than or equal to 120 ℃; the second stage mainly removes middle fractions, and controls the pressure to be-95 to-85 KPa, the top temperature to be 115 to 120 ℃ and the kettle temperature to be 135 to 130 ℃; in the third stage, primary products are collected, the pressure is controlled to be-95 to-85 KPa, the top temperature is controlled to be 120 to 125 ℃, and the kettle temperature is controlled to be 135 to 140 ℃; after being treated by an intermittent purification tower, a qualified N-methyl pyrrolidone primary product is obtained;
3. a gas stripping purification section: the primary N-methyl pyrrolidone product obtained by the intermittent purification tower is sent to a gas stripping tower, and the gas tower is mainly used for removing light components and partial particles which are not removed by intermittent rectification. The N-methyl pyrrolidone primary product obtained in the previous step is sent to a stripping tower, the N-methyl pyrrolidone is fed from the top of the stripping tower, is uniformly dispersed by a distributor, and is subjected to convection and dispersion with nitrogen entering from the bottom of the stripping tower in a countercurrent manner between the surface of the filler and the N-methyl pyrrolidone to remove light components such as free amine and partial particles in the N-methyl pyrrolidoneDischarging the purified product from the bottom of the tower kettle and entering the next working procedure; controlling the ratio of N-methyl pyrrolidone to nitrogen to be 1t/9m3Controlling the temperature of nitrogen (stripping temperature) to be 120 ℃; the nitrogen exchanges heat with hot materials discharged after the reaction and then reaches the required temperature.
4. A second-stage continuous rectification section: the first stage of rectification is mainly to remove substances which have boiling points close to or form azeotropic points with the N-methyl pyrrolidone. Controlling the pressure to be-98 to-96 KPa, the top temperature to be 95 to 100 ℃, the middle temperature to be 108 to 112 ℃, the kettle temperature to be 116 to 121 ℃, and the feeding amount to be less than or equal to 2500L/h; the number of the plates of the first-stage rectifying tower is 50, and a feed inlet is arranged on the 20 th plate; the tower body filler is filled in four sections, the stripping section filler is a grating plate filler or a perforated corrugated filler, and the rectifying section filler is a pulse filler; the height ratio of the stripping section to the rectifying section is 1: 2.3; the first-stage rectifying tower is provided with an internal condenser and an external condenser, a part of the tower top extract treated by the external condenser flows back to the tower, a part of the tower top extract is extracted as a light component, and the reflux ratio (namely the ratio of reflux amount to the extracted amount) is controlled to be 1: 0.6; part of the tower bottom effluent is used as a raw material of the second-stage rectification, part of the tower bottom effluent returns to the feeding of the first rectification tower again, the feeding hole of the tower bottom effluent is positioned on the 18 th plate, and the ratio of the feeding of the tower bottom effluent returning to the first-stage rectification tower to the amount of the tower bottom effluent withdrawn and entering the second-stage rectification tower is controlled to be 0.5: 1;
the second stage of rectification is a rectifying tower with top extraction and side extraction to obtain qualified products meeting the quality requirements. Controlling the pressure to be-98 to-96 KPa, the top temperature to be 96-101 ℃, the middle temperature to be 106-111 ℃, the kettle temperature to be 113-118 ℃ and the feeding amount to be less than or equal to 3000L/h; the number of the plates of the secondary rectifying tower is 55, and the feed inlet is arranged on 22 plates; the tower body filler is filled in six sections, and the filler is ceramic plate corrugation; the stripping section comprises: the height ratio of the rectifying section is 1: 2.5; the raw material of the second-stage rectifying tower comes from tower bottom liquid discharged by the first-stage rectifying tower to realize bubble point feeding of the second-stage rectifying tower; and the tower top produced material of the second-stage rectifying tower is treated by a condenser, and then flows back to the tower in parts, one part of the tower top produced material is fed into the tower again as the feeding material of the second-stage rectifying tower, the other part of the tower top produced material is produced as a product, and the proportion of the three parts is controlled to be 1: 0.5: 1; and a side line extraction outlet of the second-stage rectification tower is positioned on a 52 th theoretical plate and between the uppermost first layer of packing and the second layer of packing, the extracted material is a qualified product meeting the quality standard, and the ratio of the extracted amount to the reflux amount of the top extracted material is controlled to be 1:1.
6. pressure (pressure swing) adsorption filtration, wherein the N-methyl pyrrolidone which is treated by the steps and reaches the SEMI C8 standard is conveyed to a dust-free workshop through a pipeline; filling a reinforced ceramic fiber filter material with the aperture of 0.05-0.10 mu m in a pressure tank lined with polytetrafluoroethylene or fluorinated ethylene propylene; before N-methyl pyrrolidone begins to be fed, heating and activating the filter material at the temperature of 100-120 ℃; then, replacing and maintaining the pressure of the pressure filter tank by using dry hot nitrogen; under the control of a feeding pressure control device, the pressure (N-methyl pyrrolidone) is alternately changed every 5 to 10 seconds to feed into the treated pressure filter tank, and the pressure is controlled to be 0.2 to 0.4MPa and 0.6 to 0.8MPa respectively.
Example 9
Example 9 is the same as the synthesis method of example 6, except that the titanium-based heterogeneous amination complex catalyst obtained in example 4 is loaded during the amination reaction.
Example 10
Example 10 is the same as the synthesis method of example 7 except that the titanium-based heterogeneous amination complex catalyst obtained in example 5 is loaded during the amination reaction.
Comparative example 4
Comparative example 4 is the same as the synthesis method of example 7 except that the titanium-based heterogeneous amination complex catalyst obtained in comparative example 1 is loaded during the amination reaction.
Comparative example 5
Comparative example 5 is the same as the synthesis method of example 7 except that the titanium-based heterogeneous amination complex catalyst obtained in comparative example 2 is loaded during the amination reaction.
Comparative example 6
Comparative example 6 is the same as the synthesis method of example 7 except that the titanium-based heterogeneous amination complex catalyst obtained in comparative example 3 is loaded during the amination reaction.
Respectively detecting N-methyl pyrrolidone products obtained after secondary rectification in examples 6-10 and comparative examples 4-6 by ICP-MS, wherein the detection results meet the SEMI C8 standard, and the specific detection results are shown in Table 4; and meanwhile, products subjected to pressure adsorption filtration are respectively detected, the detection results meet the SEMI C12 standard, the specific detection results are shown in Table 5, and the SEMI international standard grade of the technical chemicals is shown in Table 3.
TABLE 3 International Standard ratings for Process Chemicals SEMI
TABLE 4C8Metal ion detection result (unit: ppb)
TABLE 5C12Metal ion detection result (unit: ppb)
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (22)
1. The titanium-based heterogeneous amination composite catalyst is characterized by comprising, by mass, 25-35% of Ti, 5-10% of Si, 2-10% of Co, 2-5% of Mn, 1-3% of Mo, 0.5-1.0% of Mg, 0.2-0.5% of Ag, and the balance of a carrier.
2. The process for preparing a titanium-based heterogeneous amination complex catalyst as claimed in claim 1, comprising the steps of:
(1) mixing Al (NO)3)3·9H2O、Mo(NO3)3·5H2O、Ni(NO3)2·6H2O、H2PtCl6·6H2Dissolving two or three of O in deionized water to prepare a solution of 0.5-1 mol/L, heating to 60-80 ℃, adding a carrier, fully and uniformly stirring, gradually dropwise adding 0.02-0.5 mol/L dilute nitric acid or dilute sulfuric acid in the stirring process, fully mixing, controlling the pH value to be 5-6, and gradually reducing to room temperature to obtain a mixed solution A;
(2) c is to be16H36O4Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dropwise adding C16H36O4Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 10-15 h, transferring to a hydration thermal reaction kettle, reacting for 24-36 h at 160-200 ℃, cooling to room temperature, performing suction filtration and washing, placing a filter cake in a drying oven for drying for 10-20 h at 120-160 ℃, then roasting for 1-2 h at 500-600 ℃, and grinding to obtain a catalyst carrier C;
(3) gradually heating the solution A to 55-70 ℃, refluxing for 30-90 min while stirring, cooling to room temperature, slowly dropwise adding a precipitator for neutralization until the pH value is 8-9, aging for 12-18 h at room temperature, performing suction filtration and washing, placing a filter cake in a drying oven at 120-160 ℃, drying for 5-8 h, then roasting for 3-4 h at 600-800 ℃, and grinding to obtain a catalyst carrier D;
(4) preparing an isovolumetric impregnation liquid B containing active components of Co, Mn, Mg and Ag, impregnating the catalyst carrier C and the catalyst carrier D in the impregnation liquid B, uniformly stirring, ultrasonically oscillating, standing for a period of time, filtering, placing a filter cake in a drying oven, drying for 5-8 h at 120-160 ℃, roasting for 3-4 h at 600-800 ℃, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
3. The method for preparing a titanium-based heterogeneous amination complex catalyst as claimed in claim 2, wherein the step (1) of Al (NO)3)3·9H2O、Mo(NO3)3·5H2O、Ni(NO3)2·6H2O、H2PtCl6·6H2The mol ratio of Al, Mo, Ni and Pt in O is 1: 0.5-1.5: 0-0.8: 0 to 0.05.
4. A production method of N-methyl pyrrolidone for a liquid crystal panel is characterized by comprising a reaction section, wherein the amination reaction step of the reaction section is as follows:
(1) respectively pumping monomethylamine and gamma-butyrolactone into a mixing and stirring tank by a feed pump, controlling the stirring and preheating temperature to be 30-40 ℃, and stirring for 5-10 min to obtain a mixed solution;
(2) pumping the mixed solution into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst as claimed in claim 1 through a metering pump to carry out amination reaction to obtain a crude solution of N-methylpyrrolidone;
(3) the N-methyl pyrrolidone crude liquid is discharged from a material outlet of the fixed bed reactor, and the content of gamma-butyrolactone in the N-methyl pyrrolidone crude liquid discharged from the material outlet is controlled to be less than or equal to 0.01 percent.
5. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 4, wherein in the step (1), the molar ratio of monomethylamine to γ -butyrolactone is 1.2 to 1.5: 1; the temperature of the amination reaction is 200-260 ℃, the reaction pressure is 5-6 MPa, and the liquid hourly space velocity is 0.5-10 h～1。
6. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 4, wherein the mixed solution is preheated again before being fed into the fixed bed reactor, and the preheating temperature is 120-200 ℃.
7. The method according to claim 4, wherein the reaction step further comprises a complex reaction, comprising the steps of:
(A) preparing a metal ion complexing agent solution with the concentration of 0.5-1.0 mol/L;
(B) continuously and uniformly adding the metal ion complexing agent solution into the N-methyl pyrrolidone crude liquid through a dosing device, controlling the reaction temperature to be 80-100 ℃, and reacting for 10-25 min;
(C) and (3) sending the N-methyl pyrrolidone crude liquid subjected to the complexation reaction to an intermittent purification section.
8. The method according to claim 4, wherein the reaction step further comprises a complexing reaction, comprising the steps of:
(A) preparing a metal ion complexing agent solution with the concentration of 0.5-1.0 mol/L;
(B) adding the metal ion complexing agent solution into raw material gamma-butyrolactone before feeding in the amination reaction, and pumping the raw material gamma-butyrolactone into a mixing and stirring tank along with the gamma-butyrolactone through a feeding pump;
or continuously and uniformly adding the metal ion complexing agent solution into a mixing and stirring tank for amination reaction through a dosing device.
9. The method according to claim 7, wherein the ratio of the mass of the N-methylpyrrolidone to the volume of the metal ion complexing agent solution in the step (A) is 10000 kg: (2-3) L.
10. The process according to claim 8, wherein the ratio of the mass of γ -butyrolactone to the volume of metal ion complexing agent solution in step (A) is 10000 kg: (2-3) L.
11. The method for producing N-methylpyrrolidone for liquid crystal panels according to any of claims 4-10, further comprising the following steps of subsequently purifying the crude N-methylpyrrolidone liquid:
(S1) batch purification section
Conveying the N-methyl pyrrolidone crude liquid into an intermittent purification tower to remove monomethylamine, water and light components to obtain an N-methyl pyrrolidone primary product with the purity of more than 99.8%;
(S2) a stripping purification section
Feeding the N-methyl pyrrolidone primary product from the top of a stripping tower, uniformly dispersing the N-methyl pyrrolidone primary product by a distributor, and removing light components and partial particles in the N-methyl pyrrolidone primary product by convection and dispersion with nitrogen which enters from the bottom of the tower in a countercurrent manner on the surface of a filler, discharging the purified product from the bottom of a tower kettle, and entering the next procedure;
(S3) two-stage continuous rectification section
First-stage rectification: the purified N-methyl pyrrolidone discharged from the bottom of the stripping tower enters a first-stage rectifying tower with the tower plate number of 45-50 from a 15 th-20 th plate, and substances with the boiling point close to or forming the azeotropic point with the N-methyl pyrrolidone are removed; taking part of tower bottoms discharged from the first-stage rectifying tower as a raw material of the second-stage rectifying tower according to the ratio of 0.2-0.5: 1, returning the other part of the tower bottoms to a feed inlet of the first-stage rectifying tower, and returning the other part of the tower bottoms to the feed inlet of the first-stage rectifying tower on the 13 th-18 th plates;
second-stage rectification: the raw material of the second-stage rectifying tower is bubble point feeding, the number of tower plates of the second-stage rectifying tower is 50-55, tower bottom liquid discharged from the first-stage rectifying tower enters a feeding hole of the second-stage rectifying tower on 18 th-22 th plates, and tower top produced substances are treated by a condenser and then are mixed according to the weight ratio of 0.8-1: 0.2-0.5: 1, refluxing a part of the mixture to the second-stage rectifying tower, taking a part of the mixture as a feed, sending the other part of the mixture to the second-stage rectifying tower again, and taking the rest of the mixture as a product to be extracted to obtain the N-methylpyrrolidone meeting the quality requirement.
12. The process for producing N-methylpyrrolidone for liquid crystal panels according to claim 11, wherein the operation of the batch purification column in step (S1) is mainly composed of three stages:
in the first stage, water and monomethylamine are mainly removed, the pressure is controlled to be-80 to-75 KPa, the top temperature is less than or equal to 60 ℃, the kettle temperature is less than or equal to 90 ℃, after most of water and monomethylamine are extracted, the pressure is gradually controlled to be-90 to-85 KPa, the top temperature is controlled to be less than or equal to 110 ℃, and the kettle temperature is controlled to be less than or equal to 120 ℃;
the second stage mainly removes middle fractions, and controls the pressure to be-95 to-85 KPa, the top temperature to be 115 to 120 ℃ and the kettle temperature to be 135 to 130 ℃;
and (3) the primary product is collected in the third stage, the pressure is controlled to be-95 to-85 KPa, the top temperature is controlled to be 120 to 125 ℃, and the kettle temperature is controlled to be 135 to 140 ℃.
13. A method of producing N-methylpyrrolidone for liquid crystal panels, according to claim 11, wherein the ratio of N-methylpyrrolidone primary product to nitrogen gas in step (S2) is 1 t: (5 to 9) m3And controlling the temperature of the nitrogen to be 80-120 ℃.
14. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 11, wherein in the step (S3), the pressure in the first-stage rectification tower is-98 KPa to-96 KPa, the top temperature is 95-100 ℃, the intermediate temperature is 108-112 ℃, the kettle temperature is 116-121 ℃, and the feeding amount is less than or equal to 2500L/h.
15. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 11, wherein in step (S3), the first-stage rectification tower is provided with an internal condenser and an external condenser, a part of the overhead product treated by the external condenser is refluxed into the tower, and the other part of the overhead product is extracted as light components, and the reflux ratio is controlled to be 1: 0.5-0.8.
16. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 11, wherein in the step (S3), the pressure in the second-stage rectification tower is-98 KPa to-96 KPa, the top temperature is 96KPa to 101 ℃, the middle temperature is 106 ℃ to 111 ℃, the kettle temperature is 113 ℃ to 118 ℃, and the feeding amount is less than or equal to 3000L/h.
17. The method of claim 11, wherein the second-stage rectification column in the step (S3) further comprises a side draw port between the first-layer packing and the second-layer packing or between the second-layer packing and the third-layer packing at the top of the 48 th-53 th plates, and the ratio of the draw amount to the reflux amount of the top draw is 1: 0.8 to 1.
18. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 11, wherein the packing of the batch purification tower, the stripping tower, the first-stage rectification tower and the second-stage rectification tower is high-silicon ceramic packing, and the silicon content is not less than 70%.
19. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 11, further comprising a pressure adsorption filtration operation, comprising the following steps:
conveying the rectified and purified N-methyl pyrrolidone to a dust-free workshop through a pipeline, and filling a reinforced ceramic fiber filter material with the aperture of 0.05-0.10 mu m into a pressure filter tank lined with polytetrafluoroethylene or fluorinated ethylene propylene;
before feeding, heating and activating the filtering material at the temperature of 100-120 ℃, and then replacing and maintaining pressure of the pressure filtering tank by using dry hot nitrogen;
under the control of a feeding pressure control device, the pressure is alternatively changed into the processed pressure filter tank at intervals of 5-10 seconds, and the pressure is controlled to be 0.2-0.4 MPa and 0.6-0.8 MPa respectively.
20. N-methylpyrrolidone for liquid crystal panels, produced by the method according to any one of claims 11 to 18, wherein the overall yield of N-methylpyrrolidone is 98% or more, the purity is 99.95% or more, the metal ion content is 0.5ppb or less, and the particle size is 0.5 μm or more and 5 particles/ml or less.
21. N-methylpyrrolidone for liquid crystal panels, produced by the method of claim 19, wherein the N-methylpyrrolidone has a purity of 99.95% or more, a metal ion content of 0.1ppb or less, and a particle size of 0.2 μm or more and 3 particles/ml or less.
22. Use of N-methylpyrrolidone for liquid crystal panels according to any of claims 20 to 21, wherein N-methylpyrrolidone is used as a cleaning agent or stripping liquid for electronic components.
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| CN111892525A (en) | 2020-11-06 |
| CN111974411A (en) | 2020-11-24 |
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