CN105749954B - A kind of no catalytic hydrogenation and its application for being catalyzed 1,5- dinitronaphthalene hydrogenation reactions - Google Patents
A kind of no catalytic hydrogenation and its application for being catalyzed 1,5- dinitronaphthalene hydrogenation reactions Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
Abstract
The present invention discloses a kind of application of the 1,5 dinitronaphthalene hydrogenation reactions of preparation method and its catalysis of no catalytic hydrogenation.Preparation method of the present invention without catalytic hydrogenation, including use infusion process to prepare nitrogen doped carbon nanotube by nitrogen source of melamine or in-situ synthesis is used to prepare nitrogen doped carbon nanotube by nitrogen source of ammonia.The application of the present invention is then that gained catalyst is applied in 1,5 dinitronaphthalene hydrogenation reactions.The present invention, as 1,5 dinitronaphthalene hydrogenation catalyst, is not loaded any metal active constituent, reaches hydrogenation catalyst purpose merely with nitrating method of modifying using nitrogen doped carbon nanotube.Entire reaction process avoids the use of noble metal, has saved cost, and do not pollute the environment, while can reuse.The method for preparing catalyst of the present invention is simple, and production cost is low plus hydrogen effect is good, reacts easy to control, and catalyst is environmentally friendly, will not cause secondary pollution to environment, can be widely applied in all kinds of hydrogenation reactions.
Description
Technical field
The present invention relates to material preparation and field of chemical engineering, more particularly to a kind of no catalytic hydrogenation and its catalysis
The application of 1,5- dinitronaphthalene hydrogenation reactions.
Background technology
Currently, the catalyst used in most of catalytic hydrogenation reaction is all the catalysis of the noble metal support type used
Agent, although noble metal catalyst activity is high, cost is also very high, and be easy to cause heavy metal pollution, also uses
The non-precious metal catalysts such as metal such as ambrose alloy are crossed, but since catalytic activity is relatively low, metal consumption is larger and reaction is inevitable
The metal solution-off that will appear can not but reduce the cost of catalyst, or even one so even if the cost reduction of carried metal
Determine to also improve the cost of catalyst in degree.
In recent years, since the mechanics of carbon nanotube exception, electricity and chemical property and carbon nanotube and nano material are ground
That studies carefully gos deep into, and wide application prospect is also constantly shown, and Heteroatom doping carbon nanotube can not change former carbon
Its catalytic performance is obviously improved under conditions of the structure of nanotube.
Zhang Wei et al.（CN101575295A）1,5-diaminonaphthalene has been synthesized by the loaded catalyst of palladium of active component,
The use of noble metal increases catalyst cost.Liu Pingle et al.（CN103497113A）One kind has been invented using palladium carbon as catalyst
The method of hydrogenation synthesis 1,5-diaminonaphthalene has higher activity, and reaction temperature is relatively low, but catalyst preparation at
This height, heavy metal can cause environmental pollution.The seminar（CN102172528A）One kind be also invented using carbon nanotubes as carrier
The standby hydrogenation catalyst of load iron, manganese, cobalt made of metal, catalyst cost has apparent reduction compared with noble metal catalyst, but is urging
There are still the losses of metal in change reaction process, increase catalysis cost, and cause environmental pollution.
In conclusion noble metal catalyst manufacturing cost is high, easily occurs the loss of metal solution-off in reaction, do not only result in activity
Continuous decline, and environmental pollution can be caused.And although base metal greatly reduces catalyst preparation cost, but catalyst
Technique and step are complicated, are unfavorable for operating in engineering, and metal consumption is big, while also inevitably having showing for metal loss
As causing environmental pollution.
Invention content
In order to solve the above technical problems, the present invention provides a kind of preparation method of no catalytic hydrogenation and its is being catalyzed
The application of 1,5- dinitronaphthalene hydrogenation reactions.
The technical scheme is that：
A kind of preparation method of no catalytic hydrogenation, including infusion process is used to prepare nitrating by nitrogen source of melamine
Carbon nanotube uses in-situ synthesis to prepare nitrogen doped carbon nanotube by nitrogen source of ammonia；
It uses infusion process to prepare nitrogen doped carbon nanotube by nitrating agent of melamine, includes the following steps：
（1）Carbon nanotube oxidation processes：It is 1 by solid-to-liquid ratio:60 ~ 120 are added nitration mixture acidification 8 ~ 15 to carbon nanotube
H, after centrifuging washing, washing is dried to obtain oxide/carbon nanometer tube；
（2）By step（1）Gained oxide/carbon nanometer tube presses 1 with melamine：1 ~ 1.2 mass ratio mixing, is then added
Deionized water, then by formaldehyde and melamine 2 ~ 3：Formaldehyde is added in 1 mass ratio, then impregnates 10 ~ 20 h；
（3）To step（2）Alkali or basic salt are added in acquired solution, adjusts pH 10 ~ 12, then heats to 70 ~ 90 DEG C instead
Answer 30 ~ 60min；
（4）Wait for step（3）Gained reaction solution is cooled to 40 DEG C hereinafter, weak acid for adjusting pH 2 ~ 3 is added, and then stirs 10 ~ 20
h；
（5）By step（4）Gained reaction solution is centrifuged, and drying simultaneously roasts to obtain final product, i.e., adds without metal
Hydrogen catalyst nitrogen doped carbon nanotube；
It uses in-situ synthesis to prepare nitrogen doped carbon nanotube by nitrating agent of ammonia, includes the following steps：
（a）By Fe (NO3)3·9H2O and-Al2O3By 1 ~ 1.2：The ratio between 1 amount of substance is dissolved in deionized water, is stirred
It is 24 ~ 48 hours dry at 80 ~ 120 DEG C after mixing 20 ~ 40 h, obtain iron-aluminum catalyst；
（b）Iron-aluminum catalyst is roasted into 2 ~ 4 h at 400 ~ 600 DEG C；
（c）By step（b）Gained catalyst is placed in quartz ampoule, and 20 ~ 50 min are rinsed with pure hydrogen, it is warming up to 450 ~
The h of 550 DEG C of reductase 12s ~ 4；
（d）It is passed through methane gas, argon gas and ammonia, is warming up to 750 ~ 850 DEG C of 2 ~ 4 h of reaction；
（e）40 DEG C are cooled to hereinafter, highly basic is added in products obtained therefrom, 1 ~ 4 h is impregnated at 70 ~ 100 DEG C, and to go
Ion water washing removes iron-aluminum catalyst；
（f）1 ~ 2h of acid dip is added, washing is dried to obtain no catalytic hydrogenation nitrogen-doped nanometer carbon pipe.
Further, step（3）Alkali or the preferred sodium hydroxide of basic salt, potassium hydroxide, sodium carbonate or potassium carbonate in
One or more, concentration are preferably 0.5 ~ 2mol/L.
Further, step（4）The preferred acetic acid of weak acid or citric acid, more preferably acetic acid.
Further, step（5）In, drying temperature is 80 ~ 120 DEG C, and the time is 12 ~ 48h；Calcination temperature is 400 ~ 600
DEG C, the time is 2 ~ 12h.
Further, step（c）Heating rate preferably 2 ~ 5 DEG C/min.
Further, step（d）In, methane, argon gas, ammonia air-flow ratio preferably 1：1：1, preferably 4 ~ 8 DEG C of heating rate/
min。
Further, step（e）In, the preferred potassium hydroxide of highly basic or sodium hydroxide.
Further, step（f）In, acid preferably hydrochloric acid or sulfuric acid, a concentration of 0.5 ~ 2mol/L.
Above-mentioned preparation method prepare without catalytic hydrogenation in the application of catalysis 1,5- dinitronaphthalene hydrogenation reactions, packet
Include following steps：
（A）1,5- dinitronaphthalene and its above-mentioned nitrogen-doped nanometer carbon pipe of quality 5 ~ 20% are added in reaction kettle, and are added
Solvent；
（B）It shuts after reaction kettle and is replaced 1 ~ 6 time with hydrogen, then pass to hydrogen and be stirred, be warming up to 80 ~ 200 DEG C；
（C）Reach and pressure is transferred to 0.3 ~ 3MPa after reaction temperature, reacts 6 ~ 18 hours.
Further, step（A）Solvent be DMF（N,N-dimethylformamide）, aniline, cyclohexylamine, hexamethylene diamine, three second
One or more of amine or triethanolamine.
The beneficial effects of the present invention are：
The present invention, as 1,5- dinitronaphthalene hydrogenation catalysts, is avoided using noble metal, section using nitrogen doped carbon nanotube
About cost, and do not pollute the environment, while can reuse.The method for preparing catalyst of the present invention is simple, production cost
Low plus hydrogen effect is good, reaction is easy to control, and catalyst is environmentally friendly, will not cause secondary pollution to environment, can be widely applied
Into all kinds of hydrogenation reactions.
Description of the drawings
Fig. 1 is the process flow diagram of nitrogen doped carbon nanotube obtained by infusion process of the present invention.
Fig. 2 is the process flow diagram of nitrogen doped carbon nanotube obtained by in-situ synthesis of the present invention.
Specific implementation mode
It is further illustrated the present invention with reference to embodiment.
Embodiment 1
A kind of preparation method of no catalytic hydrogenation uses infusion process to prepare nitrating carbon as nitrogen source using melamine and receives
Mitron specifically comprises the following steps：
（1）Carbon nanotube oxidation processes：It is 1 that carbon nanotube, which is pressed solid-to-liquid ratio,:80 addition volume ratios are 3：1 concentrated sulfuric acid with
The nitration mixture of concentrated nitric acid carries out acidification 12h, and dry 12h obtains oxide/carbon nanometer tube at 80 DEG C after centrifugation washing.
（2）It takes above-mentioned oxide/carbon nanometer tube appropriate, 1 is pressed with melamine:1 mass ratio mixing, is added deionized water, and
The formaldehyde of 2 times of appropriate melamine quality is added, impregnates 12h；
（3）1mol/L NaOH are added dropwise into above-mentioned solution, adjust pH to 10 or so；
（4）It is warming up to 75 DEG C of 30 min of reaction；
（5）Acetic acid is added after being cooled to room temperature, it is 2.5 or so to adjust pH, stirs 12h at room temperature；
（6）The liquid of above-mentioned steps is centrifuged after washing 24 hours dry at 80 DEG C；
（7）By above-mentioned solid in tube furnace under nitrogen atmosphere 500 DEG C roast 4 hours, obtain no catalytic hydrogenation
Nitrogen doped carbon nanotube.
Embodiment 2
A kind of preparation method of no catalytic hydrogenation, uses infusion process to prepare nitrating carbon by nitrating agent of melamine
Nanotube specifically comprises the following steps：
（1）Carbon nanotube oxidation processes：It is 1 that carbon nanotube, which is pressed solid-to-liquid ratio,:60 addition volume ratios are 3：1 concentrated sulfuric acid with
The nitration mixture of concentrated nitric acid carries out acidification 15h, and dry 12h obtains oxide/carbon nanometer tube at 100 DEG C after centrifugation washing.
（2）It takes above-mentioned oxide/carbon nanometer tube appropriate, 1 is pressed with melamine:1.1 mass ratio mixing, is added deionized water,
And the formaldehyde of 3 times of appropriate melamine quality is added, impregnate 10h；
（3）0.5mol/L KOH are added dropwise into above-mentioned solution, adjust pH to 11 or so；
（4）It is warming up to 70 DEG C of 60 min of reaction；
（5）Acetic acid is added after being cooled to room temperature, it is 3 or so to adjust pH, stirs 10h at room temperature；
（6）The liquid of above-mentioned steps is centrifuged after washing 24 hours dry at 120 DEG C；
（7）By above-mentioned solid in tube furnace under nitrogen atmosphere 600 DEG C roast 2 hours, obtain no catalytic hydrogenation
Nitrogen doped carbon nanotube.
Embodiment 3
A kind of preparation method of no catalytic hydrogenation, uses infusion process to prepare nitrating carbon by nitrating agent of melamine
Nanotube specifically comprises the following steps：
（1）Carbon nanotube oxidation processes：It is 1 that carbon nanotube, which is pressed solid-to-liquid ratio,:120 addition volume ratios are 3：1 concentrated sulfuric acid
Acidification 8h is carried out with the nitration mixture of concentrated nitric acid, dry 12h obtains oxide/carbon nanometer tube at 80 DEG C after centrifugation washing.
（2）It takes above-mentioned oxide/carbon nanometer tube appropriate, 1 is pressed with melamine:1.2 mass ratio mixing, is added deionized water,
And the formaldehyde of 2 times of appropriate melamine quality is added, impregnate 20h；
（3）2mol/L NaCO are added dropwise into above-mentioned solution3, adjust pH to 12 or so；
（4）It is warming up to 80 DEG C of 30 min of reaction；
（5）Citric acid is added after being cooled to room temperature, it is 2 or so to adjust pH, stirs 20h at room temperature；
（6）The liquid of above-mentioned steps is centrifuged after washing 48 hours dry at 100 DEG C；
（7）By above-mentioned solid in tube furnace under nitrogen atmosphere 400 DEG C roast 10 hours, obtain no catalytic hydrogenation
Nitrogen doped carbon nanotube.
Embodiment 4
A kind of preparation method of no catalytic hydrogenation, uses in-situ synthesis to prepare nitrating carbon by nitrating agent of ammonia
Nanotube specifically comprises the following steps：
（a）By Fe (NO3)3·9H2O and-Al2O3By 1：The ratio between 1 amount of substance is dissolved in deionized water, and stirring is for 24 hours
Afterwards, 24 hours dry at 100 DEG C, obtain iron iron Al catalysts；
（b）Iron-aluminum catalyst is roasted into 2 h at 450 DEG C；
（c）By step（b）Gained catalyst is placed in quartz ampoule, 30 min is rinsed with pure hydrogen, with the heating of 3 DEG C/min
Rate is warming up to 500 DEG C of reductase 12 h；
（d）It is passed through methane gas, argon gas and ammonia, air-flow ratio is 1：1：1, it is warming up to 800 with the heating rate of 5 DEG C/min
DEG C reaction 2 h；
（e）It is cooled to room temperature, KOH is added in products obtained therefrom, 2 h are impregnated at 80 DEG C, and wash with deionized water,
Remove iron-aluminum catalyst；
（f）The hydrochloric acid solution that 1mol/L is added impregnates 2 h, to remove not clean Fe ions, is washed out and is dried to obtain
Without catalytic hydrogenation nitrogen-doped nanometer carbon pipe.
Embodiment 5
A kind of preparation method of no catalytic hydrogenation, uses in-situ synthesis to prepare nitrating carbon by nitrating agent of ammonia
Nanotube specifically comprises the following steps：
（a）By Fe (NO3)3·9H2O and-Al2O3By 1.1：The ratio between 1 amount of substance is dissolved in deionized water, stirring
It is 48 hours dry at 80 DEG C after 20h, obtain iron-aluminum catalyst；
（b）Iron-aluminum catalyst is roasted into 4 h at 400 DEG C；
（c）By step（b）Gained catalyst is placed in quartz ampoule, 50 min is rinsed with pure hydrogen, with the heating of 2 DEG C/min
Rate is warming up to 450 DEG C of 4 h of reduction；
（d）It is passed through methane gas, argon gas and ammonia, air-flow ratio is 1：1：1, it is warming up to 750 with the heating rate of 6 DEG C/min
DEG C reaction 4 h；
（e）It is cooled to room temperature, NaOH is added in products obtained therefrom, 4 h are impregnated at 70 DEG C, and wash with deionization
It washs, removes iron-aluminum catalyst；
（f）The sulfuric acid solution that 0.5mol/L is added impregnates 2 h, to remove not clean Fe ions, is washed out dry
To no catalytic hydrogenation nitrogen-doped nanometer carbon pipe.
Embodiment 6
A kind of preparation method of no catalytic hydrogenation, uses in-situ synthesis to prepare nitrating carbon by nitrating agent of ammonia
Nanotube specifically comprises the following steps：
（a）By Fe (NO3)3·9H2O and-Al2O3By 1.2：The ratio between 1 amount of substance is dissolved in deionized water, stirring
It is 30 hours dry at 90 DEG C after 40h, obtain iron-aluminum catalyst；
（b）Iron-aluminum catalyst is roasted into 3 h at 600 DEG C；
（c）By step（b）Gained catalyst is placed in quartz ampoule, 60 min is rinsed with pure hydrogen, with the heating of 4 DEG C/min
Rate is warming up to 550 DEG C of 3 h of reduction；
（d）It is passed through methane gas, argon gas and ammonia, air-flow ratio is 1：1：1, it is warming up to 850 with the heating rate of 7 DEG C/min
DEG C reaction 2 h；
（e）It is cooled to room temperature, KOH is added in products obtained therefrom, 1 h is impregnated at 100 DEG C, and wash with deionization
It washs, removes iron-aluminum catalyst；
（f）The hydrochloric acid solution that 2mol/L is added impregnates 1 h, to remove not clean Fe ions, is washed out and is dried to obtain
Without catalytic hydrogenation nitrogen-doped nanometer carbon pipe.
Embodiment 7
A kind of no catalytic hydrogenation includes the following steps in the application of catalysis 1,5- dinitronaphthalene hydrogenation reactions：
（A）100ml reactions are added in 1 gained nitrogen-doped nanometer carbon pipe catalyst of 1,5- dinitronaphthalene 1g and 0.1g embodiment
In kettle, and 20 ml solvent DMFs are added；
（B）It shuts after reaction kettle and is replaced 4 times with hydrogen, then pass to hydrogen and be stirred, be warming up to 120 DEG C；
（C）Reach and pressure is transferred to 2MPa after reaction temperature, reacts 13 hours.
It is analyzed using internal standard method, the results show that 1,5- dinitronaphthalene conversion ratio is 30.28%, 1,5-diaminonaphthalene is received
Rate is 1.2%, and 1,5-diaminonaphthalene is selectively 4%, and the selectivity of intermediate product is 96%.
Embodiment 8
It is other same as Example 7, unlike：Using 2 gained catalyst of embodiment, and dosage is 0.05g, and solvent is
Aniline.
It is analyzed using internal standard method, the results show that 1,5- dinitronaphthalene conversion ratio is 35.67%, 1,5-diaminonaphthalene
Yield is 3.2%, and 1,5-diaminonaphthalene is selectively 9%, and the selectivity of intermediate product is 91%.
Embodiment 9
It is other same as Example 7, unlike：Using 3 gained catalyst of embodiment, and dosage is 0.2g, and solvent is
Hexamethylene diamine.
It is analyzed using internal standard method, the results show that 1,5- dinitronaphthalene conversion ratio is 28.1%, 1,5-diaminonaphthalene is received
Rate is 0.9%, and 1,5-diaminonaphthalene is selectively 3.2%, and the selectivity of intermediate product is 96.8%.
Embodiment 10
It is other same as Example 7, unlike：Using 4 gained catalyst of embodiment.
It is analyzed using internal standard method, the results show that 1,5- dinitronaphthalene conversion ratio is 41%, 1,5-diaminonaphthalene yield
It is 4.8%, the selectivity of 1,5-diaminonaphthalene selectivity 11.7%, intermediate product is 88.3%.
Embodiment 11
It is other same as Example 7, unlike：Using 5 gained catalyst of embodiment.
It is analyzed using internal standard method, the results show that 1,5- dinitronaphthalene conversion ratio is 46%, 1,5-diaminonaphthalene yield
It is 5.1%, 1,5-diaminonaphthalene is selectively 11.1%, and the selectivity of intermediate product is 88.9%.
Embodiment 12
It is other same as Example 7, unlike：Using 6 gained catalyst of embodiment.
It is analyzed using internal standard method, the results show that 1,5- dinitronaphthalene conversion ratio is 43%, 1,5-diaminonaphthalene yield
It is 4.5%, 1,5-diaminonaphthalene is selectively 10.5%, and the selectivity of intermediate product is 89.5%.
Claims (10)
1. a kind of preparation method of no catalytic hydrogenation, which is characterized in that including using infusion process using melamine as nitrogen
Source prepares nitrogen doped carbon nanotube or in-situ synthesis is used to prepare nitrogen doped carbon nanotube by nitrogen source of ammonia；
It uses infusion process to prepare nitrogen doped carbon nanotube by nitrogen source of melamine, includes the following steps：
（1）Carbon nanotube oxidation processes：It is 1 by solid-to-liquid ratio:60 ~ 120 are added 8 ~ 15 h of nitration mixture acidification to carbon nanotube, from
After heart separating, washing, washing is dried to obtain oxide/carbon nanometer tube；
（2）By step（1）Gained oxide/carbon nanometer tube presses 1 with melamine:1 ~ 1.2 mass ratio mixing, then be added go from
Sub- water, then by formaldehyde and melamine 2 ~ 3:Formaldehyde is added in 1 mass ratio, then impregnates 10 ~ 20 h；
（3）To step（2）Alkali or basic salt are added in acquired solution, adjusts pH 10 ~ 12, then heats to 70 ~ 90 DEG C of reactions 30
~60min；
（4）Wait for step（3）Gained reaction solution is cooled to 40 DEG C hereinafter, weak acid for adjusting pH 2 ~ 3 is added, and then stirs 10 ~ 20 h；
（5）By step（4）Gained reaction solution is centrifuged, and drying simultaneously roasts to obtain final product, i.e., without metal N doping
Carbon nanotube hydrogenation catalyst；
It uses in-situ synthesis to prepare nitrogen doped carbon nanotube by nitrogen source of ammonia, includes the following steps：
（a）By Fe (NO3)3·9H2O and-Al2O3By 1 ~ 1.2：The ratio between 1 amount of substance is dissolved in deionized water, and stirring 20 ~
It is 24 ~ 48 hours dry at 80 ~ 120 DEG C after 40 h, obtain iron-aluminum catalyst；
（b）Iron-aluminum catalyst is roasted into 2 ~ 4 h at 400 ~ 600 DEG C；
（c）By step（b）Gained catalyst is placed in quartz ampoule, is rinsed 20 ~ 50 min with pure hydrogen, is warming up to 450 ~ 550 DEG C
The h of reductase 12 ~ 4；
（d）It is passed through methane gas, argon gas and ammonia, is warming up to 750 ~ 850 DEG C of 2 ~ 4 h of reaction；
（e）40 DEG C are cooled to hereinafter, highly basic is added in products obtained therefrom, 1 ~ 4 h is impregnated at 70 ~ 100 DEG C, and with deionization
Water washing removes iron-aluminum catalyst；
（f）1 ~ 2h of acid dip is added, washing is dried to obtain no metal nitrogen-doped nanometer carbon pipe hydrogenation catalyst.
2. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（3）Alkali or
Basic salt is sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, a concentration of 0.5 ~ 2mol/L.
3. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（4）Weak acid
For acetic acid or citric acid.
4. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（5）In, it is dry
Temperature is 80 ~ 120 DEG C, and the time is 12 ~ 48h；Calcination temperature is 400 ~ 600 DEG C, and the time is 2 ~ 12h.
5. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（c）Heating
Rate is 2 ~ 5 DEG C/min.
6. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（d）In, first
Alkane, argon gas, ammonia air-flow ratio be 1：1：1, heating rate is 4 ~ 8 DEG C/min.
7. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（e）In, highly basic
For potassium hydroxide or sodium hydroxide.
8. the preparation method of no catalytic hydrogenation according to claim 1, which is characterized in that step（f）In, acid is
Hydrochloric acid or sulfuric acid, a concentration of 0.5 ~ 2mol/L.
9. prepared by claim 1 to 8 any one of them preparation method is being catalyzed 1,5- dinitros without catalytic hydrogenation
The application of naphthalene hydrogenation reaction, which is characterized in that include the following steps：
（A）1,5- dinitronaphthalene and its above-mentioned nitrogen-doped nanometer carbon pipe of quality 5 ~ 20% are added in reaction kettle, and are added molten
Agent；
（B）It shuts after reaction kettle and is replaced 1 ~ 6 time with hydrogen, then pass to hydrogen and be stirred, be warming up to 80 ~ 200 DEG C；
（C）Reach and pressure is transferred to 0.3 ~ 5MPa after reaction temperature, reacts 6 ~ 24 hours.
10. no catalytic hydrogenation according to claim 9 catalysis 1,5- dinitronaphthalene hydrogenation reactions application,
It is characterized in that, step（A）Solvent be DMF, aniline, cyclohexylamine, hexamethylene diamine, triethylamine or triethanolamine.
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| CN111974381A (en) * | 2020-09-17 | 2020-11-24 | 福建省晋蓝环保科技有限公司 | Ozone catalytic oxidation catalyst and preparation process thereof |
| CN113680370A (en) * | 2021-09-10 | 2021-11-23 | 润泰化学（泰兴）有限公司 | Preparation method and application of single-atom catalyst for synthesizing 1, 2-dimethyl cyclohexanedicarboxylate from dimethyl phthalate |
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