CN102531912B - Preparation method of N-alkyl arylamine - Google Patents
Preparation method of N-alkyl arylamine Download PDFInfo
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- CN102531912B CN102531912B CN 201110459653 CN201110459653A CN102531912B CN 102531912 B CN102531912 B CN 102531912B CN 201110459653 CN201110459653 CN 201110459653 CN 201110459653 A CN201110459653 A CN 201110459653A CN 102531912 B CN102531912 B CN 102531912B
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Abstract
The invention discloses a preparation method of N-alkyl arylamine. The preparation method comprises the following steps of: mixing an aromatic nitro compound and fatty alcohol with 1-6 carbon atoms with water to obtain a mixed solution; completely reacting in a fixed bed reactor under the action of a PtSn/Al2O3 catalyst at the pressure of 180 DEG C and under the pressure condition of 2.0 MPa; andperforming post-treatment on a reaction liquid to obtain N-alkyl arylamine. The defect of the need of externally adding hydrogen in the prior art is overcome, the production safety is enhanced, and production steps are simplified, so that the method has the characteristics of easiness and convenience for operating, simple process flow, low equipment requirement, increase in production efficiency,reduction in production cost and avoidance of equipment corrosion and environmental pollution; moreover, a catalyst prepared with the method has higher catalyzing performance than a catalyst preparedwith the conventional immersion method; and in particular, the stability of the catalyst is enhanced greatly.
Description
(1) technical field
The present invention relates to a kind of preparation method of N-alkylarylamine, particularly a kind of method that is prepared the N-alkylarylamine by aromatic nitro compound single stage method in fixed-bed reactor.
(2) background technology
The N-arylalkylamine compound is organic raw material and the organic reaction intermediate of using always as the important derivatives of arylamine, is widely used in aspects such as dyestuff, pigment, medicine, agricultural chemicals.The synthetic method of N-alkylarylamine generally is that the corresponding aromatic nitro compound of employing is raw material, through obtaining arylamine after the reduction, carries out alkylated reaction with alkylating reagent in the presence of catalyzer more then after separating, and obtains the N-alkylarylamine at last.The alkylating reagent that the arylamine alkylated reaction is commonly used has three kinds: be the substituted alkylated of alkylating reagent with alcohol, halogenated alkane and ester class; Be the condensating reductive alkylation of reagent with aldehyde and ketone; Be the addition alkylation of alkylating reagent with acrylic acid derivative, epoxy compounds etc.Wherein, halogenated alkane and ester class are alkylating reagent, the reaction conditions gentleness, and therefore monoalkylation reagent price height, and environment polluted, is that the substituted alkylated of alkylating reagent is most widely used alkylation process with alcohol under catalyst action.
Chinese patent CN101792393A has reported that Taiyuan chemical inc He Fenxia etc. is in fixed-bed reactor, arylamine and alkylating reagent fatty alcohol mixture are fed in the reactor that the catalyzer that activating and reducing crosses is housed, and the space-time speed of liquid is 0.35～1.25/ hour
-1, under normal pressure, temperature of reaction is 100～400 ℃ and carries out alkylated reaction, is neutralized to the pH value by alkali lye and is 6-8, underpressure distillation makes the N-alkylarylamine behind the standing demix.Chinese patent CN1127748A has reported Wu Zu Wang of Dalian University of Technology etc. in autoclave, adds the nitro thing simultaneously, and hydrogenation catalyst and alkylating reagent Fatty Alcohol(C12-C14 and C12-C18) are 0.5～4.0MPa at hydrogen pressure, and the hydrogenation reaction temperature is 50～150 ℃.0.5～3.0 hour reaction times, after becoming arylamine, do not separate nitro thing hydrogenating reduction, continue 50～150 ℃ of temperature, pressure 0.2～3.0MPa, the reaction times is that the alkylated reaction that carries out arylamine under 10～30 hours makes the N-alkylarylamine.Chinese patent CN1814582A has reported Lee of Zhejiang Polytechnical University off year etc. in autoclave, the mixing liquid of 1 part of aromatic nitro compound of quality and 1.8 parts of C1 of quality～C2 Fatty Alcohol(C12-C14 and C12-C18) is joined in the reactor, the Raney's nickel catalyst that adds the quality 15% that feeds intake, 80～250 ℃ of temperature of reaction, isothermal reaction is 20 hours under reaction pressure 1.0～4.0MPa, obtains the N-alkylarylamine after removing by filter catalyzer and excess ethanol.Simultaneously in fixed-bed reactor, the mixing liquid of the aromatic nitro compound of 1 part of quality and the C1 of 12 parts of quality～C2 Fatty Alcohol(C12-C14 and C12-C18) is joined in the reaction tubes that Raney's nickel catalyst is housed the space-time speed of mixing liquid 1.0 hours
-1, 80～250 ℃ of temperature of reaction, under reaction pressure 1.0～4.0MPa, obtaining product liquid through gas-liquid separation after the reaction, product liquid is removed excess fats alcohol and is namely obtained the N-alkylarylamine.
The two-step reaction that becomes reducing aromatic nitro compound arylamine and arylamine alkylation to generate the N-alkylamine in autoclave of existing report is combined into the technology in a step, needing the outside that hydrogen is provided is arylamine with reducing aromatic nitro compound, thereby hydrogen producer or added hydrogen need be provided, there is potential safety hazard.Prepare the technology of N-alkylarylamine with the aromatic nitro compound single stage method, though do not need directly to use added hydrogen, exist reactions steps many, need shortcomings such as separating catalyst and reaction product.Adopting arylamine in fixed-bed reactor is that initial feed is directly carried out the N-alkylated reaction or is the synthetic alkylating technology of N-of raw material single stage method with the aromatic nitro compound.Though do not need filtering catalyst, all exist reaction efficiency low, reaction is to shortcomings such as equipment requirements height.
(3) summary of the invention
The object of the invention provides that a kind of operating process is simple, reaction efficiency is high, do not need to use add hydrogen source prepare the method for N-alkylarylamine as the raw material single stage method with aromatic nitro compound.
The technical solution used in the present invention is:
A kind of preparation method of N-alkylarylamine, described method is: (1) is mixed and made into mixed solution with aromatic nitro compound and C1～C6 Fatty Alcohol(C12-C14 and C12-C18) and water, at PtSn/Al
2O
3Under the effect of catalyzer, at 180 ℃, under the pressure condition of 2.0MPa, after reacting completely in fixed-bed reactor, the reaction solution aftertreatment makes the N-alkylarylamine; Described aromatic nitro compound is one of following: oil of mirbane, ortho-methylnitrobenzene, meta-methylnitrobenzene, para-methylnitrobenzene, O-methoxy oil of mirbane, to methoxy nitrobenzene, parachloronitrobenzene, 3,4-dichloronitrobenzene or 3-chloro-4-fluoronitrobenzene; The mass ratio of described aromatic nitro compound and fatty alcohol and water is 1: 875～1187.5: 62.5～375, and the liquid hourly space velocity rate of described mixed solution is 7.5 hours
-1, etching speed is the volume feeding rate of aromatic nitro compound and the ratio of the stacking volume of described catalyzer in reactor during described liquid; The quality consumption of described catalyzer is according to the hourly space velocity calibration; Described PtSn/Al
2O
3Catalyzer prepares as follows: 1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; Carrier is added 0.69～1.73g/mlSnCl
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
3Described SnCl
22H
2O aqueous solution volumetric usage is counted 3.3ml/g with the carrier quality, and the loading of Sn counts 0.19～0.58% with the carrier quality; 2. dibenzalacetone, sodium acetate and ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 0.12g/ml K
2PtCl
4The aqueous solution was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
3Described dibenzalacetone, sodium acetate, ethanol and K
2PtCl
4K in the aqueous solution
2PtCl
4The amount of substance ratio is 0.3: 1: 50: 1; 3. with precursor Pt
2(dba)
3Add in the carbonate propanediol ester solution, reacted 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature, obtaining reaction solution is the Pt nanoparticles solution; The volumetric usage of described carbonate propanediol ester solution is with precursor Pt
2(dba)
3Quality is counted 1428～2857ml/g; 4. the Sn/Al that 1. step is made
2O
3Mix with the Pt nanoparticles solution that 3. step obtains, stir under the electric power stirring action and spend the night, filter, filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer (also can be expressed as Pt
3Sn/Al
2O
3); The volumetric usage of described Pt nanoparticles solution is with Sn/Al
2O
3Quality is counted 40ml/g; The loading of Pt counts 0.5～1% with the carrier quality in the described catalyzer, and the loading of Sn counts 0.19～0.58% with the carrier quality in the described catalyzer.
Described C1～C6 Fatty Alcohol(C12-C14 and C12-C18) is preferably methyl alcohol, ethanol, Virahol or hexalin, more preferably ethanol.
Described reaction solution post-treating method is: after reaction finishes, the product collection of fixed-bed reactor outlet gets up, adopt Rotary Evaporators to steam the excess ethanol aqueous solution, the solid that obtains is crossed post with 200-300 order silicagel column, adopt ether: the ethyl acetate volume ratio be 15: 1 as elutriant, namely obtain described N-alkylarylamine.
Further, preferred described catalyzer prepares as follows: 1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The SnCl that carrier 3g is added 10ml 1.16mg/ml
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
33g; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
384mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature (20 ℃), and obtaining reaction solution is Pt nanoparticles solution 120ml; 4. the Sn/Al that 1. step is made
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer 3g; The loading of Pt counts 1% with the carrier quality in the described catalyzer, and the loading of Sn counts 0.39% with the carrier quality in the catalyzer.
PtSn/Al of the present invention
2O
3In the catalyzer, the loading of Pt calculates as follows: according to precursor Pt
2(dba)
3The content Sn/Al of Mass Calculation Pt
2O
3With the filtrate clarification of gained after the Pt nanoparticles solution hybrid reaction, the light absorption value with Pt in the ultraviolet spectrophotometry detection filtrate according to Pt content in the quantitative filtrate of Pt typical curve absorption curve, further draws PtSn/Al
2O
3The loading of Pt in the catalyzer.
Pt content detects as follows in the described filtrate: 1. weighing 0.970g H
2PtCl
6Pt6H
2O is made into the 100ml aqueous solution, get the above-mentioned solution of 14ml and put into the 1000ml volumetric flask, drip the concentrated hydrochloric acid of one times of dilution to scale marks, distribute get 2,4,6,8,10,12, this solution of 14ml adds in the 100ml volumetric flask, to scale, in each volumetric flask, add the saturated SnCl of 2ml with distilled water diluting
2Solution is surveyed its absorbancy respectively at the 403nm place, the data drafting pattern with recording namely obtains the Pt typical curve.2. get 10ml filtrate in the 100ml volumetric flask, add the hydrochloric acid of one times of 5ml dilution, use the distilled water constant volume, survey it in 403nm place absorbancy, namely know the content of contained Pt in the filtrate according to the Pt typical curve.
The present invention is raw material with the mixture of aromatic nitro compound and Fatty Alcohol(C12-C14 and C12-C18) alkylating reagent, with this mixture and water at PtSn/Al
2O
3Under the effect of catalyzer, at 180 ℃, under the pressure of 2.0MPa, in fixed-bed reactor, take place finally to make the N-alkylarylamine by the N-alkylated reaction of Fatty Alcohol(C12-C14 and C12-C18)/water hydrogen production reaction, aromatic nitro compound hydrogenation reaction and arylamine.
In reaction of the present invention, Fatty Alcohol(C12-C14 and C12-C18) be solvent, again be the hydrogen donor of aromatic nitro compound hydrogenating reduction, also be the alkylating alkylating reagent of arylamine.PtSn/Al
2O
3Catalyzer is the catalyzer of fatty alcohol aqueous solution reformation hydrogen production, is again the catalyzer of aromatic nitro compound hydrogenating reduction, also is the catalyzer of arylamine alkylated reaction.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: overcome the shortcoming that prior art needs added hydrogen, improved the security of producing, and the approach of a preparation N-alkylarylamine is provided for the enterprise that does not have hydrogen producer.The arylamine that makes through aromatic nitro compound does not need separation directly to finish the N-alkylated reaction in same reactor, has simplified production stage.Therefore, another characteristics of present method be easy and simple to handle, technical process is simple, and is low for equipment requirements, improved production efficiency, reduce production costs, and can not cause equipment corrosion and environmental pollution.Adopt the catalyzer of absorption method preparation, simple to operate, do not need through H
2Reduction process, and improved catalyst performance, especially the stability of catalyzer is improved greatly.
(4) embodiment
The PtSn/Al that Fig. 1 embodiment 7 is prepared
2O
3TEM figure;
Fig. 2 embodiment 7 product analysis gas chromatograms;
Fig. 3 embodiment 14 product analysis gas chromatograms;
Fig. 4 Pt typical curve.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1 absorption method prepares PtSn/Al
2O
3Catalyzer
1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The SnCl that carrier 3g is added 10ml 1.16mg/ml
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
33g; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
384mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature (20 ℃), and obtaining reaction solution is Pt nanoparticles solution 120ml; 4. the Sn/Al that 1. step is made
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer 3g; The filtrate clarification that obtains, get 10ml filtrate in the 100ml volumetric flask, add the hydrochloric acid of one times of 5ml dilution, use the distilled water constant volume, survey it in the absorbancy at 403nm place, according to the Pt typical curve, shown in Figure 4, the result does not detect filtrate and contains Pt, illustrates that Pt all is adsorbed on the carrier, the loading of Pt counts 1% with the carrier quality in the described catalyzer, and the loading of Sn counts 0.39% with the carrier quality in the described catalyzer.
Embodiment 2 preparation PtSn/Al
2O
3Catalyzer
1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The SnCl that carrier 3g is added 10ml 0.58mg/ml
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
33g; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
342mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature (20 ℃), and obtaining reaction solution is Pt nanoparticles solution 120ml; 4. the Sn/Al that 1. step is made
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer 3g; The loading of Pt counts 0.5% to calcine back carrier quality in the described catalyzer, and the loading of Sn counts 0.19% with the carrier quality in the described catalyzer.
Embodiment 3 preparation PtSn/Al
2O
3Catalyzer
1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The SnCl that carrier 3g is added 10ml 1.73mg/ml
22H
2Among the O, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
33g; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
384mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature, and obtaining reaction solution is Pt nanoparticles solution 120ml; 4. the Sn/Al that 1. step is made
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer 3g; The loading of Pt counts 1% with the carrier quality in the described catalyzer, and the loading of Sn counts 0.57% with the carrier quality in the described catalyzer.
Embodiment 4Pt/Al
2O
3Preparation of catalysts
1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
384mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature, obtains Pt nanoparticles solution 120ml; 4. the carrier A l after 1. step being calcined
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires Pt/Al
2O
3Catalyzer 3g; The loading of Pt in the described catalyzer (measuring method is with embodiment 1) counts 1% with the carrier quality, and the loading of Sn counts 0% with the carrier quality in the described catalyzer.
Embodiment 5 preparation PtSn/Al
2O
3Catalyzer
1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The SnCl that carrier 3g is added 10ml 0.69mg/ml
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
33g; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
384mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature, obtains Pt nanoparticles solution 120ml; 4. the Sn/Al that 1. step is made
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer 3g; The loading of Pt in the described catalyzer (measuring method is with embodiment 1) counts 1% with the carrier quality, and the loading of Sn counts 0.23% with the carrier quality in the described catalyzer.
Embodiment 6 immersion process for preparing PtSn/Al
2O
3Catalyzer
1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The H that carrier 3g is added 4.2ml 0.02g/ml
2PtCl
66H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcining is 3 hours under 350 ℃ of nitrogen protections, uses the nitrogen replacement air more then, uses hydrogen reducing 2h down at 250 ℃, obtains Pt/Al
2O
33g; 2. the Pt/Al that 1. step is made
2O
33g adds 10ml 1.16mg/ml SnCl
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcining is 3 hours under 350 ℃ of nitrogen protections, uses the nitrogen replacement air more then, uses hydrogen reducing 2h down at 250 ℃, obtains PtSn/Al
2O
3Catalyzer 3g, the loading of Pt counts 1% with the carrier quality in the described catalyzer, and the loading of Sn counts 0.39% with the carrier quality in the described catalyzer.
Embodiment 7
The PtSn/Al that in the fixed bed stainless steel reactor of 50cm * 0.52cm, adds the preparation of embodiment 1 method
2O
3Catalyzer 3g is that 1: 1187.5: 62.5 mixing liquid joins in the reactor with the input speed of 1.0ml/min with mass ratio with oil of mirbane, second alcohol and water, and the liquid hourly space velocity rate of mixed solution is 7.5 hours
-1, adjusting temperature of reaction is 180 ℃, reaction pressure is 2.0MPa, use gas chromatographic analysis behind the product of reactor outlet, adopt fid detector, SE-30 capillary chromatographic column, column temperature are 180 ℃, detector is 260 ℃, sampler is that 250 ℃ of each components contents are: the selectivity 9.0% of N-ethylaniline, N, the selectivity 89.2% of N-Diethyl Aniline, other by products 1.5%, oil of mirbane and aniline content are 0.Be 550 hours the steady time of catalyzer, catalyzer steady time for the reactor of packing into from catalyzer to this section of catalyst deactivation reaction times.Wherein the transformation efficiency of oil of mirbane is lower than 80% and is considered as catalyst deactivation.
The mixing liquid that with oil of mirbane, ethanol and the aqueous solution with mass ratio is 1: 1125: 125 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 44.1% of N-ethylaniline, N, the selectivity 47.8% of N-Diethyl Aniline, other by products 6.4%, aniline content are 1.7%, and nitrobenzene is 0.
Embodiment 9
The mixing liquid that with oil of mirbane, second alcohol and water with mass ratio is 1: 1000: 250 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 33.9% of N-ethylaniline, N, the selectivity 63.5% of N-Diethyl Aniline, other by products 2.3%, aniline content are 0.4%, and nitrobenzene is 0.
Embodiment 10
The mixing liquid that with oil of mirbane, ethanol and the aqueous solution with mass ratio is 1: 875: 375 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 42.5% of N-ethylaniline, N, the selectivity 44.6% of N-Diethyl Aniline, other by products 12%, aniline content are 0.9%, and nitrobenzene is 0.
Embodiment 11
The Pt/Al that in the fixed bed stainless steel reactor of 50cm * 0.52cm, adds the preparation of embodiment 4 methods
2O
3Catalyzer 3g, the mixing liquid that with oil of mirbane, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 0 of N-ethylaniline, N, the selectivity 24.7% of N-Diethyl Aniline, other by products 29.4%, aniline content is 45.9%, and nitrobenzene is 0.Be 20 hours the steady time of catalyzer.
Embodiment 12
The PtSn/Al that in the fixed bed stainless steel reactor of 50cm * 0.52cm, adds the preparation of embodiment 6 methods
2O
3Catalyzer 3g, the mixing liquid that with oil of mirbane, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 30.1% of N-ethylaniline, N, the selectivity 63.1% of N-Diethyl Aniline, other by products 4.5%, aniline content is 2.3%, and nitrobenzene is 0.Be 95 hours the steady time of catalyzer.Comparative example 7 as can be known, to the product selectivity height, and the stability of catalyzer more has superiority method of the present invention than traditional catalyst prepared.
Embodiment 13
The mixing liquid that with ortho-methylnitrobenzene, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 58.4% of N-ethyl Ortho Toluidine, N, the selectivity 34.9% of N-diethyl-o-toluidine, other by products 3.5%, the content of Ortho Toluidine are 3.2%, and ortho-methylnitrobenzene content is 0.
Embodiment 14
The mixing liquid that with meta-methylnitrobenzene, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 21.0% of N-ethyl-m-toluidine, N, the selectivity 75.0% of N-diethyl-m-toluidine, other by products 2.9%, the content of meta-aminotoluene are 0.1%, and meta-methylnitrobenzene content is 0.
Embodiment 15
The mixing liquid that with para-methylnitrobenzene, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 7.8% of N-ethyl-p-toluidiine, N, the selectivity 89.2% of N-diethyl-p-tlouidine, other by products 3.9%, the content of para-totuidine are 0.1%, and para-methylnitrobenzene content is 0.
Embodiment 16
The mixing liquid that with O-methoxy oil of mirbane, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 33.1% of N-ethyl ORTHO ANISIDINE, N, the selectivity 64.7% of N-diethyl ORTHO ANISIDINE, other by products 2.0%, the content of ORTHO ANISIDINE are 0.2%, and the O-methoxy nitrobenzene is 0.
Embodiment 17
To be that 1: 1187.5: 62.5 mixing liquid joins in the reactor with the input speed of 1.0ml/min with mass ratio to methoxy nitrobenzene, second alcohol and water, other operations are with embodiment 7, the selectivity 17.7% of N-ethyl P-nethoxyaniline, N, the selectivity 79.9% of N-diethyl P-nethoxyaniline, other by products 1.9%, the content of P-nethoxyaniline are 0.5%, are 0 to methoxy nitrobenzene content.
Embodiment 18
The mixing liquid that with parachloronitrobenzene, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 36.6% of N-ethyl p-Chlorobenzoic acid amide, N, the selectivity 52.3% of N-diethyl p-Chlorobenzoic acid amide, other by products 9.3%, the content of p-Chlorobenzoic acid amide are 1.8%, and parachloronitrobenzene content is 0.
Embodiment 19
The mixing liquid that with 3-chloro-4-fluoronitrobenzene, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 9.9% of N-ethyl-3-chloro-4-fluoroaniline, N, the selectivity 86.6% of N-diethyl-3-chloro-4-fluoroaniline, other by products 2.7%, the content of 3-chloro-4-fluoroaniline are that 0.8%, 3-chloro-4-fluoronitrobenzene content is 0.
The mixing liquid that with 3,4-dichloronitrobenzene, second alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, and other are operated with embodiment 7, N-ethyl-3, the selectivity 16.8% of 4-dichlorphenamide bulk powder, N, N-diethyl-3, the selectivity 77.8% of 4-dichlorphenamide bulk powder, other by products 2.6%, 3, the content of 4-dichlorphenamide bulk powder are 2.8%, 3,4-dichloronitrobenzene content is 0.
Embodiment 21
The mixing liquid that with oil of mirbane, first alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 25.1% of methylphenylamine, N, the selectivity 60.4% of accelerine, other by products 6.1%, aniline content are 8.4%, and nitrobenzene is 0.
Embodiment 22
The mixing liquid that with oil of mirbane, isopropyl alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 1.5% of N-isopropyl aniline, N, the selectivity 72.6% of N-diisopropyl aniline, other by products 3.5%, aniline content are 22.4%, and nitrobenzene is 0.
Embodiment 23
The mixing liquid that with oil of mirbane, hexamethylene alcohol and water with mass ratio is 1: 1187.5: 62.5 joins in the reactor with the input speed of 1.0ml/min, other operations are with embodiment 7, the selectivity 2.7% of N-cyclohexyl aniline, N, the selectivity 69.9% of N-dicyclohexyl aniline, other by products 10.8%, aniline content are 16.6%, and nitrobenzene is 0.
Claims (4)
1. the preparation method of a N-alkylarylamine is characterized in that described method is: aromatic nitro compound and C1～C6 Fatty Alcohol(C12-C14 and C12-C18) and water are mixed and made into mixed solution, at PtSn/Al
2O
3Under the effect of catalyzer, at 180 ℃, under the pressure condition of 2.0MPa, after reacting completely in fixed-bed reactor, the reaction solution aftertreatment makes the N-alkylarylamine; Described aromatic nitro compound is one of following: oil of mirbane, ortho-methylnitrobenzene, meta-methylnitrobenzene, para-methylnitrobenzene, O-methoxy oil of mirbane, to methoxy nitrobenzene, parachloronitrobenzene, 3,4-dichloronitrobenzene or 3-chloro-4-fluoronitrobenzene; The mass ratio of described aromatic nitro compound and fatty alcohol and water is 1:875～1187.5:62.5～375, and the liquid hourly space velocity rate of described mixed solution is 7.5 hours
-1, the ratio of the volume feeding rate that described liquid hourly space velocity rate is aromatic nitro compound and the stacking volume of described catalyzer in reactor; Described PtSn/Al
2O
3Catalyzer prepares as follows: 1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; Carrier is added 0.69～1.73mg/ml SnCl
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
3Described SnCl
22H
2O aqueous solution volumetric usage is counted 3.3ml/g with the carrier quality; 2. every preparation 1.5g precursor Pt
2(dba)
3Method be: 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
3Add in the carbonate propanediol ester solution, reacted 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature, obtaining reaction solution is the Pt nanoparticles solution; The volumetric usage of described carbonate propanediol ester solution is with precursor Pt
2(dba)
3Quality is counted 1428～2857ml/g; 4. the Sn/Al that 1. step is made
2O
3Mix with the Pt nanoparticles solution that 3. step obtains, stir under the electric power stirring action and spend the night, filter, filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer; The volumetric usage of described Pt nanoparticles solution is with Sn/Al
2O
3Quality is counted 40ml/g.
2. the preparation method of N-alkylarylamine as claimed in claim 1 is characterized in that described C1～C6 Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol, ethanol, Virahol or hexalin.
3. the preparation method of N-alkylarylamine as claimed in claim 1, it is characterized in that described reaction solution post-treating method is: after reaction finishes, the product collection of fixed-bed reactor outlet gets up, adopt Rotary Evaporators to steam the excess ethanol aqueous solution, the enriched material that obtains is crossed post with 200-300 order silicagel column, adopt ether: the ethyl acetate volume ratio be 15:1 as elutriant, namely obtain described N-alkylarylamine; Described C1～C6 Fatty Alcohol(C12-C14 and C12-C18) is ethanol.
4. the preparation method of N-alkylarylamine as claimed in claim 1 is characterized in that described catalyzer prepares as follows: 1. with γ-Al
2O
3Place 500 ℃ to calcine 3 hours down, obtain carrier; The SnCl that carrier 3g is added 10ml1.16mg/ml
22H
2In the O aqueous solution, magnetic agitation 1 hour, dipping spends the night, and at 60 ℃ stirred in water bath evaporate to dryness, calcines 3 hours down in 350 ℃ then, obtains Sn/Al
2O
33g; 2. 2.36g dibenzalacetone, 2.8g sodium acetate and 60ml ethanol are mixed, 50 ℃ of following stirring and dissolving, add mass concentration 10%K
2PtCl
4Aqueous solution 12ml was heated to 90 ℃ of following back flow reaction 2 hours, stopped heating, stirred and was cooled to room temperature, and standing over night is filtered, and the filter cake distilled water wash cleans with Skellysolve A again, filters again, and filter cake is precursor Pt
2(dba)
31.5g; 3. with precursor Pt
2(dba)
384mg adds 120ml carbonate propanediol ester solution, reacts 2 hours in stainless steel cauldron under 1500rad/min, 4.0MPa, room temperature, and obtaining reaction solution is Pt nanoparticles solution 120ml; 4. the Sn/Al that 1. step is made
2O
33g mixes with the Pt nanoparticles solution 120ml that 3. step obtains, and stirs under the electric power stirring action and spends the night, and filters, and filter cake cleans back drying for several times with acetone, acquires PtSn/Al
2O
3Catalyzer 3g.
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| CN115894259A (en) * | 2022-12-12 | 2023-04-04 | 浙江工业大学 | Continuous production process of N- (2-propoxyethyl) -2,6-diethylaniline |
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| CN1127748A (en) * | 1995-12-18 | 1996-07-31 | 大连理工大学 | Preparation of N-monoalkyl arylamine by nitro-compound reduction-alkylation |
| CN1814582A (en) * | 2006-02-24 | 2006-08-09 | 浙江工业大学 | One-step method for preparing N-alkyl aromatic amine from aromatic nitro substance |
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| CN1127748A (en) * | 1995-12-18 | 1996-07-31 | 大连理工大学 | Preparation of N-monoalkyl arylamine by nitro-compound reduction-alkylation |
| CN1814582A (en) * | 2006-02-24 | 2006-08-09 | 浙江工业大学 | One-step method for preparing N-alkyl aromatic amine from aromatic nitro substance |
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