CN101906046B - Method and device for producing o-phenylenediamine by continuous liquid phase hydrogenation - Google Patents
Method and device for producing o-phenylenediamine by continuous liquid phase hydrogenation Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 173
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000007791 liquid phase Substances 0.000 title claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 207
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 238000007599 discharging Methods 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000004062 sedimentation Methods 0.000 description 73
- 239000002904 solvent Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 238000004891 communication Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002826 coolant Substances 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 aromatic nitro compound Chemical class 0.000 description 1
- RIOXQFHNBCKOKP-UHFFFAOYSA-N benomyl Chemical compound C1=CC=C2N(C(=O)NCCCC)C(NC(=O)OC)=NC2=C1 RIOXQFHNBCKOKP-UHFFFAOYSA-N 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention discloses a method and a device for producing o-phenylenediamine by continuous liquid phase hydrogenation. The reaction is performed in a first-order hydrogenation reactor and a second-order hydrogenation reactor connected in series. The method comprises the following steps of: adding methanol accounting for 50-70% of the reactors by volume to the first-order hydrogenation reactor and the second-order hydrogenation reactor, then adding a catalyst accounting for 0.5-1.5% of the methanol by weight, and continuously introducing hydrogen gas to the first-order hydrogenation reactor and the second-order hydrogenation reactor in a stirring state; after a certain pressure is reached in the first-order hydrogenation reactor and the second-order hydrogenation reactor, continuously adding the methanol and o-nitroaniline to the first-order hydrogenation reactor, continuing maintaining the pressure of the first-order hydrogenation reactor and the second-order hydrogenation reactor, discharging materials from the first-order hydrogenation reactor to the second-order hydrogenation reactor and continuously discharging materials from the second-order hydrogenation reactor simultaneously; recovering the catalyst by introducing a reaction liquid exhausted from the second-order hydrogenation reactor to a settling tank; and removing the methanol and water by rectifying the reaction liquid with catalyst recovered, and continuously rectifying to obtain the finished product of o-phenylenediamine. The method and the device have low cost, high yield, good safety and environment protection.
Description
Technical field
The present invention relates to method and the device of production method and the device, particularly producing o-phenylenediamine by continuous liquid phase hydrogenation of O-Phenylene Diamine.
Background technology
O-Phenylene Diamine is important organic chemical industry's intermediate, except being used for DYE PRODUCTION, or the raw material of the sterilant such as pesticide carbendazim, F-1991, thiophanate.The main production of domestic production O-Phenylene Diamine is take o-Nitraniline as raw material at present, is got by sodium sulfide reducing.The shortcoming of this method is: product yield is low, and total recovery is less than 80%; Environmental pollution is serious, produce a large amount of red water of sulfur compound after the Sodium Sulphide reaction, owing to containing inorganic salt in the sewage, be difficult to take the method for rectifying, can only wash the crystallization and purification product, and the solubleness of O-Phenylene Diamine in water is larger, contains the large-tonnage product O-Phenylene Diamine in the sewage, and not only yield is low but also the waste water control cost is high.
Domestic report (the Jilin Institute of Chemical Technology journal 2005 that also has the shortening method to produce O-Phenylene Diamine, (2): 55-58), but all adopt interrupter method production, the interrupter method equipment capacity is low, operation labour intensity is large, need in the production process reactor is carried out hydrogen exchange, hydrogen consumption is high, poor stability.
Summary of the invention
The object of the invention is to: method and the device of producing o-phenylenediamine by continuous liquid phase hydrogenation are provided, and method and device have that cost is low, yield is high, the good and eco-friendly characteristics of security, solve the technical problem that exists in the existing technique.
Production method of the present invention is that reaction is carried out in the firsts and seconds hydrogenation reaction kettle of series connection, the method may further comprise the steps: at first, in the firsts and seconds hydrogenation reaction kettle, add respectively the methyl alcohol that is equivalent to reactor volume 50-70%, add respectively again the catalyzer that is equivalent to above-mentioned methyl alcohol weight 0.5-1.5%, under whipped state, pass into continuously hydrogen to the firsts and seconds hydrogenation reaction kettle simultaneously; Secondly, after reaching certain pressure in the firsts and seconds hydrogenation reaction kettle, in the one-level hydrogenation reaction kettle, add continuously methyl alcohol and o-Nitraniline, continue to keep the firsts and seconds hydrogenation reaction kettle under above-mentioned pressure, simultaneously by the one-level hydrogenation reaction kettle to the discharging of secondary hydrogenation reaction kettle and by secondary hydrogenation reaction kettle continuous discharge; Then, secondary hydrogenation reaction kettle reaction solution out reclaims catalyzer through subsider, and catalyzer is applied mechanically; At last, the reaction solution behind the recovery catalyzer continues distillation and obtains the O-Phenylene Diamine finished product by rectifying desolvation first alcohol and water.
Wherein, add continuously in methyl alcohol and the o-Nitraniline process to the one-level hydrogenation reaction kettle, the volume ratio of methyl alcohol and o-Nitraniline charging is 1.7-12: 1.
Wherein, the speed that adds continuously methyl alcohol in the one-level hydrogenation reaction kettle be in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 3.6-15.5 hour.
Wherein, temperature of reaction is controlled at 90-120 ℃.
Wherein, the speed that passes into hydrogen is that the reaction pressure that guarantees the firsts and seconds hydrogenation reaction kettle is controlled at 1.3-2.5MPa and counts.
Wherein, catalysts is skeleton nickel.
Production equipment of the present invention: comprise the o-Nitraniline storage tank, the methyl alcohol storage tank, the one-level hydrogenation reaction kettle, the secondary hydrogenation reaction kettle, the catalyst sedimentation groove, solvent and water fractionate and product rectifying tower, one-level hydrogenation reaction kettle series connection secondary hydrogenation reaction kettle, on the one-level hydrogenation reaction kettle, connect o-Nitraniline storage tank and methyl alcohol storage tank by pipeline through volume pump respectively, one, establish hydrogen inlet on the secondary hydrogenation reaction kettle, the discharge port of secondary hydrogenation reaction kettle is through two catalyst sedimentation grooves of pipeline communication, the discharge port of catalyst sedimentation groove is through the pipeline communication fractionate, and fractionate is through the pipeline communication rectifying tower.
Wherein, on the I and II hydrogenation reaction kettle, connect catalyzer by pipeline through ball valve respectively and add tank.
Wherein, one, the secondary hydrogenation reaction kettle is by lower cover, upper cover and straight tube form, weld respectively up and down upper cover in straight tube, lower cover consists of reactor, rinse mouth is established in bottom at lower cover, guide shell is installed in straight tube, annular space between guide shell and the straight tube is installed heat exchange coil, barrel in straight tube is established entrance of cooling water, cooling water outlet and discharge port, establish the o-Nitraniline opening for feed at upper cover, the methyl alcohol import, hydrogen inlet, the thermometer mouth, gauge port and catalyzer are added mouth, stirring rake is installed by flange in top at upper cover, and the impeller of stirring arm is positioned at guide shell.
Wherein, establish manhole, visor mouth and relief valve port at upper cover.
Wherein, establish the thermometer mouth at lower cover.
Wherein, the sectional area of guide shell is S1, and the net sectional area of the annular space between guide shell and the straight tube is S2, and S2 is 1-1.5 times of S1.
Wherein, the upper end of guide shell exceeds 5-10cm than the superiors of heat exchange coil, aligns with the orlop of heat exchange coil in the lower end of guide shell, and the lower end of guide shell is not less than the lower surface of straight tube.
Wherein, the diameter of the impeller of the stirring rake in guide shell is the 30-70% of draft tube diameter.
Wherein, be provided with the discharging weir in the inboard of the straight tube of discharge port one side, the top on discharging weir is airtight, the bottom on discharging weir and reactor internal communication, and the bottom on discharging weir is not less than 1/4th of guide shell height to the distance of guide shell lower end.
Wherein, the catalyst sedimentation groove is made of top straight tube and bottom cone, lower end side in straight tube is provided with discharge port, the bottom of discharge port as far as possible close straight tube under the prerequisite that satisfies the apparatus processing condition, the cone angle of the cone of catalyst sedimentation groove is established the catalyst recovery mouth less than 90 degree in the bottom of cone.
The present invention has the following advantages: 1, the nitro of aromatic nitro compound is amino by hydrogen reducing under catalyst action, and temperature, the pressure of reaction are lower, and equipment manufacturing cost is low; 2, adopt methyl alcohol to make solvent, increase the touch opportunity of catalyzer, hydrogen, nitro-compound, solvent low price, in liberal supply; 3, the speed of response according to reduction reaction obtains reaction time, determines input speed by reaction time, and from reaction time as can be known, operation of equipment elasticity is large; 4, product yield is high, and in o-Nitraniline, total recovery is greater than 95%; 5, produce continuously, labour intensity is little; 6, cleaner production greatly reduces the environmental pollution of sulfuration alkaline process; 7, serialization production, the o-Nitraniline total content is low in the system, has avoided the large shortcoming of material total amount in the interrupter method system, need to not carry out repeatedly hydrogen exchange in production process, accomplishes essential safety.
Description of drawings
Fig. 1 is production equipment block diagram of the present invention.
Fig. 2 is the structural representation of hydrogenation reaction kettle.
Fig. 3 is the vertical view of Fig. 2.
Fig. 4 is the structural representation of catalyst sedimentation groove.
Among the figure: 1 o-Nitraniline storage tank, 2 volume pumps, 3 methyl alcohol storage tanks, 4 volume pumps, 5 one-level hydrogenation reaction kettles, 6 ball valves, 7 catalyzer are added tank, 8 secondary hydrogenation reaction kettles, 9 ball valves, 10 catalyzer are added tank, 11 catalyst sedimentation grooves, 12 catalyst sedimentation grooves, 13 solvents and water fractionate, 14 product rectifying tower, 15 rinse mouths, 16 lower covers, 17 thermometer mouths, 18 guide shells, 19 heat exchange coils, 20 straight tubes, 21 entrance of cooling water, 22 upper covers, 23 o-Nitraniline opening for feeds, 24 flanges, 25 hydrogen inlets, 26 cooling water outlets, 27 discharge ports, 28 discharging weirs, 29 visor mouths, 30 manholes, 31 methanol feeding mouths, 32 visor mouths, 33 thermometer mouths, 34 gauge ports, 35 catalyzer are added mouth, 36 relief valve port, 37 agitators, 38 subsider discharge ports, 39 catalyst recovery mouths.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.Should be understood that these examples just in order to demonstrate the invention, but not limit the scope of the invention by any way.The those of ordinary skill of the industry can be made many modification and improvement, for example changes the charging metering method, and the mouth of pipe of reactor is adjusted, and increases the quantity of reactor, and all these modification, adjustment, improvement all should be considered as protection scope of the present invention.
Shown in Fig. 1-4, production equipment of the present invention: comprise o-Nitraniline storage tank 1, methyl alcohol storage tank 3, one-level hydrogenation reaction kettle 5, secondary hydrogenation reaction kettle 8, catalyst sedimentation groove 11,12, fractionate 13 and rectifying tower 14, one-level hydrogenation reaction kettle 5 series connection secondary hydrogenation reaction kettles 8, on one-level hydrogenation reaction kettle 5 respectively by pipeline through volume pump 2,4 connect o-Nitraniline storage tank 1 and methyl alcohol storage tank 3, one, secondary hydrogenation reaction kettle 5, establish hydrogen inlet on 8, the discharge port of secondary hydrogenation reaction kettle is through two catalyst sedimentation grooves 11 of pipeline communication, 12, the discharge port of catalyst sedimentation groove is through pipeline communication fractionate 13, and fractionate 13 is through pipeline communication rectifying tower 14.
Wherein, on I and II hydrogenation reaction kettle 5,8, connect catalyzer by pipeline through ball valve 6,9 respectively and add tank 7,10.
Wherein, one, the secondary hydrogenation reaction kettle is by lower cover 16, upper cover 22 and straight tube 19 form, weld respectively up and down upper cover 22 in straight tube 19, lower cover 16 consists of reactor, establish rinse mouth 15 in the bottom of lower cover 16, at straight tube 19 interior installation guide shells 18, annular space between guide shell 18 and the straight tube 19 is installed heat exchange coil 20, establish entrance of cooling water 21 at the barrel of straight tube 19, cooling water outlet 26 and discharge port 27, establish o-Nitraniline opening for feed 23 at upper cover 22, methyl alcohol import 31, hydrogen inlet 25, thermometer mouth 33, tensimeter 34 and catalyzer are added mouth 35, stirring rake 37 is installed by flange 24 in top at upper cover 22, and the impeller of stirring arm 37 is positioned at guide shell 18.
Wherein, establish manhole 30, visor 29,32 and relief valve port 36 at upper cover 22.
Wherein, establish thermometer mouth 17 at lower cover 16.
Wherein, the sectional area of guide shell 18 is S1, and the net sectional area of the annular space between guide shell 18 and the straight tube 19 is S2, and S2 is 1-1.5 times of S1.
Wherein, the upper end of guide shell 18 exceeds 5-10cm than the superiors of heat exchange coil 20, aligns with the orlop of heat exchange coil 20 in the lower end of guide shell 18, and the lower end of guide shell 18 is not less than the lower surface of straight tube 19.
Wherein, the diameter of the impeller of the stirring rake in guide shell 18 37 is the 30-70% of draft tube diameter.
Wherein, be provided with discharging weir 28 in the inboard of the straight tube 19 of discharge port 27 1 sides, the top on discharging weir 28 is airtight, the bottom on discharging weir 28 and reactor internal communication, and the bottom on discharging weir 28 is not less than 1/4th of guide shell height to the distance of guide shell 18 lower ends.
Wherein, the catalyst sedimentation groove is made of top straight tube and bottom cone, lower end side in straight tube is provided with subsider discharge port 38, the bottom of subsider discharge port 38 as far as possible close straight tube under the prerequisite that satisfies the apparatus processing condition, the cone angle of the cone of catalyst sedimentation groove is established catalyst recovery mouth 39 less than 90 degree in the bottom of cone.
Embodiment 1: produce O-Phenylene Diamine according to following steps:
(1) in one-level hydrogenation reaction kettle 5 and secondary hydrogenation reaction kettle 8, add respectively first the methyl alcohol that is equivalent to reactor total volume 50%, add again the skeleton nickel that is equivalent to above-mentioned methyl alcohol weight 1.5%;
(2) water coolant of unlatching heat exchange coil keeps temperature of reaction at 90 ℃;
(3) under whipped state in the time of 90 ℃, to one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8 interior hydrogen that pass into continuously; The speed that passes into hydrogen remains on 1.3MPa to guarantee the pressure in one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8;
(4) when hydrogen pressure reaches 1.3MPa in the still, to one-level hydrogenation reaction kettle 5 interior continuous adding methyl alcohol and o-Nitranilines, the speed that adds methyl alcohol take the residence time of methyl alcohol by one-level hydrogenation reaction kettle 5 as 15.5, the volume ratio of methyl alcohol and o-Nitraniline charging is 1.7: 1;
(5) in implementation step (2), (3), (4), by the discharge port of one-level hydrogenation reaction kettle 5 to the 8 interior dischargings of secondary hydrogenation reaction kettle, also simultaneously by the discharge port of secondary hydrogenation reaction kettle 8 to the 11 interior dischargings of catalyst sedimentation groove, when catalyst sedimentation groove 11 is filled, by the discharge port of secondary hydrogenation reaction kettle 8 to 12 dischargings of catalyst sedimentation groove;
(6) the material sedimentation in the catalyst sedimentation groove is after 4 hours, by the discharge port 38 of catalyst sedimentation groove to follow-up rectifying tower 13 dischargings, after 5 batches of the catalyst sedimentation groove sedimentations, reclaim catalyzer for step (1) by the catalyst recovery mouth of catalyst sedimentation groove, secondary hydrogenation reaction kettle 8 hockets to catalyst sedimentation groove 11,12 discharging;
(7) when one-level hydrogenation reaction kettle 5 or secondary hydrogenation 8 interior suction hydrogen rate slow down, add tank 7,10 by catalyzer and add catalyzer in one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8, the catalytic amount of at every turn adding is the 1-2% of the initial dosage of catalyzer;
(8) remove solvent methanol and water in the reaction solution by rectifying tower 13, in rectifying tower 14, continue distillation and obtain the O-Phenylene Diamine finished product; O-Phenylene Diamine mass content 99.9% is take the yield of o-Nitraniline as 96.5%.
Embodiment 2: produce O-Phenylene Diamine according to following steps:
(1) in one-level hydrogenation reaction kettle 5 and secondary hydrogenation reaction kettle 8, add respectively first the methyl alcohol that is equivalent to reactor total volume 60%, add again the skeleton nickel that is equivalent to above-mentioned methyl alcohol weight 1%;
(2) water coolant of unlatching heat exchange coil keeps temperature of reaction at 100 ℃;
(3) under whipped state in the time of 100 ℃, to one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8 interior hydrogen that pass into continuously; The speed that passes into hydrogen remains on 2.0MPa to guarantee the pressure in one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8;
(4) when hydrogen pressure reaches 2.0MPa in the still, to one-level hydrogenation reaction kettle 5 interior continuous adding methyl alcohol and o-Nitranilines, the speed that adds methyl alcohol in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 10 hours, the volume ratio of methyl alcohol and o-Nitraniline charging is 5: 1;
(5) in implementation step (2), (3), (4), by the discharge port of one-level hydrogenation reaction kettle 5 to the 8 interior dischargings of secondary hydrogenation reaction kettle, also simultaneously by the discharge port of secondary hydrogenation reaction kettle 8 to the 11 interior dischargings of catalyst sedimentation groove, when catalyst sedimentation groove 11 is filled, by the discharge port of secondary hydrogenation reaction kettle 8 to 12 dischargings of catalyst sedimentation groove;
(6) the material sedimentation in the catalyst sedimentation groove is after 4 hours, by the discharge port 38 of catalyst sedimentation groove to follow-up rectifying tower 13 dischargings, after 5 batches of the catalyst sedimentation groove sedimentations, reclaim catalyzer for step (1) by the catalyst recovery mouth of catalyst sedimentation groove, secondary hydrogenation reaction kettle 8 hockets to catalyst sedimentation groove 11,12 discharging;
(7) when one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8 interior suction hydrogen rate slow down, add tank 7,10 by catalyzer and add catalyzer in one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8, the catalytic amount of at every turn adding is the 1-2% of the initial dosage of catalyzer;
(8) remove solvent methanol and water in the reaction solution by rectifying tower 13, in rectifying tower 14, continue distillation and obtain the O-Phenylene Diamine finished product; O-Phenylene Diamine mass content 99.8% is take the yield of o-Nitraniline as 95.8%.
Embodiment 3: produce O-Phenylene Diamine according to following steps:
(1) in one-level hydrogenation reaction kettle 5 and secondary hydrogenation reaction kettle 8, add respectively first the methyl alcohol that is equivalent to reactor total volume 70%, add again the skeleton nickel that is equivalent to above-mentioned methyl alcohol weight 0.5%;
(2) water coolant of unlatching heat exchange coil keeps temperature of reaction at 120 ℃;
(3) under whipped state in the time of 120 ℃, to one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8 interior hydrogen that pass into continuously; The speed that passes into hydrogen remains on 2.0MPa to guarantee the pressure in one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8;
When (4) hydrogen pressure reaches 2.0MPa in the still, to one-level hydrogenation reaction kettle 5 interior continuous adding methyl alcohol and o-Nitranilines, the speed that adds methyl alcohol in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 8 hours, the volume ratio of methyl alcohol and o-Nitraniline charging is 7: 1;
(5) when implementation step (2), (3), (4), by the discharge port of one-level hydrogenation reaction kettle 5 to the 8 interior dischargings of secondary hydrogenation reaction kettle, also simultaneously by the discharge port of secondary hydrogenation reaction kettle 8 to the 11 interior dischargings of catalyst sedimentation groove, when catalyst sedimentation groove 11 is filled, by the discharge port of secondary hydrogenation reaction kettle 8 to 12 dischargings of catalyst sedimentation groove;
(6) the material sedimentation in the catalyst sedimentation groove is after 4 hours, by the discharge port 38 of catalyst sedimentation groove to follow-up rectifying tower 13 dischargings, after 5 batches of the catalyst sedimentation groove sedimentations, reclaim catalyzer for step (1) by the catalyst recovery mouth of catalyst sedimentation groove, secondary hydrogenation reaction kettle 8 hockets to catalyst sedimentation groove 11,12 discharging;
(7) when one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8 interior suction hydrogen rate slow down, add tank 7,10 by catalyzer and add catalyzer in one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8, the catalytic amount of at every turn adding is the 1-2% of the initial dosage of catalyzer;
(8) remove solvent methanol and water in the reaction solution by rectifying tower 13, in rectifying tower 14, continue distillation and obtain the O-Phenylene Diamine finished product; O-Phenylene Diamine mass content 99.8% is take the yield of o-Nitraniline as 96.0%.
Embodiment 4: produce O-Phenylene Diamine according to following steps:
(1) in one-level hydrogenation reaction kettle 5 and secondary hydrogenation reaction kettle 8, add respectively first the methyl alcohol that is equivalent to reactor total volume 70%, add again the skeleton nickel that is equivalent to above-mentioned methyl alcohol weight 1%;
(2) open the coil pipe water coolant, keep temperature of reaction at 95 ℃;
(3) under whipped state in the time of 95 ℃, to one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8 interior hydrogen that pass into continuously; The speed that passes into hydrogen remains on 1.5MPa to guarantee the pressure in one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8;
(4) when hydrogen pressure reaches 1.5MPa in the still, to one-level hydrogenation reaction kettle 5 interior continuous adding methyl alcohol and o-Nitranilines, the speed that adds methyl alcohol in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 5 hours, the volume ratio of methyl alcohol and o-Nitraniline charging is 3: 1;
(5) when implementation step (2), (3), (4), by the discharge port of one-level hydrogenation reaction kettle 5 to the 8 interior dischargings of secondary hydrogenation reaction kettle, also simultaneously by the discharge port of secondary hydrogenation reaction kettle 8 to the 11 interior dischargings of catalyst sedimentation groove, when catalyst sedimentation groove 11 is filled, by the discharge port of secondary hydrogenation reaction kettle 8 to 12 dischargings of catalyst sedimentation groove;
(6) the material sedimentation in the catalyst sedimentation groove is after 4 hours, by the discharge port 38 of catalyst sedimentation groove to follow-up rectifying tower 13 dischargings, after 5 batches of the catalyst sedimentation groove sedimentations, reclaim catalyzer for step (1) by the catalyst recovery mouth of catalyst sedimentation groove, secondary hydrogenation reaction kettle 8 hockets to catalyst sedimentation groove 11,12 discharging;
(7) when one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8 interior suction hydrogen rate slow down, add tank 7,10 by catalyzer and add catalyzer in one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8, the catalytic amount of at every turn adding is the 1-2% of the initial dosage of catalyzer;
(8) remove solvent methanol and water in the reaction solution by rectifying tower 13, in rectifying tower 14, continue distillation and obtain the O-Phenylene Diamine finished product; O-Phenylene Diamine mass content 99.9% is take the yield of o-Nitraniline as 97.0%.
Embodiment 5: produce O-Phenylene Diamine according to following steps:
(1) in one-level hydrogenation reaction kettle 5 and secondary hydrogenation reaction kettle 8, add respectively first the methyl alcohol that is equivalent to reactor total volume 70%, add again the skeleton nickel that is equivalent to above-mentioned methyl alcohol weight 1%;
(2) water coolant of unlatching heat exchange coil keeps temperature of reaction at 120 ℃;
(3) under whipped state in the time of 120 ℃, to one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8 interior hydrogen that pass into continuously; The speed that passes into hydrogen remains on 2.5MPa to guarantee the pressure in one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8;
(4) when hydrogen pressure reaches 2.5MPa in the still, to one-level hydrogenation reaction kettle 5 interior continuous adding methyl alcohol and o-Nitranilines, the speed that adds methyl alcohol in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 3.6 hours, the volume ratio of methyl alcohol and o-Nitraniline charging 3: 1;
(5) when implementation step (2), (3), (4), by the discharge port of one-level hydrogenation reaction kettle 5 to the 8 interior dischargings of secondary hydrogenation reaction kettle, also simultaneously by the discharge port of secondary hydrogenation reaction kettle 8 to the 11 interior dischargings of catalyst sedimentation groove, when catalyst sedimentation groove 11 is filled, by the discharge port of secondary hydrogenation reaction kettle 8 to 12 dischargings of catalyst sedimentation groove;
(6) the material sedimentation in the catalyst sedimentation groove is after 4 hours, by the discharge port 38 of catalyst sedimentation groove to follow-up rectifying tower 13 dischargings, after 5 batches of the catalyst sedimentation groove sedimentations, reclaim catalyzer for step (1) by the catalyst recovery mouth of catalyst sedimentation groove, secondary hydrogenation reaction kettle 8 hockets to catalyst sedimentation groove 11,12 discharging;
(7) when one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8 interior suction hydrogen rate slow down, add tank 7,10 by catalyzer and add catalyzer in one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8, the catalytic amount of at every turn adding is the 1-2% of the initial dosage of catalyzer;
(8) remove solvent methanol and water in the reaction solution by rectifying tower 13, in rectifying tower 14, continue distillation and obtain the O-Phenylene Diamine finished product; O-Phenylene Diamine mass content 99.9% is take the yield of o-Nitraniline as 95.0%.
Embodiment 6: produce O-Phenylene Diamine according to following steps
(1) in one-level hydrogenation reaction kettle 5 and secondary hydrogenation reaction kettle 8, add respectively first the methyl alcohol that is equivalent to reactor total volume 70%, add again the skeleton nickel that is equivalent to above-mentioned methyl alcohol weight 1%;
(2) water coolant of unlatching heat exchange coil keeps temperature of reaction at 120 ℃;
(3) under whipped state in the time of 120 ℃, to one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8 interior hydrogen that pass into continuously; The speed that passes into hydrogen remains on 2.5MPa to guarantee the pressure in one-level hydrogenation reaction kettle 5 and the secondary hydrogenation reaction kettle 8;
(4) when hydrogen pressure reaches 2.5MPa in the still, to one-level hydrogenation reaction kettle 5 interior continuous adding methyl alcohol and o-Nitranilines, the speed that adds methyl alcohol in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 3.6 hours, the volume ratio of methyl alcohol and o-Nitraniline charging is 12: 1;
(5) when implementation step (2), (3), (4), by the discharge port of one-level hydrogenation reaction kettle 5 to the 8 interior dischargings of secondary hydrogenation reaction kettle, also simultaneously by the discharge port of secondary hydrogenation reaction kettle 8 to the 11 interior dischargings of catalyst sedimentation groove, when catalyst sedimentation groove 11 is filled, by the discharge port of secondary hydrogenation reaction kettle 8 to 12 dischargings of catalyst sedimentation groove;
(6) the material sedimentation in the catalyst sedimentation groove is after 4 hours, by the discharge port 38 of catalyst sedimentation groove to follow-up rectifying tower 13 dischargings, after 5 batches of the catalyst sedimentation groove sedimentations, reclaim catalyzer for step (1) by the catalyst recovery mouth of catalyst sedimentation groove, secondary hydrogenation reaction kettle 8 hockets to catalyst sedimentation groove 11,12 discharging;
(7) when one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8 interior suction hydrogen rate slow down, add tank 7,10 by catalyzer and add catalyzer in one-level hydrogenation reaction kettle 5 or secondary hydrogenation reaction kettle 8, the catalytic amount of at every turn adding is the 1-2% of the initial dosage of catalyzer;
(8) remove solvent methanol and water in the reaction solution by rectifying tower 13, in rectifying tower 14, continue distillation and obtain the O-Phenylene Diamine finished product; O-Phenylene Diamine mass content 99.9% is take the yield of o-Nitraniline as 95.5%.
Claims (2)
1. the method for producing o-phenylenediamine by continuous liquid phase hydrogenation, it is characterized in that: this production method is that reaction is carried out in the firsts and seconds hydrogenation reaction kettle of series connection, the method may further comprise the steps: at first, in the firsts and seconds hydrogenation reaction kettle, add respectively the methyl alcohol that is equivalent to reactor volume 50-70%, add respectively again the catalyzer that is equivalent to above-mentioned methyl alcohol weight 0.5-1.5%, under whipped state, pass into continuously hydrogen to the firsts and seconds hydrogenation reaction kettle simultaneously; Secondly, after reaching certain pressure in the firsts and seconds hydrogenation reaction kettle, in the one-level hydrogenation reaction kettle, add continuously methyl alcohol and o-Nitraniline, continue to keep the firsts and seconds hydrogenation reaction kettle under above-mentioned pressure, simultaneously by the one-level hydrogenation reaction kettle to the discharging of secondary hydrogenation reaction kettle and by secondary hydrogenation reaction kettle continuous discharge; Then, secondary hydrogenation reaction kettle reaction solution out reclaims catalyzer through subsider, and catalyzer is applied mechanically; At last, the reaction solution behind the recovery catalyzer continues distillation and obtains the O-Phenylene Diamine finished product by rectifying desolvation first alcohol and water; Wherein, catalysts is skeleton nickel.
2. the method for producing o-phenylenediamine by continuous liquid phase hydrogenation according to claim 1, it is characterized in that: wherein, add continuously in methyl alcohol and the o-Nitraniline process to the one-level hydrogenation reaction kettle, the volume ratio of methyl alcohol and o-Nitraniline charging is 1.7-12:1; Wherein, the speed that adds continuously methyl alcohol in the one-level hydrogenation reaction kettle be in the residence time of methyl alcohol by the one-level hydrogenation reaction kettle at 3.6-15.5 hour; Wherein, temperature of reaction is controlled at 90-120 ℃; Wherein, the speed that passes into hydrogen is that the reaction pressure that guarantees the firsts and seconds hydrogenation reaction kettle is controlled at 1.3-2.5MPa and counts.
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