CN110092723A - The method of aniline is continuously manufactured by by the catalytic hydrogenation of p-nitrophenyl - Google Patents
The method of aniline is continuously manufactured by by the catalytic hydrogenation of p-nitrophenyl Download PDFInfo
- Publication number
- CN110092723A CN110092723A CN201810275653.9A CN201810275653A CN110092723A CN 110092723 A CN110092723 A CN 110092723A CN 201810275653 A CN201810275653 A CN 201810275653A CN 110092723 A CN110092723 A CN 110092723A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aniline
- hydrogenator
- nitrobenzene
- reaction
- 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
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
Abstract
The method and catalyst therefore of aniline are continuously manufactured by the present invention provides through the catalytic hydrogenation of p-nitrophenyl.
Description
Technical field
The present invention relates to aniline manufacturing technology field, it is specifically related to continuously make by the catalytic hydrogenation of p-nitrophenyl
The method for making aniline.
Background technique
Process is well-known by the catalytic hydrogenation of p-nitrophenyl continuously to produce aniline.It can be in gas phase or liquid
Mutually execute the process.Many manufacturers seem more to favor liquid phase process.Itd is proposed many different catalyst, from it is Ni-based to
Noble metal base has.
Summary of the invention
According to an aspect of the invention, there is provided being continuously manufactured by the side of aniline by the catalytic hydrogenation of p-nitrophenyl
Method, comprising the following steps:
A. using active carbon, palladium, platinum and at least two base metals in the period 4 selected from the periodic table of elements as raw material, manufacture is urged
Agent;Optionally, the base metal be the periodic table of elements period 4 transition metal, or for the periodic table of elements period 4 with
8th race is at least two base metals in 12 races.
B. nitrobenzene, hydrogen and the catalyst are sent in hydrogenator and carry out catalytic hydrogenation reaction;Optionally, should
The temperature of catalytic hydrogenation reaction is 200 DEG C, pressure 1.7-1.8MPa.
C. the outlet effluent of hydrogenator enters polishing reactor and generally stops the lower time, such as optionally
Residence time is lower than 5 minutes, to be stirred by lasting by the nitre of any residual volume in the case where not feeding new nitrobenzene
Base benzene or intermediate are converted into aniline.
D. catalyst pulp is filtered out from the product stream that the polishing reactor is discharged, obtains the product of not catalyst
Stream;
E. the hydrogenator is returned to using the catalyst pulp filtered out as concentration slurry;
F. reaction water is isolated from the product stream of the not catalyst, obtains crude benzol amine;
G. the reaction water is extracted using nitrobenzene to recycle the aniline wherein dissolved, and to reaction extracted
Water is stripped to recycle nitrobenzene, and reaction water is discharged into biological effluent treatment equipment later;
H. it distills the crude benzol amine and is dissolved in water therein to remove;Optionally, distillation is joined using this field common process
Number carries out, such as the temperature on destilling tower top is 60 DEG C, pressure 10KPa.
I. high-boiling-point impurity is converted by the cyclohexanone by-product in crude benzol amine;Optionally, the step is at a temperature of 150 DEG C
It is carried out under 30-50KPa pressure.
J. the crude benzol amine that distilation steps i is obtained obtains pure aniline and a small amount of high-boiling-point impurity.Optionally, distillation uses
This field Conventional process parameters, such as destilling tower tip temperature are 110 DEG C, pressure 10KPa.
Preferably, in the step a, with manufacture the catalysis in the individually unit of main Aniline Production integration of equipments
Agent.The method as known in the art for preparing noble metal catalyst as carrier using active carbon can be used in the preparation method of catalyst,
Such as method described in United States Patent (USP) US6818720B and Chinese patent application CN1582199A, it is incorporated herein by reference
Herein.Optionally, the total amount that palladium deposits on the activated carbon is 4-5% weight, and the total amount that platinum deposits on the activated carbon is 0-1% weight
Amount, the total amount that described two base metals deposit on the activated carbon are 3-5% weight.
Preferably, in the step a, the active carbon is the acid-washed active carbon of 5 micron of -100 micron range.
Preferably, in the step b, the hydrogenator is that tank reactor is sufficiently stirred in CSTR type, with gas
Mutually arrive the interior recirculation of liquid phase.
Preferably, the step b further includes that steam is produced using reaction heat, in the steam covering Aniline Production equipment
Institute is in need, and exports a large amount of steam to other consumer.
Preferably, in the step b, in order to control temperature, water is fed to the cooling coil in hydrogenator, is exchanged heat
The water by heating is flashed afterwards and generates steam.
Preferably, the step i is carried out in individual reactor, by make cyclohexanone by-product and and aniline reaction incite somebody to action
Cyclohexanone by-product is converted into high-boiling-point impurity.
Preferably, in the step j, crude benzol amine is sent to destilling tower and is distilled, obtain the pure aniline of final product, and
A small amount of high-boiling-point impurity is removed in the bottom of destilling tower.
Preferably, in the step j, the high-boiling-point impurity is tar.
Preferably, the step e further include: fresh catalyst is supplemented in Xiang Suoshu hydrogenator to remain appropriate
Catalytic activity, so that essentially all nitrobenzene is converted to aniline;Alternatively, removing used catalyst described hydrogen will be added anti-
The catalyst concn inside device is answered to maintain required level.
One key feature of the process invented is to manufacture adding used in hydrogen by commercially available raw material in factory
Noble metal catalyst.The catalyst is the high-quality acid based on the approximate granular size range with 5 microns -100 microns
Active carbon is washed, this is contrasted with some other business processes that acetylene black is used as carrier, referring for example to patent application US 2,
823,235 and US 4,415,754.Acetylene black has small about 1000 times of the granular size of specific activity charcoal, this to be very difficult to
Catalyst is filtered out from product stream so as to which catalyst is recovered to hydrogenator.In addition, there are catalyst for the system
The risk of increased loss, and therefore there is the risk of the increased loss of valuable noble metal.
On the other hand, it is easy to filter out the catalyst based on active carbon and is recovered to hydrogenator, therefore can be used
Cheap filter.It avoids the loss of the system can be much easier, allows to the catalyst from deactivation, used catalyst
Nearly all noble metal is recycled, therefore minimizes the net loss of valuable metal.In addition, being urged from cheap Activated Carbon Production is own
Agent can be generally more cheaper than the manufactured catalyst from one of main supplier purchase similar type.
As known in the prior art, the formula for producing catalyst includes Pd and Pt, but it also includes from period of element
Minimum two kinds of base metal promoters that the period 4 of table is selected.Catalysis is optimized relative to noble metal and base metal composition
Agent is to provide excellent selectivity.When the execution under high temperature (for example, 200 ± 20 DEG C) plus hydrogen, can recycle from exothermic reaction
The heat for developing into steam is even more important.High reaction temperature generally tends to reduce the selectivity to desired product.
Detailed description of the invention
Fig. 1 is the simplified flowchart of the method for the invention.
Specific embodiment
The process of invention is described in detail below with reference to Fig. 1.
Via route 5 by nitrobenzene be continuously fed to extractor 6 with extract formed in reaction according to the following formula it is molten
Aniline in Xie Yushui:
Nitrobenzene+3H2→ aniline+2H2O
The nitrobenzene containing the aniline extracted is fed to the hydrogenator 14 being sufficiently stirred via route 7.Simultaneously
Hydrogen is fed to hydrogenator so that pressure is maintained desired level via route 9.By equipped with the spy for being in liquid phase
Gaseous state head space is continuously separated into liquid phase by the hollow shaft stirrer of different suction impeller again.By batch process in reactor
Catalyst is produced from the active carbon added via route 11 and via the catalyst component that route 12 adds in 10.It passes through when needed
Essentially all nitrobenzene is converted to benzene to maintain catalytic activity appropriate by the catalyst made of the addition recently of route 13
Amine.In order to control temperature, the water that supercharged steam generator is fed is fed to the cooling coil 15 inside hydrogenator via route 16,
And then it will be fed to container 18 by the water of heating via route 17, by being flashed to the water by being pressurized and heating
And generate steam 19.Generated steam covers all steam demands in factory and is largely output to other factories.
Product mixtures containing aniline, reaction water and solid catalyst spill into polishing reactor 21 via route 20,
Wherein hydrogen continues through hollow shaft stirrer and is distributed in liquid to complete to exist in the outlet of hydrogenator 14
A small amount of nitrobenzene and intermediate to aniline conversion.This is possible to realize in only several minutes, because of not new nitrobenzene
It is fed to this part.Product mixtures are fed to filter 23 from the bottom of polishing reactor 21 via route 22.It filters out and urges
Agent and make its via route 24 as slurry back to hydrogenator.Used catalysis is removed via route 25 when needed
Agent is to maintain desired level for the catalyst concn inside hydrogenator 14.Used urge can be recycled at outside plant
In agent almost 100% noble metal, and be returned to factory and be further used as the part (route 12) of catalyst component,
To manufacture new catalyst in reactor 10.
The product of not catalyst is fed to tank 27 via route 26, so that reaction water is separated with crude benzol amine.Via line
Reaction water is fed to extractor 6 by road 8, wherein extracting the aniline of dissolution using nitrobenzene.Via route 4 by not aniline
Water is fed to stripper 1, wherein removing nitrobenzene saturated water is to recycle nitrobenzene.It sends nitrobenzene to via route 3 and adds hydrogen
Reactor.The water phase being stripped is removed via route 2, and can send it to biological effluent treatment factory, is discharged into later
Container.
The bottom of tank 27 is mutually fed to destilling tower 29 via route 28, to remove dissolution water, via route 30 with it is some
Aniline returns to tank 27 together.Reactor 31 is sent from the bottom of destilling tower 29 by the aniline of not water, by making hexamethylene
Ketone by-product and aniline reaction and convert higher boiling ingredient for cyclohexanone by-product.Via route 32 by the outlet of reactor 31
It is fed to destilling tower 33, wherein via route 35 in top removal final product aniline, and moved via route 34 in the bottom of tower
Except a small amount of tar.
The stable state impurity content (%) of 1 gas chromatography of table measurement
1Number represents the percentage of respective metal on carrier.AC=active carbon, CB=carbon black
c-HexNH2Cyclohexylamine
C-HexOH- cyclohexanol
C-HexO- cyclohexanone
C-HexAN-N- cyclohexyl aniline
C-HexyAN-N- cyclohexylidene aniline
Catalyst according to the invention:
In one embodiment, using active carbon, palladium Pd, platinum Pt and iron Fe, nickel as raw material, catalyst is manufactured.Wherein,
The amount of the Pd of deposition on the activated carbon is 5% weight, and the amount that the amount of Pt is 0, Fe is 4% weight, and the amount of Ni is 1% weight.
In another embodiment, using active carbon, palladium Pd, platinum Pt and iron Fe, copper Cu as raw material, catalyst is manufactured.It is heavy
The amount of the Pd of product on the activated carbon is 3.5% weight, and the amount of Pt is 0.5% weight, and the amount of Fe is 2.5% weight, and the amount of Cu is
0.5% weight.
Claims (10)
1. being continuously manufactured by the method for aniline by the catalytic hydrogenation of p-nitrophenyl, which comprises the following steps:
A. using active carbon, palladium, platinum and at least two base metals in the period 4 selected from the periodic table of elements as raw material, catalyst is manufactured;
B. nitrobenzene, hydrogen and the catalyst are sent in hydrogenator and carry out catalytic hydrogenation reaction;
C. the outlet effluent of hydrogenator enters polishing reactor and generally stops the lower time, thus new not feeding
Nitrobenzene in the case where, aniline by the nitrobenzene of any residual volume or intermediate is converted by lasting stirring;
D. catalyst pulp is filtered out from the product stream that the polishing reactor is discharged, obtains the product stream of not catalyst;
E. the hydrogenator is returned to using the catalyst pulp filtered out as concentration slurry;
F. reaction water is isolated from the product stream of the not catalyst, obtains crude benzol amine;
G. the reaction water is extracted using nitrobenzene to recycle the aniline wherein dissolved, and to reaction water extracted into
Reaction water is discharged into biological effluent treatment equipment later to recycle nitrobenzene by row stripping;
H. it distills the crude benzol amine and is dissolved in water therein to remove;
I. high-boiling-point impurity is converted by the cyclohexanone by-product in crude benzol amine;
J. the crude benzol amine that distilation steps i is obtained obtains pure aniline and a small amount of high-boiling-point impurity.
2. method according to any one of the preceding claims, which is characterized in that in the step a, with main Aniline Production
The catalyst is manufactured in the individually unit of integration of equipments.
3. method according to any one of the preceding claims, which is characterized in that in the step a, the active carbon is 5 micro-
The acid-washed active carbon of -100 micron ranges of rice.
4. method according to any one of the preceding claims, which is characterized in that in the step b, the hydrogenator is
Tank reactor is sufficiently stirred in CSTR type, the interior recirculation with gas phase to liquid phase.
5. method according to any one of the preceding claims, which is characterized in that the step b further includes being produced using reaction heat
Steam, it is in need that the steam covers the institute in Aniline Production equipment, and exports a large amount of steam to other consumer.
6. method according to any one of the preceding claims, which is characterized in that in the step b, in order to control temperature, by water
The cooling coil being fed in hydrogenator flashes the water by heating after heat exchange and generates steam.
7. method according to any one of the preceding claims, which is characterized in that the step i in individual reactor into
Row converts high-boiling-point impurity for cyclohexanone by-product and making cyclohexanone by-product and aniline reaction.
8. method according to any one of the preceding claims, which is characterized in that in the step j, crude benzol amine is sent to distillation
Tower is distilled, and obtains the pure aniline of final product, and remove a small amount of high-boiling-point impurity in the bottom of destilling tower.
9. method according to any one of the preceding claims, which is characterized in that in the step j, the high-boiling-point impurity is
Tar.
10. method according to any one of the preceding claims, which is characterized in that the step e further include:
Fresh catalyst is supplemented into the hydrogenator to maintain catalytic activity appropriate, thus by essentially all nitre
Base benzene is converted to aniline;Or
Used catalyst is removed so that the catalyst concn inside the hydrogenator is maintained required level.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2018100950801 | 2018-01-31 | ||
CN201810095080 | 2018-01-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110092723A true CN110092723A (en) | 2019-08-06 |
Family
ID=67443542
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810275653.9A Pending CN110092723A (en) | 2018-01-31 | 2018-03-29 | The method of aniline is continuously manufactured by by the catalytic hydrogenation of p-nitrophenyl |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110092723A (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2823235A (en) * | 1955-05-10 | 1958-02-11 | Du Pont | Hydrogenation of nitro compounds to amines and catalyst therefor |
JPS584750A (en) * | 1981-07-02 | 1983-01-11 | Mitsui Toatsu Chem Inc | Preparation of high purity aniline |
CN101205189A (en) * | 2006-12-15 | 2008-06-25 | 住友化学株式会社 | Preparation method of aromatic amine and reaction device |
CN101239916A (en) * | 2008-03-24 | 2008-08-13 | 清华大学 | Aniline post processing system and method |
CN101302166A (en) * | 2007-03-29 | 2008-11-12 | 住友化学株式会社 | Preparation of aromatic amine |
CN105080567A (en) * | 2014-04-22 | 2015-11-25 | 中国科学院长春应用化学研究所 | Catalyst and aromatic amino compound preparation method |
CN106179400A (en) * | 2016-06-30 | 2016-12-07 | 浙江工业大学 | Activated carbon supported type composite metal catalyst and preparation method and application |
-
2018
- 2018-03-29 CN CN201810275653.9A patent/CN110092723A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2823235A (en) * | 1955-05-10 | 1958-02-11 | Du Pont | Hydrogenation of nitro compounds to amines and catalyst therefor |
JPS584750A (en) * | 1981-07-02 | 1983-01-11 | Mitsui Toatsu Chem Inc | Preparation of high purity aniline |
CN101205189A (en) * | 2006-12-15 | 2008-06-25 | 住友化学株式会社 | Preparation method of aromatic amine and reaction device |
CN101302166A (en) * | 2007-03-29 | 2008-11-12 | 住友化学株式会社 | Preparation of aromatic amine |
CN101239916A (en) * | 2008-03-24 | 2008-08-13 | 清华大学 | Aniline post processing system and method |
CN105080567A (en) * | 2014-04-22 | 2015-11-25 | 中国科学院长春应用化学研究所 | Catalyst and aromatic amino compound preparation method |
CN106179400A (en) * | 2016-06-30 | 2016-12-07 | 浙江工业大学 | Activated carbon supported type composite metal catalyst and preparation method and application |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4792626A (en) | Production of aromatic diamino compounds using a modified Raney catalyst | |
CN106164028B (en) | Composite metal catalyst composition and the method and apparatus for being used to prepare 1,4 cyclohexane dimethanol using it | |
CN103228604B (en) | The preparation method of isophorone | |
TWI225854B (en) | Method for producing xylylenediamine | |
CN107428673A (en) | The method for preparing the trimethyl cyclohexylamine of 3 amino methyl 3,5,5 | |
CN106810455B (en) | A kind of production method of high-quality essence hexamethylene diamine | |
TW200930691A (en) | Process for the manufacture of amines by hydrogenation of nitrile compounds | |
JP2002523483A (en) | Method for producing improved hexamethylenediamine | |
US2976320A (en) | Catalytic hydrogenation of the dinitro derivatives of toluene | |
CN106187693B (en) | The cracking of butanol and octanol waste liquid collection and the separation method for adding hydrogen | |
CN107382745B (en) | A kind of method of nitrobenzene continuous liquid phase hydrogenation synthesis aniline | |
CN110092723A (en) | The method of aniline is continuously manufactured by by the catalytic hydrogenation of p-nitrophenyl | |
US9475786B2 (en) | Method for synthesising 2,5-di(hydroxymethyl)furan and 2,5-di(hydroxymethyl)tetrahydrofuran by selective hydrogenation of furan-2,5-dialdehyde | |
JP2001181223A (en) | Method for producing 1, 4-cyclohexanedimethanol | |
CN105461526B (en) | A kind of method that cyclopentanol dehydrogenation prepares cyclopentanone | |
KR101639487B1 (en) | Manufacturing apparatus of trans-1,4-cyclohexanedimethanol for simplifying process | |
JP2009051798A (en) | Production method of hexafluoroisopropanol | |
RU2294920C2 (en) | Two-stage method for hydrogenation of maleic acid to 1,4-butanediol | |
JP4754058B2 (en) | Method for producing isopropyl alcohol | |
KR20160056208A (en) | Method of direct conversion to trans-1,4-cyclohexanedimethanol | |
US6331651B1 (en) | Process for making hexamethylene diamine using ozone-treated adiponitrile that contains phosphorous compounds | |
CN106946819A (en) | Levulic acid is changed into the process for selective of γ valerolactones | |
CN112479824A (en) | Method for recovering crystallization mother liquor in production process of 4-chloro-3, 5-dimethylphenol | |
JPS6147446A (en) | Preparation of aniline | |
US3184513A (en) | Production of hexamethylene glycol |
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: 20190806 |
|
RJ01 | Rejection of invention patent application after publication |