CN1944393A - Process for continuously preparing nitro-xylene isomer monomer - Google Patents
Process for continuously preparing nitro-xylene isomer monomer Download PDFInfo
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- CN1944393A CN1944393A CN 200610083840 CN200610083840A CN1944393A CN 1944393 A CN1944393 A CN 1944393A CN 200610083840 CN200610083840 CN 200610083840 CN 200610083840 A CN200610083840 A CN 200610083840A CN 1944393 A CN1944393 A CN 1944393A
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- 238000000034 method Methods 0.000 title claims abstract description 50
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000000178 monomer Substances 0.000 title claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 146
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 85
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000003738 xylenes Chemical class 0.000 claims abstract description 26
- HDFQKJQEWGVKCQ-UHFFFAOYSA-N 1,3-dimethyl-2-nitrobenzene Chemical compound CC1=CC=CC(C)=C1[N+]([O-])=O HDFQKJQEWGVKCQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- HFZKOYWDLDYELC-UHFFFAOYSA-N 1,2-dimethyl-4-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1C HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 claims abstract description 19
- BBUPBICWUURTNP-UHFFFAOYSA-N 2,4-dimethyl-1-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C(C)=C1 BBUPBICWUURTNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- BSFHJMGROOFSRA-UHFFFAOYSA-N 1,4-dimethyl-2-nitrobenzene Chemical compound CC1=CC=C(C)C([N+]([O-])=O)=C1 BSFHJMGROOFSRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 125
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 111
- 239000002253 acid Substances 0.000 claims description 94
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 87
- 239000002351 wastewater Substances 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 51
- 238000006396 nitration reaction Methods 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 46
- 241000282326 Felis catus Species 0.000 claims description 44
- 239000003513 alkali Substances 0.000 claims description 42
- 238000000926 separation method Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000010992 reflux Methods 0.000 claims description 35
- 238000006386 neutralization reaction Methods 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 12
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 12
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 abstract 2
- 230000001546 nitrifying effect Effects 0.000 abstract 1
- 229940078552 o-xylene Drugs 0.000 abstract 1
- 238000013386 optimize process Methods 0.000 abstract 1
- 239000008236 heating water Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 9
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 4
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- -1 dinitro compound Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- MEJYDZQQVZJMPP-ULAWRXDQSA-N (3s,3ar,6r,6ar)-3,6-dimethoxy-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan Chemical compound CO[C@H]1CO[C@@H]2[C@H](OC)CO[C@@H]21 MEJYDZQQVZJMPP-ULAWRXDQSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VLKYKLNZVULGQK-UHFFFAOYSA-N 1,2-dimethyl-3,4-dinitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1C VLKYKLNZVULGQK-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005518 chemical engineering design Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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Abstract
The present invention is continuous xylene isomer monomer nitrifying and rectifying process with sulfuric acid and nitric acid mixture to obtain nitro xylene isomer monomer. The optimized process has product yield over 97 %; consumption of xylene, nitric acid and sulfuric acid of 750kg/ton, 465kg/ton and 40kg/ton separately; and purity of the 2, 6-dimethyl nitrobenzene, 2, 4-dimethyl nitrobenzene, 3, 4-dimethyl nitrobenzene, 2, 3-dimethyl nitrobenzene and 2, 5-dimethyl nitrobenzene up to 99.5 %. When the process has the material changed from xylene to o-xylene or p-xylene and the technological conditions changed correspondingly, 3, 4-dimethyl nitrobenzene, 2, 3-dimethyl nitrobenzene and 2, 5-dimethyl nitrobenzene may be produced.
Description
Technical field
The present invention relates to prepare with nitre, sulphur nitration mixture and xylene isomer monomer continuous nitrification and continuous rectification the method for nitro-xylene isomer monomer, be specifically related to prepare with meta-xylene, ortho-xylene, paraxylene nitration reaction and rectifying respectively with nitre, sulphur nitration mixture the method for 2-nitro meta-xylene, 4-Nitro-m-xylene, 4-nitro ortho-xylene, 3-nitro ortho-xylene and 2-nitro paraxylene.
Technical background
Nitroxylene has six kinds of isomers, and molecular formula all is C8H
9NO
2, have five kinds of industrial application value are arranged: 2-nitro meta-xylene is also referred to as 2,6-dimethyl nitrobenzene or 2-nitro-1,3-dimethyl benzene; 4-Nitro-m-xylene is also referred to as 2,4-dimethyl nitrobenzene or 4-nitro-1,3-dimethyl benzene; 4-nitro ortho-xylene is also referred to as 3,4-dimethyl nitrobenzene or 1,2-dimethyl-4-nitrobenzene; 3-nitro ortho-xylene is also referred to as 2,3-dimethyl nitrobenzene or 1,2-dimethyl-3-nitrobenzene; 2-nitro paraxylene is also referred to as 2,5-dimethyl nitrobenzene or Isosorbide-5-Nitrae-dimethyl-2-nitrobenzene. Physical data such as following table:
The classical nitration method of dimethylbenzene is to use HNO3-H
2SO
4Nitration mixture prepares nitro-xylene isomer monomer with the mixture of dimethylbenzene or xylene isomer monomer nitration reaction and rectifying. 2,6-, 2,4-, 3,4-, 2,3-and 2,5-dimethyl nitrobenzene are used as respectively the important intermediate of agricultural chemicals, medicine, veterinary drug, spices and dyestuff.
Classical these isomerism vivo reaction types of preparation are respectively:
" dye industry " the 2nd phase " 2 in 2000,4 and 2,6-dimethyl nitrobenzene preparation method's improvement " literary composition thinks: ripe through the nitrated industrial route of nitration mixture take meta-xylene as raw material at present, but existing problems are productive rate not high (85-90%), the nitration mixture consumption is large, particularly the sulfuric acid consumption is large, and the spent acid amount is many. Two authors consumption for improving productive rate and reducing nitration mixture (mainly being sulfuric acid), with atent solvent 1, the solvent of 2-dichloroethanes during as mixed acid nitrification, productive rate reaches 96%, and the consumption of nitration mixture greatly descends. " Chemical Engineering Design " 2000,10 (2) " New Process of Pipe Type Continuous Nitrations " literary composition is thought: take meta-xylene as raw material, it Duos a methyl than toluene on phenyl ring, character is comparatively active, easier generation cascade reaction produces dinitride and oxidation reaction produces the accessory substances such as nitrophenol, and accessory substance is difficult to control, and accessory substance is far longer than other aromatic hydrocarbons one nitrated level. This not only increases consumption, and also increases unsafe factor, brings very large difficulty for the isomer separation of postorder. The author develops tubular type continuous nitrification technique and overcomes the above problems. " dyestuff and dyeing " in August, 2003 " catalysis location nitration 3, the 4-dimethyl nitrobenzene " disclose ortho-xylene in the presence of catalyst, 10-30 ℃, carry out nitrated with theoretical amount nitric acid, in the itrated compound 3,4-dimethyl nitrobenzene yield is higher than 88%, and content reaches 70-75%, improve more than 30% than old technology, and wastewater flow rate reduces 4/5 than original. " chemistry of forest product and industry " in March, 98 " isomer 2,4 and 2,6-dimethyl nitrobenzene separate " disclose isomer 2,4 and 2, the separation of 6-dimethyl nitrobenzene is by meta- xylene system 2,4 and the critical process of 2,6-dimethylaniline, meta-xylene is in the nitrification liquid that nitration reaction generates, contain 2,4 and 2,6-dimethyl nitrobenzene and a small amount of 3, the impurity such as 5-dimethyl nitrobenzene and dinitro compound, adopt the intermittent rectification under vacuum mode, 2.2 meters of novel combination type compounded mixs, 40 of the numbers of plates, reflux ratio 5-6, vacuum 666.6Pa, can obtain pure 2,4 and 2,6-dimethyl nitrobenzene. " agricultural chemicals " 95 years the 1st phases, " batch fractionating separated 2,4 and 2, the 6-dimethyl nitrobenzene " be disclosed in 20 millimeters of internal diameters, the high 1200 millimeters filling extract rectification post, adopt the method for intermittent rectification under vacuum get content greater than 98% 2,4 and 2, the 6-dimethyl nitrobenzene, reflux ratio 7-9, capital pressure 0.002MPa.
CN90102390.6 " 2,4-dimethylaniline and 2, the preparation method of 6-dimethylaniline ", wherein illustrated 2,4-and 2, the preparation method of 6-dimethyl nitrobenzene: be mixed with nitration mixture with 28-32 part nitric acid, 52-60 part sulfuric acid, 12-16 part water, drop into 100 kilograms in the 500 liter nitrating pots and contain 98% meta-xylene, the control reaction temperature is 15-20 ℃, mixing speed is 150 rev/mins, evenly drips 100 kilograms of nitration mixture in 1 hour, then under same mixing speed, the control reaction temperature is at 25-30 ℃, continuation evenly dripped 100 kilograms of nitration mixture in 1 hour, then continue stirring reaction half an hour, discarded lower floor's spent acid after leaving standstill, with the washing of 6% aqueous sodium carbonate, wash with water to neutrality again. To be washed till in the neutral about 240.8 kilograms of input rectifying columns of meta-xylene itrated compound, control rectifying reflux ratio is 6: 1; The about 0.087MPa of the serious reciprocal of duty cycle of control tower, collecting 108 ℃ of fore-runnings mainly is about 0.8 kilogram of meta-xylene, wherein 2,4-dimethyl nitrobenzene and 2,6-dimethyl nitrobenzene content are all less than 0.1%; The top vacuum degree is brought up to 0.099MPa, collect the 108-110 ℃ of section of heating up in a steamer content and be 97.48% 2, about 23.8 kilograms of 6-dimethyl nitrobenzene, wherein 2,4-dimethyl nitrobenzene content is less than 0.10%; Collect about 38.0 kilograms of the 110-120 ℃ section of heating up in a steamer, wherein 2,6-dimethyl nitrobenzene content is that 28.27%, 2,4-dimethyl nitrobenzene content is 70.75%; Raffinate is about 173.5 kilograms in the tower, and wherein 2,4-dimethyl nitrobenzene content is that 91.61%, 2,6-dimethyl nitrobenzene content is less than 0.10%. 0.8 kilogram fore-running product is again as nitrated raw material, the 110-120 ℃ of section of heating up in a steamer product again rectifying in next batch, the 108-110 ℃ of section of heating up in a steamer product---main component is 2, the 6-dimethyl nitrobenzene is as raw material, raffinate in the tower---main component be 2,4-dimethyl nitrobenzene as raw material, be respectively applied to Hydrogenation standby 2,6-dimethylaniline and 2,4-dimethylaniline.
United States Patent (USP) 3371122 has disclosed the nitration mixture (19.50%HNO that drops into 2720 Pounds Per Hours3、62.53％H
2SO
4Form with 17.97% water) continuously flow into stainless steel reactor with the mixture of 9340 Pounds Per Hours of dimethylbenzene, 45 ℃ of reaction temperatures, input the stirring energy of 30 horsepowers/1000 gallons of materials, 14 minutes time of staying, the nitroxylene productive rate is 95.5%, finished product contains unreacted dimethylbenzene 0.80%, dinitro dimethylbenzene 0.84%, nitrophenol 0.011%. United States Patent (USP) 6703532 has disclosed the nitrated improvement technique of a kind of xylene isomer, does the catalyst still reaction with zeolite, and high selectivity generates 4-nitro neighbour and meta-xylene. Exempted the post processing of spent acid and salkali waste fully. It comprises substrate and nitric acid nitrating reaction, and the mol ratio of dimethylbenzene and nitric acid is 1: 0.8 to 1: 1.5, and reaction is 4 hours under the solvent refluxing temperature, reclaims nitrated end product with conventional method. But nitric acid adds with control device in specified period in an embodiment of the present invention. Concentration of nitric acid is 70% in another embodiment, and dimethylbenzene and nitric acid mol ratio are preferred 1: 1.0 to 1: 1.25 in another embodiment. The solvent that is used in another embodiment reaction is selected from one or more of dichloroethanes, carrene, carbon tetrachloride and dimethylbenzene. Range of reaction temperature is 90～120 ℃ in another embodiment, 4 hours cycles.
Both at home and abroad to generally believe that nitration mixture demonstrates in Dan Ji and the reaction of double-basis aromatic series itrated compound isomers low selective and be corrosive for experts, also usually produced itrated compound or oxidized byproduct in excessive nitration mixture. Another major defect is to need the spent acid post processing. Industry development has been concentrated focus at environmentally friendly solid acids such as zeolite, zirconium sulfate and sulfonic perfluoro tree vinegar and has been made catalyst at present, particularly effectively replaces the chemicals that environment is had destruction with the Friedel-Crafts nitration reaction.
The present invention fully absorbs the domestic and international mature technology of the nitrated dimethylbenzene of nitric-sulfuric acid, optimization technological process, continuous nitrification and rectifying, without catalyst or solvent, solved that the ubiquitous productive rate of nitric-sulfuric acid nitrification process that aforementioned each piece document points out is not high, nitration mixture consumption large (particularly the sulfuric acid consumption is large), the spent acid amount is many, accessory substance is more and dangerous, poor product quality, energy consumption of unit product height, automaticity are difficult to the problems such as raising, productive rate reaches more than 97%, the sulfuric acid consumption is less, the norm quota of consumption of dimethylbenzene, nitric acid and sulfuric acid is respectively 750kg/t, 465kg/t, 40kg/t, about 400 yuan of finished product energy consumption per ton, finished product 2 after the rectifying, 6-, 2,4-, 3,4-, 2,3-and 2,5-dimethyl nitrobenzene purity are more than 99.5%; Cross itrated compound content≤0.5% before the rectifying in the crude mixture, crude product through hot water prewashing, sodium hydroxide solution is refining and hot wash after nitrophenols sodium content≤10PPm, acid-base value≤40PPm. According to 2 of the present invention's design, 4-and 2,6-dimethyl nitrobenzene production line change respectively raw material into ortho-xylene or paraxylene by meta-xylene, corresponding change process conditions just can be produced respectively 4-nitro ortho-xylene and 3-nitro ortho-xylene or 2-nitro paraxylene.
Summary of the invention
The technical problem to be solved in the present invention provide a kind of continuous nitrification and continuous rectification prepare nitro-xylene isomer monomer method, the method is compared than prior art and is easy to large-scale industrial production, guarantee the safety and stability of producing and the quality of product, reduce raw-material consumption, reduce the generation of waste water.
Overall technological scheme of the present invention is the method for preparing nitro-xylene isomer monomer with nitric-sulfuric acid continuous nitrification xylene isomer monomer and rectifying, comprising:
A) first step is to generate the nitroxylene mixture with nitric acid reaction in xylene isomer monomer and the nitric-sulfuric acid, and xylene isomer monomer is selected from a kind of in meta-xylene, ortho-xylene, the paraxylene,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again xylene isomer monomer is continuously flowed into reactor (1), (2), strong agitation and cooling guarantee that reaction is under constant temperature in reactor (2), 85% above xylene isomer monomer and nitric acid reaction generate the nitroxylene mixture, the material overflow enters in the reactor (3)
(ii) strong agitation and cooling guarantee that reaction is under constant temperature in reactor (3), xylene isomer monomer more than 95% and nitric acid reaction generate the nitroxylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) in reactor (1) under the stirring condition, extract the itrated compound of spent acid in autoreactor (3) separator with xylene isomer monomer, wherein xylene isomer monomer generates the nitroxylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under the stirring condition, add the hot wash itrated compound in reactor (4), it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) in reactor (5) under the stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with the rectification under vacuum system to obtain nitro-xylene isomer monomer,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of xylene isomer monomer and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms nitroxylene monomer finished product behind overhead condenser, the a small amount of backflow satisfied operating condition, a large amount of pan tanks of introducing, tower bottoms is introduced rectifying column (9)
(iii) in the rectifying column (9), reboiler is evaporated to cat head with the volatile components in the material, forms nitroxylene monomer finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
Above-mentioned method is characterised in that the xylene isomer monomer purity of adding is more than 99%, the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of xylene isomer monomer, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 65-75% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3Sulfuric acid valid density Φ value is 60-70% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 The temperature of reactor (1), (2), (3) is 10-49 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 16-34 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 80～140 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 136～168 ℃ of tower reactor temperature, 50～90 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 130～168 ℃ of tower reactor temperature, 84～107 ℃ of tower top temperatures, reflux ratio 4-11; Rectifying column (9) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 130～171 ℃ of tower reactor temperature, 100～127 ℃ of tower top temperatures, reflux ratio 0.4-6.
The method of a kind of concrete production 2-nitro meta-xylene and 4-Nitro-m-xylene finished product comprises:
A) first step is that nitric acid reaction generates the mixture that comprises 2-nitro meta-xylene and 4-nitro meta-xylene in meta-xylene and the nitric-sulfuric acid,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again meta-xylene is continuously flowed into reactor (1), (2), guarantee that in reactor (2) strong agitation and cooling reaction is under constant temperature, 85% above meta-xylene and nitric acid reaction generate nitro meta-xylene mixture, the material overflow enters in the reactor (3)
(ii) guarantee that in reactor (3) strong agitation and cooling reaction is under constant temperature, meta-xylene more than 95% and nitric acid reaction generate nitro meta-xylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) under reactor (1) stirring condition, extract itrated compound in autoreactor (3) the separator spent acid with meta-xylene, wherein meta-xylene generates nitro meta-xylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under reactor (4) stirring condition, add the hot wash itrated compound, it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) under reactor (5) stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with the rectification under vacuum system to obtain 2-nitro meta-xylene and 4-Nitro-m-xylene finished product,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of meta-xylene and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms 2-nitro meta-xylene finished product behind overhead condenser, the a small amount of backflow satisfied operating condition, a large amount of pan tanks of introducing, tower bottoms is introduced rectifying column (9)
(iii) in the rectifying column (9), reboiler is evaporated to cat head with the volatile components in the material, forms the 4-Nitro-m-xylene finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
Said method is characterised in that the meta-xylene purity of adding more than 99%, and the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of meta-xylene, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 67-72% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 65-69% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 Reactor (1), (2), (3) temperature are 20-47 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 20-25 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 103～125 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 146～158 ℃ of tower reactor temperature, 60～80 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 149～152 ℃ of tower reactor temperature, 94～97 ℃ of tower top temperatures, reflux ratio 4-11; Rectifying column (9) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 145～151 ℃ of tower reactor temperature, 114～117 ℃ of tower top temperatures, reflux ratio 0.4-6.
Said method is further characterized in that concentration of nitric acid is less than or equal to 1.5% (quality), density 1.50-1.60g/cm in the reactor (1)3 Itrated compound forms in the reactor (3): 2-nitro meta-xylene 15～27%, 4-nitro meta-xylene 65～77%, 5-nitro meta-xylene 0.8～1.5%, meta-xylene is less than or equal to 8%, cross itrated compound and be less than or equal to 0.5%, the phenol sodium content is less than or equal to 10ppm in the crude product of reactor (6) discharging, acid-base value is less than or equal to 40ppm, rectifying column (8) overhead condensation is drawn 2-nitro meta-xylene finished product purity more than 99.5%, and rectifying column (9) overhead condensation is drawn 4-Nitro-m-xylene finished product purity more than 99.5%.
Another kind of concrete method of producing 3-nitro ortho-xylene and 4-nitro ortho-xylene comprises:
A) first step is that nitric acid reaction generates the mixture that comprises 3-nitro ortho-xylene and 4-nitro ortho-xylene in ortho-xylene and the nitric-sulfuric acid,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again ortho-xylene is continuously flowed into reactor (1), (2), guarantee that in reactor (2) strong agitation and cooling reaction is under constant temperature, 85% above ortho-xylene and nitric acid reaction generate nitro ortho-xylene mixture, the material overflow enters in the reactor (3)
(ii) guarantee that in reactor (3) strong agitation and cooling reaction is under constant temperature, ortho-xylene more than 95% and nitric acid reaction generate nitro ortho-xylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) under reactor (1) stirring condition, extract itrated compound in autoreactor (3) the separator spent acid with ortho-xylene, wherein ortho-xylene generates nitro ortho-xylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under reactor (4) stirring condition, add the hot wash itrated compound, it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) under reactor (5) stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with distillation system to obtain 3-nitro ortho-xylene and 4-nitro ortho-xylene finished product,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of ortho-xylene and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms 3-nitro ortho-xylene finished product behind overhead condenser, the a small amount of backflow satisfied operating condition, a large amount of pan tanks of introducing, tower bottoms is introduced rectifying column (9)
(iii) in the rectifying column (9), reboiler is evaporated to cat head with the volatile components in the material, forms 4-nitro ortho-xylene finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
Above-mentioned method is characterised in that the ortho-xylene purity of adding more than 99%, and the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of ortho-xylene, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 67-72% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 65-69% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 Reactor (1), (2), (3) temperature are 10-35 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 16-34 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 103～125 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 146～158 ℃ of tower reactor temperature, 60～80 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 1499～60 ℃ of tower reactor temperature, 104～107 ℃ of tower top temperatures, reflux ratio 4-11; Rectifying column (9) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 155～171 ℃ of tower reactor temperature, 124～127 ℃ of tower top temperatures, reflux ratio 0.4-6.
Above-mentioned method is further characterized in that concentration of nitric acid is less than or equal to 1.5% (quality), density 1.50-1.60g/cm in the reactor (1)3 Itrated compound forms in the reactor (3): 3-nitro ortho-xylene 30～45%, 4-nitro ortho-xylene 47～72%, ortho-xylene is less than or equal to 8%, cross itrated compound and be less than or equal to 0.5%, the phenol sodium content is less than or equal to 10ppm in the crude product of reactor (6) discharging, acid-base value is less than or equal to 40ppm, rectifying column (8) overhead condensation is drawn 3-nitro ortho-xylene finished product purity should be more than 99.5%, and rectifying column (9) overhead condensation is drawn 4-nitro ortho-xylene finished product purity should be more than 99.5%.
A kind of method of the 2-of production nitro paraxylene is arranged again, comprising:
A) first step is that nitric acid reaction generates 2-nitro paraxylene mixture in paraxylene and the nitric-sulfuric acid,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again paraxylene is continuously flowed into reactor (1), (2), guarantee that in reactor (2) strong agitation and cooling reaction is under constant temperature, 85% above paraxylene and nitric acid reaction generate nitro paraxylene mixture, the material overflow enters in the reactor (3)
(ii) guarantee that in reactor (3) strong agitation and cooling reaction is under constant temperature, paraxylene more than 95% and nitric acid reaction generate nitro paraxylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) under reactor (1) stirring condition, extract itrated compound in autoreactor (3) the separator spent acid with paraxylene, wherein paraxylene generates nitro paraxylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under reactor (4) stirring condition, add the hot wash itrated compound, it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) under reactor (5) stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with distillation system to obtain 2-nitro paraxylene finished product,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of paraxylene and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms 2-nitro paraxylene finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
The paraxylene purity that above-mentioned method characteristic is to add is more than 99%, and the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of paraxylene, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 67-72% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 65-69% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 Reactor (1), (2), (3) temperature are 10-35 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 16-34 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 103～125 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 146～158 ℃ of tower reactor temperature, 60～80 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 140～150 ℃ of tower reactor temperature, 98～110 ℃ of tower top temperatures, reflux ratio 0.4-6.
Description of drawings:
Fig. 1 is the process flow diagram of realizing making continuously toluene between 2-, 4-nitro;
Fig. 2 is the process flow diagram of realizing making continuously 3-, the adjacent toluene of 4-nitro;
Fig. 3 realizes making continuously the 2-nitro to the process flow diagram of toluene;
The specific embodiment
Can not be used for being construed to restriction invention protection domain in the example below.
Embodiment 1: each reactor and rectifying column process regulation such as following table:
| Raw material | 90% sulfuric acid (l/h) | 90% nitric acid (l/h) | 99% meta-xylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 82 | 67 | 168 | 212 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 10 | 10 | 250 | 65.69 | 0.11 | 20 | In | |
| 2 | 10 | 10 | 317 | 67.29 | 0.50 | 20 | Strongly | |
| 3 | 10 | 10 | 317 | 66.22 | 0.38 | 20 | Strongly | |
| 4 | 60 | 65 | 417 (containing heating water 100l/h) | ＜0.15 | ＜0.15 | 20 | A little less than | |
| 5 | 60 | 65 | 422 (contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 20 | A little less than | |
| 6 | 60 | 65 | 534 (containing heating water 112l/h) | ＜0.001 | ＜0.001 | 20 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 60 | 146 | 0.008 | 0.01 | ≤7 | 0.4 | 350 | 17.4 |
| 8 | 94 | 149 | 0.001 | 0.004 | ≤7 | 11 | 332.6 | 45.27 |
| 9 | 114 | 145 | 0.001 | 0.004 | ≤7 | 0.4 | 287.3 | 281.7 |
Embodiment 2: each reactor and rectifying column process regulation such as following table:
| Raw material | 95% sulfuric acid (l/h) | 95% nitric acid (l/h) | 99% meta-xylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 164 | 134 | 390 | 424 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 20 | 20 | 250 | 65.69 | 0.11 | 20 | In | |
| 2 | 20 | 20 | 688 | 67.29 | 2.00 | 20 | Strongly | |
| 3 | 20 | 20 | 688 | 66.22 | 0.98 | 20 | Strongly | |
| 4 | 90 | 90 | 888 (containing heating water 200l/h) | ＜0.15 | ＜0.15 | 20 | A little less than | |
| 5 | 90 | 90 | 898 (contain and add alkali lye 10l/h) | ＜0.01 | ＜0.01 | 20 | A little less than | |
| 6 | 90 | 90 | 1122 (containing heating water 224l/h) | ＜0.001 | ＜0.001 | 20 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 80 | 158 | 0.01 | 0.014 | ≤7 | 0.4 | 700 | 34.8 |
| 8 | 97 | 152 | 0.004 | 0.008 | ≤7 | 11 | 665.2 | 90.54 |
| 9 | 117 | 151 | 0.004 | 0.009 | ≤7 | 0.4 | 574.66 | 563.4 |
Embodiment 3: each reactor and rectifying column process regulation such as following table:
| Raw material | 98% sulfuric acid (l/h) | 98% nitric acid (l/h) | 99.5% meta-xylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 98.4 | 80.4 | 168 | 254.4 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 26 | 26 | 250 | 65.69 | 0.11 | 23 | In | |
| 2 | 27 | 27 | 346.8 | 67.29 | 0.50 | 23 | Strongly | |
| 3 | 28 | 28 | 346.8 | 66.22 | 0.38 | 23 | Strongly | |
| 4 | 65 | 65 | (446.8 containing heating water 100l/h) | ＜0.15 | ＜0.15 | 23 | A little less than | |
| 5 | 65 | 65 | (451.8 contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 23 | A little less than | |
| 6 | 65 | 65 | (606.2 containing heating water 154.4l/h) | ＜0.001 | ＜0.001 | 23 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 70 | 150 | 0.008 | 0.01 | ≤4 | 0.4 | 360 | 21.2 |
| 8 | 95 | 151 | 0.002 | 0.004 | ≤4 | 11 | 338.8 | 53.9 |
| 9 | 116 | 148 | 0.002 | 0.004 | ≤4 | 0.4 | 284.9 | 279.8 |
Embodiment 4: each reactor and rectifying column process regulation such as following table:
| Raw material | 90% sulfuric acid (l/h) | 90% nitric acid (l/h) | 99% ortho-xylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 93 | 74 | 179 | 232 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 10 | 10 | 250 | 65.69 | 0.11 | 16 | In | |
| 2 | 10 | 10 | 346 | 67.29 | 0.50 | 16 | Strongly | |
| 3 | 10 | 10 | 346 | 66.22 | 0.38 | 16 | Strongly | |
| 4 | 60 | 65 | 446 (containing heating water 100l/h) | ＜0.15 | ＜0.15 | 16 | A little less than | |
| 5 | 60 | 65 | 451 (contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 16 | A little less than | |
| 6 | 60 | 65 | 583 (containing heating water 132l/h) | ＜0.001 | ＜0.001 | 16 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 60 | 146 | 0.01 | 0.013 | ≤7 | 0.4 | 370 | 19.3 |
| 8 | 104 | 149 | 0.001 | 0.004 | ≤7 | 11 | 350.7 | 145 |
| 9 | 124 | 155 | 0.001 | 0.004 | ≤7 | 0.4 | 205.7 | 197.3 |
Embodiment 5: each reactor and rectifying column process regulation such as following table:
| Raw material | 95% sulfuric acid (l/h) | 95% nitric acid (l/h) | 99% ortho-xylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 186 | 148 | 370 | 464 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 35 | 35 | 250 | 65.69 | 0.11 | 34 | In | |
| 2 | 35 | 35 | 704 | 67.29 | 2.00 | 34 | Strongly | |
| 3 | 35 | 35 | 704 | 66.22 | 0.98 | 34 | Strongly | |
| 4 | 90 | 90 | 904 (containing heating water 200l/h) | ＜0.15 | ＜0.15 | 34 | A little less than | |
| 5 | 90 | 90 | 914 (contain and add alkali lye 10l/h) | ＜0.01 | ＜0.01 | 34 | A little less than | |
| 6 | 90 | 90 | 1178 (containing heating water 264l/h) | ＜0.001 | ＜0.001 | 34 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 80 | 158 | 0.01 | 0.014 | ≤7 | 0.4 | 730 | 42.2 |
| 8 | 104 | 160 | 0.004 | 0.009 | ≤7 | 10 | 687.8 | 265.3 |
| 9 | 127 | 171 | 0.004 | 0.008 | ≤7 | 0.4 | 422.5 | 401.7 |
Embodiment 6: each reactor and rectifying column process regulation such as following table:
| Raw material | 98% sulfuric acid (l/h) | 98% nitric acid (l/h) | 99.5% ortho-xylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 97 | 83 | 250 | 190 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 17 | 17 | 250 | 65.69 | 0.11 | 16 | In | |
| 2 | 17 | 17 | 370 | 67.29 | 0.50 | 20 | Strongly | |
| 3 | 17 | 17 | 370 | 66.22 | 0.38 | 20 | Strongly | |
| 4 | 69 | 69 | 470 (containing heating water 100l/h) | ＜0.15 | ＜0.15 | 20 | A little less than | |
| 5 | 69 | 69 | 475 (contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 20 | A little less than | |
| 6 | 69 | 69 | 625 (containing heating water 150l/h) | ＜0.001 | ＜0.001 | 20 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 71 | 151 | 0.008 | 0.011 | ≤4 | 0.4 | 398 | 23.5 |
| 8 | 105 | 152 | 0.002 | 0.004 | ≤5 | 11 | 374.5 | 153.2 |
| 9 | 126 | 161 | 0.002 | 0.005 | ≤6 | 0.4 | 221.3 | 210.9 |
Embodiment 7: each reactor and rectifying column process regulation such as following table:
| Raw material | 90% sulfuric acid (l/h) | 90% nitric acid (l/h) | 99% paraxylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 169 | 129 | 339 | 241 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 35 | 35 | 250 | 65.69 | 0.11 | 34 | In | |
| 2 | 35 | 35 | 637 | 67.29 | 2.00 | 34 | Strongly | |
| 3 | 35 | 35 | 637 | 66.22 | 1.04 | 34 | Strongly | |
| 4 | 90 | 90 | 737 (containing heating water 100l/h) | ＜0.15 | ＜0.15 | 34 | A little less than | |
| 5 | 90 | 90 | 742 (contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 34 | A little less than | |
| 6 | 90 | 90 | 883 (containing heating water 141l/h) | ＜0.001 | ＜0.001 | 34 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 80 | 150 | 0.01 | 0.014 | ≤7 | 0.4 | 712 | 37.6 |
| 8 | 127 | 150 | 0.001 | 0.006 | ≤7 | 0.4 | 674.4 | 661.7 |
Embodiment 8: each reactor and rectifying column process regulation such as following table:
| Raw material | 95% sulfuric acid (l/h) | 95% nitric acid (l/h) | 99% paraxylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 82 | 67 | 168 | 212 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 10 | 10 | 250 | 65.69 | 0.11 | 20 | In | |
| 2 | 10 | 10 | 317 | 67.29 | 0.50 | 20 | Strongly | |
| 3 | 10 | 10 | 317 | 66.22 | 0.38 | 20 | Strongly | |
| 4 | 60 | 65 | 417 (containing heating water 100l/h) | ＜0.15 | ＜0.15 | 20 | A little less than | |
| 5 | 60 | 65 | 422 (contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 20 | A little less than | |
| 6 | 60 | 65 | 534 (containing heating water 112l/h) | ＜0.001 | ＜0.001 | 20 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 60 | 136 | 0.008 | 0.01 | ≤7 | 4 | 350 | 17.4 |
| 8 | 100 | 145 | 0.004 | 0.009 | ≤7 | 4 | 332.6 | 327.5 |
Embodiment 9: each reactor and rectifying column process regulation such as following table:
| Raw material | 98% sulfuric acid (l/h) | 98% nitric acid (l/h) | 99.5% paraxylene (l/h) | Water (l/h) | Remarks: sulfuric acid, nitric acid drop into | |||
| Inventory | 92 | 70 | 190 | 231 | ||||
| Reactor | Temperature in the kettle (℃) | Separator temperature (℃) | Flow (l/h) | Sulfuric acid concentration (%) | Concentration of nitric acid (%) | Arrhea the time (min) | | |
| 1 | 20 | 20 | 250 | 65.69 | 0.11 | 20 | In | |
| 2 | 20 | 20 | 352 | 67.29 | 0.50 | 20 | Strongly | |
| 3 | 20 | 20 | 352 | 66.22 | 0.38 | 20 | Strongly | |
| 4 | 70 | 70 | 452 (containing heating water 100l/h) | ＜0.15 | ＜0.15 | 20 | A little less than | |
| 5 | 70 | 70 | 457 (contain and add alkali lye 5l/h) | ＜0.01 | ＜0.01 | 20 | A little less than | |
| 6 | 70 | 70 | 588 (containing heating water 131l/h) | ＜0.001 | ＜0.001 | 20 | A little less than | |
| Rectifying column | Tower top temperature (℃) | The tower reactor temperature (℃) | Tower top pressure (MPa) | Tower reactor pressure (MPa) | Pressure reduction (KPa) | Reflux ratio | Flow (kg/h) | Overhead extraction amount (kg/h) |
| 7 | 72 | 140 | 0.01 | 0.012 | ≤4 | 0.4 | 372 | 20.6 |
| 8 | 110 | 147 | 0.002 | 0.004 | ≤4 | 0.4 | 351.4 | 341.9 |
Although in above illustrating, describe the present invention in detail, should be understood that described details only is used for illustrating, those skilled in the art can make change to it within not deviating from the spirit and scope that claim of the present invention limits.
Claims (10)
1, a kind ofly prepare the method for nitro-xylene isomer monomer with nitric-sulfuric acid continuous nitrification xylene isomer monomer and rectifying, described method comprises:
A) first step is to generate the nitroxylene mixture with nitric acid reaction in xylene isomer monomer and the nitric-sulfuric acid, and xylene isomer monomer is selected from a kind of in meta-xylene, ortho-xylene, the paraxylene,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again xylene isomer monomer is continuously flowed into reactor (1), (2), strong agitation and cooling guarantee that reaction is under constant temperature in reactor (2), 85% above xylene isomer monomer and nitric acid reaction generate the nitroxylene mixture, the material overflow enters in the reactor (3)
(ii) strong agitation and cooling guarantee that reaction is under constant temperature in reactor (3), xylene isomer monomer more than 95% and nitric acid reaction generate the nitroxylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) in reactor (1) under the stirring condition, extract the itrated compound of spent acid in autoreactor (3) separator with xylene isomer monomer, wherein xylene isomer monomer generates the nitroxylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under the stirring condition, add the hot wash itrated compound in reactor (4), it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) in reactor (5) under the stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with the rectification under vacuum system to obtain nitro-xylene isomer monomer,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of xylene isomer monomer and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms nitroxylene monomer finished product behind overhead condenser, the a small amount of backflow satisfied operating condition, a large amount of pan tanks of introducing, tower bottoms is introduced rectifying column (9)
(iii) in the rectifying column (9), reboiler is evaporated to cat head with the volatile components in the material, forms nitroxylene monomer finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
2, method according to claim 1, the xylene isomer monomer purity that it is characterized in that adding is more than 99%, the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of xylene isomer monomer, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 65-75% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 60-70% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 The temperature of reactor (1), (2), (3) is 10-49 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 16-34 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 80～140 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 136～168 ℃ of tower reactor temperature, 50～90 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 130～168 ℃ of tower reactor temperature, 84～107 ℃ of tower top temperatures, reflux ratio 4-11; Rectifying column (9) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 130～171 ℃ of tower reactor temperature, 100～127 ℃ of tower top temperatures, reflux ratio 0.4-6.
3, method according to claim 2, its feature comprises:
A) first step is that nitric acid reaction generates the mixture that comprises 2-nitro meta-xylene and 4-nitro meta-xylene in meta-xylene and the nitric-sulfuric acid,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again meta-xylene is continuously flowed into reactor (1), (2), guarantee that in reactor (2) strong agitation and cooling reaction is under constant temperature, 85% above meta-xylene and nitric acid reaction generate nitro meta-xylene mixture, the material overflow enters in the reactor (3)
(ii) guarantee that in reactor (3) strong agitation and cooling reaction is under constant temperature, meta-xylene more than 95% and nitric acid reaction generate nitro meta-xylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) under reactor (1) stirring condition, extract itrated compound in autoreactor (3) the separator spent acid with meta-xylene, wherein meta-xylene generates nitro meta-xylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under reactor (4) stirring condition, add the hot wash itrated compound, it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) under reactor (5) stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with the rectification under vacuum system to obtain 2-nitro meta-xylene and 4-Nitro-m-xylene finished product,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of meta-xylene and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms 2-nitro meta-xylene finished product behind overhead condenser, the a small amount of backflow satisfied operating condition, a large amount of pan tanks of introducing, tower bottoms is introduced rectifying column (9)
(iii) in the rectifying column (9), reboiler is evaporated to cat head with the volatile components in the material, forms the 4-Nitro-m-xylene finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
4, method according to claim 3, the meta-xylene purity that it is characterized in that adding is more than 99%, the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of meta-xylene, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 67-72% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 65-69% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 Reactor (1), (2), (3) temperature are 20-47 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 20-25 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 103～125 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 146～158 ℃ of tower reactor temperature, 60～80 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 149～152 ℃ of tower reactor temperature, 94～97 ℃ of tower top temperatures, reflux ratio 4-11; Rectifying column (9) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 145～151 ℃ of tower reactor temperature, 114～117 ℃ of tower top temperatures, reflux ratio 0.4-6.
5, method according to claim 4 is characterized in that concentration of nitric acid is less than or equal to 1.5% (quality), density 1.50-1.60g/cm in the reactor (1)3 Itrated compound forms in the reactor (3): 2-nitro meta-xylene 15～27%, 4-Nitro-m-xylene 65～77%, 5-nitro meta-xylene 0.8～1.5%, meta-xylene is less than or equal to 8%, cross itrated compound and be less than or equal to 0.5%, the phenol sodium content is less than or equal to 10ppm in the crude product of reactor (6) discharging, acid-base value is less than or equal to 40ppm, rectifying column (8) overhead condensation is drawn 2-nitro meta-xylene finished product purity more than 99.5%, and rectifying column (9) overhead condensation is drawn 4-Nitro-m-xylene finished product purity more than 99.5%.
6, method according to claim 2, its feature comprises:
A) first step is that nitric acid reaction generates the mixture that comprises 3-nitro ortho-xylene and 4-nitro ortho-xylene in ortho-xylene and the nitric-sulfuric acid,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again ortho-xylene is continuously flowed into reactor (1), (2), guarantee that in reactor (2) strong agitation and cooling reaction is under constant temperature, 85% above ortho-xylene and nitric acid reaction generate nitro ortho-xylene mixture, the material overflow enters in the reactor (3)
(ii) guarantee that in reactor (3) strong agitation and cooling reaction is under constant temperature, ortho-xylene more than 95% and nitric acid reaction generate nitro ortho-xylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) under reactor (1) stirring condition, extract itrated compound in autoreactor (3) the separator spent acid with ortho-xylene, wherein ortho-xylene generates nitro ortho-xylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under reactor (4) stirring condition, add the hot wash itrated compound, it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) under reactor (5) stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with distillation system to obtain 3-nitro ortho-xylene and 4-nitro ortho-xylene finished product,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of ortho-xylene and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms 3-nitro ortho-xylene finished product behind overhead condenser, the a small amount of backflow satisfied operating condition, a large amount of pan tanks of introducing, tower bottoms is introduced rectifying column (9)
(iii) in the rectifying column (9), reboiler is evaporated to cat head with the volatile components in the material, forms 4-nitro ortho-xylene finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
7, method according to claim 6, the ortho-xylene purity that it is characterized in that adding is more than 99%, the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of ortho-xylene, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 67-72% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 65-69% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 Reactor (1), (2), (3) temperature are 10-35 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 16-34 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 103～125 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 146～158 ℃ of tower reactor temperature, 60～80 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 149～160 ℃ of tower reactor temperature, 104～107 ℃ of tower top temperatures, reflux ratio 4-11; Rectifying column (9) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 155～171 ℃ of tower reactor temperature, 124～127 ℃ of tower top temperatures, reflux ratio 0.4-6.
8, method according to claim 7 is characterized in that concentration of nitric acid is less than or equal to 1.5% (quality), density 1.50-1.60g/cm in the reactor (1)3 Itrated compound forms in the reactor (3): 3-nitro ortho-xylene 30～45%, 4-nitro ortho-xylene 47～72%, ortho-xylene is less than or equal to 8%, cross itrated compound and be less than or equal to 0.5%, the phenol sodium content is less than or equal to 10ppm in the crude product of reactor (6) discharging, acid-base value is less than or equal to 40ppm, rectifying column (8) overhead condensation is drawn 3-nitro ortho-xylene finished product purity should be more than 99.5%, and rectifying column (9) overhead condensation is drawn 4-nitro ortho-xylene finished product purity should be more than 99.5%.
9, method according to claim 2, its feature comprises:
A) first step is that nitric acid reaction generates 2-nitro paraxylene mixture in paraxylene and the nitric-sulfuric acid,
(i) red fuming nitric acid (RFNA), the concentrated sulfuric acid and circulation spent acid add continuously in proportion the nitration mixture machine and are made into behind the nitric-sulfuric acid again inflow reactor (2), again paraxylene is continuously flowed into reactor (1), (2), guarantee that in reactor (2) strong agitation and cooling reaction is under constant temperature, 85% above paraxylene and nitric acid reaction generate nitro paraxylene mixture, the material overflow enters in the reactor (3)
(ii) guarantee that in reactor (3) strong agitation and cooling reaction is under constant temperature, paraxylene more than 95% and nitric acid reaction generate nitro paraxylene mixture, it is spent acid and itrated compound that the material overflow enters the interior standing separation of separator, a large amount of Returning reactors (2) of lower floor's spent acid wherein, surplus enters in the reactor (1), the upper strata itrated compound enters reactor (4)
(iii) under reactor (1) stirring condition, extract itrated compound in autoreactor (3) the separator spent acid with paraxylene, wherein paraxylene generates nitro paraxylene mixture with a small amount of nitric acid in the spent acid, it is spent acid and extract that the material overflow enters the interior standing separation of separator, wherein lower floor's spent acid enter the spent acid treatment system concentrated after retrieval system recycle, the upper strata extract enters reactor (2)
(iv) under reactor (4) stirring condition, add the hot wash itrated compound, it is acid waste water and itrated compound that the material overflow enters the interior standing separation of separator, and acid waste water enters the neutralisation treatment system, and itrated compound enters reactor (5),
(v) under reactor (5) stirring condition, add in the alkali lye and the residual acid in the itrated compound, alkali lye generates sodium phenolate with the nitro oxide in the itrated compound and the reaction of nitrophenol impurity and is dissolved in the water, it is alkaline waste water and itrated compound that the material overflow enters the interior standing separation of separator, alkaline waste water enters the neutralisation treatment system with the acid waste water neutralization that comes autoreactor (4), in and waste water enter Waste Water Treatment, itrated compound enters reactor (6)
(vi) under reactor (6) stirring condition, add the hot wash itrated compound, it is waste water and itrated compound that the material overflow enters the interior standing separation of separator, waste water Returning reactor (5), itrated compound enters distillation system;
B) second step is to separate with distillation system to obtain 2-nitro paraxylene finished product,
(i) itrated compound enters rectifying column (7) after preheater heats up, reboiler is evaporated to cat head with the volatile components in the material, behind overhead condenser, form the mixture of paraxylene and water, the a small amount of backflow satisfied operating condition, draw in a large number and again add reactor (2), tower bottoms is introduced rectifying column (8)
(ii) in the rectifying column (8), reboiler is evaporated to cat head with the volatile components in the material, forms 2-nitro paraxylene finished product behind overhead condenser, and a small amount of the backflow satisfied operating condition, introduces in a large number pan tank, the bottom product collection and treatment.
10, method according to claim 9, the paraxylene purity that it is characterized in that adding is more than 99%, the concentration of the concentrated sulfuric acid, red fuming nitric acid (RFNA) is more than 90% (quality), and the mol ratio of paraxylene, red fuming nitric acid (RFNA), the concentrated sulfuric acid is 1: 0.6～1.5: 0.6～1.5; Sulfuric acid valid density Φ value is 67-72% in the nitration mixture machine, and nitric acid content is 11-14%, density 1.61-1.65g/cm3 Sulfuric acid valid density Φ value is 65-69% in the reactor (2), and nitric acid content is 0.5-2%, density 1.57-1.62g/cm3 Reactor (1), (2), (3) temperature are 10-35 ℃, 60～90 ℃ of reactors (4), (5), (6) temperature; Material is 16-34 minute in the time of staying of each reactor, and total residence time is 100-200 minute; Each reactor all is equipped with the impeller-agitator that is driven by motor, and stirring by per 1000 liters of reactants input 2.5-8.2KW can; Add alkali lye and be selected from NaOH, Na2CO
3Or ammonia is a kind of; Material 103～125 ℃ of temperature after preheater heats up, rectifying column (7) cat head pressure 0.008-0.01MPa, pressure reduction is not more than 7KPa, 146～158 ℃ of tower reactor temperature, 60～80 ℃ of tower top temperatures, reflux ratio 0.4-6; Rectifying column (8) cat head pressure 0.001-0.004MPa, pressure reduction is not more than 7KPa, 140～150 ℃ of tower reactor temperature, 98～110 ℃ of tower top temperatures, reflux ratio 0.4-6.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482194A (en) * | 2009-08-28 | 2012-05-30 | 纳幕尔杜邦公司 | Process for the nitration of o-xylene and related compounds |
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| CN105348105A (en) * | 2015-12-15 | 2016-02-24 | 绍兴贝斯美化工有限公司 | 4-nitro-o-xylene continuous synthesis system and synthesis method |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1022483C (en) * | 1990-04-21 | 1993-10-20 | 浙江工学院 | Process for preparing 2, 4-dimethylaniline and 2, 6-dimethylaniline |
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| CN101475487B (en) * | 2008-12-30 | 2012-07-18 | 江苏吉华化工有限公司 | Recycling use method of nitration acid |
| CN102482194A (en) * | 2009-08-28 | 2012-05-30 | 纳幕尔杜邦公司 | Process for the nitration of o-xylene and related compounds |
| CN102924283A (en) * | 2011-08-08 | 2013-02-13 | 吴桥大鹏医药化工有限公司 | Dimethylnitrobenzene continuous rectification process |
| CN105348105A (en) * | 2015-12-15 | 2016-02-24 | 绍兴贝斯美化工有限公司 | 4-nitro-o-xylene continuous synthesis system and synthesis method |
| CN105348113A (en) * | 2015-12-15 | 2016-02-24 | 绍兴贝斯美化工有限公司 | N-(1-ethyl propyl)-3,4-dimethylaniline continuous production system and method |
| CN105348105B (en) * | 2015-12-15 | 2017-04-12 | 绍兴贝斯美化工有限公司 | 4-nitro-o-xylene continuous synthesis system and synthesis method |
| CN105348113B (en) * | 2015-12-15 | 2017-04-19 | 绍兴贝斯美化工有限公司 | N-(1-ethyl propyl)-3,4-dimethylaniline continuous production device and method |
| CN106370610B (en) * | 2016-08-31 | 2019-05-14 | 四川北方红光特种化工有限公司 | The detection method of micro phenol content in a kind of nitro ortho-xylene |
| CN106370610A (en) * | 2016-08-31 | 2017-02-01 | 四川北方红光特种化工有限公司 | Method of detecting content of trace phenol in nitro-o-xylene |
| CN108586256A (en) * | 2018-03-20 | 2018-09-28 | 淮海工学院 | A kind of method of continuous flow upstream nitrification production dinitrobenzene |
| CN110511146A (en) * | 2019-09-17 | 2019-11-29 | 四川北方红光特种化工有限公司 | The production method and its production system of a kind of low single nitro ortho-xylene of waste acid quantity |
| CN112520757A (en) * | 2020-12-03 | 2021-03-19 | 天津大学 | Continuous production process and device for nitration synthesis of mixed acid |
| WO2023161765A1 (en) * | 2022-02-25 | 2023-08-31 | Deepak Nitrite Limited | A system and process for washing mono nitroxylenes, recovering and reusing reaction wastes |
| WO2023161698A1 (en) * | 2022-02-25 | 2023-08-31 | Deepak Nitrite Limited | Ortho xylene nitration process and system |
| CN115028558A (en) * | 2022-06-13 | 2022-09-09 | 湖北广富林生物制剂有限公司 | Preparation method of o-nitro-p-methylsulfonyl toluene |
| CN119431153A (en) * | 2025-01-09 | 2025-02-14 | 台州普渡机械设备有限公司 | A method for continuously preparing 2,6-dimethylaniline |
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