CN101434548A - Method for preparing diaminobenzene from dinitrobenzene - Google Patents
Method for preparing diaminobenzene from dinitrobenzene Download PDFInfo
- Publication number
- CN101434548A CN101434548A CNA2008101745923A CN200810174592A CN101434548A CN 101434548 A CN101434548 A CN 101434548A CN A2008101745923 A CNA2008101745923 A CN A2008101745923A CN 200810174592 A CN200810174592 A CN 200810174592A CN 101434548 A CN101434548 A CN 101434548A
- Authority
- CN
- China
- Prior art keywords
- dinitrobenzene
- reaction
- diaminobenzene
- catalyst
- adds
- 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.)
- Granted
Links
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 20
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 11
- 238000004904 shortening Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000011541 reaction mixture Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 230000001502 supplementing effect Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 11
- 229910000564 Raney nickel Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 150000002828 nitro derivatives Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 amino compound Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing diaminobenzene by using dinitrobenzene, wherein the dinitrobenzene refers to p-dinitrobenzene or m-dinitrobenzene. Adding dinitrobenzene into a reaction kettle, adding ethanol and a supported catalyst, sealing the reaction kettle, completely replacing air in the reaction kettle with hydrogen, keeping the pressure in the kettle at normal pressure, heating and stirring, introducing the hydrogen into the kettle after the temperature reaches 60 ℃, keeping the pressure in the kettle to be 1.0-3.0 MPa, starting hydrogenation reaction, and after about 3-8 hours of hydrogenation, the conversion rate reaches more than 95-99%, then separating out a reaction mixture and the catalyst, returning the separated catalyst to the reaction kettle for continuous use, and supplementing the lost catalyst; and separating reaction products of the reaction mixture, namely the clear solution, so as to obtain the diaminobenzene.
Description
Technical field
The present invention relates to the method for preparing diaminobenzene from dinitro benzene, dinitrobenzene described here is meant paradinitrobenzene, or Meta-dinitrobenzene.
Background technology
Nitro-compound is by being reduced to aminocompound, be method preparation the earliest by iron powder and hydrochloric acid, this method is seriously polluted, expressly provide the operational path that to abolish at no distant date for country, most of in recent years this type of produced and all adopted Raney's nickel catalyst, promptly be that catalyzer passes through shortening and realizes by nitro having following shortcoming to amino conversion but use Raney's nickel catalyst to carry out shortening with the Raney's nickel:
1) uses extremely inconvenience.Because carrying out the Raney's nickel catalyst of shortening, to have active composition be skeleton nickel, but skeleton nickel is very easily caught fire in air, can't preserve, can only be as commodity with nickel-Al alloy powder form, need before the use aluminium to be dissolved away, under the condition of secluding air, add reaction system behind the wash clean with alkali; In addition, the catalytic activity of Raney's nickel often because of treatment condition (as alkali molten with wash conditions) different changing a lot.
Its byproduct of reaction amount is bigger when 2) using Raney's nickel catalyst, and product yield is low.The Raney's nickel catalyst hydrogenation makes nitro be converted into the amino higher temperature that often needs, general temperature requiredly to be higher than 100 ℃, and the product amino compound that hydrogenation generates is being higher than the easy by product (the industrial tar that is referred to as) that generates under 100 ℃ of temperature, this makes product yield reduce on the one hand, also may have influence on reaction on the other hand and normally carry out.
3) the catalyst consumption amount is big.Because the raney ni catalysis activity is low, the catalytic amount of required adding is bigger, and is extremely difficult because of catalyst recovery on the other hand, causes the consumption of catalyzer excessive, causes production cost higher.
4) exist huge potential safety hazard in the production.Because Raney's nickel sees that air easily catches fire, careless slightly in the operation will presence of fire; There is hydrogen in the hydrogenation workshop simultaneously, very easily blasts.
Summary of the invention
The invention provides a kind of prior art deficiency that overcomes, have the method for the preparing diaminobenzene from dinitro benzene of higher-security and higher yields.
Among the present invention, the method of preparing diaminobenzene from dinitro benzene is: add earlier dinitrobenzene, ethanol and loaded catalyst in reactor respectively, wherein the amount of alcohol of Jia Ruing is 10～30% of the dinitrobenzene quality that adds, the nickel catalyst carried amount that adds is 3～6% of the dinitrobenzene quality that adds, carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, after finishing, reaction carries out solid-liquid separation, separated liquid supernatant is carried out the product separation, and isolated solid catalyst is failed back reaction system again and continued to use.
The method that dinitrobenzene shortening of the present invention prepares diaminobenzene can be to change reaction mass over to the insulation jar to be incubated sedimentation after reaction is finished, and isolates supernatant liquor and carries out the product separation, obtains dinitrobenzene; By new dinitrobenzene and the ethanol of aforementioned quantities adding, will from be incubated jar, fail back reactor continuation use again by isolated bottom solidliquid mixture (catalyzer and a small amount of reaction mixture) simultaneously in the reactor.
The method that dinitrobenzene shortening of the present invention prepares diaminobenzene can also be that the supported catalyst dosage that adds is 4% of dinitrobenzene quality, and temperature of reaction is 90 ℃, and the still internal pressure during hydrogenation is 1.5MPa.
Method of the present invention has adopted the load-type nickel hydrogenation catalyst, the aerial kindling temperature of this catalyzer is greater than 150 ℃, because catalyzer of the present invention has carried out purification process with the blended inert gas, make its part be in passive state, therefore it can safe storage, the use that in use can directly feed intake need not to carry out activation treatment again.Through actual measurement, its hydrogenation catalyst starting temperature of catalyzer of the present invention is 60 ℃, and the hydrogenation catalyst temperature of reaction is lower than 100 ℃, and can be used for all kinds of nitro-compound hydrogenation catalysts.Because catalyst temperature of reaction of the present invention is less than 100 ℃, therefore can avoid in reactant, generating polymers such as tar fully, reaction is carried out continuously, test also shows, catalyzer of the present invention can be reused, and this catalyzer consumption in use is lower than existing all kinds of catalyzer, also is lower than 6504K catalyzer and 0104G catalyzer, and its catalytic effect is higher than existing all kinds of catalyzer, therefore has tangible cost advantage.Pressure during shortening of the present invention is also lower, from after chat embodiment as seen, hydrogenation pressure only is 1.5MPa in its optimised process, this pressure obviously will be lower than prior art.In addition, from the present invention as seen, this method can also be simplified whole production technique.
Embodiment
Embodiment: preparing diaminobenzene from dinitro benzene
The dinitrobenzene that in reactor, adds 100 grams earlier, 20% the concentration that adds the dinitrobenzene quality again is 95% ethanol, 3～6% the loaded catalyst that adds the dinitrobenzene quality again, closed reactor, with the air in the complete replacement reaction kettle of hydrogen, keep being in the still normal pressure (being about 0.1MPa) then, and beginning heated and stirred, after reaching 60 ℃, temperature feeds hydrogen in the still, make the still internal pressure remain to 1.0～3.0MPa (test shows that its optimum pressure should be about 1.5MPa), the beginning hydrogenation reaction, temperature in the kettle remains in 60～90 ℃ of scopes in hydrogenation process, hydrogenation after about 3 to 8 hours transformation efficiency promptly reach more than 95～99%, isolate reaction mixture and catalyzer then, isolated catalyzer returns reactor to be continued to use, the catalyzer of replenish loss amount, and test shows that the catalytic amount that at every turn only need add is about 30 milligrams; To reaction mixture, promptly clear liquid carries out the reaction product separation, obtains about 61～64 grams of diaminobenzene.In the present invention, the concrete grammar that is adopted is earlier reaction system to be changed over to sedimentation in the insulation slurry tank to carry out separating of catalyzer and reaction mixture.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding is 4% of the dinitrobenzene quality that adds, and the still internal pressure during hydrogenation is 1.5Mpa, and when temperature of reaction was 90 ℃, transformation efficiency promptly reached more than 99.0% in 4 hours.
The used supported catalyst preparation method of the present invention following (also can be called the Chinese invention patent application of " a kind of method for preparing catalyst and catalyzer that is used for catalytic hydrogenation of nitro compound " about loaded catalyst of the present invention) referring to name:
The used supported catalyst preparation method of the present invention following (also can be called the Chinese invention patent application of " a kind of method for preparing catalyst and catalyzer that is used for catalytic hydrogenation of nitro compound " about loaded catalyst of the present invention) referring to name:
The diatomaceous processing of A
Find according to experiment, very big as the impurity in the diatomite of carrier to the influence of catalyzer, and wherein with the influence of iron for, for effectively removing the iron in the diatomite, generally all adopt acid cleaning process, but find according to relevant test, diatomite is handled and has been adopted following technology that best effect can be arranged, it not only can effectively remove wherein impurity, particularly iron, but also can make catalyst product that best catalytic effect is arranged:
Earlier diatomite is added volume ratio and be its 3 times, concentration is to stir in 3～20% the aqueous hydrochloric acid, continues stirring 1 hour after being warmed up to 90 ℃ again, leach diatomite and wash with water after carry out drying treatment, obtain diatomite as support of the catalyst.
Show after testing, handle resulting diatomite in total hole volume 0.15～0.4ml/g scope through the present invention; Its specific surface area is 120～200m
2/ g.Show that according to test it is 10% best that diatomite is handled used best aqueous hydrochloric acid concentration.
The B Preparation of catalysts
Nickel is made nitrate earlier, be mixed with the aqueous solution of 1M again, the amount of getting nickel is 45～58% a nickel salt aqueous solution of catalyzer final product quality, add the silica aqueous solution that contains silicon-dioxide 20% again, the amount of the silica aqueous solution that is added should guarantee to make silica volume wherein to account for 1～4% of catalyzer final product quality, system is heated to 50～80 ℃, 35～55% of adding catalyzer final product quality diatomite under agitation condition, pH value with system transfers to 7.5～8.5 again, under 50～80 ℃ of conditions, stirred 12～16 hours, carry out solid-liquid separation after the cooling, carrying out granulating and drying after resulting solid washes with water handles, use hydrogen reduction at 500～700 ℃, under cooling conditions, carry out obtaining the catalyzer finished product after the Passivation Treatment with the Air mixing inert gas that contains volume ratio 5% again.
In the above preparation process, nickel is 55% with catalyzer final product quality ratio in the nitrate of used nickel, and system temperature is 60 ℃ in the reaction, and the pH value transfers to 7.8, can obtain the catalyzer of best catalytic effect when the hydrogen reduction temperature is 550 ℃.
The catalyzer actual measurement parameter that obtains through above-mentioned technology is as follows:
(1) nickel content is 45～58% (the best is 55%);
(2) bulk density is 0.6～0.9g/ml (optimum value is 0.75);
(3) total hole volume 0.15～0.4ml/g (optimum value is 0.35);
(4) specific surface area 120～200m
2(optimum value is 160m to/g
2/ g);
(5) nickel crystal size 40～
(optimum value is
);
(6) catch fire in the air 170 ℃ of warm spots
(7) reduction ratio (NiO/NiO) 60～80% (optimum value is 70%).
Catalyzer of the present invention and foreign similar catalyst contrast test data see the following form:
| Catalyzer of the present invention | The Germany Louis product 6504K of that company | The product 0104G of U.S. An Geer company | |
| Nickel content (%) | 55 | 58 | 58 |
| Specific surface area (m 2/g) | 158 | 129 | 109 |
| Total pore volume (ml/g) | 0.36 | 0.36 | 0.35 |
| Bulk density (g/cm 3) | 11.7 | 11.7 | 11.6 |
| Brilliant size (the A of nickel 0) | 55～65 | 55～65 | 55～65 |
| Spontaneous ignition temperature (C 0) | ≥150 | ≥150 | ≥150 |
| The hydrogenation catalyst starting temperature | ≥60 | ≥90 | ≥90 |
Claims (3)
1, the dinitrobenzene shortening prepares the method for diaminobenzene, it is characterized in that in reactor, adding dinitrobenzene, ethanol and loaded catalyst, wherein the amount of alcohol of Jia Ruing is 10～30% of the dinitrobenzene quality that adds, the nickel catalyst carried amount that adds is 3～6% of the dinitrobenzene quality that adds, carried out hydrogenation reaction 3～8 hours at 60～90 ℃, hydrogenation reaction pressure is 1.5～3.0MPa, after finishing, reaction carries out solid-liquid separation, separated liquid supernatant is carried out the product separation, and isolated solid is failed back reaction system again and continued to use.
2, dinitrobenzene shortening according to claim 1 prepares the method for diaminobenzene, it is characterized in that changing reaction mass over to the insulation jar after reaction is finished is incubated sedimentation, isolates supernatant liquor and carries out the product separation, obtains diaminobenzene; The interior aforementioned quantities of pressing of reactor adds new dinitrobenzene and ethanol, will fail back reactor continuation use again by isolated bottom solidliquid mixture from the insulation jar simultaneously.
3, dinitrobenzene shortening according to claim 1 and 2 prepares the method for diaminobenzene, it is characterized in that the supported catalyst dosage that adds is 4% of dinitrobenzene quality, and temperature of reaction is 90 ℃, and the still internal pressure during hydrogenation is 1.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745923A CN101434548B (en) | 2008-11-07 | 2008-11-07 | Method for preparing diaminobenzene from dinitro benzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101745923A CN101434548B (en) | 2008-11-07 | 2008-11-07 | Method for preparing diaminobenzene from dinitro benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101434548A true CN101434548A (en) | 2009-05-20 |
| CN101434548B CN101434548B (en) | 2012-03-21 |
Family
ID=40709202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101745923A Expired - Fee Related CN101434548B (en) | 2008-11-07 | 2008-11-07 | Method for preparing diaminobenzene from dinitro benzene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101434548B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942485A (en) * | 2012-10-25 | 2013-02-27 | 浙江龙盛化工研究有限公司 | Method for m-dinitrobenzene refinement and effective byproduct utilization |
| CN104592036A (en) * | 2014-12-24 | 2015-05-06 | 上海安赐机械设备有限公司 | Nitrobenzene/dinitrobenzene catalyst recovery device and recovery method thereof |
| CN110467534A (en) * | 2019-09-17 | 2019-11-19 | 四川北方红光特种化工有限公司 | A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059432C (en) * | 1996-05-09 | 2000-12-13 | 河南省科学院化学研究所 | Preparation aromatic amine compound |
| CN100441293C (en) * | 2005-09-26 | 2008-12-10 | 天津大学 | Supported nickel catalyst for synthesizing chlora aniline by hydrogenation of chloronitrobenzene and its preparation method thereof |
| CN1850329A (en) * | 2006-05-30 | 2006-10-25 | 华东师范大学 | Load-type nickel-metal catalyst and its use |
-
2008
- 2008-11-07 CN CN2008101745923A patent/CN101434548B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942485A (en) * | 2012-10-25 | 2013-02-27 | 浙江龙盛化工研究有限公司 | Method for m-dinitrobenzene refinement and effective byproduct utilization |
| CN102942485B (en) * | 2012-10-25 | 2014-12-10 | 浙江龙盛化工研究有限公司 | Method for m-dinitrobenzene refinement and effective byproduct utilization |
| CN104592036A (en) * | 2014-12-24 | 2015-05-06 | 上海安赐机械设备有限公司 | Nitrobenzene/dinitrobenzene catalyst recovery device and recovery method thereof |
| CN104592036B (en) * | 2014-12-24 | 2016-10-26 | 上海安赐环保科技股份有限公司 | A kind of Nitrobenzol, dinitro benzene catalyst recovery devices and recovery method thereof |
| CN110467534A (en) * | 2019-09-17 | 2019-11-19 | 四川北方红光特种化工有限公司 | A kind of technique of the solvent-free catalytic hydrogenation synthesis phenylenediamine of dinitrobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101434548B (en) | 2012-03-21 |
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