CN101481314A - Method for preparing X-substituted aniline from X-substituted nitrobenzene - Google Patents
Method for preparing X-substituted aniline from X-substituted nitrobenzene Download PDFInfo
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- CN101481314A CN101481314A CNA2008101742037A CN200810174203A CN101481314A CN 101481314 A CN101481314 A CN 101481314A CN A2008101742037 A CNA2008101742037 A CN A2008101742037A CN 200810174203 A CN200810174203 A CN 200810174203A CN 101481314 A CN101481314 A CN 101481314A
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- oil
- replaces
- mirbane
- reaction
- hydrogenation
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 150000005181 nitrobenzenes Chemical class 0.000 title abstract 3
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000004904 shortening Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- 239000001257 hydrogen Substances 0.000 abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 150000002431 hydrogen Chemical class 0.000 abstract description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 230000009466 transformation Effects 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 11
- 229910000564 Raney nickel Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 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
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process 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
- 235000021050 feed intake Nutrition 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 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
- 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 X-substituted aniline by catalytic hydrogenation of X-substituted nitrobenzene, wherein X can be-F, -Cl, -Br or-OCH3Any one of-OH or-R, wherein R is saturated alkyl with 1 or more carbon, and the position of X in nitrobenzene is ortho-position or meta-position or para-position of nitro, the method comprises the steps of firstly adding X-substituted nitrobenzene into a reaction kettle, then adding ethanol and a supported catalyst, sealing the reaction kettle, completely replacing air in the reaction kettle with hydrogen, then keeping the interior of the kettle at normal pressure, heating and stirring, introducing hydrogen into the kettle after the temperature reaches 60 ℃, keeping the pressure in the kettle at 1.0-3.0 MPa, starting hydrogenation reaction, keeping the temperature in the kettle at 60-90 ℃ in the hydrogenation process, and after about 3-8 hours of hydrogenation, obtaining the conversion rate of 95-99%, and then separating out a reaction mixture and the catalyst.
Description
Technical field
The present invention relates to the method that oil of mirbane shortening that X replaces prepares the aniline that X replaces, the X here can be-F ,-Cl ,-Br ,-OCH
3,-OH or-among the R any, wherein R is the saturated hydrocarbyl of 1 carbon or 1 above carbon, the position of X in oil of mirbane is ortho position or a position or the contraposition of nitro.
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 realizes having following shortcoming by the conversion of nitro to amino but use Raney's nickel catalyst to carry out shortening by 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 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, the oil of mirbane shortening with the X replacement with higher-security and higher yields prepares the method for the aniline of X replacement.
Among the present invention, the method that the oil of mirbane shortening that X replaces prepares the aniline of X replacement is: add earlier the oil of mirbane that X replaces in reactor respectively, ethanol and loaded catalyst, wherein 10～30% of the oil of mirbane quality that replaces for the X that adds of the amount of alcohol of Jia Ruing, 3～6% of the oil of mirbane quality that the nickel catalyst carried amount that adds replaces for the X 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 the oil of mirbane shortening that X of the present invention replaces prepares the aniline of X replacement 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 the aniline that X replaces; The interior aforementioned quantities of pressing of reactor adds oil of mirbane and the ethanol that new X replaces, and will fail back reactor continuation use again by isolated bottom solidliquid mixture (catalyzer and a small amount of reaction back mixture) from the insulation jar simultaneously.
The method that the oil of mirbane shortening that X of the present invention replaces prepares the aniline that X replaces can also be that the supported catalyst dosage that adds is 4% of the oil of mirbane quality that replaces of X, 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 catalytic hydrogenation of nitro compound.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
The aniline that the oil of mirbane preparation-F that embodiment 1:-F replaces replaces, in this example-position of F replacement is the ortho position at nitro.
Oil of mirbane 100 grams that adding-F replaces in reactor earlier, 20% of the oil of mirbane quality of adding-F replacement concentration is 95% ethanol again, 3～6% of the oil of mirbane quality that replaces of adding-F loaded catalyst 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain aniline 75～78 grams that F replaces.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-oil of mirbane quality that F replaces 4%, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
The aniline that the oil of mirbane preparation-Cl that embodiment 2:-Cl replaces replaces, in this example-position that Cl replaces is between nitro.
Oil of mirbane 100 grams that adding-Cl replaces in reactor earlier, 20% of the oil of mirbane quality of adding-Cl replacement concentration is 95% ethanol again, 3～6% of the oil of mirbane quality that replaces of adding-Cl loaded catalyst 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain-aniline 77～80 grams that Cl replaces.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-oil of mirbane quality that Cl replaces 4%, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
The aniline that the oil of mirbane preparation-Br that embodiment 3:-Br replaces replaces, in this example-position of Br replacement is the contraposition at nitro.
Oil of mirbane 100 grams that adding-Br replaces in reactor earlier, 20% of the oil of mirbane quality of adding-Br replacement concentration is 95% ethanol again, 3～6% of the oil of mirbane quality that replaces of adding-Br loaded catalyst 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain-aniline 81～84 grams that Br replaces.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-oil of mirbane quality that Br replaces 4%, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
Embodiment 4:-OCH
3Oil of mirbane preparation-the OCH that replaces
3The aniline that replaces, in this example-OCH
3The position that replaces is the position between nitro.
Adding-the OCH in reactor of elder generation
3Oil of mirbane 100 gram, the adding-OCH again that replace
320% concentration of the oil of mirbane quality that replaces is 95% ethanol, adding-OCH again
33～6% loaded catalyst of the oil of mirbane quality that replaces, 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain-OCH
3Aniline 76～79 grams that replace.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-OCH
34% of the oil of mirbane quality that replaces, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
The aniline that the oil of mirbane preparation-OH that embodiment 5:-OH replaces replaces, in this example-position of OH replacement is the ortho position at nitro.
Oil of mirbane 100 grams that adding-OH replaces in reactor earlier, 20% of the oil of mirbane quality of adding-OH replacement concentration is 95% ethanol again, 3～6% of the oil of mirbane quality that replaces of adding-OH loaded catalyst 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain-aniline 73～76 grams that OH replaces.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-oil of mirbane quality that OH replaces 4%, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
The aniline that the oil of mirbane preparation-OH that embodiment 6:-OH replaces replaces, in this example-position of OH replacement is the contraposition at nitro.
Oil of mirbane 100 grams that adding-OH replaces in reactor earlier, 20% of the oil of mirbane quality of adding-OH replacement concentration is 95% ethanol again, 3～6% of the oil of mirbane quality that replaces of adding-OH loaded catalyst 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain-aniline 73～76 grams that OH replaces.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows, in above-mentioned reaction process, the supported catalyst dosage of adding for add-oil of mirbane quality that OH replaces 4%, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
Embodiment 7:-C
2H
5Oil of mirbane preparation-the C that replaces
2H
5The aniline that replaces, in this example-C
2H
5The position that replaces is the ortho position at nitro.
Adding-the C in reactor of elder generation
2H
5Oil of mirbane 100 gram, the adding-C again that replace
2H
520% concentration of the oil of mirbane quality that replaces is 95% ethanol, adding-C again
2H
53～6% loaded catalyst of the oil of mirbane quality that replaces, 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 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 90 milligrams; To reaction mixture (be clear liquid } carry out reaction product and separate, obtain-C
2H
5Aniline 76～79 grams that replace.In the present invention, the concrete grammar that is adopted is reaction system to be changed over to carry out in the insulation slurry tank separating of catalyzer and reaction mixture earlier.
Test shows that in above-mentioned reaction process, the supported catalyst dosage of adding is what add :-C
2H
54% of the oil of mirbane quality that replaces, the still internal pressure during hydrogenation is 1.5Mpa, when temperature of reaction was 90 ℃, transformation efficiency can reach more than 99.0% in 4 hours.
Relevant experiment also shows, adopts method of the present invention to be used for 1 carbon or oil of mirbane that the stable hydrocarbon more than 1 carbon is replaced carries out shortening, and be used for-F ,-Cl ,-Br ,-OCH
3Or-OH replace and the oil of mirbane of its position in other position of nitro carry out shortening the result similar with aforementioned result all arranged.
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 40～200
(optimum value is 60
(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 |
| The brilliant size (A °) of nickel | 55～65 | 55～65 | 55～65 |
| Spontaneous ignition temperature (C °) | ≥150 | ≥150 | ≥150 |
| The hydrogenation catalyst starting temperature | ≥60 | ≥90 | ≥90 |
Claims (3)
1, the oil of mirbane shortening that replaces of X prepares the method for the aniline that X replaces, and X is-F ,-Cl ,-Br ,-OCH
3-OH, perhaps-among the R any, wherein R is the stable hydrocarbon of 2 carbon or 2 above carbon, the position of X in oil of mirbane is ortho position or a position or the contraposition of nitro, it is characterized in that in reactor, adding the oil of mirbane that X replaces, ethanol and loaded catalyst, wherein 10～30% of the oil of mirbane quality that replaces for the X that adds of the amount of alcohol of Jia Ruing, 3～6% of the oil of mirbane quality that the nickel catalyst carried amount that adds replaces for the X 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, the oil of mirbane shortening of X replacement according to claim 1 prepares the method for the aniline of X replacement, it is characterized in that changing reaction mass over to the insulation jar after reaction is finished is incubated sedimentation, isolate supernatant liquor and carry out the product separation, obtain the aniline that X replaces; Interior oil of mirbane and the ethanol of pressing the new X replacement of aforementioned quantities adding of reactor will be failed back reactor continuation use by isolated bottom solidliquid mixture simultaneously again from the insulation jar.
3, the oil of mirbane shortening of X replacement according to claim 1 and 2 prepares the method for the aniline of X replacement, it is characterized in that the supported catalyst dosage that adds is 4% of the oil of mirbane quality that replaces of X, temperature of reaction is 90 ℃, and the still internal pressure during hydrogenation is 1.5MPa.
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| CN2008101742037A CN101481314B (en) | 2008-11-07 | 2008-11-07 | Method for preparing X substituted aniline from X substituted nitrobenzene |
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| CN101481314B CN101481314B (en) | 2012-05-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333072A (en) * | 2013-07-16 | 2013-10-02 | 如皋市众昌化工有限公司 | Preparation method of 2-ethylaniline |
| CN103351303A (en) * | 2013-07-17 | 2013-10-16 | 临邑县鲁晶化工有限公司 | Continuation method of manufacturing o-Aminoethylbenzene through hydrogenation by o-Nitroethylbenzene |
| CN107118109A (en) * | 2017-06-14 | 2017-09-01 | 浙江解氏新材料股份有限公司 | The preparation method of adjacent fluoroaniline |
| CN116023271A (en) * | 2023-01-13 | 2023-04-28 | 山东国邦药业有限公司 | Synthesis method of p-fluoroaniline |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081818A (en) * | 2007-06-18 | 2007-12-05 | 大连理工大学 | Preparation method for methoxyaniline by highly-selective catalytic hydrogenation of methoxyl nitro compound |
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2008
- 2008-11-07 CN CN2008101742037A patent/CN101481314B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333072A (en) * | 2013-07-16 | 2013-10-02 | 如皋市众昌化工有限公司 | Preparation method of 2-ethylaniline |
| CN103333072B (en) * | 2013-07-16 | 2015-02-04 | 如皋市众昌化工有限公司 | Preparation method of 2-ethylaniline |
| CN103351303A (en) * | 2013-07-17 | 2013-10-16 | 临邑县鲁晶化工有限公司 | Continuation method of manufacturing o-Aminoethylbenzene through hydrogenation by o-Nitroethylbenzene |
| CN107118109A (en) * | 2017-06-14 | 2017-09-01 | 浙江解氏新材料股份有限公司 | The preparation method of adjacent fluoroaniline |
| CN116023271A (en) * | 2023-01-13 | 2023-04-28 | 山东国邦药业有限公司 | Synthesis method of p-fluoroaniline |
| CN116023271B (en) * | 2023-01-13 | 2023-06-20 | 山东国邦药业有限公司 | Synthesis method of p-fluoroaniline |
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| CN101481314B (en) | 2012-05-23 |
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