CN109574852A - A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene - Google Patents
A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene Download PDFInfo
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- CN109574852A CN109574852A CN201811431494.3A CN201811431494A CN109574852A CN 109574852 A CN109574852 A CN 109574852A CN 201811431494 A CN201811431494 A CN 201811431494A CN 109574852 A CN109574852 A CN 109574852A
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- benzene
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- butyl titanate
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 117
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 62
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010792 warming Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000005292 vacuum distillation Methods 0.000 abstract description 2
- 238000006396 nitration reaction Methods 0.000 description 24
- 230000000802 nitrating effect Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006172 aromatic nitration reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, comprising the following steps: by nitromethane/nitric acid/N obtained2O5Mixture is added in reaction kettle, and catalyst is added, and controls temperature at 0-10 DEG C, is passed through N2After 10-15min, lower dropwise addition benzene is stirred, being warming up to 30-40 DEG C after being added dropwise to complete is reacted, and after the reaction was completed, is filtered, is washed, and nitrobenzene is made in vacuum distillation.A large amount of spent acid will not be generated in the preparation method production process of the application, it is environmentally protective, and the reaction process mild condition, production process are highly-safe.
Description
Technical field
The present invention relates to aromatic ring nitration fields, prepare nitrobenzene using dinitrogen pentoxide nitrification benzene more particularly to a kind of
Method.
Background technique
Nitration reaction is most one of universal, the organism unit reaction found earliest, is that the C into organic compound molecule is former
Introducing-NO on son2Reaction.The nitrification of aromatic compound is an important organic reaction, and the nitration product of aromatic hydrocarbons is one
The important industrial chemicals of class, may be used as the intermediate of explosive, pesticide, medicine, dyestuff etc..Nitrobenzene is a kind of important base
This organic chemistry raw material is widely used in a variety of medicine such as production aniline, benzidine and dinitrobenzene and dyestuff intermediate, it is also possible to
Make the raw material of pesticide, explosive and thiofide, there is very wide application range.
Current aromatic nitration generallys use traditional nitric-sulfuric acid nitrification process, but its there are some drawbacks: (1) produced
Journey is dangerous, since nitration reaction is a kind of quick strong exothermal reaction process, easily causes temperature to be ascended to heaven, overflow is even exploded
The phenomenon that；(2) it will cause environmental pollution, nitric-sulfuric acid technique can generate acid waste water largely containing organic matter, cause tight
The environmental pollution of weight；(2) aromatic hydrocarbons Regioselective Nitration problem.Therefore, selection control more accurate, stabilizing energy-saving nitrification system
System and highly selective green nitration technology, are the key that solve the problems, such as aromatic nitration.
Green nitration research has been achieved for many progress, and major technique includes solid acid catalysis liquid phase green nitre
Change, solid acid catalysis gas phase green nitration, Louis acid catalysis liquid phase green nitration, liquid acid/nitric acid salt system liquid phase
Green nitration etc. in green nitration, ionic liquid.Wherein solid acid catalysis green nitration completely eliminates spent acid
Pollution, and the separation and recycling of solid acid catalyst are easy, while acid active sites and substrate or nitrating agent on solid acid
Synergistic effect has apparent difference, significantly affects so that it has the regioselectivity of nitration product, and solid acid includes viscous
Great soil group catalyst, molecular sieve catalyst, metal oxide-type catalyst, heteropolyacid catalyst.
In addition to the improvement on catalyst, the improvement of nitrating agent, and improve nitration reaction safety, the limited hand of the feature of environmental protection
Section.It is nitrified using dinitrogen pentoxide as nitrating agent, not only overcomes the various deficiencies of non-green nitrification system, and base
This does not have side reaction, can nitrify to acid-sensitive, water sensitivity and the substance for being easy to aoxidize.It can be not only used for the material containing energy
The synthesis of material can be used for producing the manufacturings such as basic Organic Ingredients, and medicine, dyestuff and pesticide.Therefore, as
Clean nitrating agent, N2O5Application prospect it is very wide.
Chinese patent CN200410082930.2 discloses a kind of tubular plant for producing nitrobenzene by nitrifying benzene, including mixed
Acid and benzene inlet tube, nitration reaction pipe, nitrating mixture outlet, nitrating mixture separator；It is characterized in that nitration mixture and benzene
An intersegmental part is at least arranged between inlet tube and nitrating mixture outlet to be equipped with to the material flowed in pipe immixture
The nitration reaction pipe of chemical filler or hybrid element, nitration mixture and benzene inlet tube are connected with nitration reaction tube inlet end, nitration reaction
Pipe outlet end is connected with nitrating mixture outlet, and nitrating mixture outlet is connected with nitrating mixture separator；It is arranged more
When section nitration reaction pipe, docking connection can be used between nitration reaction pipe or use connecting tube connection.The invention advantage are as follows: make nitro
Benzene manufacture realizes that pipeline metaplasia produces, and installation area is small, is easy to arrange, equipment investment is few；Device operating flexibility is big；Device knot
Structure is simple, easily operated.But the nitration reaction carried out using the device, spent acid can be still generated, environmental pollution is caused.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, this method productions
A large amount of spent acid will not be generated in the process, it is environmentally protective, and the reaction process mild condition, production process are highly-safe.
To achieve the above object, the invention adopts the following technical scheme:
A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene, comprising the following steps:
(1) ethanol solution that butyl titanate is added after mixing ethyl orthosilicate with triethylamine is made molten after mixing
Glue, the ethyl alcohol that silica solution is added to butyl titanate after mixing under ultrasound condition with tetrapropylammonium hydroxide solution are molten
Liquid, continual ultrasonic stir 1-2h after, under the conditions of placing it in 70-90 DEG C crystallization for 24 hours after, be added into step 1 preparation colloidal sol
In, after reacting 54h under the conditions of 120-140 DEG C, it is cooled to room temperature, it is washed, dry, roast, grind after product is filtered
Grind to obtain catalyst；
(2) nitromethane is added in reaction kettle, controlled at 0-5 DEG C, after addition nitric acid is uniformly mixed later,
Under stirring condition, N is added portionwise2O5, after the completion of addition, continue to stir 15-25min, mixture is made in filtering；
(3) mixture made from step (2) is added in reaction kettle, catalyst is added, controlled temperature at 0-10 DEG C, be passed through
N2After 10-15min, lower dropwise addition benzene is stirred, being warming up to 30-40 DEG C after being added dropwise to complete is reacted, and after the reaction was completed, filtering is washed
It washs, is evaporated under reduced pressure, nitrobenzene is made.
Preferably, ethyl orthosilicate in the step (1), triethylamine, butyl titanate use molar ratio be 35:2:1；
The molar concentration of butyl titanate is 5-7mol/L in the ethanol solution of butyl titanate.
Preferably, silica solution, tetrapropylammonium hydroxide, butyl titanate 45:4:1 in the step (1).
Preferably, the volume ratio of nitromethane and nitric acid is 10:1 in the step (2), and the mass fraction of nitric acid is
100%.
Preferably, N in the mixture prepared in the step (2)2O5Concentration be 1mol/L.
Preferably, the usage amount mass volume ratio of catalyst and mixture is 0.3-0.4g/mL in the step (3).
Preferably, the usage amount volume ratio of mixture and benzene is 2-4:1 in the step (3).
The invention has the advantages that
1, use the TS-1 type Titanium Sieve Molecular Sieve being prepared as catalyst, carry out catalytic nitration reaction, effectively mention
The high conversion ratio of benzene, and using after the catalyst, the selectivity of reaction increases, and reduces the generation of by-product, whole to receive
Rate improves.
2, the TS-1 type Titanium Sieve Molecular Sieve of the application synthesis has good hole configurations, and biggish specific surface area can be with
So that reactant comes into full contact in molecular sieve surface, to improve catalytic efficiency.
3, nitrification system used in this application is generated without spent acid, environmentally protective, and reaction condition is mild, production
Safety coefficient is high, is very suitable for large-scale industrial production.
Specific embodiment
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene, comprising the following steps:
(1) ethanol solution that butyl titanate is added after mixing ethyl orthosilicate with triethylamine is made molten after mixing
Glue, the ethyl alcohol that silica solution is added to butyl titanate after mixing under ultrasound condition with tetrapropylammonium hydroxide solution are molten
Liquid, continual ultrasonic stir 1h after, under the conditions of placing it in 70 DEG C crystallization for 24 hours after, be added into step 1 preparation colloidal sol in,
It after reacting 54h under the conditions of 120 DEG C, is cooled to room temperature, after product is filtered, washed, dry, roasting, grinding are made and urge
Agent, wherein ethyl orthosilicate, triethylamine, butyl titanate use molar ratio be 35:2:1；The ethyl alcohol of butyl titanate is molten
The molar concentration of butyl titanate is 5mol/L in liquid；Silica solution, tetrapropylammonium hydroxide, butyl titanate 45:4:1；
(2) nitromethane is added in reaction kettle, controlled at 0 DEG C, after addition nitric acid is uniformly mixed later, nitre
The volume ratio of methylmethane and nitric acid is 10:1, and the mass fraction of nitric acid is 100%, and under stirring condition, N is added portionwise2O5, it is added
After the completion, continue to stir 15min, mixture is made, wherein N in filtering2O5Concentration be 1mol/L；
(3) mixture made from step (2) is added in reaction kettle, catalyst, the use of catalyst and mixture is added
Amount mass volume ratio is 0.3g/mL, controls temperature at 0 DEG C, is passed through N2After 10min, stir it is lower be added dropwise benzene, mixture and benzene make
Dosage volume ratio is 2-4:1, and 30 DEG C are warming up to after being added dropwise to complete and is reacted, and after the reaction was completed, filters, washs, vacuum distillation,
Nitrobenzene is made.
The purity of the nitrobenzene of preparation is 98.4%, and the conversion ratio of benzene is 90.3%.
Embodiment 2
A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene, comprising the following steps:
(1) ethanol solution that butyl titanate is added after mixing ethyl orthosilicate with triethylamine is made molten after mixing
Glue, the ethyl alcohol that silica solution is added to butyl titanate after mixing under ultrasound condition with tetrapropylammonium hydroxide solution are molten
Liquid, continual ultrasonic stir 2h after, under the conditions of placing it in 70 DEG C crystallization for 24 hours after, be added into step 1 preparation colloidal sol in,
It after reacting 54h under the conditions of 140 DEG C, is cooled to room temperature, after product is filtered, washed, dry, roasting, grinding are made and urge
Agent, wherein ethyl orthosilicate, triethylamine, butyl titanate use molar ratio be 35:2:1；The ethyl alcohol of butyl titanate is molten
The molar concentration of butyl titanate is 7mol/L in liquid；Silica solution, tetrapropylammonium hydroxide, butyl titanate 45:4:1；
(2) nitromethane is added in reaction kettle, controlled at 0 DEG C, after addition nitric acid is uniformly mixed later, nitre
The volume ratio of methylmethane and nitric acid is 10:1, and the mass fraction of nitric acid is 100%, and under stirring condition, N is added portionwise2O5, it is added
After the completion, continue to stir 15min, mixture is made, wherein N in filtering2O5Concentration be 1mol/L；
(3) mixture made from step (2) is added in reaction kettle, catalyst, the use of catalyst and mixture is added
Amount mass volume ratio is 0.4g/mL, controls temperature at 10 DEG C, is passed through N2After 10min, stir it is lower be added dropwise benzene, mixture and benzene
Usage amount volume ratio is 2-4:1, and 40 DEG C are warming up to after being added dropwise to complete and is reacted, and after the reaction was completed, is filtered, washing, decompression is steamed
It evaporates, nitrobenzene is made.
The purity of the nitrobenzene of preparation is 99.0%, and the conversion ratio of benzene is 91.1%.
Embodiment 3
A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene, comprising the following steps:
(1) ethanol solution that butyl titanate is added after mixing ethyl orthosilicate with triethylamine is made molten after mixing
Glue, the ethyl alcohol that silica solution is added to butyl titanate after mixing under ultrasound condition with tetrapropylammonium hydroxide solution are molten
Liquid, continual ultrasonic stir 2h after, under the conditions of placing it in 80 DEG C crystallization for 24 hours after, be added into step 1 preparation colloidal sol in,
It after reacting 54h under the conditions of 130 DEG C, is cooled to room temperature, after product is filtered, washed, dry, roasting, grinding are made and urge
Agent, wherein ethyl orthosilicate, triethylamine, butyl titanate use molar ratio be 35:2:1；The ethyl alcohol of butyl titanate is molten
The molar concentration of butyl titanate is 6mol/L in liquid；Silica solution, tetrapropylammonium hydroxide, butyl titanate 45:4:1；
(2) nitromethane is added in reaction kettle, controlled at 2 DEG C, after addition nitric acid is uniformly mixed later, nitre
The volume ratio of methylmethane and nitric acid is 10:1, and the mass fraction of nitric acid is 100%, and under stirring condition, N is added portionwise2O5, it is added
After the completion, continue to stir 20min, mixture is made, wherein N in filtering2O5Concentration be 1mol/L；
(3) mixture made from step (2) is added in reaction kettle, catalyst, the use of catalyst and mixture is added
Amount mass volume ratio is 0.35g/mL, controls temperature at 5 DEG C, is passed through N2After 15min, stir it is lower be added dropwise benzene, mixture and benzene
Usage amount volume ratio is 2-4:1, and 35 DEG C are warming up to after being added dropwise to complete and is reacted, and after the reaction was completed, is filtered, washing, decompression is steamed
It evaporates, nitrobenzene is made.
The purity of the nitrobenzene of preparation is 99.3%, and the conversion ratio of benzene is 91.7%.
Embodiment 4
A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene, comprising the following steps:
(1) ethanol solution that butyl titanate is added after mixing ethyl orthosilicate with triethylamine is made molten after mixing
Glue, the ethyl alcohol that silica solution is added to butyl titanate after mixing under ultrasound condition with tetrapropylammonium hydroxide solution are molten
Liquid, continual ultrasonic stir 1h after, under the conditions of placing it in 70 DEG C crystallization for 24 hours after, be added into step 1 preparation colloidal sol in,
It after reacting 54h under the conditions of 140 DEG C, is cooled to room temperature, after product is filtered, washed, dry, roasting, grinding are made and urge
Agent, wherein ethyl orthosilicate, triethylamine, butyl titanate use molar ratio be 35:2:1；The ethyl alcohol of butyl titanate is molten
The molar concentration of butyl titanate is 6mol/L in liquid；Silica solution, tetrapropylammonium hydroxide, butyl titanate 45:4:1；
(2) nitromethane is added in reaction kettle, controlled at 4 DEG C, after addition nitric acid is uniformly mixed later, nitre
The volume ratio of methylmethane and nitric acid is 10:1, and the mass fraction of nitric acid is 100%, and under stirring condition, N is added portionwise2O5, it is added
After the completion, continue to stir 25min, mixture is made, wherein N in filtering2O5Concentration be 1mol/L；
(3) mixture made from step (2) is added in reaction kettle, catalyst, the use of catalyst and mixture is added
Amount mass volume ratio is 0.4g/mL, controls temperature at 0-10 DEG C, is passed through N2After 14min, lower dropwise addition benzene, mixture and benzene are stirred
Usage amount volume ratio be 3:1,35 DEG C are warming up to after being added dropwise to complete and is reacted, after the reaction was completed, filter, washing, decompression steam
It evaporates, nitrobenzene is made.
The purity of the nitrobenzene of preparation is 98.8%, and the conversion ratio of benzene is 90.5%.
Claims (7)
1. a kind of method for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: the following steps are included:
(1) colloidal sol is made in the ethanol solution that butyl titanate is added after mixing ethyl orthosilicate with triethylamine after mixing,
Silica solution and tetrapropylammonium hydroxide solution are added to the ethanol solution of butyl titanate after mixing under ultrasound condition,
Continual ultrasonic stir 1-2h after, under the conditions of placing it in 70-90 DEG C crystallization for 24 hours after, be added into step 1 preparation colloidal sol in,
After reacting 54h under the conditions of 120-140 DEG C, it is cooled to room temperature, after product is filtered, washed, dry, roasting, grinding
Catalyst is made；
(2) nitromethane is added in reaction kettle, controlled at 0-5 DEG C, after addition nitric acid is uniformly mixed later, stirring
Under the conditions of, N is added portionwise2O5, after the completion of addition, continue to stir 15-25min, mixture is made in filtering；
(3) mixture made from step (2) is added in reaction kettle, catalyst is added, controlled temperature at 0-10 DEG C, be passed through N210-
After 15min, lower dropwise addition benzene is stirred, being warming up to 30-40 DEG C after being added dropwise to complete is reacted, and after the reaction was completed, is filtered, and washing subtracts
Pressure distillation, is made nitrobenzene.
2. the method according to claim 1 for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: described
Ethyl orthosilicate in step (1), triethylamine, butyl titanate use molar ratio be 35:2:1；The ethyl alcohol of butyl titanate is molten
The molar concentration of butyl titanate is 5-7mol/L in liquid.
3. the method according to claim 1 for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: described
Silica solution, tetrapropylammonium hydroxide, butyl titanate 45:4:1 in step (1).
4. the method according to claim 1 for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: described
The volume ratio of nitromethane and nitric acid is 10:1 in step (2), and the mass fraction of nitric acid is 100%.
5. the method according to claim 1 for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: described
N in the mixture prepared in step (2)2O5Concentration be 1mol/L.
6. the method according to claim 1 for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: described
The usage amount mass volume ratio of catalyst and mixture is 0.3-0.4g/mL in step (3).
7. the method according to claim 1 for preparing nitrobenzene using dinitrogen pentoxide nitrification benzene, it is characterised in that: described
The usage amount volume ratio of mixture and benzene is 2-4:1 in step (3).
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| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
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| US5977418A (en) * | 1998-01-20 | 1999-11-02 | Damavarapu; Reddy | Regioselective nitration of aromatic compounds by dinitrogen pentoxide and the reaction products thereof |
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| CN113563196A (en) * | 2021-07-27 | 2021-10-29 | 安徽江泰新材料科技有限公司 | Preparation method of 2,4(2,6) -dimethyl nitrobenzene |
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