CN111530472B - Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel - Google Patents
Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel Download PDFInfo
- Publication number
- CN111530472B CN111530472B CN202010383330.9A CN202010383330A CN111530472B CN 111530472 B CN111530472 B CN 111530472B CN 202010383330 A CN202010383330 A CN 202010383330A CN 111530472 B CN111530472 B CN 111530472B
- Authority
- CN
- China
- Prior art keywords
- methylpyrrolidone
- tower
- temperature
- methyl pyrrolidone
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 238000005576 amination reaction Methods 0.000 title claims abstract description 66
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 62
- 239000010936 titanium Substances 0.000 title claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000001914 filtration Methods 0.000 claims abstract description 37
- 238000000746 purification Methods 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 9
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 88
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 68
- 239000000047 product Substances 0.000 claims description 67
- 239000007788 liquid Substances 0.000 claims description 66
- 239000000945 filler Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 55
- 239000000243 solution Substances 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 47
- 238000003756 stirring Methods 0.000 claims description 46
- 238000012856 packing Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 239000008139 complexing agent Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 15
- 238000010668 complexation reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005086 pumping Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- XIUFWXXRTPHHDQ-UHFFFAOYSA-N prop-1-ene;1,1,2,2-tetrafluoroethene Chemical group CC=C.FC(F)=C(F)F XIUFWXXRTPHHDQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000012264 purified product Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000011226 reinforced ceramic Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 15
- 238000000605 extraction Methods 0.000 description 14
- 230000009286 beneficial effect Effects 0.000 description 13
- 239000012535 impurity Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 9
- 239000011800 void material Substances 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006210 cyclodehydration reaction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012071 phase Substances 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
- 238000001308 synthesis method Methods 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
- 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
- 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
- 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
- 238000009826 distribution Methods 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
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012528 membrane 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
- 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- 101710134784 Agnoprotein Proteins 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
- 238000003915 air pollution Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit 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
- 229910052799 carbon Inorganic materials 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
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 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
- 238000004508 fractional distillation Methods 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
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052749 magnesium 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
- 229910052748 manganese Inorganic materials 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
- 238000003199 nucleic acid amplification method 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
- 239000003973 paint Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000007639 printing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 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
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 N-methyl pyrrolidone for liquid crystal panels, and comprises a reaction section, an intermittent purification section, a gas stripping purification section and a secondary rectification purification section, wherein the conventional fiber filtration is not needed, the N-methyl pyrrolidone product can reach the standard of SEMI C8 completely through innovation of reaction raw materials, reaction process and purification process and strict control of technological parameters, and the product quality can basically reach the standard of SEMI C12 after pressurized adsorption filtration.
Description
Technical Field
The invention relates to the technical field of fine chemical product preparation, in particular to a titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal panels.
Background
N-methyl pyrrolidone is a fine chemical with excellent performance, and has very strong dissolving capacity to polar or nonpolar substances, so that the N-methyl pyrrolidone is called as a universal solvent and is widely used as a solvent or an organic raw material in the industrial fields of paint, printing ink, electronic chemicals, advanced cleaning agents, power lithium ion batteries and the like.
The problems of dehydration of N-methylpyrrolidone and removal of metal ions are widely focused, and for the dehydration problem of N-methylpyrrolidone, CN101696182A is to adsorb N-methylpyrrolidone to be purified through a molecular sieve column to remove water, and the N-methylpyrrolidone is limited by the limitations of adsorption speed and adsorption capacity, and the treatment capacity is only 0.4-0.8 liter/hour; CN200910064504.9 discloses a purifying method of N-methyl pyrrolidone, adding water-blocking agent into raw material N-methyl pyrrolidone, then feeding into three-tower component rectification system to make continuous reduced pressure distillation, and the purity of the obtained product is greater than 99.9% and water content is less than 0.01%.
For removing impurity metal ions in N-methylpyrrolidone, U.S. Pat. No. 5, 4965370 removes impurity metal ions by adding alkali metal or alkali metal salt, and then high-purity NMP is obtained by continuous fractional distillation; CN110551051a discloses a method for removing metal ion content and granularity, which is a technology for preparing N-methylpyrrolidone by amination of monomethylamine and gamma-butyrolactone (GBL), wherein the most critical metal ion particle removal is in the filtration and demagnetization control stage of the last step, but there is no requirement of replacing the fiber after filtration, such as whether the fiber needs to be updated or revived; the preparation process of high purity N-methyl pyrrolidone CN108299266A includes eliminating water from the material liquid with a permeable sliding film assembly, and filtering metal ion or particle with strong acid styrene cation exchange resin or weak acid acrylic acid cation exchange resin; in the production method of CN102399179B ultra-pure N-methyl pyrrolidone, industrial grade N-methyl pyrrolidone is used as a raw material, and is subjected to pretreatment, adsorption dehydration by a 4A molecular sieve, two times of membrane filtration are respectively carried out by a beta-cyclodextrin composite membrane and an 18-crown-6-composite membrane, the filtrate is subjected to reduced pressure rectification, and the collected fraction is condensed and then is subjected to three-stage membrane filtration by a microporous membrane to obtain a target product; CN102190611 and CN102001986a disclose that resin is used for treatment and filtration, but resin needs regeneration and material replacement, industrial sewage treatment and material waste are large, metal ion content in the product belongs to trace impurities, and a regeneration liquid such as hydrochloric acid used in a resin regeneration link needs a high-purity reagent, so that the content of the metal impurities is difficult to ensure, the production and environmental protection treatment cost is indirectly increased, and the method is not suitable for industrial production and purification. However, in general, the above methods have complex operation process, difficult operation control, high energy consumption and low efficiency.
In addition, the purity of the N-methyl pyrrolidone in China is between 99.5 and 99.9 percent at present, the metal particle content is basically between 20 and 30ppb, the control requirement on the granularity of the N-methyl pyrrolidone is not yet proposed in the national standard, but the requirement of the liquid crystal panel enterprises in China on the metal ion content in the N-methyl pyrrolidone is generally less than or equal to 5ppb, and the particle content is less than or equal to 5 particles/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 application thereof in N-methyl pyrrolidone production, which not only effectively controls the metal ion impurity content of N-methyl pyrrolidone products, but also greatly improves the purity of the products.
In order to achieve the above purpose, the present 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 and can Up to 600-800 m 2 And the compressive strength is high and is more than 150N/cm, the catalyst framework structure and the pore canal structure are improved, the shrinkage rate in the reduction process is low, the leakage flow and bias flow of reaction materials in a catalyst bed layer are effectively prevented, the mechanical strength and the thermal stability of the catalyst are enhanced, the corrosion to equipment and the environmental pollution are reduced, the method is more suitable for industrialization, the production efficiency of N-methylpyrrolidone can be effectively improved, no metal ions in the catalyst are separated out in the amination synthesis process, and the metal ion content is effectively controlled from the source when the method is used for synthesizing N-methylpyrrolidone.
The invention also discloses a preparation method of the titanium-based heterogeneous amination composite catalyst, which comprises the following steps:
(1) Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、Ni(NO 3 ) 2 ·6H 2 O、H 2 PtCl 6 ·6H 2 Dissolving two or three of O in deionized water to prepare 0.5-1 mol/L solution, 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 cooling to room temperature to obtain a mixed solution A;
(2) C is C 16 H 36 O 4 Dissolving Si (butyl orthosilicate) in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to 20-30 ℃, and dropwise adding C 16 H 36 O 4 Ti (tetrabutyl titanate), 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 heat reaction kettle, reacting for 24-36 h at 160-200 ℃, cooling to room temperature, carrying out suction filtration, washing, placing a filter cake in a drying box, drying for 10-20 h at 120-160 ℃, 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 dripping a precipitator for neutralization until the pH value is 8-9, ageing for 12-18 h at room temperature, filtering, washing, placing a filter cake in a drying oven for drying for 5-8 h at 120-160 ℃, roasting for 3-4 h at 600-800 ℃, and grinding to obtain a catalyst carrier D;
(4) From Co (NO) 3 ) 2 .6H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Mg(NO 3 ) 2 .6H 2 O、AgNO 3 Preparing an equal volume impregnating solution B containing Co, mn, mg, ag active components, impregnating the catalyst carrier C and the catalyst carrier D into the impregnating solution B, uniformly stirring, carrying out ultrasonic oscillation, standing for a period of time, filtering, drying a filter cake in a drying oven at 120-160 ℃ for 5-8 h, roasting at 600-800 ℃ for 3-4 h, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Preferably, in the above method for preparing a titanium-based heterogeneous amination complex catalyst, step (1) Al (NO 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、Ni(NO 3 ) 2 ·6H 2 O、H 2 PtCl 6 ·6H 2 The molar ratio of the Al, mo, ni, pt components in O is 1:0.5 to 1.5:0 to 0.8:0 to 0.05.
The beneficial effects of the technical scheme are as follows: the catalyst activity is an important parameter for evaluating whether a process can be commercialized, and the active components and the composition ratio are important control indexes in the catalyst preparation process. Taking the active component nickel in the catalyst as an example, the grain size of the metal rapidly grows up and is sintered along with the temperature rise, niO and certain elements in the carrier generate strong interaction to generate NiAl which is difficult to reduce 2 O 4 Spinel, etc., the conversion activity is reduced by more than 30%, so that the addition amount of substances is required to be strictly controlled in the preparation process of the catalyst, when the molar ratio of Ni to Al element is more than 0.8, the reduction rate of the specific surface area of the catalyst under the same condition is more than 20% when the molar ratio of Ni to Al element is 0-0.8:1, and after the Ni content is increased, the grain size of the metal is rapidly grown along with the temperature rise, the absolute value of sintering is increased, the influence on the activity of the catalyst is larger, and the speed is higher.
Preferably, in the preparation method of the titanium-based heterogeneous amination composite catalyst, the steps are as follows(3) Wherein the precipitant is ammonia water and NaHCO 3 、NaOH、K 2 CO 3 And KHCO 3 One or a mixture of several of them.
In the preparation process of the catalyst, the high correlation between the deactivation of the carbon deposition of the catalyst and the pore diameter thereof is found, which is the reason that the capillary coagulation phenomenon of the intermediate is serious, si, pore expanding agent and the like are introduced in the preparation of the catalyst, the average pore diameter of the catalyst is increased to 28nm, and the catalyst has a bimodal structure; it has also been 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 fact that the pore size becomes large and the toughness decreases after the Si content increases, making the catalyst susceptible to collapse.
The heterogeneous amination composite catalyst based on heterogeneous titanium comprises the components calculated by oxide, 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 byproducts such as N-methylpiperidine, the addition amount is too small, the inhibition effect is not obvious, and the activity of the catalyst is reduced when the addition amount is too large.
Further to be described is: the invention optimizes the content of each active component and components and the preparation process, so that the performance of the catalyst is fully exerted in the process technology, under the condition of the required quantity, the catalyst activity can be greatly improved, the service life of the catalyst can be longer, the process conditions of the invention, such as pressure, temperature and the like, are greatly optimized compared with the prior art (the preparation of NMP by amination of pure monomethylamine and GBL), the operation process is safer, and the energy-saving effect is more obvious.
The invention also discloses a production method of the N-methyl pyrrolidone for the liquid crystal display panel, which comprises a reaction section, wherein the amination reaction step of the reaction section is as follows:
(1) Pumping monomethylamine and gamma-butyrolactone into a mixing stirring tank by a feed pump respectively, controlling the stirring 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 through a metering pump to perform amination reaction to obtain N-methyl pyrrolidone crude liquid with the pH value of 9-11;
(3) The crude N-methyl pyrrolidone liquid is discharged from a material outlet of the fixed bed reactor, and the content of gamma-butyrolactone in the crude N-methyl pyrrolidone liquid discharged from the 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 N-methyl pyrrolidone, wherein the cyclodehydration step has slower reaction and is a reaction control step which needs to be carried out at high temperature and high pressure; the conventional theory that monomethylamine reacts with gamma-butyrolactone in a reactor to prepare N-methylpyrrolidone suggests that water in a 40% aqueous monomethylamine solution can promote the cyclodehydration of the second step, reduce the delta E value of the reaction, promote the smooth progress of the cyclodehydration reaction of the second step, and generally require the control of the reaction temperature of 265-270 ℃ and the pressure of 7-9 MPa even under favorable conditions.
Under the action of a specific screened titanium-based heterogeneous amination composite catalyst, the amination reaction can obtain N-methylpyrrolidone at relatively low temperature and pressure, the conversion rate of GBL is high and can reach 99.5%, the content of gamma-butyrolactone in crude liquid discharged from a monitoring discharge port is less than or equal to 0.01%, the primary reaction yield of N-methylpyrrolidone can reach 99%, and the superiority of the catalyst performance is shown.
Preferably, in the above method for producing N-methylpyrrolidone for liquid crystal panels, in the step (1), the total mass content of dimethylamine, trimethylamine, and amine in monomethylamine is not more than 0.05%, and the total mass content of 3-methyl- γ -butyrolactone, 4-methyl- γ -butyrolactone, and 5-methyl- γ -butyrolactone in γ -butyrolactone is not more than 0.05%.
The beneficial effects of the technical scheme are as follows: the titanium-based heterogeneous amination composite catalyst for the amination reaction optimizes the reaction process of preparing N-methylpyrrolidone by traditional amination, so that the aim of adopting pure monomethylamine is mainly 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, so that the application requirements of N-methylpyrrolidone in the liquid crystal panel industry or the semiconductor industry are met.
In particular, even a small amount of water is advantageous for the reaction in the subsequent dehydrative ring closure step, the catalyst activity is lowered when the water content at the outlet of the reactor is too high, and water forms azeotropy with low boiling point substances in N-methylpyrrolidone, which makes it difficult to remove cleanly in the subsequent refining process, so that the metal ions and the particle size are relatively large.
Meanwhile, the process of preparing NMP by amination of monomethylamine and GBL is also a process of generating water, and the generated water not only promotes the reaction together with the titanium-based catalyst, but also forms an aqueous solution with monomethylamine (with a lower boiling point) in the subsequent deamination refining process, so that the monomethylamine with a low boiling point is prevented from drifting to a great extent; in order to match with the synthesis process characteristics in the invention, the design of the follow-up refining process, the design of the rectifying tower, the selection of the packing 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 crude N-methylpyrrolidone product, so that a better effect is obtained, and the produced N-methylpyrrolidone product can meet the requirements of liquid crystal panel enterprises.
Preferably, in the above-mentioned method for producing N-methylpyrrolidone for a liquid crystal panel, in the step (1), the molar ratio of the monomethylamine to the 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 >.
The beneficial effects of the technical scheme are as follows: since the subsequent complexation reaction is required 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 the theoretical value required by the reaction; in addition, excessive monomethylamine is separated in the intermittent purification process, but the boiling point of monomethylamine is lower, the monomethylamine is easy to fly into the air to cause air pollution, so that the phenomenon of so-called white smoke is generated, therefore, water generated in the amination reaction process and monomethylamine do not necessarily form an azeotropic point, but can be separated together in the purification process to form an aqueous monomethylamine solution, the phenomenon of the aforesaid white smoke is avoided, and meanwhile, the amine is separated thoroughly in the intermittent purification process, the pressure of subsequent purification is reduced, the quality of a final product is ensured, and meanwhile, the recovered aqueous monomethylamine solution can be used as a raw material for producing low-quality N-methylpyrrolidone.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the mixed solution is preheated again before being fed into a fixed bed reactor, and the preheating temperature is 120 to 200 ℃.
The beneficial effects of the technical scheme are as follows: 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 rapid 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 is a step of speed determination. Therefore, after the heat exchange between the crude product and the raw materials, the reaction process has the following main beneficial effects: firstly, the crude product at 200-260 ℃ from the reactor exchanges heat with the raw materials, so that the waste of heat is avoided; secondly, the problem of temperature gradient of the reaction is solved, the mixture of GBL and monomethylamine after preheating 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, indirectly increases the flow speed of raw materials, increases the heat transfer coefficient, enlarges the heat exchange area and timely removes the heat of the ring-opening reaction, 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 activity of the dehydration reaction is reduced to 44KJ/mol under the action of the high-efficiency catalyst, the NMP selectivity is increased to be more than or equal to 99.0 percent under the same condition, and the GBL content of an 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 a liquid crystal panel, the reaction section further includes 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 the reaction time to be 10-25 min;
(C) The N-methyl pyrrolidone crude liquid after the complexation reaction is sent to a batch purification section.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the reaction section further includes 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) Before the amination reaction is carried out, adding the metal ion complexing agent solution into raw material gamma-butyrolactone, and pumping the raw material gamma-butyrolactone into a mixing and stirring tank by a feed pump along with the gamma-butyrolactone;
or continuously and uniformly adding the metal ion complexing agent solution in a mixing and stirring tank for amination reaction through a dosing device.
The beneficial effects of the technical scheme are as follows: the complex can be finally reserved to the tower kettle as a high-boiling point substance to be discharged after the metal ion complexing agent (which is used in an alkaline environment) is added in the purification, the content of the metal ions in the NMP product can be effectively reduced through the treatment of the step, and the requirement of SEMIC8 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, and the two adding modes have the same effect, but the adding amount of the metal ion complexing agent in the former method is smaller.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the metal ion complexing agent solution in the step (a) is a solution in which any one or a mixture of hydroxyethylidene diphosphonic acid, hydroxyethylethylenediamine triacetic acid, triethylenetetramine hexaacetic acid, and ethylene glycol ditetraacetic acid is dissolved in ethanol.
The beneficial effects of the technical scheme are as follows: the complexing agent selected by the invention can lead metal ions in the crude liquid to be almost totally complexed and precipitated at the bottom of the kettle in an alkaline environment, and other impurity ions (mainly light molecular weight) introduced by the complex can be almost totally removed by the gas stripping tower.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the volume ratio of the mass of the N-methylpyrrolidone to the metal ion complexing agent solution in the step (a) is 10000kg: (2-3) L.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the volume ratio of the mass of the γ -butyrolactone to the metal ion complexing agent solution in the step (a) is 10000kg: (2-3) L.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, further comprising the following steps of:
(S1) batch purification section
Conveying the N-methyl pyrrolidone crude liquid into an intermittent purifying tower to remove monomethylamine, water and light components, so as to obtain an N-methyl pyrrolidone primary product with the purity of more than 99.8%;
(S2) gas stripping purification section
Feeding the N-methyl pyrrolidone primary product from the top of the stripping tower, uniformly dispersing the N-methyl pyrrolidone primary product by a distributor, and then carrying out convection and dispersion on the N-methyl pyrrolidone primary product and nitrogen entering from the bottom of the stripping tower in a countercurrent manner on the surface of a filler to remove light components and part of particles in the N-methyl pyrrolidone primary product, and discharging the purified product from the bottom of the stripping tower to enter the next working procedure;
(S3) two-stage continuous rectification section
The purified N-methyl pyrrolidone discharged from the bottom of the stripping tower enters a first-stage rectifying tower to remove substances with the boiling point close to that of the N-methyl pyrrolidone or with the N-methyl pyrrolidone forming an azeotropic point; one part of tower bottom liquid discharged from the first-stage rectifying tower is used as the raw material of the second-stage rectifying tower, and the other part returns to the feed inlet of the first-stage rectifying tower;
The raw material of the second-stage rectifying tower is bubble point feeding, a part of tower top extract is refluxed into the second-stage rectifying tower after being treated by a condenser, a part of tower top extract is fed into the second-stage rectifying tower again as feeding, and the rest part of tower top extract is extracted as a product, so that N-methylpyrrolidone meeting the quality requirement is obtained.
Preferably, in the above-mentioned method for producing N-methylpyrrolidone for a liquid crystal panel, the operation of the batch purification column in the step (S1) has mainly three stages:
the first stage is to take the water and monomethylamine as main components, control the pressure to minus 80 to minus 75KPa, the top temperature to minus 60 ℃, the kettle temperature to minus 90 ℃, gradually control the pressure to minus 90 to minus 85KPa, control the top temperature to minus 110 ℃ and control the kettle temperature to minus 120 ℃ after most of water and monomethylamine are extracted;
the second stage takes middle distillate removal as a main part, the pressure is controlled to be-95 to-85 KPa, the top temperature is 115 to 120 ℃, and the kettle temperature is 135 to 130 ℃;
and in the third stage, the primary product is extracted, the pressure is controlled to be-95 to-85 KPa, the top temperature is 120 to 125 ℃, and the kettle temperature is 135 to 140 ℃.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the ratio of the N-methylpyrrolidone primary product to nitrogen in the step (S2) is 1t: (5-9) m 3 And controlling the temperature of the nitrogen to be 80-120 ℃, and after the nitrogen exchanges heat with the hot materials discharged after the reaction, the nitrogen reaches the required temperature.
Preferably, in the above-mentioned method for producing N-methylpyrrolidone for a liquid crystal panel, ultrapure water is added in an amount of 0.05% by mass of the total amount of feed into the stripping column before the N-methylpyrrolidone is fed into the stripping column.
The beneficial effects of the technical scheme are as follows: if the content of free amine after the treatment of the gas purification section is slightly higher, incomplete removal in the ten-thousand-grade and two-grade continuous rectification is avoided, a small amount of ultrapure water is added before the feeding of the stripping tower, the addition of the ultrapure water is controlled to be 0.05% 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 the accidental result of the invention.
Preferably, in the above-mentioned method for producing N-methylpyrrolidone for a liquid crystal panel, in the step (S2), the filler is one of a light porcelain filler, a saddle filler, and a pall ring filler; further preferred are pall ring packing;
if the light porcelain filler is selected, the specification requirements are as follows: the packing stacking weight is 280-350 kg/m 3 The stacking void ratio is more than or equal to 72%, the apparent porosity is more than or equal to 15%, and the total void ratio is more than 85%; the ceramic filler has strong adhesion and adsorption capacity to impurities and good purification effect, and is preferably one of a ceramic multi-tooth ring, a ceramic wave grating ring and a ceramic flying saucer ring;
If saddle packing is selected, the specification requirements are as follows: specific surface area is more than or equal to 80m 2 /m 3 Void ratio is more than or equal to 0.7m 3 /m 3 The stacking weight is more than or equal to 480kg/m 3 The stacking number is more than or equal to 5500; the filler changes the smooth arc side surface of the saddle filler into a zigzag or grain protruding side surface, so that the contact gap between the fillers is increased in the filler bed layer, the flow and dispersion of gas and liquid in the filler layer are more facilitated, and the characteristics of pressure reduction and high mass transfer efficiency are achieved.
If pall ring packing is selected, the specification requirements are as follows: the specific surface area is more than or equal to 120m 2 /m 3 Void ratio is more than or equal to 0.7m 3 /m 3 . Taking a pall ring with a specification of 25X25 as an example, the specific surface area is about 350m 2 /m 3 Void fraction of about 0.7m 3 /m 3 About 42000 stacks and about 600kg/m stacks 3 The open pores of the wall of the packing ring greatly improve the distribution performance of gas and liquid compared with Raschig rings, and especially the inner surface area of the rings can be fully utilized.
Preferably, in the above production method of N-methylpyrrolidone for liquid crystal panels, in the step (S3), the pressure in the first-stage rectifying tower is-98 to-96 KPa, the top temperature is 95 to 100 ℃, the middle 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 a liquid crystal panel, the number of trays of the first-stage rectifying column in the step (S3) is 45 to 50, and the purified N-methylpyrrolidone is fed to the 15 th to 20 th tray.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the tower body filler of the first-stage rectifying tower is filled in four segments, wherein the two segments of equally high stripping segment filler are grid plate filler or puncture corrugated filler, and the two segments of equally high rectifying segment filler are pulse filler; the height ratio of the stripping section to the packing of the rectifying section is 1:1.9 to 2.3, more preferably 1:2.1.
the beneficial effects of the technical scheme are as follows: the filler can form a porous diamond-shaped channel with a locking neck, the longitudinal flow channel is alternately contracted and expanded, and when the gas phase and the liquid phase pass through, the strong turbulence is generated, and at the necking position, the gas speed is highest, and the turbulence is strong, so that the mass transfer is enhanced, and the gas speed is reduced to the minimum in the expansion section, and the high-efficiency separation of the two phases is realized, so that the azeotropic point of a gamma-butyrolactone and N-methylpyrrolidone azeotropic system is changed by the designed technological process, the selected filler material and the designed filler filling mode, and the separation difficulty is reduced.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, in the step (S3), the first-stage rectifying column is provided with an internal condenser and an external condenser, and a part of the overhead product treated by the external condenser is refluxed into the column, and the other part is recovered as a light component, and the reflux ratio is controlled to be 1:0.5 to 0.8, and more preferably 0.6.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the ratio of the raw material of the second-stage rectifying column to the feed port returned to the first-stage rectifying column in the column bottoms discharged from the first-stage rectifying column in step (S3) is 0.2 to 0.5:1, and the feed port returned to the first-stage rectifying column is at 13 th to 18 th plates.
Preferably, in the above production method of N-methylpyrrolidone for liquid crystal panels, in the step (S3), the pressure in the second-stage rectifying tower is-98 to-96 KPa, the top temperature is 96 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.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the number of trays of the second-stage rectifying column in the step (S3) is 50 to 55, and the feed inlet of the liquid column discharged from the first-stage rectifying column into the second-stage rectifying column is 18 to 22 th.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, in the step (S3), the tower body packing of the second-stage rectifying tower is packed in six sections including three stripping sections with equal heights and three rectifying sections with equal heights, and the tower body packing is a ceramic plate ripple; the specification requirements of the ceramic plate corrugated filler are as follows: specific surface area of 350-700 m 2 /m 3 Void ratio of 72-78 m 3 /m 3 The bulk density is 470-650 kg/m 3 The inclination angle is 30 degrees or 45 degrees, and regular holes are formed on the filler sheet according to the interval of 10 mm; thus, the gas and liquid distribution between the adjacent meshes is more uniform, and almost no amplification effect exists. Taking specific surface area 350 as an example, specific surface area 350m 2 /m 3 Void fraction 78m 3 /m 3 Pressure drop of 2.5mmHg/m, bulk density of 470kg/m 3 An inclination angle of 45 degrees; ceramic corrugated filler with specific surface area of 400 and specific surface area of 400m is preferable 2 /m 3 Void fraction 75m 3 /m 3 Pressure drop of 3mmHg/m, bulk density 500kg/m 3 The inclined angle is 45 degrees, and the separation effect is optimal just corresponding to the structure and the load of the designed tower.
The height ratio of the packing materials in the stripping section and the rectifying section is 1:1.8 to 2.5, more preferably 1:2.3.
the beneficial effects of the technical scheme are as follows: the turbulence of the extremely thin liquid film and the inclined tortuous channel of the air flow can promote the air flow but not block the air flow, so that the ceramic filler can be compared with the metal filler, the surface structure has good wetting property, the liquid can flow quickly, the liquid stagnation of the filler is reduced to the minimum, and the opportunities of overheating, polymerization and coking are reduced; and the corrosion resistance, the high temperature resistance and the cleaning performance (introducing impurity metal ions) of the metal wire mesh filler are incomparable.
Preferably, in the above-mentioned method for producing N-methylpyrrolidone for a liquid crystal panel, the reflux in the second-stage rectifying column in step (S3) is carried out into the second-stage rectifying column, and the ratio of the overhead offtake taken as a feed to the second-stage rectifying column again is 0.8 to 1:0.2 to 0.5:1.
preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, in the step (S3), the second rectifying tower further includes a side offtake located between the 48 th-53 th plate and located between the uppermost first layer packing and the second layer packing or between the uppermost second layer packing and the third layer packing, and a ratio of a offtake amount to a reflux amount of the top product is 1:0.8 to 1.
Preferably, in the above production method of N-methylpyrrolidone for liquid crystal panels, the packing materials of the batch purification tower, the stripping tower, the first-stage rectification tower and the second-stage rectification tower are all high-silicon ceramic packing materials, the silicon content of which is more than or equal to 70%, and 75-80% is preferable in consideration of processing cost and packing difficulty.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the packing support devices of the intermittent purification tower, the gas stripping tower, the first-stage rectification tower, and the second-stage rectification tower are all porous pipe type packing support devices with polytetrafluoroethylene or polyperfluoroethylene propylene wrapped on the outer layer.
The beneficial effects of the technical scheme are as follows: the pore tube type packing support device has the characteristics of high flux and low pressure drop, provides different channels for gas and liquid, avoids countercurrent passing of gas and liquid from the same pore groove in the plate type support, and avoids accumulation of liquid on the plate, thereby being beneficial to uniform redistribution of the liquid.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, foam-removing devices are disposed in the intermittent purifying tower, the first-stage rectifying tower, and the second-stage rectifying tower, and are all perfluoroethylene propylene silk-screen foam-removing devices.
The invention designs the refining and purifying process flows of the intermittent purifying section, the gas stripping purifying section and the secondary continuous rectifying section, which can better realize the aim that the quality of the product to be realized reaches the SEMIC8 standard.
Firstly, the crude N-methyl pyrrolidone after the complexation reaction enters an intermittent purification section, and the temperature at the top of the tower and the temperature at the bottom of the tower are controlled by controlling the vacuum degree of the rectifying tower in different time periods, so that light components in the crude N-methyl pyrrolidone can be better removed in the stage, and the obtained monomethylamine aqueous solution and the middle distillate with higher purity can be respectively used as raw materials after being concentrated by a certain amount; the N-methyl pyrrolidone obtained in the section has the indexes of purity, free amine, moisture, pH value and the like meeting the requirements except that the granularity and the metal ion index 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 invention designs a second-stage continuous rectifying section, in particular to a rectifying section, a rectifying section stripping section, a rectifying section, a feeding plate position and a discharging plate position of the rectifying tower, which can thoroughly separate impurities with the boiling point close to that of N-methyl pyrrolidone, GBL and NMP have the boiling point difference of only 2 ℃, if the impurities are difficult to separate by conventional rectifying and purifying, the invention designs an internal condenser and an external condenser in the first-stage rectifying tower; a side line extraction is arranged in the second-stage rectification, and the side line extraction outlet is positioned between the 48 th-53 th plate and the uppermost first-layer packing and the second-layer packing or between the uppermost second-layer packing and the third-layer packing;
and the process parameters of the optimal design are also key to the success of the invention, the azeotropic point of the azeotropic system formed by the azeotropic system and the N-methyl pyrrolidone is broken through by the treatment of the step, the separation difficulty is reduced, and the separation efficiency is improved by adopting proper number of tower plates and proper height of the tower plates on the basis of the process parameters.
Preferably, in the above production method of N-methylpyrrolidone for a liquid crystal panel, the method further comprises a pressure adsorption filtration operation, and the specific steps are as follows:
n-methyl pyrrolidone obtained through rectification and purification is conveyed to a dust-free workshop through a pipeline, and reinforced ceramic fiber filtering materials with the pore diameter of 0.05-0.10 mu m are filled in a pressure filtering tank lined with polytetrafluoroethylene or poly perfluoroethylene propylene;
then replacing the pressure filtering tank with dry hot nitrogen and maintaining the pressure;
under the control of the feeding pressure control device, the pressure is alternately changed every 5-10 seconds to feed the treated pressure filtration tank, and the pressure control is respectively 0.2-0.4 MPa and 0.6-0.8 MPa.
It is further preferred that the pressure is alternately shifted every 8 seconds to feed the treated pressure filtration tank with pressure control of 0.3MPa and 0.7MPa, respectively.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the filter material is heated and activated at a temperature of 100 to 120 ℃ before the N-methylpyrrolidone obtained by rectification and purification starts to be fed.
Preferably, in the above method for producing N-methylpyrrolidone for a liquid crystal panel, the pressure adsorption filtration may be replaced by pressure-variable vacuum filtration adsorption, and the two effects are the same, and have no influence on the product quality.
The invention also discloses the N-methyl pyrrolidone for the liquid crystal display panel, which is produced by the method, if the operation of pressure adsorption and filtration is not performed, 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 ion is less than or equal to 0.5ppm, the granularity is more than 0.5 mu m and less than or equal to 5 per ml, and the N-methyl pyrrolidone is superior to the standard of SEMIC 8.
The invention also discloses the N-methyl pyrrolidone for the liquid crystal display panel, which is produced by the method, wherein the purity of the N-methyl pyrrolidone is more than or equal to 99.95 percent, the metal ion is less than or equal to 0.1ppm, the granularity is more than 0.2 mu m and less than or equal to 3 per ml after the operation of pressure adsorption and filtration, the standard of SEMIC12 is basically reached, 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 a cleaning agent or stripping liquid for electronic components.
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 SEMIC8 and SEMIC12 through innovation of reaction raw materials, reaction process and purification process and strict control of technological 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 and even can reach 99.99 percent, the particle content of impurity particles in the N-methyl pyrrolidone obtained by the method is less than or equal to 5 particles/ml when the particle size of the impurity particles in the N-methyl pyrrolidone is more than 0.5 mu m, the metal ion content of the N-methyl pyrrolidone is less than or equal to 1ppb, the metal ion content is effectively reduced, and the product with low granularity is obtained while the purity is satisfied;
(3) The electronic grade or high-purity N-methyl pyrrolidone prepared by the method is used as a cleaning solution or stripping solution in the manufacturing process of the liquid crystal display panel and as a cleaning solution in the semiconductor manufacturing step, and the electronic grade or high-purity N-methyl pyrrolidone is used as an environment-friendly electronic element cleaning agent, so that powerful support is provided for the development of liquid crystal televisions and liquid crystal displays.
Description of the embodiments
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
The embodiment 1 of the invention discloses a titanium-based heterogeneous amination composite catalyst, which is prepared by the following method:
(1) Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、Ni(NO 3 ) 2 ·6H 2 O is dissolved in deionized water to prepare 0.5mol/L solution, the temperature is raised to 60 ℃, the carrier is added and fully and uniformly stirred, 0.02mol/L dilute nitric acid or dilute sulfuric acid is gradually added dropwise in the stirring process, the mixture is fully mixed, the pH value is controlled to be 5-6, and the mixture is gradually cooled to room temperature to obtain a mixed solution A; al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、Ni(NO 3 ) 2 ·6H 2 The mole ratio of the contents of the Al, mo and Ni components in O is 1:1.2:0.5;
(2) C is C 16 H 36 O 4 Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dripping C 16 H 36 O 4 Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 10h, transferring to a hydration heat reaction kettle, reacting at 160 ℃ for 36h, cooling to room temperature, carrying out suction filtration and washing, placing a filter cake in a drying oven, drying at 120 ℃ for 20h, roasting at 500 ℃ for 2h, 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 dripping a precipitator for neutralization until the pH value is 8-9, ageing for 12h at room temperature, filtering, washing, placing a filter cake in a drying oven, drying at 120 ℃ for 8h, roasting at 600 ℃ for 4h, and grinding to obtain a catalyst carrier D;
(4) Preparing an equal volume of impregnating solution B containing Co, mn, mg, ag active components, impregnating the catalyst carrier C and the catalyst carrier D into the impregnating solution B, uniformly stirring, carrying out ultrasonic oscillation, standing for a period of time, filtering, placing a filter cake into a drying oven, drying at 120 ℃ for 8 hours, roasting at 600 ℃ for 4 hours, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Examples
The embodiment 2 of the invention discloses a titanium-based heterogeneous amination composite catalyst, which is prepared by the following method:
(1) Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O is dissolved in deionized water to prepare 1mol/L solution, and the temperature is raised toAdding the carrier, fully and uniformly stirring at 60-80 ℃, gradually dripping 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 cooling to room temperature to obtain a mixed solution A; al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 The molar ratio between the contents of Al and Mo components in O is 1:0.9;
(2) C is C 16 H 36 O 4 Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dripping C 16 H 36 O 4 Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 15h, transferring to a hydration heat reaction kettle, reacting at 200 ℃ for 24h, cooling to room temperature, carrying out suction filtration and washing, placing a filter cake in a drying oven, drying at 160 ℃ for 10h, 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 dripping a precipitator for neutralization until the pH value is 8-9, ageing for 18h at room temperature, filtering, washing, drying a filter cake in a drying oven at 160 ℃ for 5h, roasting at 800 ℃ for 3h, and grinding to obtain a catalyst carrier D;
(4) Preparing an equal volume of impregnating solution B containing Co, mn, mg, ag active components, impregnating the catalyst carrier C and the catalyst carrier D into the impregnating solution B, uniformly stirring, carrying out ultrasonic oscillation, standing for a period of time, filtering, placing a filter cake into a drying box, drying at 160 ℃ for 5h, roasting at 800 ℃ for 3h, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Examples
The embodiment 3 of the invention discloses a titanium-based heterogeneous amination composite catalyst, which is prepared by the following method:
(1) Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、H 2 PtCl 6 ·6H 2 O is dissolved in deionized water to prepare 0.8mol/L solution, the temperature is raised to 70 ℃, the carrier is added and fully and uniformly stirred, 0.3mol/L dilute nitric acid or dilute sulfuric acid is gradually added dropwise in the stirring process, and the mixture is fully mixed and controlledThe pH value is 5-6, and gradually cooled to room temperature to obtain a mixed solution A; al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、H 2 PtCl 6 ·6H 2 The mole ratio of the contents of the Al, mo and Pt components in O is 1:1.1:0.05;
(2) C is C 16 H 36 O 4 Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dripping C 16 H 36 O 4 Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 12h, transferring to a hydration heat reaction kettle, reacting for 30h at 180 ℃, cooling to room temperature, carrying out suction filtration and washing, placing a filter cake in a drying oven, drying for 15h at 14 ℃, roasting for 1.5h at 550 ℃, 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 dripping a precipitator for neutralization until the pH value is 8-9, ageing for 5h at room temperature, filtering, washing, drying a filter cake in a drying oven at 140 ℃ for 6.5h, roasting at 700 ℃ for 3.5h, and grinding to obtain a catalyst carrier D;
(4) Preparing an equal volume of impregnating solution B containing Co, mn, mg, ag active components, impregnating the catalyst carrier C and the catalyst carrier D into the impregnating solution B, uniformly stirring, carrying out ultrasonic oscillation, standing for a period of time, filtering, drying a filter cake in a drying oven at 140 ℃ for 6.5h, roasting at 700 ℃ for 3.5h, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
Examples
Example 4 was identical to the preparation of example 1, except that the catalyst components were present in different amounts, see in particular Table 1.
Examples
Example 5 was identical to the preparation of example 3, except that the catalyst component contents were different, see in particular Table 1.
Comparative example 1
Comparative example 1 was identical to the preparation method of example 3 except that the catalyst was different in the content of each component, and the Si content in comparative example 1 was 11%, exceeding the proportion range of 5 to 10% by mass of Si of the present invention.
Comparative example 2
Comparative example 2 was identical to the preparation of example 3, except that Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O and Ni (NO) 3 ) 2 ·6H 2 O was dissolved in deionized water with a molar ratio of Al to Ni of 1:0.9.
Comparative example 3
Comparative example 3 the same preparation as example 3 was carried out, except that Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O and H 2 PtCl 6 ·6H 2 O was dissolved in deionized water with a molar ratio of Al to Pt of 1:0.1.
In the above catalyst preparation process, the content of each component in the catalyst and the molar ratio of each component added in the step (1) have an important influence on the performance of the catalyst, and thus examples 1 to 5 and comparative examples 1 to 3 are obtained by changing the content of each component in the catalyst and the molar ratio of each component in the step (1), and the change in the content of each component in the catalyst is specifically shown in table 1.
TABLE 1
/>
The performance of the catalysts obtained in examples 1 to 5 and comparative examples 1 to 3 was examined, and the results obtained are shown in Table 2.
TABLE 2 detection results
The titanium-based heterogeneous amination complex catalysts obtained in examples 1 to 5 and comparative examples 1 to 3 were used to synthesize N-methylpyrrolidone for liquid crystal panels, respectively, as follows:
examples
1. And (3) a reaction section: comprises two steps of reaction.
First step amination reaction: firstly, pumping monomethylamine and gamma-butyrolactone with a molar ratio of 1.2:1 into a mixing stirring tank by a feed pump respectively, controlling the stirring preheating temperature to be 30 ℃, stirring for 5min, preheating again, wherein the preheating temperature is 120 ℃, and pumping the mixture into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst obtained in the example 1 by a metering pump for amination reaction, wherein the reaction temperature is 200 ℃ and the reaction pressure is 5MPa; the liquid hourly space velocity is 0.5h < -1 >, the crude liquid of N-methyl pyrrolidone is obtained, the crude liquid is discharged through a material outlet of the reactor, and the content of gamma-butyrolactone in the crude liquid discharged through a discharge port is controlled to be less than or equal to 0.01 percent;
and a second step of complexation reaction: the pH value of the crude liquid containing 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 according to every 10 tons of crude liquid of N-methyl pyrrolidone through a dosing device; controlling the reaction temperature to 80 ℃ and the reaction time to 10min; the crude liquid containing N-methyl pyrrolidone after the complexation reaction is sent to a gap purification section;
2. Batch purification section: the crude liquid containing N-methyl pyrrolidone obtained by the reaction stage is sent to a batch purifying tower to obtain a primary product, and the batch purifying tower mainly takes the removal of monomethylamine, water and light components (middle distillate) as main components. The operation of the intermittent purifying tower mainly comprises three stages, wherein the first stage mainly comprises the steps of removing water and monomethylamine, controlling the pressure to-80 to-75 KPa, the top temperature to be less than or equal to 60 ℃, controlling the kettle temperature to be less than or equal to 90 ℃, gradually controlling the pressure to-90 to-85 KPa after most of water and monomethylamine are extracted, controlling the top temperature to be less than or equal to 110 ℃ and controlling the kettle temperature to be less than or equal to 120 ℃; the second stage takes middle distillate removal as a main part, the pressure is controlled to be-95 to-85 KPa, the top temperature is 115 to 120 ℃, and the kettle temperature is 135 to 130 ℃; in the third stage, the primary product is extracted, the pressure is controlled to be-95 to-85 KPa, the top temperature is 120 to 125 ℃, and the kettle temperature is 135 to 140 ℃; after being treated by an intermittent purifying tower, the qualified N-methyl pyrrolidone primary product is obtained;
3. and (3) gas stripping and purifying section: the primary N-methyl pyrrolidone product obtained by the intermittent purifying 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 the intermittent rectification. The N-methyl pyrrolidone primary product obtained in the previous step is sent to a stripping tower, N-methyl pyrrolidone is fed from the top of the stripping tower and uniformly dispersed by a distributor, and then is subjected to convection and dispersion with nitrogen entering from the bottom of the tower in countercurrent between the surface of a filler and N-methyl pyrrolidone to remove light components such as free amine and partial particles in the N-methyl pyrrolidone, and the purified product is discharged from the bottom of the tower to enter the next working procedure; controlling the ratio of N-methyl pyrrolidone to nitrogen to be 1t/5m 3 Controlling the temperature of nitrogen (stripping temperature) to 80 ℃; the nitrogen gas exchanges heat with the hot material discharged after the reaction to reach the required temperature.
4. A secondary continuous rectifying section: the first stage of rectification is mainly to remove substances with boiling points close to or forming azeotropic points with N-methylpyrrolidone. Controlling the pressure to be minus 98 to minus 96KPa, the top temperature to be 95-100 ℃, the middle temperature to be 108-112 ℃, the kettle temperature to be 116-121 ℃ and the feeding amount to be less than or equal to 2500L/h; the number of tower plates of the primary rectifying tower is 45, and a feed inlet is formed in a 15 th plate; the tower body filler is filled in four sections, the stripping section filler is grid plate filler or puncture corrugated filler, and the rectifying section filler is 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 tower top extract treated by the external condenser flows back into the tower, a part of the tower top extract is extracted as a light component, and the reflux ratio (namely the ratio of reflux quantity to extraction quantity) is controlled to be 1:0.5; a part of the effluent of the tower bottom is used as the raw material of the second-stage rectification, a part of the effluent returns to the feed of the first-stage rectification tower again, the feed inlet is arranged on the 13 th plate, and the ratio of the feed returned to the first-stage rectification tower to the amount extracted into 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, so as to obtain qualified products meeting the quality requirements. Controlling the pressure to be minus 98 to minus 96KPa, the top temperature to be 96-101 ℃, the middle temperature to be 106-111 ℃, the kettle temperature to be 113-118 ℃ and the feeding quantity to be less than or equal to 3000L/h; the number of the tower plates of the secondary rectifying tower is 50, and the feeding port is formed in 18 plates; the tower body filler is filled in six sections, and the filler is ceramic plate corrugation; the stripping section: the height ratio of the rectifying section is 1:1.8; the raw materials of the second-stage rectifying tower come from tower bottom liquid discharged by the first-stage rectifying tower, so that bubble point feeding of the second-stage rectifying tower is realized; and after the tower top extract of the second-stage rectifying tower is treated by a condenser, a part of the tower top extract flows back into the tower, a part of the tower top extract is taken as the feed of the second-stage rectifying tower and is sent into the tower again, the other part of the tower top extract is taken as the product, and the ratio of the tower top extract to the second-stage rectifying tower to the third extract is controlled to be 0.8:0.2:1, a step of; the side extraction port of the second-stage rectifying tower is positioned on the 49 th theoretical plate and between the uppermost first-layer packing and the second-layer packing, the extracted product is a qualified product meeting the quality standard, and the ratio of the extracted quantity to the reflux quantity of the top extracted product is controlled to be 1:0.8.
5. pressurizing (pressure swing) adsorption filtration, and conveying the N-methyl pyrrolidone which is treated by the steps and reaches SEMIC8 standard to a dust-free workshop through a pipeline; filling a reinforced ceramic fiber filter material with the pore diameter of 0.05-0.10 mu m into a pressure tank lined with polytetrafluoroethylene or poly perfluoroethylene propylene; before starting the feeding of N-methyl pyrrolidone, heating and activating the filtering material at the temperature of 100-120 ℃; replacing the pressure filtering tank with dry hot nitrogen and maintaining the pressure; under the control of the feeding pressure control device, the pressure is alternately changed every 5-10 seconds to feed (N-methyl pyrrolidone) into the treated pressure filtration tank, and the pressure control is respectively 0.2-0.4 MPa and 0.6-0.8 MPa.
Examples
1. And (3) a reaction section: comprises two steps of reaction.
First step amination reaction: firstly, 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 and preheating temperature to 35 ℃, stirring for 8min, preheating again, wherein the preheating temperature is 160 ℃, and pumping the mixture into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst obtained in the embodiment 2 by a metering pump for amination reaction, wherein the reaction temperature is 230 ℃ and the reaction pressure is 5.5MPa; the liquid hourly space velocity is 5h < -1 >, the crude liquid of N-methyl pyrrolidone is obtained, the crude liquid is discharged from a material outlet of the reactor, and the content of gamma-butyrolactone in the crude liquid discharged from the discharge outlet is controlled to be less than or equal to 0.01 percent;
and a second step of complexation reaction: the pH value of the crude liquid containing 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 according to every 10 tons of crude liquid of N-methyl pyrrolidone through a dosing device; controlling the reaction temperature to 90 ℃ and the reaction time to 18min; the crude liquid containing N-methyl pyrrolidone after the complexation reaction is sent to a gap purification section;
2. Batch purification section: the crude liquid containing N-methyl pyrrolidone obtained by the reaction stage is sent to a batch purifying tower to obtain a primary product, and the batch purifying tower mainly takes the removal of monomethylamine, water and light components (middle distillate) as main components. The operation of the intermittent purifying tower mainly comprises three stages, wherein the first stage mainly comprises the steps of removing water and monomethylamine, controlling the pressure to-80 to-75 KPa, the top temperature to be less than or equal to 60 ℃, controlling the kettle temperature to be less than or equal to 90 ℃, gradually controlling the pressure to-90 to-85 KPa after most of water and monomethylamine are extracted, controlling the top temperature to be less than or equal to 110 ℃ and controlling the kettle temperature to be less than or equal to 120 ℃; the second stage takes middle distillate removal as a main part, the pressure is controlled to be-95 to-85 KPa, the top temperature is 115 to 120 ℃, and the kettle temperature is 135 to 130 ℃; in the third stage, the primary product is extracted, the pressure is controlled to be-95 to-85 KPa, the top temperature is 120 to 125 ℃, and the kettle temperature is 135 to 140 ℃; after being treated by an intermittent purifying tower, the qualified N-methyl pyrrolidone primary product is obtained;
3. and (3) gas stripping and purifying section: the primary N-methyl pyrrolidone product obtained by the intermittent purifying 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 the intermittent rectification. The N-methyl pyrrolidone primary product obtained in the previous step is sent to a stripping tower, N-methyl pyrrolidone is fed from the top of the stripping tower and uniformly dispersed by a distributor, and then is subjected to convection and dispersion with nitrogen entering from the bottom of the tower in countercurrent between the surface of a filler and N-methyl pyrrolidone to remove light components such as free amine and partial particles in the N-methyl pyrrolidone, and the purified product is discharged from the bottom of the tower to enter the next working procedure; controlling the ratio of N-methyl pyrrolidone to nitrogen to be 1t /7m 3 Controlling the nitrogen temperature (stripping temperature) to be 100 ℃; the nitrogen gas exchanges heat with the hot material discharged after the reaction to reach the required temperature.
4. A secondary continuous rectifying section: the first stage of rectification is mainly to remove substances with boiling points close to or forming azeotropic points with N-methylpyrrolidone. Controlling the pressure to be minus 98 to minus 96KPa, the top temperature to be 95-100 ℃, the middle temperature to be 108-112 ℃, the kettle temperature to be 116-121 ℃ and the feeding amount to be less than or equal to 2500L/h; the number of tower plates of the primary rectifying tower is 48, and a feed inlet is formed in the 18 th plate; the tower body filler is filled in four sections, the stripping section filler is grid plate filler or puncture corrugated filler, and the rectifying section filler is 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 tower top extract treated by the external condenser flows back into the tower, a part of the tower top extract is extracted as a light component, and the reflux ratio (namely the ratio of reflux quantity to extraction quantity) is controlled to be 1:0.6; a part of the effluent of the tower bottom is used as the raw material of the second-stage rectification, a part of the effluent returns to the feed of the first-stage rectification tower again, the feed inlet of the effluent is arranged on the 15 th plate, and the ratio of the feed returned to the first-stage rectification tower to the amount extracted from the effluent 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, so as to obtain qualified products meeting the quality requirements. Controlling the pressure to be minus 98 to minus 96KPa, the top temperature to be 96-101 ℃, the middle temperature to be 106-111 ℃, the kettle temperature to be 113-118 ℃ and the feeding quantity to be less than or equal to 3000L/h; the number of the tower plates of the secondary rectifying tower is 53, and the feeding port is formed in 20 plates; the tower body filler is filled in six sections, and the filler is ceramic plate corrugation; the stripping section: the height ratio of the rectifying section is 1:2.3; the raw materials of the second-stage rectifying tower come from tower bottom liquid discharged by the first-stage rectifying tower, so that bubble point feeding of the second-stage rectifying tower is realized; and after the tower top extract of the second-stage rectifying tower is treated by a condenser, a part of the tower top extract flows back into the tower, a part of the tower top extract is taken as the feed of the second-stage rectifying tower to be sent into the tower again, the other part of the tower top extract is taken as the product to be extracted, and the ratio of the three is controlled to be 0.9:0.3:1, a step of; the side extraction port of the second-stage rectifying tower is positioned on the 51 th theoretical plate and between the uppermost second-layer packing and the third-layer packing, the extracted product is a qualified product meeting the quality standard, and the ratio of the extracted quantity to the reflux quantity of the top extracted product is controlled to be 1:0.9.
5. pressurizing (pressure swing) adsorption filtration, and conveying the N-methyl pyrrolidone which is treated by the steps and reaches SEMIC8 standard to a dust-free workshop through a pipeline; filling a reinforced ceramic fiber filter material with the pore diameter of 0.05-0.10 mu m into a pressure tank lined with polytetrafluoroethylene or poly perfluoroethylene propylene; before starting the feeding of N-methyl pyrrolidone, heating and activating the filtering material at the temperature of 100-120 ℃; replacing the pressure filtering tank with dry hot nitrogen and maintaining the pressure; under the control of the feeding pressure control device, the pressure is alternately changed every 5-10 seconds to feed (N-methyl pyrrolidone) into the treated pressure filtration tank, and the pressure control is respectively 0.2-0.4 MPa and 0.6-0.8 MPa.
Examples
1. And (3) a reaction section: comprises two steps of reaction.
First step amination reaction: firstly, pumping monomethylamine and gamma-butyrolactone with a molar ratio of 1.5:1 into a mixing stirring tank by a feed pump, controlling the stirring preheating temperature to 40 ℃, stirring for 10min, preheating again, wherein the preheating temperature is 200 ℃, and pumping into a fixed bed reactor filled with the titanium-based heterogeneous amination composite catalyst obtained in the embodiment 3 by a metering pump for amination reaction, wherein the reaction temperature is 260 ℃ and the reaction pressure is 6MPa; the liquid hourly space velocity is 10h < -1 >, the crude liquid of N-methyl pyrrolidone is obtained, the crude liquid is discharged from a material outlet of the reactor, and the content of gamma-butyrolactone in the crude liquid discharged from the discharge outlet is controlled to be less than or equal to 0.01 percent;
and a second step of complexation reaction: the pH value of the crude liquid containing 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 with 3L complexing agent solution according to every 10 tons of crude liquid of N-methyl pyrrolidone through a dosing device; controlling the reaction temperature to be 100 ℃ and the reaction time to be 25min; the crude liquid containing N-methyl pyrrolidone after the complexation reaction is sent to a gap purification section;
2. Batch purification section: the crude liquid containing N-methyl pyrrolidone obtained by the reaction stage is sent to a batch purifying tower to obtain a primary product, and the batch purifying tower mainly takes the removal of monomethylamine, water and light components (middle distillate) as main components. The operation of the intermittent purifying tower mainly comprises three stages, wherein the first stage mainly comprises the steps of removing water and monomethylamine, controlling the pressure to-80 to-75 KPa, the top temperature to be less than or equal to 60 ℃, controlling the kettle temperature to be less than or equal to 90 ℃, gradually controlling the pressure to-90 to-85 KPa after most of water and monomethylamine are extracted, controlling the top temperature to be less than or equal to 110 ℃ and controlling the kettle temperature to be less than or equal to 120 ℃; the second stage takes middle distillate removal as a main part, the pressure is controlled to be-95 to-85 KPa, the top temperature is 115 to 120 ℃, and the kettle temperature is 135 to 130 ℃; in the third stage, the primary product is extracted, the pressure is controlled to be-95 to-85 KPa, the top temperature is 120 to 125 ℃, and the kettle temperature is 135 to 140 ℃; after being treated by an intermittent purifying tower, the qualified N-methyl pyrrolidone primary product is obtained;
3. and (3) gas stripping and purifying section: the primary N-methyl pyrrolidone product obtained by the intermittent purifying 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 the intermittent rectification. The N-methyl pyrrolidone primary product obtained in the previous step is sent to a stripping tower, N-methyl pyrrolidone is fed from the top of the stripping tower and uniformly dispersed by a distributor, and then is subjected to convection and dispersion with nitrogen entering from the bottom of the tower in countercurrent between the surface of a filler and N-methyl pyrrolidone to remove light components such as free amine and partial particles in the N-methyl pyrrolidone, and the purified product is discharged from the bottom of the tower to enter the next working procedure; controlling the ratio of N-methyl pyrrolidone to nitrogen to be 1t/9m 3 Controlling the temperature of nitrogen (stripping temperature) to be 120 ℃; the nitrogen gas exchanges heat with the hot material discharged after the reaction to reach the required temperature.
4. A secondary continuous rectifying section: the first stage of rectification is mainly to remove substances with boiling points close to or forming azeotropic points with N-methylpyrrolidone. Controlling the pressure to be minus 98 to minus 96KPa, the top temperature to be 95-100 ℃, the middle temperature to be 108-112 ℃, the kettle temperature to be 116-121 ℃ and the feeding amount to be less than or equal to 2500L/h; the number of the tower plates of the primary rectifying tower is 50, and the feeding port is arranged on the 20 th plate; the tower body filler is filled in four sections, the stripping section filler is grid plate filler or puncture corrugated filler, and the rectifying section filler is 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 tower top extract treated by the external condenser flows back into the tower, a part of the tower top extract is extracted as a light component, and the reflux ratio (namely the ratio of reflux quantity to extraction quantity) is controlled to be 1:0.6; a part of the effluent of the tower bottom is used as the raw material of the second-stage rectification, a part of the effluent returns to the feed of the first-stage rectification tower again, the feed inlet is arranged on the 18 th plate, and the ratio of the feed returned to the first-stage rectification tower to the amount extracted into 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, so as to obtain qualified products meeting the quality requirements. Controlling the pressure to be minus 98 to minus 96KPa, the top temperature to be 96-101 ℃, the middle temperature to be 106-111 ℃, the kettle temperature to be 113-118 ℃ and the feeding quantity to be less than or equal to 3000L/h; the number of the tower plates of the secondary rectifying tower is 55, and the feeding port is formed in 22 plates; the tower body filler is filled in six sections, and the filler is ceramic plate corrugation; the stripping section: the height ratio of the rectifying section is 1:2.5; the raw materials of the second-stage rectifying tower come from tower bottom liquid discharged by the first-stage rectifying tower, so that bubble point feeding of the second-stage rectifying tower is realized; and after the tower top extract of the second-stage rectifying tower is treated by a condenser, a part of the tower top extract flows back into the tower, a part of the tower top extract is taken as the feed of the second-stage rectifying tower to be sent into the tower again, the other part of the tower top extract is taken as the product to be extracted, and the ratio of the three is controlled to be 1:0.5:1, a step of; the side extraction port of the second-stage rectifying tower is positioned on the 52 th theoretical plate and between the uppermost first-layer packing and the second-layer packing, the extracted product is a qualified product meeting the quality standard, and the ratio of the extracted quantity to the reflux quantity of the top extracted product is controlled to be 1:1.
6. pressurizing (pressure swing) adsorption filtration, and conveying the N-methyl pyrrolidone which is treated by the steps and reaches SEMIC8 standard to a dust-free workshop through a pipeline; filling a reinforced ceramic fiber filter material with the pore diameter of 0.05-0.10 mu m into a pressure tank lined with polytetrafluoroethylene or poly perfluoroethylene propylene; before starting the feeding of N-methyl pyrrolidone, heating and activating the filtering material at the temperature of 100-120 ℃; replacing the pressure filtering tank with dry hot nitrogen and maintaining the pressure; under the control of the feeding pressure control device, the pressure is alternately changed every 5-10 seconds to feed (N-methyl pyrrolidone) into the treated pressure filtration tank, and the pressure control is respectively 0.2-0.4 MPa and 0.6-0.8 MPa.
Examples
Example 9 was identical to the synthesis of example 6, except that the titanium-based heterogeneous amination complex catalyst obtained in example 4 was packed during the amination reaction.
Examples
Example 10 was identical to the synthesis of example 7, except that the titanium-based heterogeneous amination complex catalyst obtained in example 5 was packed during the amination reaction.
Comparative example 4
Comparative example 4 was identical to the synthesis method of example 7, except that the titanium-based heterogeneous amination complex catalyst obtained in comparative example 1 was packed during the amination reaction.
Comparative example 5
Comparative example 5 was identical to the synthesis method of example 7, except that the titanium-based heterogeneous aminated composite catalyst obtained in comparative example 2 was packed during the amination reaction.
Comparative example 6
Comparative example 6 was identical to the synthesis method of example 7, except that the titanium-based heterogeneous amination complex catalyst obtained in comparative example 3 was packed during the amination reaction.
The N-methylpyrrolidone products obtained after the secondary rectification in examples 6 to 10 and comparative examples 4 to 6 are respectively detected by ICP-MS, the detection results meet SEMIC8 standard, and the specific detection results are shown in Table 4; meanwhile, products after pressurized adsorption filtration are respectively detected, the detection results meet SEMIC12 standard, the specific detection results are shown in Table 5, and the SEMI international standard grade of the process chemicals is shown in Table 3.
TABLE 3 SEMI International Standard grade for Process chemicals
TABLE 4C8 Metal ion detection results (Unit: ppb)
/>
TABLE 5C12 Metal ion detection results (Unit: ppb)
/>
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
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 (20)
1. The application of the titanium-based heterogeneous amination composite catalyst in preparing N-methylpyrrolidone 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;
The preparation method of the titanium-based heterogeneous amination composite catalyst comprises the following steps:
(1) Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、Ni(NO 3 ) 2 ·6H 2 O、H 2 PtCl 6 ·6H 2 O is dissolved in deionized water to prepare 0.5-1 mol/L solution, the temperature is raised to 60-80 ℃, the carrier is added and fully and uniformly stirred, 0.02-0.5 mol/L dilute nitric acid or dilute sulfuric acid is gradually added dropwise in the stirring process, the mixture is fully mixed, the pH value is controlled to be 5-6, and the mixture is gradually cooled to room temperature to obtain mixed solution A; said Al (NO) 3 ) 3 ·9H 2 O、Mo(NO 3 ) 3 ·5H 2 O、Ni(NO 3 ) 2 ·6H 2 O、H 2 PtCl 6 ·6H 2 The molar ratio of the Al, mo, ni, pt components in O is 1:0.5 to 1.5:0 to 0.8:0 to 0.05;
(2) C is C 16 H 36 O 4 Dissolving Si in 0.02mol/L dilute nitric acid or dilute sulfuric acid, controlling the temperature to be 20-30 ℃, and dripping C 16 H 36 O 4 Ti, stirring, dropwise adding ammonia water, controlling the pH value to be 6.5-7.5, continuously stirring for 10-15 h, transferring into a hydration heat reaction kettle, reacting for 24-36 h at 160-200 ℃, cooling to room temperature, carrying out suction filtration, washing, placing a filter cake into a drying box, drying for 10-20 h at 120-160 ℃, 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 dripping a precipitator for neutralization until the pH value is 8-9, ageing for 12-18 h at room temperature, filtering, washing, placing a filter cake in a drying oven for drying for 5-8 h at 120-160 ℃, roasting for 3-4 h at 600-800 ℃, and grinding to obtain a catalyst carrier D;
(4) Preparing an equal volume impregnating solution B containing Co, mn, mg, ag active components, impregnating the catalyst carrier C and the catalyst carrier D into the impregnating solution B, uniformly stirring, carrying out ultrasonic oscillation, standing for a period of time, filtering, drying a filter cake in a drying oven at 120-160 ℃ for 5-8 h, roasting at 600-800 ℃ for 3-4 h, and forming to obtain the titanium-based heterogeneous amination composite catalyst.
2. The production method of the N-methyl pyrrolidone for the liquid crystal display panel is characterized by comprising a reaction section, wherein the amination reaction step of the reaction section is as follows:
(1) Pumping monomethylamine and gamma-butyrolactone into a mixing stirring tank by a feed pump respectively, controlling the stirring 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 perform amination reaction to obtain N-methyl pyrrolidone crude liquid;
(3) The crude N-methyl pyrrolidone liquid is discharged from a material outlet of the fixed bed reactor, and the content of gamma-butyrolactone in the crude N-methyl pyrrolidone liquid discharged from the outlet is controlled to be less than or equal to 0.01 percent.
3. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 2, wherein in the step (1), a molar ratio of the monomethylamine to the 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 。
4. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 2, wherein the mixed solution is preheated again before being fed into a fixed bed reactor at a temperature of 120 to 200 ℃.
5. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 2, wherein the reaction section further comprises a complexation 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 the reaction time to be 10-25 min;
(C) The N-methyl pyrrolidone crude liquid after the complexation reaction is sent to a batch purification section.
6. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 2, wherein the reaction section further comprises a complexation reaction, comprising the steps of:
(A) Preparing a metal ion complexing agent solution with the concentration of 0.5-1.0 mol/L;
(B) Before the amination reaction is carried out, adding the metal ion complexing agent solution into raw material gamma-butyrolactone, and pumping the raw material gamma-butyrolactone into a mixing and stirring tank by a feed pump along with the gamma-butyrolactone;
Or continuously and uniformly adding the metal ion complexing agent solution in a mixing and stirring tank for amination reaction through a dosing device.
7. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 5, wherein the volume ratio of the mass of the N-methylpyrrolidone crude liquid to the metal ion complexing agent solution is 10000kg: (2-3) L.
8. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 6, wherein a volume ratio of the mass of the γ -butyrolactone to the metal ion complexing agent solution is 10000kg: (2-3) L.
9. The method for producing N-methylpyrrolidone for a liquid crystal panel according to any one of claims 2 to 8, further comprising the subsequent purification of the N-methylpyrrolidone crude liquid, comprising the steps of:
(S1) batch purification section
Conveying the N-methyl pyrrolidone crude liquid into an intermittent purifying tower to remove monomethylamine, water and light components, so as to obtain an N-methyl pyrrolidone primary product with the purity of more than 99.8%;
(S2) gas stripping purification section
Feeding the N-methyl pyrrolidone primary product from the top of the stripping tower, uniformly dispersing the N-methyl pyrrolidone primary product by a distributor, and then carrying out convection and dispersion on the N-methyl pyrrolidone primary product and nitrogen entering from the bottom of the stripping tower in a countercurrent manner on the surface of a filler to remove light components and part of particles in the N-methyl pyrrolidone primary product, and discharging the purified product from the bottom of the stripping tower to enter the next working 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 number of tower plates of 45-50 from 15-20 to remove substances with the boiling point close to that of the N-methyl pyrrolidone or with the N-methyl pyrrolidone to form an azeotropic point; part of tower bottom liquid discharged from the first-stage rectifying tower is used as the raw material of the second-stage rectifying tower according to the proportion of 0.2-0.5:1, and the other part of tower bottom liquid returns to the feed inlet of the first-stage rectifying tower and returns to the 13 th-18 th plate of the feed inlet of the first-stage rectifying tower;
second-stage rectification: the raw materials of the second-stage rectifying tower are bubble point feed, 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 the 18 th-22 th plate of the feed inlet of the second-stage rectifying tower, and tower top extract is processed by a condenser and then is processed according to the ratio of 0.8-1: 0.2 to 0.5:1, one part of the mixture is refluxed into the second-stage rectifying tower, the other part of the mixture is fed into the second-stage rectifying tower again as feed, and the rest part of the mixture is extracted as a product, so that the N-methylpyrrolidone meeting the quality requirement is obtained.
10. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 9, wherein the batch purification column in step (S1) is operated mainly in three stages:
The first stage is to take the water and monomethylamine as main components, control the pressure to minus 80 to minus 75KPa, the top temperature to minus 60 ℃, the kettle temperature to minus 90 ℃, gradually control the pressure to minus 90 to minus 85KPa, control the top temperature to minus 110 ℃ and control the kettle temperature to minus 120 ℃ after most of water and monomethylamine are extracted;
the second stage takes middle distillate removal as a main part, the pressure is controlled to be-95 to-85 KPa, the top temperature is 115 to 120 ℃, and the kettle temperature is 135 to 130 ℃;
and in the third stage, the primary product is extracted, the pressure is controlled to be-95 to-85 KPa, the top temperature is 120 to 125 ℃, and the kettle temperature is 135 to 140 ℃.
11. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 9, wherein the ratio of the N-methylpyrrolidone primary product to nitrogen in the step (S2) is 1t: (5-9) m 3 And the nitrogen temperature is controlled to be 80-120 ℃.
12. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 9, wherein in the step (S3), the pressure in the first-stage rectifying column is-98 to-96 KPa, the top temperature is 95-100 ℃, the middle temperature is 108-112 ℃, the kettle temperature is 116-121 ℃, and the feeding amount is less than or equal to 2500L/h.
13. The method according to claim 9, wherein in the step (S3), the first-stage rectifying tower is provided with an internal condenser and an external condenser, and a part of the overhead product treated by the external condenser is refluxed into the tower, and the other part is recovered as a light component, and the reflux ratio is controlled to be 1:0.5-0.8.
14. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 9, wherein in the step (S3), the pressure in the second-stage rectifying column is-98 to-96 KPa, the top temperature is 96-101 ℃, the middle temperature is 106-111 ℃, the kettle temperature is 113-118 ℃, and the feeding amount is less than or equal to 3000L/h.
15. The method according to claim 9, wherein the second rectifying column further comprises a side offtake located between 48 th and 53 th plates and located between the uppermost first layer packing and the second layer packing or between the uppermost second layer packing and the third layer packing, and the ratio of the offtake to the reflux amount of the overhead offtake is 1:0.8 to 1.
16. The method for producing N-methylpyrrolidone for liquid crystal panels according to claim 9, wherein the packing materials of the batch purification column, the stripping column, the first-stage rectification column and the second-stage rectification column are all high-silicon ceramic packing materials, and the silicon content is not less than 70%.
17. The method for producing N-methylpyrrolidone for a liquid crystal panel according to claim 9, further comprising a pressure adsorption filtration operation, comprising the specific steps of:
N-methyl pyrrolidone obtained through rectification and purification is conveyed to a dust-free workshop through a pipeline, and reinforced ceramic fiber filtering materials with the pore diameter of 0.05-0.10 mu m are filled in a pressure filtering tank lined with polytetrafluoroethylene or poly perfluoroethylene propylene;
before starting feeding, heating and activating the filter material at the temperature of 100-120 ℃, and then replacing and maintaining the pressure of the pressure filter tank by using dry hot nitrogen;
under the control of the feeding pressure control device, the pressure is alternately changed every 5-10 seconds to feed the treated pressure filtration tank, and the pressure control is respectively 0.2-0.4 MPa and 0.6-0.8 MPa.
18. An N-methylpyrrolidone for a liquid crystal panel produced by the method of any one of claims 9 to 16, wherein the N-methylpyrrolidone has a comprehensive yield of not less than 98%, a purity of not less than 99.95%, metal ions of not more than 0.5 ppb, and a particle size of not more than 0.5 μm and not more than 5/ml.
19. The N-methylpyrrolidone for liquid crystal panels produced by the method of claim 17, wherein the purity of the N-methylpyrrolidone is not less than 99.95%, the metal ion is not more than 0.1ppb, and the granularity is not more than 0.2 μm and not more than 3/ml.
20. Use of N-methylpyrrolidone for a liquid crystal panel according to any one of claims 18 to 19, characterized in that the N-methylpyrrolidone is used as a cleaning agent for electronic components or a stripping liquid.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010383330.9A CN111530472B (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel |
| CN202010808764.9A CN111892525A (en) | 2020-05-08 | 2020-05-08 | N-methyl pyrrolidone for liquid crystal panel and production process thereof |
| CN202010807543.XA CN111974411A (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010383330.9A CN111530472B (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010808764.9A Division CN111892525A (en) | 2020-05-08 | 2020-05-08 | N-methyl pyrrolidone for liquid crystal panel and production process thereof |
| CN202010807543.XA Division CN111974411A (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111530472A CN111530472A (en) | 2020-08-14 |
| CN111530472B true CN111530472B (en) | 2023-10-31 |
Family
ID=71970519
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010807543.XA Pending CN111974411A (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and preparation method and application thereof |
| CN202010383330.9A Active CN111530472B (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel |
| CN202010808764.9A Pending CN111892525A (en) | 2020-05-08 | 2020-05-08 | N-methyl pyrrolidone for liquid crystal panel and production process thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010807543.XA Pending CN111974411A (en) | 2020-05-08 | 2020-05-08 | Titanium-based heterogeneous amination composite catalyst and preparation method and application thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010808764.9A Pending CN111892525A (en) | 2020-05-08 | 2020-05-08 | N-methyl pyrrolidone for liquid crystal panel and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN111974411A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185441A (en) * | 2021-04-26 | 2021-07-30 | 宁波南大光电材料有限公司 | Purification method for reducing chroma of N-methyl pyrrolidone |
| CN116409839B (en) * | 2023-06-12 | 2023-08-08 | 东莞市鹏锦机械科技有限公司 | NMP waste liquid purification system and technology |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101045A (en) * | 1990-06-07 | 1992-03-31 | Basf Aktiengesellschaft | Preparation of n-substituted pyrrolidones |
| JPH10118495A (en) * | 1996-10-22 | 1998-05-12 | Catalysts & Chem Ind Co Ltd | Titania-alumina carrier, its manufacturing method and hydrogenating catalyst using this carrier |
| CN1186453A (en) * | 1995-06-02 | 1998-07-01 | 陶氏化学公司 | Catalyst and process for producing amides |
| KR20070075550A (en) * | 2006-01-13 | 2007-07-24 | 삼성에스디아이 주식회사 | Electrode for fuel cell, manufacturing method thereof, and fuel cell employing the same |
| CN101081362A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Carrier containing magnalium complexes and method for preparing the same |
| CN101781219A (en) * | 2009-12-31 | 2010-07-21 | 茂名云龙工业发展有限公司 | Method for continuous production of N-methyldiethanolamine |
| KR20110037895A (en) * | 2009-10-07 | 2011-04-13 | 에스케이이노베이션 주식회사 | PROCESS FOR PREPARING OF γ-BUTYROLACTONE AND N-METHYL PYRROLIDONE FROM 1,4-BUTANEDIOL |
| CN105237456A (en) * | 2015-10-19 | 2016-01-13 | 北京石油化工学院 | Production method of pyrrolidone products |
| CN105399940A (en) * | 2015-11-10 | 2016-03-16 | 万华化学集团股份有限公司 | Preparation method of polyether amine |
| CN106492818A (en) * | 2015-09-07 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation MX |
| CN108794371A (en) * | 2017-04-27 | 2018-11-13 | 迈奇化学股份有限公司 | A kind of process for purification of N-Methyl pyrrolidone product |
| CN110526849A (en) * | 2019-09-29 | 2019-12-03 | 迈奇化学股份有限公司 | A kind of method that the amination of 1,4- butanediol prepares alkyl pyrrolidone |
-
2020
- 2020-05-08 CN CN202010807543.XA patent/CN111974411A/en active Pending
- 2020-05-08 CN CN202010383330.9A patent/CN111530472B/en active Active
- 2020-05-08 CN CN202010808764.9A patent/CN111892525A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101045A (en) * | 1990-06-07 | 1992-03-31 | Basf Aktiengesellschaft | Preparation of n-substituted pyrrolidones |
| CN1186453A (en) * | 1995-06-02 | 1998-07-01 | 陶氏化学公司 | Catalyst and process for producing amides |
| JPH10118495A (en) * | 1996-10-22 | 1998-05-12 | Catalysts & Chem Ind Co Ltd | Titania-alumina carrier, its manufacturing method and hydrogenating catalyst using this carrier |
| KR20070075550A (en) * | 2006-01-13 | 2007-07-24 | 삼성에스디아이 주식회사 | Electrode for fuel cell, manufacturing method thereof, and fuel cell employing the same |
| CN101081362A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Carrier containing magnalium complexes and method for preparing the same |
| KR20110037895A (en) * | 2009-10-07 | 2011-04-13 | 에스케이이노베이션 주식회사 | PROCESS FOR PREPARING OF γ-BUTYROLACTONE AND N-METHYL PYRROLIDONE FROM 1,4-BUTANEDIOL |
| CN101781219A (en) * | 2009-12-31 | 2010-07-21 | 茂名云龙工业发展有限公司 | Method for continuous production of N-methyldiethanolamine |
| CN106492818A (en) * | 2015-09-07 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation MX |
| CN105237456A (en) * | 2015-10-19 | 2016-01-13 | 北京石油化工学院 | Production method of pyrrolidone products |
| CN105399940A (en) * | 2015-11-10 | 2016-03-16 | 万华化学集团股份有限公司 | Preparation method of polyether amine |
| CN108794371A (en) * | 2017-04-27 | 2018-11-13 | 迈奇化学股份有限公司 | A kind of process for purification of N-Methyl pyrrolidone product |
| CN110526849A (en) * | 2019-09-29 | 2019-12-03 | 迈奇化学股份有限公司 | A kind of method that the amination of 1,4- butanediol prepares alkyl pyrrolidone |
Non-Patent Citations (2)
| Title |
|---|
| 关于制取长链烷基N,N-二甲基叔胺的催化剂的研究;张贤丰;《当代化工》;19891231(第05期);第39-43页 * |
| 还原胺化合成乙二胺催化剂的制备及表征;孙果宋等;《化工技术与开发》;20101015(第10期);第8-11页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111974411A (en) | 2020-11-24 |
| CN111530472A (en) | 2020-08-14 |
| CN111892525A (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111530472B (en) | Titanium-based heterogeneous amination composite catalyst and application thereof in production of N-methylpyrrolidone for liquid crystal display panel | |
| CN105418368A (en) | Technology and device for producing high-purity ethyl alcohol | |
| CN113461644A (en) | Method for recovering tetrahydrofuran from waste solvent | |
| CN107805203A (en) | A kind of preparation method of hexamethylene diamine | |
| CN112647085A (en) | Method for synthesizing high-purity disilane through electrocatalysis | |
| CN210787302U (en) | Device for continuously producing high-purity potassium alkoxide or sodium alkoxide by using microchannel reactor | |
| CN110483234B (en) | Method for purifying electronic grade octafluorocyclopentene | |
| CN103819344A (en) | Synthesis method of 1,2-propane diamine | |
| CN102796011A (en) | Preparation method for p-aminodiphenylamine | |
| CN112047832A (en) | N, N-dimethylacetamide wastewater recovery process | |
| CN110526849B (en) | Method for preparing alkyl pyrrolidone by 1, 4-butanediolamine | |
| CN214830033U (en) | Battery level NMP production system | |
| CN105585503B (en) | The method that ethylenediamine is produced using monoethanolamine and liquefied ammonia as raw material | |
| CN114656342A (en) | Method for producing acetophenone by removing 2-phenylisopropanol impurity from hazardous waste | |
| CN109824498B (en) | Diacetone alcohol continuous production device and production process | |
| CN113620844A (en) | Dicyandiamide crystallization separation method and device | |
| CN112663074A (en) | System for synthesizing high-purity disilane through electrocatalysis | |
| CN113979910B (en) | Continuous preparation method of N-methyl pyrrolidone | |
| EP4119532B1 (en) | Method for preraring isopropyl alcohol | |
| CN220159254U (en) | Separation system of N, N-dimethylformamide | |
| CN114452669B (en) | Reclaimed material liquid rectifying and purifying system containing NMP | |
| CN109626358A (en) | Using cobalt aluminium as the purification method of carbon nanometer pipe of principal metal impurities and by its carbon nanotube after purification | |
| CN218853495U (en) | Baffle tower for concentration and purification of propiolic alcohol | |
| CN114477186B (en) | Polysilicon cold hydrogenation production system | |
| CN114920787B (en) | Preparation method of fructose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |