CN114349643A - Method for preparing nitro compound by solid acid nitration of aromatic compound - Google Patents
Method for preparing nitro compound by solid acid nitration of aromatic compound Download PDFInfo
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- 238000006396 nitration reaction Methods 0.000 title claims abstract description 73
- 239000011973 solid acid Substances 0.000 title claims abstract description 57
- 150000002828 nitro derivatives Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 30
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- 238000007670 refining Methods 0.000 claims abstract description 12
- 239000002826 coolant Substances 0.000 claims description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910021389 graphene Inorganic materials 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 17
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 4
- 229910016287 MxOy Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 7
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 7
- 230000008676 import Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003068 static effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJIHIZOVLAWHFM-UHFFFAOYSA-N n-(3-acetylphenyl)-2,2,2-trifluoroacetamide Chemical compound CC(=O)C1=CC=CC(NC(=O)C(F)(F)F)=C1 QJIHIZOVLAWHFM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- -1 nitro aromatic hydrocarbon Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of organic chemistry, and particularly relates to a method for preparing a nitro compound by solid acid nitration of an aromatic compound. The method is characterized in that an aromatic hydrocarbon compound and nitric acid are subjected to nitration reaction in a tubular reactor filled with a solid acid catalyst, and a nitration reaction product is subjected to alkali washing, water washing and refining to obtain a nitro compound. The invention adopts the solid acid to fill the tubular reactor for nitration, does not need waste acid separation, concentration and recycling, has simple production process and can realize the continuous and stable production of the aromatic hydrocarbon compound.
Description
Technical Field
The invention belongs to the technical field of organic chemical industry, relates to a method for preparing a nitro compound by catalytic nitration of aromatic compound solid acid, and particularly relates to a method for preparing a nitro compound by catalytic nitration of graphene-coated solid acid.
Background
The industrial production process of nitro compound includes isothermal nitration and adiabatic nitration, and the nitration reaction is carried out by mixing aromatic compound and mixed acid, such as benzene nitration to prepare nitrobenzene, chlorobenzene nitration to prepare nitrochlorobenzene, toluene nitration to prepare dinitrotoluene, etc., wherein sulfuric acid is used as catalyst, and after reaction, separation and concentration, the sulfuric acid is used for reuse.
The traditional nitration process is that aromatic hydrocarbon compounds react with mixed acid, nitration products enter a nitration separator to separate waste acid and an organic phase, the waste acid is recycled after concentration, and the organic phase is subjected to alkali neutralization, water washing, preliminary distillation and rectification to obtain nitro compound products. The traditional mixed acid nitration process needs to recover sulfuric acid after nitration reaction, not only has high energy consumption and long flow, but also needs to use expensive anticorrosive materials. In addition, the mixed acid system is required to strictly control the reaction temperature and the ratio of the mixed acid so as to avoid side reactions such as polynitroation and oxidation.
The solid acid overcomes the defects of the traditional mixed acid nitration, has the characteristics of easy separation from a liquid phase reaction system, no corrosion to equipment, simple post-treatment, little environmental pollution, high selectivity and the like, can be used in a higher temperature range, and expands the application range of acid catalytic reaction which can be possibly carried out thermodynamically, so that the solid acid catalyst has wide application prospect.
The aged people and the like investigate MCM-41, Al-MCM-41, ZSM-5, beta-zeolite, SAPO-11 and Y-type molecular sieve NH4Solid acids such as Y, ReY, SSY, phosphomolybdic acid and phosphotungstic acid to benzene, toluene andcatalytic performance of chlorobenzene nitration. For the nitration of benzene with concentrated nitric acid, the solid acids MCM-41(T), MCM-41(W), ZSM-5 and NH4The catalytic activity of Y is higher. When MCM-41(T) is used as a catalyst, the yield of nitrobenzene is 85.6 percent under better reaction conditions; for the nitration reaction of toluene, ReY and high-silicon ZSM-5 have better catalytic activity, and the yield of nitrotoluene is 62.7 percent under the better reaction condition by using ReY as a catalyst; for chlorobenzene nitration, the catalyst exhibits catalytic activity at higher temperatures. At 100 ℃, the MCM-41(T) has the highest catalytic activity, and the yield of the nitrochlorobenzene is 27.23 percent.
Patent CN106431930B discloses a method for preparing nitrobenzene by nitrifying benzene with nitrogen oxides (NOx), that is, a method for preparing nitrobenzene with high selectivity by transferring from a "strong acid" method to a "non-acid" method, replacing a "nitric acid/sulfuric acid" environment, adopting NOx as a nitrating agent, using a novel high-stability and high-activity solid acid as a catalyst, implementing a high atom economy green technology, and carrying out a nitration reaction on benzene.
CN110511145A discloses a nitration method of aromatic hydrocarbon compound, in particular to a method for preparing nitro aromatic hydrocarbon compound by nitration reaction of aromatic hydrocarbon compound, liquid dinitrogen tetroxide and oxygen-containing gas flow in the presence of solid acid catalyst and a small amount of sulfuric acid.
At present, the solid acid catalyst is widely applied to the catalytic nitration of aromatic compounds, but the problems that a small amount of sulfuric acid is required to be added as bottom acid in the reaction process, the service life of the catalyst is short, the catalyst needs to be regenerated repeatedly, and the catalytic activity and selectivity are low exist, and the application of the solid acid catalyst is not combined with a high-efficiency reactor to optimize the nitration process, so that ideal reaction performance is obtained.
At present, the nitration reaction of aromatic compounds adopts two main reactors: tank reactors and tubular reactors. The tubular reactor has the advantages of simple structure, low energy consumption, easy amplification and the like. Therefore, the temperature stability of the industrial high-viscosity material in the reactor is effectively controlled, the advantages of the solid acid catalyst are fully exerted, the solid acid catalyst is combined with the tubular reactor to form a novel nitration production process, the product yield can be effectively improved, and the production cost is reduced.
Disclosure of Invention
Aiming at the defects of the traditional homogeneous catalytic nitration process, a tubular reactor filled with solid acid and used for liquid-liquid two-phase strong exothermic reaction and a method for preparing a nitro compound by using the tubular reactor for isothermal tubular reaction of aromatic compounds are provided.
The invention provides a method for preparing a nitro compound by solid acid nitration of an aromatic hydrocarbon compound, wherein the aromatic hydrocarbon compound and nitric acid are subjected to nitration reaction in a tubular reactor filled with a solid acid catalyst, and a nitration reaction product is subjected to alkali washing, water washing and refining to prepare the nitro compound.
The tubular reactor is used for liquid-liquid two-phase reaction, and particularly relates to a tubular reactor disclosed in Chinese utility model patent (granted patent number ZL 201621443119.7).
The number of coolant inlets of the tubular reactor connected with the coolant distribution pipe is 2-8.
The axial temperature of the tubular reactor is adjusted by different coolant inlet flows.
The axial temperature difference in the tubular reactor is less than or equal to +/-0.5 ℃.
The solid acid catalyst takes graphene as a shell layer, and SO4 2-/MxOyThe type solid acid catalyst is used as a core, and the constructed graphene coated solid acid catalyst.
The solid acid catalyst has an average particle size of 1-10 mm and a specific surface area of 800-1000 m2The pore diameter of 50-100 nm is more than or equal to 80 percent, and the acidity is 4-6 mmol H +/g.
The aromatic hydrocarbon compound is benzene, toluene or chlorobenzene.
The mass percentage of the nitric acid is 90% -98%.
The molar ratio of the aromatic hydrocarbon compound to HNO3 is 1.0-1.05: 1.
The invention has the technical effects that:
(1) taking a graphene carbon layer of a graphene carbon material with good chemical stability, high specific surface area and uniform pore structure as a shell, and taking SO4 2-/MxOyThe solid acid catalyst is a coreThe component graphene coated solid acid catalyst is used for nitration reaction of aromatic hydrocarbon compounds, has the characteristics of high activity, easy recovery and high stability of the solid acid catalyst, and improves the stability of an active center, thereby prolonging the service life of the catalyst;
(2) the tubular reactor is filled with the graphene coated solid acid catalyst, the nitration reaction temperature is accurately controlled through the inner heat exchange tube and the coolant distribution tube, byproducts are effectively prevented from being generated, and the quality stability of the nitration product is improved;
(3) because the solid acid is filled in the reactor, the catalyst does not need to be separated after the reaction, the aromatic compound is excessive, the waste acid does not need to be separated and recycled after the reaction, the process flow is shortened, and the production cost is effectively reduced.
Drawings
FIG. 1 is a schematic structural diagram of a tubular reactor for nitration reaction in the example of the present invention.
Fig. 2 is a schematic view of a coolant distribution pipe in an embodiment.
In fig. 1, 1 — material inlet 1; 2-material inlet 2; 3-a static mixer; 4-coolant inlet; 5-coolant distribution pipe; 6-reactor shell; 7-heat exchange tubes; 8-coolant outlet; 9-material outlet; 10-solid acid catalyst.
In FIG. 2, 1-reactor shell; 2-coolant inlet; 3-heat exchange tube array; 4-coolant distribution pipes.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
In the method for preparing the nitro compound by nitrating the aromatic hydrocarbon compound solid acid in the embodiment, a tubular reactor is adopted for nitration reaction, and graphene coated solid acid catalyst is filled in the tubular reactor, as shown in figure 1. Tubular reactor front end sets up nitration raw materials import (1) and nitric acid import (2), and import (1, 2) and static mixer (3) intercommunication of installing in the reactor, get into reactor casing (6) after making nitric acid and nitration raw materials mix through static mixer (3) and contact the back reaction with solid acid (10) of packing, reactor casing (6) externally mounted coolant import (4), reactor casing (6) internally mounted heat transfer tubulation (7) and coolant distribution pipe (5) (refer to figure 2), coolant import (4) and heat transfer tubulation (7) are through coolant distribution pipe (5) intercommunication, flow control tubular reactor internal temperature through adjusting coolant in different coolant imports (4).
The nitration reaction product is directly washed by alkali to neutralize a small amount of residual acid, and then washed by water and refined to prepare the nitro compound.
Example 1
According to the specific embodiment, the mass percent of the nitric acid is 96 percent, and the benzene and the HNO are3The molar ratio of (1.03: 1), the nitration temperature is controlled to be 80 ℃, 8 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene coats SO4 2-/TiO2-ZrO2The average particle diameter of the solid acid catalyst is 10mm, and the specific surface area is 800m2Per g, 50-100 nm pore diameter is more than or equal to 87%, acidity is 4.0mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 80.1 ℃ at most and 79.8 ℃ at most; the continuous operation is carried out for 1000 hours, the selectivity of nitrobenzene is highest 100 percent and lowest 99.8 percent; the yield of the refined nitrobenzene product is more than or equal to 99.2 percent.
Example 2
According to the specific embodiment, the mass percent of the nitric acid is 90 percent, and the toluene and the HNO are3The molar ratio of (1.01: 1), the nitration temperature is controlled to be 60 ℃, 6 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene coats SO4 2-/TiO2-ZrO2-CoO2The average particle diameter of the solid acid catalyst is 1mm, and the specific surface area is 1000m2Per g, 50-100 nm pore diameter is more than or equal to 88%, acidity is 5.5mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 60.3 ℃ at most and 59.7 ℃ at most; the continuous operation is carried out for 1000 hours, the total selectivity of nitrotoluene (3 isomers) is 99.5 percent at most and 99.0 percent at least; the total yield of the refined nitrotoluene (3 isomers) product is more than or equal to 98.5 percent.
Example 3
According to the specific embodiment, the mass percent of the nitric acid is 98 percent, and the chlorobenzene and the HNO are3The molar ratio of (1.05: 1), the nitration temperature is controlled to be 70 ℃, 2 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene coats SO4 2-/TiO2-ZrO2The average particle diameter of the solid acid catalyst is 4mm, and the specific surface area is 850m2Per g, 50-100 nm pore diameter is not less than 84%, acidity is 4.4mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 70.2 ℃ at most and 99.9 ℃ at most; the continuous operation is carried out for 1000 hours, the highest total selectivity of nitrochlorobenzene (3 isomers) is 98.8 percent, and the lowest total selectivity is 98.5 percent; the total yield of the refined nitrochlorobenzene (3 isomers) products is more than or equal to 97.8 percent.
Example 4
According to the specific embodiment, the mass percentage of the nitric acid is 94 percent, and the benzene and the HNO are3The molar ratio of (1: 1), the nitration temperature is controlled to be 80 ℃, 6 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene is coated with SO4 2-/TiO2-ZrO2-CoO2The average particle diameter of the solid acid catalyst is 6mm, and the specific surface area is 900m2Per g, 50-100 nm pore diameter is more than or equal to 88%, acidity is 6.0mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 80.4 ℃ at most and 79.8 ℃ at most; the continuous operation is carried out for 1000 hours, the selectivity of nitrobenzene is 99.8 percent at most and 99.5 percent at least; the yield of the refined nitrobenzene product is more than or equal to 99.0 percent.
Example 5
According to the specific embodiment, the mass percent of the nitric acid is 92 percent, and the toluene and the HNO are3The molar ratio of (1.01: 1), the nitration temperature is controlled to be 60 ℃, 5 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene coats SO4 2-/TiO2-ZrO2The average particle diameter of the solid acid catalyst is 2mm, and the specific surface area is 850m2/g，Pore diameter of 50-100 nm is more than or equal to 85%, and acidity is 4.0mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 60.3 ℃ at most and 59.8 ℃ at most; the continuous operation is carried out for 1000 hours, the total selectivity of nitrotoluene (3 isomers) is 99.2 percent at most and 98.8 percent at least; the total yield of the refined nitrotoluene (3 isomers) product is more than or equal to 98.5 percent.
Example 6
According to the specific embodiment, the mass percent of the nitric acid is 95 percent, and the chlorobenzene and the HNO are mixed3The molar ratio of (1.05: 1), the nitration temperature is controlled to be 70 ℃, 4 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene coats SO4 2-/TiO2-ZrO2-CoO2The average particle diameter of the solid acid catalyst is 8mm, and the specific surface area is 800m2Per g, pore diameter of 50-100 nm is more than or equal to 83%, acidity is 5.2mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 70.2 ℃ at most and 69.9 ℃ at most; the continuous operation is carried out for 1000 hours, the total selectivity of the nitrochlorobenzene (3 isomers) is 99.6 percent at most and 99.3 percent at least; the total yield of the refined nitrochlorobenzene (3 isomers) products is more than or equal to 99.0 percent.
Example 7
According to the specific embodiment, the mass percentage of the nitric acid is 95 percent, and the benzene and the HNO are mixed3The molar ratio of (1.02: 1), the nitration control temperature of 80 ℃, 2-8 coolant inlets connecting the tubular reactor and the coolant distribution pipe, and the graphene coated SO4 2-/TiO2-ZrO2The average particle diameter of the solid acid catalyst is 4mm, and the specific surface area is 800m2Per g, 50-100 nm pore diameter not less than 82%, acidity 4.5mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 80.4 ℃ at most and 79.9 ℃ at most; the continuous operation is carried out for 1000 hours, the selectivity of nitrobenzene is highest 100 percent and lowest 99.6 percent; the yield of the refined nitrobenzene product is more than or equal to 99.0 percent.
Example 8
According to the specific embodiment, the mass percent of the nitric acid is 98 percent, and the toluene and the HNO are3The molar ratio of (1.02: 1), the nitration temperature is controlled to be 60 ℃, 8 coolant inlets are formed on the tubular reactor and connected with a coolant distribution pipe, and the graphene is coated with SO4 2-/TiO2-ZrO2-CoO2The average particle diameter of the solid acid catalyst is 6mm, and the specific surface area is 850m2Per g, 50-100 nm pore diameter is not less than 80%, acidity is 4.6mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 60.1 ℃ at most and 59.7 ℃ at most; the continuous operation is carried out for 1000 hours, the total selectivity of nitrotoluene (3 isomers) is 99.2 percent at most and 98.8 percent at least; the total yield of the refined nitrotoluene (3 isomers) product is more than or equal to 98.2 percent.
Example 9
According to the specific embodiment, the mass percentage of the nitric acid is 90, and the chlorobenzene and the HNO are3The molar ratio of (1.05: 1), the nitration temperature is controlled to be 70 ℃, 6 coolant inlets are arranged on the tubular reactor and connected with a coolant distribution pipe, and the graphene coats SO4 2-/TiO2-ZrO2The average particle diameter of the solid acid catalyst is 4mm, and the specific surface area is 800m2Per g, 50-100 nm pore diameter is not less than 80%, acidity is 4.8mmol H+(ii) in terms of/g. The nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
The implementation effect is as follows: the axial temperature in the tubular reactor is 70.4 ℃ at most and 69.9 ℃ at most; the continuous operation is carried out for 1000 hours, the total selectivity of the nitrochlorobenzene (3 isomers) is 99.4 percent at most and 98.9 percent at least; the total yield of the refined nitrochlorobenzene (3 isomers) products is more than or equal to 98.5 percent.
Claims (10)
1. The method for preparing the nitro compound by the solid acid nitration of the aromatic hydrocarbon compound is characterized by comprising the following steps: the aromatic hydrocarbon compound and nitric acid are subjected to nitration reaction in a tubular reactor filled with a solid acid catalyst, and the nitration reaction product is subjected to alkali washing, water washing and refining to obtain the nitro compound.
2. The method for preparing nitro compounds by solid acid nitration of aromatic compounds according to claim 1, wherein the tubular reactor is a tubular reactor for liquid-liquid two-phase reaction.
3. The method for preparing the nitro compound by the solid acid nitration of the aromatic hydrocarbon compound according to claims 1 and 2, wherein the number of the coolant inlets connected with the coolant distribution pipe of the tubular reactor is 2-8.
4. The process for the preparation of nitro compounds by solid acid nitration of aromatic compounds according to claims 1 and 2, characterized in that the tubular reactor axial temperature is adjusted by different coolant inlet flows.
5. The process for the preparation of nitro compounds by solid acid nitration of aromatic compounds according to claims 1 and 2, wherein the axial temperature difference in the tubular reactor is ≤ 0.5 ℃.
6. The method for preparing nitro compounds by the solid acid nitration of aromatic hydrocarbon compounds according to claim 1, wherein the solid acid catalyst is SO with graphene as a shell layer4 2-/MxOyThe type solid acid catalyst is used as a core, and the constructed graphene coated solid acid catalyst.
7. The method for preparing the nitro compound by the solid acid nitration of the aromatic hydrocarbon compound according to claim 1 or 6, wherein the solid acid catalyst has an average particle size of 1-10 mm and a specific surface area of 800-1000 m2Per g, 50-100 nm pore diameter is not less than 80%, acidity is 4-6 mmol H+/g。
8. The method for preparing nitro compounds by solid acid nitration of aromatic hydrocarbon compounds according to claim 1, wherein the aromatic hydrocarbon compound is benzene, toluene, or chlorobenzene.
9. The method for preparing the nitro compound by the solid acid nitration of the aromatic hydrocarbon compound according to claim 1, wherein the mass percentage of the nitric acid is 90-98%.
10. The method for preparing nitro compounds by solid acid nitration of aromatic compounds according to claim 1, wherein the aromatic compound is reacted with HNO3The molar ratio of (A) to (B) is 1.0-1.05: 1.
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| CN102827006A (en) * | 2012-09-20 | 2012-12-19 | 台州职业技术学院 | Method for preparing catalytically nitrified aromatic compound with fixed bed reactor |
| CN106431930A (en) * | 2015-08-05 | 2017-02-22 | 湘潭大学 | Method for preparing nitrobenzene from benzene |
| CN108003031A (en) * | 2017-11-23 | 2018-05-08 | 南京偌赛医药科技有限公司 | A kind of method for preparing nitro compound using graphene catalysis nitrogen dioxide |
| CN108238944A (en) * | 2016-12-27 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of method that aromatic compound isothermal pipe reaction prepares nitro compound |
| CN110511145A (en) * | 2019-09-09 | 2019-11-29 | 江苏方圆芳纶研究院有限公司 | A kind of nitration method of aromatic compound |
| CN114345341A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Graphene-coated solid acid catalyst and preparation method thereof |
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| CN102827006A (en) * | 2012-09-20 | 2012-12-19 | 台州职业技术学院 | Method for preparing catalytically nitrified aromatic compound with fixed bed reactor |
| CN106431930A (en) * | 2015-08-05 | 2017-02-22 | 湘潭大学 | Method for preparing nitrobenzene from benzene |
| CN108238944A (en) * | 2016-12-27 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of method that aromatic compound isothermal pipe reaction prepares nitro compound |
| CN108003031A (en) * | 2017-11-23 | 2018-05-08 | 南京偌赛医药科技有限公司 | A kind of method for preparing nitro compound using graphene catalysis nitrogen dioxide |
| CN110511145A (en) * | 2019-09-09 | 2019-11-29 | 江苏方圆芳纶研究院有限公司 | A kind of nitration method of aromatic compound |
| CN114345341A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Graphene-coated solid acid catalyst and preparation method thereof |
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