CN109503386A - A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine - Google Patents
A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine Download PDFInfo
- Publication number
- CN109503386A CN109503386A CN201811557522.6A CN201811557522A CN109503386A CN 109503386 A CN109503386 A CN 109503386A CN 201811557522 A CN201811557522 A CN 201811557522A CN 109503386 A CN109503386 A CN 109503386A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- phenylenediamine
- reaction
- paranitroanilinum
- passed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses the preparation methods that a kind of paranitroanilinum catalytic hydrogenation prepares p-phenylenediamine, belong to the field of chemical synthesis.This method is to stir evenly after mixing p-phenylenediamine, paranitroanilinum and nanocatalyst in the atmosphere of nitrogen and be warming up to 180~220 DEG C, later in previous reaction system, hydrogen is continuously passed through in 2~5 hours and maintenance system gauge pressure is 1~2MPa；After hydrogen is passed through, increases 5~20 DEG C of the temperature of system and react 20~40min, filter off catalyst after reaction, target product can be obtained through rectification under vacuum in reaction solution.
Description
Technical field
The present invention relates to the field of chemical synthesis, and in particular to a kind of paranitroanilinum catalytic hydrogenation prepares the system of p-phenylenediamine
Preparation Method.
Background technique
P-phenylenediamine is the intermediate of azo system disperse dyes, acid dyes, direct dyes and sulfur dye, is synthesis virtue
The important source material of synthetic fibre, polyimide resin, diisocyanate, p-phenylenediamine be largely used to prepare good anti-aging agent 288,
4030,4720 etc..In addition, p-phenylenediamine is also production gasoline polymerization inhibitor, epoxy curing agent, carbon black treatment agent, insulating paper
The primary raw material of inorganic agent and fire retardant.
Traditional p-phenylenediamine production technology is that it is thick to generate p-phenylenediamine through sodium sulfide reducing using paranitroanilinum as raw material
Most high-purity p-phenylenediamine is made through rectifying afterwards in product.The maximum defect of the technique is that industrial wastewater is more, and raw material availability is low, sternly
Heavily contaminated environment.In recent years, more successful p-phenylenediamine new technique for synthesizing is to be with skeleton Ni using ethyl alcohol or methanol as solvent
Catalyst carries out hydrogenation reaction and prepares p-phenylenediamine.Hydrogenation technique efficiently solves problem of environmental pollution, but the technique is scarce
Point be separate solvent methanol or ethyl alcohol loss and energy consumption it is higher.Methanol, ethyl alcohol are inflammable and explosive, and methanol is toxic, therefore entire
Technique production cost is higher, safety coefficient is lower and not environmentally.
Summary of the invention
The present invention overcomes defects existing for original method, provide one kind and add hydrogen to nitro using product p-phenylenediamine as solvent
Aniline prepares the preparation method of p-phenylenediamine.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of paranitroanilinum adds hydrogen to prepare the preparation method of p-phenylenediamine, method includes the following steps:
(1) it in the atmosphere of nitrogen, stirs evenly and rises after p-phenylenediamine, paranitroanilinum and nanocatalyst are mixed
Temperature is to 180~220 DEG C；
(2) in the reaction system of step (1), be continuously passed through in 2~5 hours hydrogen and maintenance system gauge pressure be 1~
2MPa；
(3) it after the hydrogen of step (2) is passed through, increases 5~20 DEG C of the temperature of system and reacts 20~40min, reaction
After filter off catalyst, target product can be obtained through rectification under vacuum in reaction solution.
In technical solution of the present invention: nickel content 20%Ni/SiO2Hydrogenation catalyst the preparation method is as follows: in Ni
(NO3)2It is stirred evenly with silica gel is added in the mixed liquor of urea；It is reacted under conditions of temperature is 90~100 DEG C later,
To complete, solid is obtained by filtration, cleans, it is dry, it is passed through hydrogen reducing under the conditions of temperature is 350-400 DEG C, after reduction
Sample is cooled to -20 DEG C of annealing, is fitted into vial after smearing hexane.
In technical solution of the present invention: preparation catalyst is used, in 0.12-0.37mol/L Ni (NO3)2And 2.4-
A certain amount of silica gel is added in the mixed liquor of 3.3mol/L urea to stir evenly, it is ensured that Ni/SiO2Ni content be 20%.It will mixing
Liquid heats at 96 DEG C, tests whether that precipitating is complete using 1% dimethylglyoxime.It is to be precipitated complete, solid is obtained by filtration, with distillation
Water is cleaned, dry at 110 DEG C.After the completion of drying, hydrogen reducing is passed through at 350-400 DEG C.Sample after reduction is cooled to-
20 DEG C of annealing, are fitted into vial after smearing hexane.
In technical solution of the present invention: the mass ratio of p-phenylenediamine, paranitroanilinum and nanocatalyst be 20~30:5~
15:0.5~1.5.
Beneficial effects of the present invention:
The present invention improves the utilization rate of raw material, simplifies tradition preparation step, save the cost.
It is low that the present invention successfully solves traditional hydroprocessing catalysts safety coefficient, at high cost, not environmentally the problem of.
Catalyst is still having very high catalytic effect after repeatedly using in preparation method provided by the invention.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto:
Embodiment one
It is accurate to prepare 678L 0.2mol/L Ni (NO3)2With the mixed liquor of 27.12L 2.5mol/L urea, 32kg silicon is added
Glue stirs evenly.Mixed liquor is heated at 96 DEG C, tests whether that precipitating is complete using 1% dimethylglyoxime.It is to be precipitated complete, mistake
Filter obtains solid, is cleaned with distilled water, dry at 110 DEG C.After the completion of drying, hydrogen reducing is passed through at 350-400 DEG C.It will be also
Sample after original is cooled to -20 DEG C of annealing, is fitted into vial after smearing hexane, obtains 40kg Ni/SiO2Catalyst.
By 1000kg p-phenylenediamine, 400kg paranitroanilinum, 40kg Ni/SiO2It puts into reaction kettle, is replaced with nitrogen,
Stirring is opened, is warming up to 180 DEG C, then hydrogen is continuously passed through in reaction kettle, maintaining hydrogen gauge pressure in kettle is 1.5MPa, when leading to hydrogen
Between 3h；Reactant stops inhaling hydrogen and terminating leading to hydrogen, and kettle temperature is improved to 190 DEG C, reaction 30 minutes is maintained；Reaction terminates, sampling
Detection, reaction conversion ratio 99.89%, reaction selectivity 100%, yield 99.89%；Catalyst is filtered off, reaction solution is through depressurizing
Rectifying obtains the white p-phenylenediamine product that purity is 99.97%.
Embodiment two
The Ni/SiO that will be separated in embodiment one2Again it puts into reaction kettle, 1000kg p-phenylenediamine is added in kettle,
400kg paranitroanilinum, is replaced with nitrogen, is opened stirring, is warming up to 180 DEG C, then hydrogen is continuously passed through in reaction kettle, is maintained
Hydrogen gauge pressure is 1.5MPa in kettle, leads to hydrogen time 3h；Reactant stops inhaling hydrogen and terminating leading to hydrogen, and kettle temperature is improved to 190 DEG C, is tieed up
Hold reaction 30 minutes；Reaction terminates, sample detection, reaction conversion ratio 99.92%, reaction selectivity 100%, and yield is
99.92%；Catalyst is filtered off, reaction solution obtains the white p-phenylenediamine product that purity is 99.98% through rectification under vacuum.
Embodiment three
The Ni/SiO that will be separated in embodiment two2Again it puts into reaction kettle, 1000kg p-phenylenediamine is added in kettle,
400kg paranitroanilinum, is replaced with nitrogen, is opened stirring, is warming up to 180 DEG C, then hydrogen is continuously passed through in reaction kettle, is maintained
Hydrogen gauge pressure is 1.5MPa in kettle, leads to hydrogen time 3h；Reactant stops inhaling hydrogen and terminating leading to hydrogen, and kettle temperature is improved to 190 DEG C, is tieed up
Hold reaction 30 minutes；Reaction terminates, sample detection, reaction conversion ratio 99.91%, reaction selectivity 100%, and yield is
99.91%；Catalyst is filtered off, reaction solution obtains the white p-phenylenediamine product that purity is 99.97% through rectification under vacuum.
Example IV
The Ni/SiO that will be separated in embodiment three2Again it puts into reaction kettle, 1000kg p-phenylenediamine is added in kettle,
400kg paranitroanilinum, is replaced with nitrogen, is opened stirring, is warming up to 180 DEG C, then hydrogen is continuously passed through in reaction kettle, is maintained
Hydrogen gauge pressure is 1.5MPa in kettle, leads to hydrogen time 3h；Reactant stops inhaling hydrogen and terminating leading to hydrogen, and kettle temperature is improved to 190 DEG C, is tieed up
Hold reaction 30 minutes；Reaction terminates, sample detection, reaction conversion ratio 99.89%, reaction selectivity 100%, and yield is
99.89%；Catalyst and 1000kg p-phenylenediamine are detained in a kettle, the reaction solution filtered out obtains pure through rectification under vacuum
The white p-phenylenediamine product that degree is 99.96%.
Embodiment five
It is detained the Ni/SiO having into example IV2In the reaction kettle of p-phenylenediamine, 400kg paranitroanilinum is put into,
It is replaced with nitrogen, opens stirring, be warming up to 180 DEG C, then hydrogen is continuously passed through in reaction kettle, hydrogen gauge pressure is in maintenance kettle
1.5MPa leads to hydrogen time 3h；Reactant stops inhaling hydrogen and terminating leading to hydrogen, and kettle temperature is improved to 190 DEG C, reaction 30 minutes is maintained；
Reaction terminates, sample detection, reaction conversion ratio 99.90%, reaction selectivity 100%, yield 99.90%；By catalyst and
1000kg p-phenylenediamine is detained in a kettle, and it is right to obtain the white that purity is 99.98% through rectification under vacuum for the reaction solution filtered out
Phenylenediamine product.
Embodiment six
Being detained into embodiment five has Ni/SiO2In the reaction kettle of p-phenylenediamine, 400kg paranitroanilinum is put into, is used
Nitrogen displacement, opens stirring, is warming up to 180 DEG C, then hydrogen is continuously passed through in reaction kettle, and hydrogen gauge pressure is in maintenance kettle
1.5MPa leads to hydrogen time 3h；Reactant stops inhaling hydrogen and terminating leading to hydrogen, and kettle temperature is improved to 190 DEG C, reaction 30 minutes is maintained；
Reaction terminates, sample detection, reaction conversion ratio 99.93%, reaction selectivity 100%, yield 99.93%；Catalyst is filtered out,
Reaction solution obtains the white p-phenylenediamine product that purity is 99.96% through rectification under vacuum.
Claims (5)
1. a kind of paranitroanilinum adds hydrogen to prepare the preparation method of p-phenylenediamine, it is characterised in that: method includes the following steps:
(1) it in the atmosphere of nitrogen, stirs evenly and is warming up to after p-phenylenediamine, paranitroanilinum and nanocatalyst are mixed
180~220 DEG C；
(2) it is continuously passed through hydrogen in the reaction system of step (1), in 2~5 hours and maintenance system gauge pressure is 1~2MPa；
(3) it after the hydrogen of step (2) is passed through, increases 5~20 DEG C of the temperature of system and reacts 20~40min, reaction terminates
After filter off catalyst, target product can be obtained through rectification under vacuum in reaction solution.
2. according to the method described in claim 1, it is characterized by: the nanocatalyst is the Ni/ that nickel content is 20%
SiO2Hydrogenation catalyst.
3. method according to claim 1 or 2, it is characterised in that: nickel content 20%Ni/SiO2Hydrogenation catalyst system
Preparation Method is as follows: in Ni (NO3)2It is stirred evenly with silica gel is added in the mixed liquor of urea；It is later 90~100 DEG C in temperature
Under the conditions of reacted, to complete, solid is obtained by filtration, cleans, it is dry, be passed through hydrogen under the conditions of temperature is 350-400 DEG C
Sample after reduction is cooled to -20 DEG C of annealing, is fitted into vial after smearing hexane by reduction.
4. according to the method described in claim 3, it is characterized by: nickel content is 20%Ni/SiO2Hydrogenation catalyst preparation side
Method is as follows: in 0.12~0.37mol/L Ni (NO3)2Silica gel stirring is equal with being added in the mixed liquor of 2.4~3.3mol/L urea
It is even, guarantee Ni (NO3)2Molar ratio with urea is 2:1, and the content of nickel is the 20% of total catalyst quality；It later will be at 96 DEG C
Heating tests whether that precipitating is complete using 1% dimethylglyoxime.It is to be precipitated that solid is obtained by filtration completely, it is cleaned with distilled water,
It is dry at 110 DEG C.After the completion of drying, hydrogen reducing is passed through at 350-400 DEG C；Sample after reduction is cooled to -20 DEG C of annealing,
It is fitted into vial after smearing hexane.
5. according to the method described in claim 1, it is characterized by: the matter of p-phenylenediamine, paranitroanilinum and nanocatalyst
Amount is than being 20~30:5~15:0.5~1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811557522.6A CN109503386A (en) | 2018-12-19 | 2018-12-19 | A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811557522.6A CN109503386A (en) | 2018-12-19 | 2018-12-19 | A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109503386A true CN109503386A (en) | 2019-03-22 |
Family
ID=65753705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811557522.6A Pending CN109503386A (en) | 2018-12-19 | 2018-12-19 | A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109503386A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001951A (en) * | 2009-09-02 | 2011-04-06 | 南化集团研究院 | Method for preparing high-purity p-phenylenediamine |
| CN102631924A (en) * | 2011-03-14 | 2012-08-15 | 江苏康恒化工有限公司 | Preparation method of o-phenylenediamine catalyst-nano nickel by hydrogenation |
| CN102633654A (en) * | 2011-03-17 | 2012-08-15 | 江苏康恒化工有限公司 | O-phenylenediamine preparation process by means of hydrogenization with nano nickel serving as catalyst |
| CN102909047A (en) * | 2012-10-25 | 2013-02-06 | 兰州理工大学 | Dinitrotoluene catalytic hydrogenation catalyst and preparation method thereof |
| CN104858413A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Preparation method of silicon-dioxide-carried precious metal nanoparticles |
| WO2017134493A1 (en) * | 2016-02-04 | 2017-08-10 | Tata Institute Of Fundamental Research | Synthesis of fibrous nano-silica spheres with controlled particle size, fibre density, and various textural properties |
| CN108658781A (en) * | 2017-03-28 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of preparation method of p-phenylenediamine |
-
2018
- 2018-12-19 CN CN201811557522.6A patent/CN109503386A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001951A (en) * | 2009-09-02 | 2011-04-06 | 南化集团研究院 | Method for preparing high-purity p-phenylenediamine |
| CN102631924A (en) * | 2011-03-14 | 2012-08-15 | 江苏康恒化工有限公司 | Preparation method of o-phenylenediamine catalyst-nano nickel by hydrogenation |
| CN102633654A (en) * | 2011-03-17 | 2012-08-15 | 江苏康恒化工有限公司 | O-phenylenediamine preparation process by means of hydrogenization with nano nickel serving as catalyst |
| CN102909047A (en) * | 2012-10-25 | 2013-02-06 | 兰州理工大学 | Dinitrotoluene catalytic hydrogenation catalyst and preparation method thereof |
| CN104858413A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Preparation method of silicon-dioxide-carried precious metal nanoparticles |
| WO2017134493A1 (en) * | 2016-02-04 | 2017-08-10 | Tata Institute Of Fundamental Research | Synthesis of fibrous nano-silica spheres with controlled particle size, fibre density, and various textural properties |
| CN108658781A (en) * | 2017-03-28 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of preparation method of p-phenylenediamine |
Non-Patent Citations (1)
| Title |
|---|
| YUNFENG ZHENG，等: "A Green Reduction of Aromatic Nitro Compoundsto Aromatic Amines Over a Novel Ni/SiO2 Catalyst Passivated with a Gas Mixture", 《CATAL LETT》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101830474B (en) | Method for preparing white carbon black | |
| CN106554286B (en) | A kind of method that noble metal catalyst continuously prepares p phenylenediamine type antioxidant | |
| CN113402395A (en) | Method for continuously and efficiently synthesizing m-phenylenediamine based on fixed bed microreactor | |
| CN113429295B (en) | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor | |
| CN101362710A (en) | Method for preparing aminobenzenesulfonic acid by catalytic hydrogenation | |
| CN108929221A (en) | A kind of preparation method of n propyl propionate | |
| CN112225642A (en) | Method for preparing resorcinol through microchannel reaction | |
| CN107715873B (en) | Preparation method and application of La-loaded modified Pt-based catalyst taking metal organic framework material as carrier | |
| CN105601588A (en) | Method for synthesizing N-hydroxyethylpiperazine and piperazine by means of co-production | |
| CN103508908B (en) | Preparation method for 4-amino-3-methylphenol | |
| CN110128278A (en) | A kind of method that 1-CHLORO-2,4-DINITROBENZENE catalytic hydrogenation prepares m-phenylene diamine (MPD) | |
| CN101003466A (en) | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin | |
| CN109503386A (en) | A kind of paranitroanilinum catalytic hydrogenation prepares the preparation method of p-phenylenediamine | |
| CN104276928B (en) | The preparation method of two [1-(4-hydroxy phenyl)-1-the methylethyl]-Resorcinol of a kind of 4,6- | |
| CN102464633B (en) | Synthetic method for (methyl) glycidyl acrylate | |
| CN103570577B (en) | Preparation method of N,N-dimethyl propionamide | |
| CN109336770A (en) | A kind of method that solvent-free hydrogenating reduction method prepares 3,4- dichloroaniline | |
| CN107597173A (en) | A kind of catalyst of phenol hydroxylation synthesizing benzene diphenol and preparation method thereof | |
| CN105924328A (en) | High-selectivity green hydrolysis technology for preparing benzyl alcohol | |
| CN102515104A (en) | Method for preparing hydrogen chloride and silicon dioxide by hydrolyzing silicon tetrachloride in organic solvent | |
| CN101195600A (en) | Method for producing 4-hydroxyindole | |
| CN108285417A (en) | The method that liquid phase continuous catalytic hydrogenation reduction nitrotoleune prepares methylaniline | |
| CN110330651B (en) | Method for preparing polyether sulfone | |
| CN101607917A (en) | The production method of high-quality p-aminophenol | |
| CN102992369B (en) | Recycling method for catalyst alumina |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190322 |
|
| RJ01 | Rejection of invention patent application after publication |