CN109438247A - The method that benzene continuous nitrification prepares dinitrobenzene - Google Patents
The method that benzene continuous nitrification prepares dinitrobenzene Download PDFInfo
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- 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
Abstract
The invention discloses the methods that benzene continuous nitrification prepares dinitrobenzene comprising following steps: nano-titanium oxide carrying tin oxide/strontium oxide strontia/bismuth oxide composite material being made first as catalyst A；Hydrotalcite-like materials load alchlor as catalyst B；Then catalyst A obtained is placed in tubular reactor, benzene and 55% nitric acid is added into tubular reactor, sealed, reaction is cooled to room temperature after reaction；By reaction product stratification, organic phase is collected；Organic by collection is added in the tank reactor equipped with catalyst B, and continuously adds 55% nitric acid, reaction, it is cooled to room temperature after reaction, reaction product stratification, collects organic phase, organic phase is dried, chromatography is used to organic phase, calculates the yield of dinitrobenzene.This method is easy to operate, and the catalyst preparation of use is simple, has stronger nitrification ability with the nitrification system of nitric acid composition, and waste water generates less, is conducive to environmental protection.
Description
Technical field:
The present invention relates to organic synthesis fields, are specifically related to the method that benzene continuous nitrification prepares dinitrobenzene.
Background technique:
Nitrobenzene is a kind of important industrial chemicals and intermediate, is widely used in production aniline, benzidine and dinitrobenzene
Etc. a variety of medicine and dyestuff intermediate, it is also possible to make the raw material of pesticide, explosive and thiofide.Traditional benzene nitrifies work
Skill is to be reacted as benzene with the liquid-phase nitration that nitration mixture composed by concentrated nitric acid and the concentrated sulfuric acid carries out, and need to use a large amount of nitric acid and sulfuric acid.
Since sulfuric acid only plays catalysis and dehydration in nitration reaction, it is not transformed into product, almost all is discharged with mother liquor, because
And the problems such as generating a large amount of acid pickles, there is corrosion equipment, pollution environment and increase post-processing expense.In addition, using nitric acid-sulfuric acid
Mixed acid system also needs the ratio of strict control reaction temperature and nitration mixture, to avoid the side reactions such as more nitrations and oxidation occur.Cause
This extensive attention for replacing the research of sulphuric acid catalysis benzene nitration reaction to obtain using solid acid.With solid acid as catalyst, nitre
When acid is nitrating agent, while keeping good nitrification effect, so that the recycling of catalyst is more convenient, it is to nitration mixture
The larger improvement of nitrification, only the oxidisability of some systems is too strong, and when use needs extreme care.
As the research for nitration reaction is more and more, acidic ion liquid is widely used in nitrification instead as catalyst
Ying Zhong, but the nitrification ability of the nitrification system of acidic ion liquid and nitric acid composition is too weak, cannot nitrify nitrobenzene substantially.
Chinese patent (200610056705.0) discloses a kind of method of preparing nitrobenzene from benzene by nitric acid nitrating.This method
Using one or two kinds of metal oxide modified MEI topological structure molecular sieves of Mg, Ca, Sr, Sb, Bi, Mo as catalyst,
65% nitric acid carries out nitration reaction as nitrating agent, using tank reactor under normal pressure；Or by above-mentioned modified molecular screen system
At preformed catalyst, carry out liquid-solid phase nitration reaction at a certain temperature using fixed bed reactors.This method realizes insulation
Nitrification, process is short, and simple process is, it can be achieved that continuous nitrification, but the nitrification system nitrification ability that this method uses is poor, cannot
P-nitrophenyl is nitrified.Chinese patent (201810231917.0) discloses a kind of continuous flow upstream nitrification production dinitrobenzene
Method, preparation method are as follows: using nitrobenzene as raw material, realized using sulfuric acid, nitric acid as nitrification system using special device
Continuous flow upstream nitration processes realize nitrophenols bring security risk in dinitrobenzene production process, but this method uses
Nitrification system nitrification ability it is weaker, the yield of dinitrobenzene is lower, and a large amount of uses of sulfuric acid can generate a large amount of acid-bearing wastewaters,
To environment nocuousness.
Summary of the invention:
In view of the deficiencies of the prior art, it is an object of the present invention to provide the sides that a kind of benzene continuous nitrification prepares dinitrobenzene
Method, this method combine to promote to react using nitrating agent and catalyst, and catalyst can effectively facilitate the nitrification of nitrating agent
Effect, thus promote the generation of nitration reaction, nitration product purity is high obtained, high income.
To achieve the above object, the invention adopts the following technical scheme:
The method that benzene continuous nitrification prepares dinitrobenzene, comprising the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；Then perfluor is added into mixed solution
After being uniformly mixed, ammonium hydroxide, stir process is added dropwise in the compound of nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate
30min is then transferred in reaction kettle, and 100-110 DEG C, reaction treatment 1-4h, mixed gel is made；
(2) butyl titanate is dissolved in dehydrated alcohol, then be added dropwise deionized water precipitated, after precipitating
Continue stir process 1-2h at 80-100 DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, still aging 10-15h, then mistake
Filter, it is dry after solid is washed, composite powder is made；
(4) composite powder obtained is added in DMF, Kynoar is then added, stirring to solid is dissolved, and is made
Spinning solution；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it in Muffle furnace
Catalyst A is made in sintering processes 2-6h at middle 400-800 DEG C；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, by mixed solution and sodium hydroxide solution
It is added in micro passage reaction, 40-70min is reacted at 50-70 DEG C, reaction terminates filtering, dry, solid dispersion obtained
In deionized water, maleic anhydride is added, is stirred to react 1-3h at 60-90 DEG C, filters, it is dry, activation houghite material is made
Material；Finally activation hydrotalcite-like materials obtained are added in the solution for the alchlor that mass concentration is 35-55%, room temperature
Lower impregnation 5-7h, it is dry, catalyst B is made；
(6) catalyst A obtained above is placed in tubular reactor, benzene and 55% nitre is added into tubular reactor
Acid, sealing, the temperature for controlling reaction is 90-100 DEG C, reacts 1-3h, is cooled to room temperature after reaction；Reaction product is stood
Organic phase is collected in layering；
(7) the organic of above-mentioned collection is added in the tank reactor equipped with catalyst B, and continuously adds 55% nitre
Acid reacts 1-2h, is cooled to room temperature after reaction, reaction product stratification at 80-110 DEG C, collects organic phase, uses
Organic phase is dried in anhydrous sodium sulfate, uses chromatography to organic phase, calculates the yield of dinitrobenzene.
As a preferred embodiment of the above technical solution, in step (1), in mixed solution, the matter of stannic chloride, strontium chloride, bismuth chloride
Measuring concentration is respectively 18-25%, 10-20%, 4-9%.
As a preferred embodiment of the above technical solution, in step (1), the stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, 12
The mass ratio of sodium alkyl sulfate is 1:(0.13-0.65): 0.05.
As a preferred embodiment of the above technical solution, in the composite powder of step (3), the mass ratio of nano-titanium oxide, tin oxide
For (2-6): 1.
As a preferred embodiment of the above technical solution, in step (4), composite powder, Kynoar mass ratio be (1-4):
10。
As a preferred embodiment of the above technical solution, in step (5), in mixed solution, the molar concentration point of magnesium chloride, iron chloride
It Wei not 1-5mol/L, 2.5-4mol/L.
As a preferred embodiment of the above technical solution, in step (5), the magnesium chloride, maleic anhydride molar ratio be 1:
(0.22-0.43)。
As a preferred embodiment of the above technical solution；In step (5), in catalyst B, hydrotalcite-like materials, alchlor are activated
Mass ratio be (2-7): 1.
As a preferred embodiment of the above technical solution, in step (6), the catalyst A, benzene, nitric acid amount ratio be (0.09-
0.35) g:80mL:100mL.
As a preferred embodiment of the above technical solution, in step (7), the catalyst B, organic phase, nitric acid amount ratio be
(0.12-0.25) g:100mL:100mL.
The invention has the following advantages:
When perfluorinated nonene oxygroup benzene sulfonic acid sodium salt is separately as surfactant, dispersibility is poor, and the present invention is using itself and ten
Sodium dialkyl sulfate compounding is used as surfactant, and not only critical micelle concentration substantially reduces the mixed system after compounding, and most
Low surface tension also reduces, and achievees the purpose that comprehensive synergy.The two compounds dispersibility and the surface that can be effectively improved catalyst A
Activity.
The plural gel being made of metal ion is made first and contains titanium gel with what tetrabutyl titanate hydrolysis obtained by the present invention
Compound it is still aging, composite powder obtained be titania precursor body, metal hydroxides presoma mixture；By its with it is poly-
Vinylidene is dissolved in DMF and the obtained composite fibre of spinning solution is made；The composite fibre is urged made from calcination processing under certain condition
Agent is the fiber-loaded tin oxide/strontium oxide strontia/bismuth oxide composite material of nano-titanium oxide；Catalyst A and nitric acid form compound nitre
Not only nitrification effect is good for change system, and catalyst A is easily recycled.
The present invention uses homemade hydrotalcite-like materials, is activated first using maleic anhydride to its surface, then will
It loads alchlor and catalyst B is made, and catalyst B made from this method can effectively be kept away while guaranteeing high nitrification effect
Exempt to generate acid waste water using sulfuric acid, is conducive to environmental protection；The present invention lives to carrier using maleic anhydride before load
Change, effectively increases the activity of catalyst.Catalyst B and the nitrification system nitrification ability that nitric acid forms are strong, can be used for nitrifying nitre
Base benzene.
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
The method that benzene continuous nitrification prepares dinitrobenzene, comprising the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；The mass concentration of three is respectively 18%,
10%, 4%, the compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate, stirring are then added into mixed solution
After mixing, ammonium hydroxide is added dropwise, stir process 30min is then transferred in reaction kettle, 100-110 DEG C, reaction treatment 1h, system
Obtain mixed gel；Wherein, stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate mass ratio be 1:0.13:
0.05；
(2) butyl titanate is dissolved in dehydrated alcohol, then be added dropwise deionized water precipitated, after precipitating
Continue stir process 1h at 80-100 DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, then still aging 10h is filtered, will
It is dry after solid washing, composite powder is made；Wherein, nano-titanium oxide in composite powder, tin oxide mass ratio be 2:1；
(4) composite powder made from 1g is added in DMF, 10g Kynoar is then added, stirred molten to solid
Spinning solution is made in solution；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it
Catalyst A is made in the sintering processes 2h at 400 DEG C in Muffle furnace；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, the molar concentration of the two is respectively
Mixed solution and sodium hydroxide solution are added in micro passage reaction by 1mol/L, 2.5mol/L, are reacted at 50-70 DEG C
40min, reaction terminates filtering, dry, and solid obtained is scattered in deionized water, and maleic anhydride is added, stirs at 60-90 DEG C
1h is reacted, is filtered, it is dry, activation hydrotalcite-like materials are made；Activation hydrotalcite-like materials obtained are finally added to quality
In the solution for the alchlor that concentration is 35%, impregnation 5h under room temperature is dry, and catalyst B is made；Wherein, magnesium chloride, horse
The molar ratio for carrying out acid anhydrides is 1:0.22；Activate hydrotalcite-like materials, the mass ratio of alchlor is 2:1；
(6) 0.09g catalyst A obtained above is placed in tubular reactor, 80mL benzene is added into tubular reactor
With 100mL55% nitric acid, sealing, the temperature for controlling reaction is 90-100 DEG C, reacts 1h, is cooled to room temperature after reaction；It will
Reaction product stratification collects organic phase；
(7) the organic of the above-mentioned collection of 100mL is added in the tank reactor equipped with 0.12g catalyst B, and continued
100mL55% nitric acid is added, at 80-110 DEG C, reacts 1h, is cooled to room temperature after reaction, reaction product stratification, receive
Collect organic phase, organic phase is dried using anhydrous sodium sulfate, chromatography is used to organic phase, calculates the receipts of dinitrobenzene
Rate.
Embodiment 2
The method that benzene continuous nitrification prepares dinitrobenzene, comprising the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；The mass concentration of three is respectively 25%,
20%, 9%, the compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate, stirring are then added into mixed solution
After mixing, ammonium hydroxide is added dropwise, stir process 30min is then transferred in reaction kettle, 100-110 DEG C, reaction treatment 4h, system
Obtain mixed gel；Wherein, stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate mass ratio be 1:0.65:
0.05；
(2) butyl titanate is dissolved in dehydrated alcohol, then be added dropwise deionized water precipitated, after precipitating
Continue stir process 2h at 80-100 DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, then still aging 15h is filtered, will
It is dry after solid washing, composite powder is made；Wherein, nano-titanium oxide in composite powder, tin oxide mass ratio be 6:1；
(4) composite powder made from 4g is added in DMF, 10g Kynoar is then added, stirred molten to solid
Spinning solution is made in solution；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it
Catalyst A is made in the sintering processes 6h at 800 DEG C in Muffle furnace；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, the molar concentration of the two is respectively
Mixed solution and sodium hydroxide solution are added in micro passage reaction by 5mol/L, 4mol/L, are reacted at 50-70 DEG C
70min, reaction terminates filtering, dry, and solid obtained is scattered in deionized water, and maleic anhydride is added, stirs at 60-90 DEG C
3h is reacted, is filtered, it is dry, activation hydrotalcite-like materials are made；Activation hydrotalcite-like materials obtained are finally added to quality
In the solution for the alchlor that concentration is 55%, impregnation 7h under room temperature is dry, and catalyst B is made；Wherein, magnesium chloride, horse
The molar ratio for carrying out acid anhydrides is 1:0.43；Activate hydrotalcite-like materials, the mass ratio of alchlor is 7:1；
(6) 0.35g catalyst A obtained above is placed in tubular reactor, 80mL benzene is added into tubular reactor
With 100mL55% nitric acid, sealing, the temperature for controlling reaction is 90-100 DEG C, reacts 3h, is cooled to room temperature after reaction；It will
Reaction product stratification collects organic phase；
(7) the organic of the above-mentioned collection of 100mL is added in the tank reactor equipped with 0.25g catalyst B, and continued
100mL55% nitric acid is added, at 80-110 DEG C, reacts 2h, is cooled to room temperature after reaction, reaction product stratification, receive
Collect organic phase, organic phase is dried using anhydrous sodium sulfate, chromatography is used to organic phase, calculates the receipts of dinitrobenzene
Rate.
Embodiment 3
The method that benzene continuous nitrification prepares dinitrobenzene, comprising the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；The mass concentration of three is respectively 19%,
13%, 5%, the compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate, stirring are then added into mixed solution
After mixing, ammonium hydroxide is added dropwise, stir process 30min is then transferred in reaction kettle, 100-110 DEG C, reaction treatment 2h, system
Obtain mixed gel；Wherein, stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate mass ratio be 1:0.22:
0.05；
(2) butyl titanate is dissolved in dehydrated alcohol, then be added dropwise deionized water precipitated, after precipitating
Continue stir process 1.2h at 80-100 DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, then still aging 11h is filtered, will
It is dry after solid washing, composite powder is made；Wherein, nano-titanium oxide in composite powder, tin oxide mass ratio be 3:1；
(4) composite powder made from 2g is added in DMF, 10g Kynoar is then added, stirred molten to solid
Spinning solution is made in solution；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it
Catalyst A is made in the sintering processes 3h at 500 DEG C in Muffle furnace；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, the molar concentration of the two is respectively
Mixed solution and sodium hydroxide solution are added in micro passage reaction by 2mol/L, 3mol/L, are reacted at 50-70 DEG C
50min, reaction terminates filtering, dry, and solid obtained is scattered in deionized water, and maleic anhydride is added, stirs at 60-90 DEG C
1.5h is reacted, is filtered, it is dry, activation hydrotalcite-like materials are made；Activation hydrotalcite-like materials obtained are finally added to matter
In the solution for measuring the alchlor that concentration is 40%, impregnation 5.5h under room temperature is dry, and catalyst B is made；Wherein, chlorination
Magnesium, maleic anhydride molar ratio be 1:0.25；Activate hydrotalcite-like materials, the mass ratio of alchlor is 3:1；
(6) 0.11g catalyst A obtained above is placed in tubular reactor, 80mL benzene is added into tubular reactor
With 100mL55% nitric acid, sealing, the temperature for controlling reaction is 90-100 DEG C, reacts 1.5h, is cooled to room temperature after reaction；
By reaction product stratification, organic phase is collected；
(7) the organic of the above-mentioned collection of 100mL is added in the tank reactor equipped with 0.15g catalyst B, and continued
100mL55% nitric acid is added, at 80-110 DEG C, reacts 1.2h, is cooled to room temperature after reaction, reaction product stratification,
Organic phase is collected, organic phase is dried using anhydrous sodium sulfate, chromatography is used to organic phase, calculates dinitrobenzene
Yield.
Embodiment 4
The method that benzene continuous nitrification prepares dinitrobenzene, comprising the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；The mass concentration of three is respectively 21%,
16%, 6%, the compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate, stirring are then added into mixed solution
After mixing, ammonium hydroxide is added dropwise, stir process 30min is then transferred in reaction kettle, 100-110 DEG C, reaction treatment 3h, system
Obtain mixed gel；Wherein, stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate mass ratio be 1:0.45:
0.05；
(2) butyl titanate is dissolved in dehydrated alcohol, then be added dropwise deionized water precipitated, after precipitating
Continue stir process 1.4h at 80-100 DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, then still aging 12h is filtered, will
It is dry after solid washing, composite powder is made；Wherein, nano-titanium oxide in composite powder, tin oxide mass ratio be 4:1；
(4) composite powder made from 3g is added in DMF, 10g Kynoar is then added, stirred molten to solid
Spinning solution is made in solution；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it
Catalyst A is made in the sintering processes 4h at 600 DEG C in Muffle furnace；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, the molar concentration of the two is respectively
Mixed solution and sodium hydroxide solution are added in micro passage reaction by 3mol/L, 3.5mol/L, are reacted at 50-70 DEG C
50min, reaction terminates filtering, dry, and solid obtained is scattered in deionized water, and maleic anhydride is added, stirs at 60-90 DEG C
2h is reacted, is filtered, it is dry, activation hydrotalcite-like materials are made；Activation hydrotalcite-like materials obtained are finally added to quality
In the solution for the alchlor that concentration is 45%, impregnation 6h under room temperature is dry, and catalyst B is made；Wherein, magnesium chloride, horse
The molar ratio for carrying out acid anhydrides is 1:0.35；Activate hydrotalcite-like materials, the mass ratio of alchlor is 5:1；
(6) 0.25g catalyst A obtained above is placed in tubular reactor, 80mL benzene is added into tubular reactor
With 100mL55% nitric acid, sealing, the temperature for controlling reaction is 90-100 DEG C, reacts 2h, is cooled to room temperature after reaction；It will
Reaction product stratification collects organic phase；
(7) the organic of the above-mentioned collection of 100mL is added in the tank reactor equipped with 0.18g catalyst B, and continued
100mL55% nitric acid is added, at 80-110 DEG C, reacts 1.4h, is cooled to room temperature after reaction, reaction product stratification,
Organic phase is collected, organic phase is dried using anhydrous sodium sulfate, chromatography is used to organic phase, calculates dinitrobenzene
Yield.
Embodiment 5
The method that benzene continuous nitrification prepares dinitrobenzene, comprising the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；The mass concentration of three is respectively 23%,
18%, 7%, the compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate, stirring are then added into mixed solution
After mixing, ammonium hydroxide is added dropwise, stir process 30min is then transferred in reaction kettle, 100-110 DEG C, reaction treatment 3.5h,
Mixed gel is made；Wherein, stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate mass ratio be 1:0.55:
0.05；
(2) butyl titanate is dissolved in dehydrated alcohol, then be added dropwise deionized water precipitated, after precipitating
Continue stir process 1.6h at 80-100 DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, then still aging 14h is filtered, will
It is dry after solid washing, composite powder is made；Wherein, nano-titanium oxide in composite powder, tin oxide mass ratio be 5:1；
(4) composite powder made from 3.5g is added in DMF, 10g Kynoar is then added, stirred molten to solid
Spinning solution is made in solution；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it
Catalyst A is made in the sintering processes 5h at 700 DEG C in Muffle furnace；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, the molar concentration of the two is respectively
Mixed solution and sodium hydroxide solution are added in micro passage reaction by 4.5mol/L, 3.5mol/L, anti-at 50-70 DEG C
60min is answered, reaction terminates filtering, and dry, solid obtained is scattered in deionized water, and maleic anhydride is added, stirs at 60-90 DEG C
Reaction 2.5h is mixed, is filtered, it is dry, activation hydrotalcite-like materials are made；Finally activation hydrotalcite-like materials obtained are added to
In the solution for the alchlor that mass concentration is 50%, impregnation 6.5h under room temperature is dry, and catalyst B is made；Wherein, chlorine
Change magnesium, the molar ratio of maleic anhydride is 1:0.39；Activate hydrotalcite-like materials, the mass ratio of alchlor is 6:1；
(6) 0.30g catalyst A obtained above is placed in tubular reactor, 80mL benzene is added into tubular reactor
With 100mL55% nitric acid, sealing, the temperature for controlling reaction is 90-100 DEG C, reacts 2.5h, is cooled to room temperature after reaction；
By reaction product stratification, organic phase is collected；
(7) the organic of the above-mentioned collection of 100mL is added in the tank reactor equipped with 0.22g catalyst B, and continued
100mL55% nitric acid is added, at 80-110 DEG C, reacts 1.6h, is cooled to room temperature after reaction, reaction product stratification,
Organic phase is collected, organic phase is dried using anhydrous sodium sulfate, chromatography is used to organic phase, calculates dinitrobenzene
Yield.
Comparative example 1
Catalyst A does not use nano-titanium oxide as carrier, other preparation conditions and embodiment 5 are identical.
Comparative example 2
The compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate is added without in catalyst A, other prepare item
Part and embodiment 5 are identical.
Comparative example 3
Maleic anhydride is not used to be activated in the preparation of catalyst B, other preparation conditions and embodiment 5 are identical.
The yield of dinitrobenzene is as shown in table 1.
Table 1
From the point of view of above-mentioned test result, catalyst can be effectively improved the nitrification energy of nitrification system using immobilized AlCl_3 catalyst
Power；When being modified using the compound of perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate carrier, it can be effectively improved
The surface-active of catalyst.Hydrotalcite-like materials after maleic anhydride activation also have preferable activity, can be effectively improved nitre
The nitrification ability of change system.
Although specific embodiments of the present invention are described, many other forms of the invention and change
Change will be apparent to those skilled in the art.It should be understood that appended claims and the present invention usually cover the present invention very
All these apparent forms and change in real spirit and scope.
Claims (10)
1. the method that benzene continuous nitrification prepares dinitrobenzene, which comprises the following steps:
(1) stannic chloride, strontium chloride, bismuth chloride are dissolved in water and mixed solution is made；Then perfluorinated nonene is added into mixed solution
The compound of oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate, after being uniformly mixed, dropwise addition ammonium hydroxide, stir process 30min, so
After be transferred in reaction kettle, 100-110 DEG C, reaction treatment 1-4h, be made mixed gel；
(2) butyl titanate is dissolved in dehydrated alcohol, deionized water is then added dropwise and is precipitated, in 80-100 after precipitating
Continue stir process 1-2h at DEG C, is made and contains titanium gel；
(3) it is mixed evenly by mixed gel obtained above and containing titanium gel, then still aging 10-15h is filtered, will
It is dry after solid washing, composite powder is made；
(4) composite powder obtained is added in DMF, Kynoar is then added, stirring to solid is dissolved, and spinning is made
Liquid；Spinning solution obtained is continuously injected into the syringe of electrostatic spinning machine, composite fibre is made, by it in Muffle furnace
Catalyst A is made in sintering processes 2-6h at 400-800 DEG C；
(5) magnesium chloride, iron chloride are dissolved in deionized water and mixed solution is made, mixed solution and sodium hydroxide solution are added
Into micro passage reaction, 40-70min is reacted at 50-70 DEG C, reaction terminates filtering, and dry, solid obtained is scattered in
In ionized water, maleic anhydride is added, is stirred to react 1-3h at 60-90 DEG C, filters, it is dry, activation hydrotalcite-like materials are made；Most
Activation hydrotalcite-like materials obtained are added in the solution for the alchlor that mass concentration is 35-55% afterwards, are soaked under room temperature
Stain handles 5-7h, dry, and catalyst B is made；
(6) catalyst A obtained above is placed in tubular reactor, benzene and 55% nitric acid is added into tubular reactor, it is close
Envelope, the temperature for controlling reaction is 90-100 DEG C, reacts 1-3h, is cooled to room temperature after reaction；By reaction product stratification,
Collect organic phase；
(7) the organic of above-mentioned collection is added in the tank reactor equipped with catalyst B, and continuously adds 55% nitric acid,
At 80-110 DEG C, 1-2h is reacted, is cooled to room temperature after reaction, reaction product stratification, collect organic phase, use is anhydrous
Organic phase is dried in sodium sulphate, uses chromatography to organic phase, calculates the yield of dinitrobenzene.
2. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that in step (1), mixing
In solution, stannic chloride, strontium chloride, bismuth chloride mass concentration be respectively 18-25%, 10-20%, 4-9%.
3. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that described in step (1)
Stannic chloride, perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, lauryl sodium sulfate mass ratio be 1:(0.13-0.65): 0.05.
4. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that step (3) it is compound
In powder, nano-titanium oxide, tin oxide mass ratio be (2-6): 1.
5. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that compound in step (4)
Powder, Kynoar mass ratio be (1-4): 10.
6. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that in step (5), mixing
In solution, magnesium chloride, iron chloride molar concentration be respectively 1-5mol/L, 2.5-4mol/L.
7. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that described in step (5)
Magnesium chloride, maleic anhydride molar ratio be 1:(0.22-0.43).
8. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that in step (5), catalysis
In agent B, hydrotalcite-like materials are activated, the mass ratio of alchlor is (2-7): 1.
9. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that described in step (6)
Catalyst A, benzene, nitric acid amount ratio be (0.09-0.35) g:80mL:100mL.
10. the method that benzene continuous nitrification as described in claim 1 prepares dinitrobenzene, which is characterized in that in step (7), institute
State catalyst B, organic phase, nitric acid amount ratio be (0.12-0.25) g:100mL:100mL.
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| CN113214087A (en) * | 2021-05-06 | 2021-08-06 | 山东科加工业技术研究院有限公司 | Preparation method and application of 4-chloro-3, 5-dinitro-benzotrifluoride |
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