CN109232257A - Pipeline prepares the method and device of methyl nitrobenzene - Google Patents
Pipeline prepares the method and device of methyl nitrobenzene Download PDFInfo
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- CN109232257A CN109232257A CN201811026728.6A CN201811026728A CN109232257A CN 109232257 A CN109232257 A CN 109232257A CN 201811026728 A CN201811026728 A CN 201811026728A CN 109232257 A CN109232257 A CN 109232257A
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- 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
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/065—Feeding reactive fluids
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the method and device that a kind of pipeline prepares methyl nitrobenzene, which includes: storage tank, nitrogen dioxide steel cylinder, ozone generator, flow pump, gas flowmeter, the reaction pipeline filled with catalyst, mixed pipe line, two T-type hybrid juctions, cooling system, heating system, counterbalance valve, receiving tanks.This method specifically includes: opening cooling system and heating system；Open ozone generator；Flow pump and gas flowmeter are set；Raw material liquid methylbenzene enters in mixed pipe line after mixing with nitrogen dioxide by the first T-type hybrid juction, after being mixed in the second T-type hybrid juction with ozone later, nitration reaction is carried out in into the reaction pipeline filled with catalyst, reaction solution obtains methyl nitrobenzene after post treatment.The method of the present invention precise automatic control, easy to operate, reaction condition is mild, and post-processing is simple, and mass-and heat-transfer is rapid, highly-safe, good in economic efficiency.
Description
Technical field
The present invention relates to tubular type nitration technical fields, and in particular to a kind of pipeline prepare methyl nitrobenzene method and
Device.
Background technique
Methyl nitrobenzene compound is a kind of important chemical intermediate, is usually used in preparing dyestuff, medicine, pesticide, synthesis
Fiber, synthetic rubber and explosive etc..Currently, introducing nitro in technique into molecule, most common nitrating agent is using concentrated nitric acid
It is nitrified with concentrated sulfuric acid nitration mixture, a large amount of Waste Sulfuric Acid can be generated in production process, and the washing of nitro compound can generate greatly
The acid phenol wastewater of amount, leads to serious environmental pollution.There is document report (ACS Sym.Ser.623 1996:214.) only to adopt
When concentrated nitric acid being used to carry out nitration processes as nitrating agent, low yield is nitrified, while nitric acid being needed to keep higher in separation process
Concentration, can just continuous separation technology be made to be carried out, this also mean that reaction raw materials must use higher concentration nitric acid,
Therefore, for some active compounds, the nitration reaction of especially methyl substituted benzene, side reaction is inevitable
, while still can not fundamentally be solved in washes problem.
Dinitrogen pentoxide can carry out nitration reaction (explosive wastewater to mono-substituted benzenes such as toluene, chlorobenzenes in sulfuric acid medium
Journal, 2000,23 (1): 25), and obtaining higher yield, but in nitrifying process while generation nitro compound also
Equimolar nitric acid is generated, the nitric acid of generation can further nitrify substrate under the action of sulfuric acid, although sulfuric acid can be reduced
Dosage, but the difference of its nitration reaction for carrying out with nitration mixture not substantially.
1980, Kyoto Univ Japan Hitomi Suzuki largely report about in ozone medium use nitrogen dioxide nitre
Change the research (Chem.Lett.1993,2:1421 of aromatic compound；J.Chem.Soc.Chem.Commun.1991,1:
1409.), so as to cause extensive concern and research (Liaoning chemical industry, 2011,40 (7), 739-741.).Nitrogen dioxide-ozone nitre
Agent is considered as the clean nitrating agent that may replace nitration mixture.But since ozone itself is a kind of stronger oxidant,
When carrying out kettle type nitration reaction, with the oxidation side reaction of significant proportion, poor selectivity.Meanwhile the generation of ozone also needs
Consume a large amount of energy.In addition, the technology is inevitably present the problems such as organic solvent recycling, so, industry at present
Change in nitrification, still based on traditional nitre/sulphur nitration mixture technique.
Summary of the invention
The present invention provides a kind of pipeline and prepares methyl for deficiency existing for current nitrogen dioxide-ozone nitration processes
The method of nitrobenzene, with overcome the deficiencies in the prior art, the process recovery ratio is high, selectivity is strong, Environmental Safety green, and has work
Industry prospect.
The second object of the present invention is to provide a kind of dedicated unit for realizing above-mentioned preparation method.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of pipeline nitrification installation, comprising:
For storing the storage tank of liquid methylbenzene；
With the tank connected flow pump of storage；
Nitrogen dioxide steel cylinder；
The gas flowmeter being connect with the nitrogen dioxide steel cylinder；
First T-type hybrid juction, the outlet of the flow pump and the outlet of gas flowmeter access first T-type
The import of hybrid juction；
With the mixed pipe line of the outlet connection of the first T-type hybrid juction；
For the cooling system cooling to the first T-type hybrid juction and mixed pipe line；
Ozone generator；
Second T-type hybrid juction, the outlet of the mixed pipe line and the outlet of ozone generator access described
The import of two T-type hybrid juctions；
Pipeline is reacted filled with catalyst with what the outlet of second T-type hybrid juction connected；
Heating system for the reaction pipeline heating to second T-type hybrid juction and filled with catalyst；
With the counterbalance valve of the outlet connection for reacting pipeline；
The mixed pipe line being connect with the back pressure valve outlet.
The inventive system comprises a: storage tank, a nitrogen dioxide steel cylinder, an ozone generator, a flow pump,
One gas flowmeter, one filled with the reaction pipeline of catalyst, a mixed pipe line, two T-type hybrid juctions, one it is cold
But system, a heating system, a counterbalance valve, a receiving tank.Wherein, raw material liquid methylbenzene is stored in storage tank, and
Flow pump, the first T-type hybrid juction entrance are sequentially connected with conduit；Nitrogen dioxide steel cylinder is mixed with gas flowmeter, the first T-type
Fitting inlet is successively connected with conduit；First T-type hybrid juction outlet connection mixed pipe line entrance；Mixed pipe line outlet and ozone
Generator exports are connected to 2 entrances of the second T-type hybrid juction, and the outlet of the second T-type hybrid juction is connected to filling
There is the reaction line entry of catalyst；Reaction tube outlet connection filled with catalyst finally connects receiving tank after valve.
The first T-type hybrid juction and mixed pipe line is immersed in cooling system；The second T-type hybrid juction and filling
There is the reaction pipeline of catalyst to be immersed in heating system.
In the present invention, the length of the mixed pipe line is 5~30m, internal diameter 6mm, outer diameter 8mm, and pipe material is
Corrosion-resistant high voltage bearing metal material, preferably Hastelloy C-276 (Hastelloy C alloys -276)；Described is filled with catalysis
The reaction length of pipe of agent is 5~30m, internal diameter 6mm, outer diameter 8mm, and pipe material is corrosion-resistant high voltage bearing metal material
Material, preferably Hastelloy C-276 (Hastelloy C alloys -276)；Catalysis in the reaction pipeline filled with catalyst
The silica gel particle that agent is the global molecular sieve that partial size is 3-5mm or partial size is 3-5mm；The receiving tank is filled with tail gas absorption
It sets.
A kind of method that pipeline prepares methyl nitrobenzene is specifically included using pipeline nitrification installation:
Catalyst is packed into reaction pipeline first, attachment device checks leakproofness；Storage tank is added in raw material liquid methylbenzene
In；Cooling system the first T-type hybrid juction of cooling and mixed pipe line are opened to -5~5 DEG C；It opens heating system and preheats the second T-type
Hybrid juction and reaction pipeline are to 25~45 DEG C；Ozone generator is opened, ozone flow is set, is adjusted backwards to valve, so that reaction
Pressure in pipeline maintains 0.5~0.8MPa；According to the molar ratio of raw material liquid methylbenzene and nitrogen dioxide, flow pump is set
And gas flowmeter；Open the valve of storage tank and the valve of nitrogen dioxide steel cylinder；Raw material liquid methylbenzene and nitrogen dioxide are -5
Enter in mixed pipe line after the mixing of the first T-type hybrid juction at~5 DEG C；By the stop of 1~5min, with ozone second
In T-type hybrid juction mix after, into filled with catalyst reaction pipeline in carry out nitration reaction；By 15~30min's
After stop, reaction solution enters receiving tank；Reaction solution obtains sterling nitration product (i.e. methyl nitrobenzene) after post treatment.
Preparation method of the present invention, the raw material liquid methylbenzene are toluene, 1,2- dimethylbenzene, 1,3- diformazan
Benzene, 1,4- dimethylbenzene or 1,3,5- trimethylbenzene.The molar ratio of the raw material liquid methylbenzene and nitrogen dioxide be 1:1.1~
1.5。
Preparation method of the present invention, the material are delivered to the first T-type by flow pump and gas flowmeter and mix
When in connector, feed ratio needed for reaction can be reached by coutroi velocity.
Preparation method of the present invention, the catalyst amount, which is subject to, fills full packages road, and with sieve by pipeline
Both ends seal, and prevent catalyst from flowing out with reaction solution.
Preparation method of the present invention, the reaction temperature of the nitration reaction are 25~45 DEG C.
Preparation method of the present invention, the reaction solution post-processing approach are that the reaction solution in receiving tank is added water quenching
It goes out, washs 2~4 times (preferably 3 times) with saturated sodium bicarbonate solution, be washed with water to neutrality and dried with anhydrous sodium sulfate,
Product finally passes through rectifying and obtains purified product (i.e. methyl nitrobenzene).
Most preferably, a method of preparing methyl nitrobenzene, using pipeline nitrification installation, mixed pipe line length is
5m, internal diameter 6mm, outer diameter 8mm, pipe material are Hastelloy C-276 (Hastelloy C alloys -276)；Filled with catalyst
Reaction length of pipe be 25m, internal diameter 6mm, outer diameter 8mm, pipe material be Hastelloy C-276 (Hastelloy C alloys-
276)；The catalyst of filling is silica gel particle, partial size 3-5mm；
This method specifically includes:
Catalyst is packed into reaction pipeline first, and is sealed pipe ends with sieve, prevents catalyst with reaction liquid stream
Out, attachment device checks leakproofness；Toluene is added in storage tank；Open cooling system the first T-type hybrid juction of cooling and mixing
Pipeline is to -5~5 DEG C；It opens heating system and preheats the second T-type hybrid juction and reaction pipeline to 35 DEG C；Ozone generator is opened,
Ozone flow is set, is adjusted backwards to valve, so that the pressure in reaction pipeline maintains 0.6MPa；According to 1,4- dimethylbenzene and dioxy
The molar ratio for changing nitrogen is 1:1.3, and flow pump and gas flowmeter is arranged；Open simultaneously the valve and nitrogen dioxide steel of storage tank
The valve of bottle；1,4- dimethylbenzene enters mixed pipe line after mixing at -5~5 DEG C by the first T-type hybrid juction with nitrogen dioxide
It is interior；By the stop of 3min, after being mixed in the second T-type hybrid juction with ozone, into the reaction pipeline for being filled with catalyst
Interior carry out nitration reaction, after the stop of 25min, reaction solution enters receiving tank；Reaction solution adds water quenching to go out in receiving tank, with full
Washed 3 times with sodium bicarbonate solution, be washed with water it is to neutrality and dry with anhydrous sodium sulfate, product finally pass through rectifying obtain it is pure
Product product (2,5- dimethyl nitre benzene), yield 92%, it is 99.7% that GC detection purity, which is 2,5- dimethyl nitre benzene, significant effect.
Compared with prior art, the present invention the beneficial effects of the present invention are:
The tubular type preparation method precise automatic control, easy to operate, reaction condition is mild, and post-processing is simple, passes
Matter heat transfer is rapidly, highly-safe, good in economic efficiency, is the environmentally protective technique for being suitable for industrialized production.
Preparation method of the present invention, catalyst are automatically separated with reaction solution, without filtering, repeat benefit
With without being refilled by.
Detailed description of the invention
Fig. 1 is the schematic diagram for the method that the present invention prepares methyl nitrobenzene using pipeline nitrification installation；
In figure, 1- storage tank, 2- nitrogen dioxide steel cylinder, 3- flow pump, 4- gas flow pump, 5- the first T-type hybrid juction, 6-
Mixed pipe line, 7- cooling system, 8- ozone generator, 9- the second T-type hybrid juction, 10- reaction pipeline, 11- heating system,
12- counterbalance valve, 13- receiving tank.
Specific embodiment
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
As shown in Figure 1, including: for the dedicated unit structure that pipeline of the invention prepares methyl nitrobenzene
One gas flow of flow pump 3, one of ozone generator 8, one of nitrogen dioxide steel cylinder 2, one of storage tank 1, one
Meter 4, one mixed pipe line 6, two of reaction pipeline 10, one T-type hybrid juction (i.e. the first T-type mixing filled with catalyst
Connector 5 and the second T-type hybrid juction 9), the 12, receiving tanks of counterbalance valve of heating system 11, one of cooling system 7, one
13.Wherein, raw material liquid methylbenzene is stored in storage tank 1, and is sequentially connected flow pump 3, the first T-type hybrid juction 5 with conduit
Entrance；Nitrogen dioxide steel cylinder 2 is successively connected with conduit with gas flowmeter 4,5 entrance of the first T-type hybrid juction；First T-type is mixed
The outlet of splice grafting head 5 connection 6 entrance of mixed pipe line；The outlet of mixed pipe line 6 is connected to the second T-type with the outlet of ozone generator 8
2 entrances of hybrid juction 9, the outlet of the second T-type hybrid juction 9 are connected to 10 entrance of reaction pipeline filled with catalyst；
The outlet of reaction pipeline 10 connection filled with catalyst finally connects receiving tank 13 after valve 12.Second T-type hybrid juction 9
It is immersed in heating system with the pipeline 10 that reacts filled with catalyst；First T-type hybrid juction 5 is soaked with mixed pipe line 6
Not in cooling system；The receiving tank 13 has device for absorbing tail gas.
The reaction unit structure of following embodiment is as above, the difference is that mixed pipe line 6 and the reaction tube filled with catalyst
10 length of road is 5~30m, internal diameter 6mm, outer diameter 8mm, and pipe material is corrosion-resistant high voltage bearing metal material, preferably
Hastelloy C-276.Wherein, the catalyst in the reaction pipeline 10 filled with catalyst is the spherical shape point that partial size is 3-5mm
The silica gel particle that son sieve or partial size are 3-5mm.
Embodiment 1:
Reaction unit structure such as Fig. 1,6 length of mixed pipe line are 5m, internal diameter 6mm, outer diameter 8mm, and pipe material is
Hastelloy C-276；10 length of reaction pipeline filled with catalyst is 30m, internal diameter 6mm, outer diameter 8mm, pipeline material
Matter is Hastelloy C-276；The catalyst of filling is global molecular sieve, partial size 3-5mm.
Operating procedure is as follows:
Catalyst is packed into reaction pipeline 10 first, and is sealed pipe ends with sieve, prevents catalyst with reaction solution
Outflow, attachment device check leakproofness；Toluene is added in storage tank 1；Open the first T-type hybrid juction 5 of cooling of cooling system 7
With 8 to -5~5 DEG C of mixed pipe line；Open 10 to 25 DEG C of pipeline of second T-type hybrid juction of the preheating of heating system 11 9 and reaction；It beats
Ozone generator 8 is opened, ozone flow is set, is adjusted backwards to valve 12, so that the pressure in reaction pipeline 10 maintains 0.5MPa；Root
It is 1:1.1 according to the molar ratio of toluene and nitrogen dioxide, flow pump 3 and gas flowmeter 4 is set；Open simultaneously storage tank 1
The valve of valve and nitrogen dioxide steel cylinder 2；Toluene and nitrogen dioxide are at -5~5 DEG C after the first T-type hybrid juction 5 mixes
Into in mixed pipe line 6；By the stop of 1min, after being mixed in the second T-type hybrid juction 9 with ozone, urged into being filled with
In 25 DEG C of progress nitration reactions in the reaction pipeline 10 of agent；After the stop of 15min, reaction solution enters receiving tank 13；Instead
It answers liquid that water quenching is added to go out, is washed 3 times with saturated sodium bicarbonate solution, is washed with water to neutrality and dry, the product with anhydrous sodium sulfate
Purified product finally is obtained by rectifying, yield 87%, it is para-nitrotoluene that GC, which detects purity: ortho-methylnitrobenzene is
53.2%:46.5%.
Embodiment 2:
Reaction unit structure such as Fig. 1,6 length of mixed pipe line are 5m, internal diameter 6mm, outer diameter 8mm, and pipe material is
Hastelloy C-276；10 length of reaction pipeline filled with catalyst is 25m, internal diameter 6mm, outer diameter 8mm, pipeline material
Matter is Hastelloy C-276；The catalyst of filling is silica gel particle, partial size 3-5mm.
Reaction raw materials are 1,2- dimethylbenzene, second T-type hybrid juction of the preheating of heating system 11 9 and reaction pipeline 10 to 35
DEG C, the molar ratio of raw material and nitrogen dioxide is 1:1.3, and the pressure reacted in pipeline 10 maintains 0.6MPa, mixed pipe line 6
Interior residence time 3min, residence time 20min in the reaction pipeline 10 filled with catalyst.Other operations are with embodiment 1, after
Product is obtained after processing, yield 90%, it is 3,4- dimethyl nitre benzene that GC, which detects purity: 2,3- dimethyl nitre benzene are 98.6%:
0.8%.
Embodiment 3:
Reaction unit structure such as Fig. 1,6 length of mixed pipe line are 10m, internal diameter 6mm, outer diameter 8mm, and pipe material is
Hastelloy C-276；10 length of reaction pipeline filled with catalyst is 30m, internal diameter 6mm, outer diameter 8mm, pipeline material
Matter is Hastelloy C-276；The catalyst of filling is global molecular sieve, partial size 3-5mm.
Reaction raw materials are 1,3- dimethylbenzene, second T-type hybrid juction of the preheating of heating system 11 9 and reaction pipeline 10 to 45
DEG C, the molar ratio of raw material and nitrogen dioxide is 1:1.5, and the pressure reacted in pipeline 10 maintains 0.8MPa, mixed pipe line 6
Interior residence time 5min, residence time 25min in the reaction pipeline 10 filled with catalyst.Other operations are with embodiment 1, after
Product is obtained after processing, yield 87%, it is 2,4- dimethyl nitre benzene that GC, which detects purity: 2,6- dimethyl nitre benzene are 98.0%:
1.3%.
Embodiment 4:
Reaction unit structure such as Fig. 1,6 length of mixed pipe line are 5m, internal diameter 6mm, outer diameter 8mm, and pipe material is
Hastelloy C-276；10 length of reaction pipeline filled with catalyst is 25m, internal diameter 6mm, outer diameter 8mm, pipeline material
Matter is Hastelloy C-276；The catalyst of filling is silica gel particle, partial size 3-5mm.
Reaction raw materials are Isosorbide-5-Nitrae-dimethylbenzene, second T-type hybrid juction of the preheating of heating system 11 9 and reaction pipeline 10 to 35
DEG C, the molar ratio of raw material and nitrogen dioxide is 1:1.3, and the pressure reacted in pipeline 10 maintains 0.6MPa, mixed pipe line 6
Interior residence time 3min, residence time 25min in the reaction pipeline 10 filled with catalyst.Other operations are with embodiment 1, after
Product is obtained after processing, yield 92%, it is 99.7% that GC detection purity, which is 2,5- dimethyl nitre benzene,.
Embodiment 5:
Reaction unit structure such as Fig. 1,6 length of mixed pipe line are 10m, internal diameter 6mm, outer diameter 8mm, and pipe material is
Hastelloy C-276；10 length of reaction pipeline filled with catalyst is 30m, internal diameter 6mm, outer diameter 8mm, pipeline material
Matter is Hastelloy C-276；The catalyst of filling is global molecular sieve, partial size 3-5mm.
Reaction raw materials are 1,3,5- trimethylbenzenes, second T-type hybrid juction of the preheating of heating system 11 9 and reaction pipeline 10 to 45
DEG C, the molar ratio of raw material and nitrogen dioxide is 1:1.5, and the pressure reacted in pipeline 10 maintains 0.8MPa, mixed pipe line 6
Interior residence time 5min, residence time 30min in the reaction pipeline 10 filled with catalyst.Other operations are with embodiment 1, after
Product is obtained after processing, yield 78%, it is 99.1% that GC detection purity, which is 2,4,6- trimethyl nitre benzene,.
Claims (10)
1. a kind of pipeline nitrification installation characterized by comprising
For storing the storage tank of liquid methylbenzene；
With the tank connected flow pump of storage；
Nitrogen dioxide steel cylinder；
The gas flowmeter being connect with the nitrogen dioxide steel cylinder；
First T-type hybrid juction, the outlet of the flow pump and the outlet of gas flowmeter access the first T-type mixing
The import of connector；
With the mixed pipe line of the outlet connection of the first T-type hybrid juction；
For the cooling system cooling to the first T-type hybrid juction and mixed pipe line；
Ozone generator；
Second T-type hybrid juction, the outlet of the mixed pipe line and the outlet of ozone generator access second T
The import of type hybrid juction；
Pipeline is reacted filled with catalyst with what the outlet of second T-type hybrid juction connected；
Heating system for the reaction pipeline heating to second T-type hybrid juction and filled with catalyst；
With the counterbalance valve of the outlet connection for reacting pipeline；
The mixed pipe line being connect with the back pressure valve outlet.
2. pipeline nitrification installation according to claim 1, which is characterized in that the first T-type hybrid juction and mixed
Pipeline is closed to be immersed in cooling system；The second T-type hybrid juction is submerged with the pipeline that reacts filled with catalyst
In heating system.
3. pipeline nitrification installation according to claim 1, which is characterized in that the length of the mixed pipe line be 5~
30m, internal diameter 6mm, outer diameter 8mm, pipe material are Hastelloy C alloys -276；
The reaction length of pipe filled with catalyst is 5~30m, internal diameter 6mm, outer diameter 8mm, and pipe material is to breathe out
Family name's alloy C-276.
4. pipeline nitrification installation according to claim 1, which is characterized in that the reaction tube filled with catalyst
The silica gel particle of global molecular sieve or partial size 3-5mm that catalyst in road is partial size 3-5mm.
5. a kind of method that pipeline prepares methyl nitrobenzene, which is characterized in that described in any item using Claims 1 to 4
Pipeline nitrification installation, specifically includes:
Catalyst is packed into reaction pipeline first, attachment device checks leakproofness；Raw material liquid methylbenzene is added in storage tank；
Cooling system the first T-type hybrid juction of cooling and mixed pipe line are opened to -5~5 DEG C；It is mixed to open heating system the second T-type of preheating
Splice grafting head and reaction pipeline are to 25~45 DEG C；Ozone generator is opened, ozone flow is set, is adjusted backwards to valve, so that reaction tube
Pressure in road maintains 0.5~0.8MPa；According to the molar ratio of raw material liquid methylbenzene and nitrogen dioxide, be arranged flow pump and
Gas flowmeter；Open the valve of storage tank and the valve of nitrogen dioxide steel cylinder；Raw material liquid methylbenzene and nitrogen dioxide are -5~5
Enter in mixed pipe line after the mixing of the first T-type hybrid juction at DEG C；By the stop of 1~5min, with ozone in the second T-type
In hybrid juction mix after, into filled with catalyst reaction pipeline in carry out nitration reaction；By the stop of 15~30min
Afterwards, reaction solution enters receiving tank；Reaction solution obtains methyl nitrobenzene after post treatment.
6. the method that pipeline according to claim 5 prepares methyl nitrobenzene, which is characterized in that the raw material liquid
Methylbenzene is toluene, 1,2- dimethylbenzene, 1,3- dimethylbenzene, 1,4- dimethylbenzene or 1,3,5- trimethylbenzene.
7. the method that pipeline according to claim 5 prepares methyl nitrobenzene, which is characterized in that the raw material liquid
Methylbenzene and the molar ratio of nitrogen dioxide are 1:1.1~1.5.
8. the method that pipeline according to claim 5 prepares methyl nitrobenzene, which is characterized in that the nitration reaction
Reaction temperature be 25~45 DEG C.
9. the method that pipeline according to claim 5 prepares methyl nitrobenzene, which is characterized in that after the reaction solution
Processing method is to add water quenching to go out the reaction solution in receiving tank, is washed 2~4 times with saturated sodium bicarbonate solution, be washed with water to
Neutral and dry with anhydrous sodium sulfate, product finally passes through rectifying and obtains methyl nitrobenzene.
10. a kind of method that pipeline prepares methyl nitrobenzene, which is characterized in that using according to any one of claims 1 to 9
Pipeline nitrification installation, mixed pipe line length are 5m, internal diameter 6mm, outer diameter 8mm, and pipe material is Hastelloy C alloys -276；
Reaction length of pipe filled with catalyst is 25m, internal diameter 6mm, outer diameter 8mm, and pipe material is Hastelloy C alloys -276；
The catalyst of filling is silica gel particle, partial size 3-5mm；
This method specifically includes:
Catalyst is packed into reaction pipeline first, and is sealed pipe ends with sieve, prevents catalyst from flowing out with reaction solution, even
Connection device checks leakproofness；Toluene is added in storage tank；Open cooling system the first T-type hybrid juction of cooling and mixed pipe line
To -5~5 DEG C；It opens heating system and preheats the second T-type hybrid juction and reaction pipeline to 35 DEG C；Open ozone generator, setting
Ozone flow is adjusted backwards to valve, so that the pressure in reaction pipeline maintains 0.6MPa；According to 1,4- dimethylbenzene and nitrogen dioxide
Molar ratio be 1:1.3, flow pump and gas flowmeter are set；Open simultaneously the valve and nitrogen dioxide steel cylinder of storage tank
Valve；1,4- dimethylbenzene enters in mixed pipe line after mixing at -5~5 DEG C by the first T-type hybrid juction with nitrogen dioxide；
By the stop of 3min, after being mixed in the second T-type hybrid juction with ozone, into filled with catalyst reaction pipeline in into
Row nitration reaction, after the stop of 25min, reaction solution enters receiving tank；Reaction solution adds water quenching to go out in receiving tank, uses saturated carbon
Sour hydrogen sodium solution washs 3 times, is washed with water to neutrality and is dried with anhydrous sodium sulfate, product finally passes through rectifying and obtains 2,5- bis-
Methyl nitre benzene.
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| CN201811026728.6A CN109232257B (en) | 2018-09-04 | 2018-09-04 | Method and device for preparing methyl nitrobenzene in pipeline mode |
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| CN201811026728.6A CN109232257B (en) | 2018-09-04 | 2018-09-04 | Method and device for preparing methyl nitrobenzene in pipeline mode |
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Citations (3)
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