CN105272863A - Preparation method for p-anisidine - Google Patents
Preparation method for p-anisidine Download PDFInfo
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- CN105272863A CN105272863A CN201510314205.1A CN201510314205A CN105272863A CN 105272863 A CN105272863 A CN 105272863A CN 201510314205 A CN201510314205 A CN 201510314205A CN 105272863 A CN105272863 A CN 105272863A
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Abstract
The invention relates to a preparation method for p-anisidine. In the presence of a ternary amorphous alloy catalyst being Ni-Mo-B or Ni-Co-P, liquid-phase p-nitroanisole is subjected to hydrogenation through intermittent hydrogenation, and therefore p-anisidine with a selectivity of more than 99.7% can be obtained. In the preparation method, reaction conditions are mild, the solvent and the catalyst can be recycled, and the preparation method is liable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of Para-Anisidine.
Background technology
Para-Anisidine, also can be described as P-nethoxyaniline, is the intermediate of important dyestuff, medicine and spices.Compared with Ortho Anisidine, the application of Para-Anisidine in dyestuffs industries is more extensive.Such as, in dyestuffs industries, Para-Anisidine is used to synthesize blue look salt VB, purplish red base GP, azoic coupling component AS-SG, AS-RL, vat scarlet.In addition, utilize Para-Anisidine can synthesize 2-amino-4-acetyl-anisidine, the latter is the important source material of dispersed dye, can be used for synthesizing a series of dispersed dye further, as C.I. dispersion blue 79,139,226,265,301,63 ,DIS,PER,SE ,Vio,let, 63 58, Disperse Navy Blue S-2GL etc.In medicine industry, Para-Anisidine is mainly used in synthesis Quinacrime, uncle quinoline, INDOMETHACIN etc., and wherein INDOMETHACIN is the kind that Para-Anisidine consumption is larger.
At the beginning of phase late 1980s, some main Para-Anisidine manufacturing enterprises of West Europe and Japan and other countries close its production equipment in succession.And in contrast, along with the emergence of China's dyestuffs industries, Para-Anisidine capacity and output increases fast, China has become global Para-Anisidine major country of production and supply country, have thousands of tons of Para-Anisidine products export every year, China's Para-Anisidine output accounts for about 80% of global ultimate production.
In traditional industrial process, domestic manufacturer mostly is employing " chemical reduction method ", namely using iron powder or sodium sulphite as reductive agent, is carried out reducing by p-Nitromethoxybenzene and prepares Para-Anisidine.But this technique also exists and consumes the shortcomings such as large, cost is high, of poor quality, especially greatly, cause serious environmental pollution, the developing direction of the green chemical industry advocated with China is runed counter to for waste water, waste sludge discharge amount.If process waste water, waste residue, not only increasing considerably cost, also likely causing secondary pollution because dealing with improperly.
In order to reduce pollution, improve productive rate and quality product, each study group has carried out the research of each side to the preparation of Para-Anisidine and has found, Para-Anisidine is prepared with " shortening method ", by product is water, and environmentally friendly, yield is high, good product quality is the ideal technology of substituted chemistry reduction method.
Disclose a kind of with the method for shortening legal system for p-Nitromethoxybenzene in Chinese patent CN1861570.The method take methyl alcohol as solvent, with nitrobenzoyl ether mixture for raw material, utilizes Raney-Ni or Pd-C for catalyzer, passes into hydrogen and carry out catalytic hydrogenating reduction reaction, in time no longer consuming hydrogen, terminate catalytic hydrogenation reaction; Reclaim catalyzer from reaction mixture after, separate oil phase through Liquid liquid Separation, and recrystallization, to obtain required Para-Anisidine.The method is a kind of process for cleanly preparing, little to equipment corrosion, can decreasing pollution.But, this method is reacted for standard terminates catalytic hydrogenating reduction with " no longer consuming hydrogen ", therefore be not very accurate to the terminal point control of reaction, thus be difficult to high yield and highly selective prepares Para-Anisidine, catalytic hydrogenation per pass conversion is only 85%, and the purity of target product is only 98%.
The people such as X.Xi are at document 1:Palladiumcomplexofpoly (4-vinylpyridine-co-acrylicacid) forhomogeneoushydrogenationofaromaticnitrocompounds, JMolCatal, 2003,192:1-7; The people such as S.Xu are at document 2:Ahomogeneouscatalystmadeofpoly (4-vinylpyridine-co-N-vinylpyrrolidone)-Pd (0) complexforhydrogenationofaromaticnitrocompounds.JMolCata l, 2000, in 160:287-292, all report with palladium base homogeneous catalyst at 0.1MPa, temperature of reaction prepares Para-Anisidine lower than under the condition of 50 DEG C, but this catalyst separating difficulty, cost is high, not easily industrialization.
F.Zhao is at document 3:Hydrogenationofnitrocompoundswithsupportedplatinumcata lystinsupercriticalcarbondioxide.CatalToday, 2004, report in 98:523-528 and prepare Para-Anisidine with Pt/C catalysis hydrogen in supercritical co of w (Pt)=5%, reaction pressure is more than 8MPa, facility investment is high, not easily promotes.
Zhao Lin is at document 4: " Synthesis of P-Aminophenol Methyl Ether by Catalytic Hydrogenation ", Henan science, in June, 2006, the 24th volume the 3rd phase, in 345-346 page, the ammonia synthesis gas disclosing a kind of synthesis ammonia plant replaces pure hydrogen to carry out catalytic reduction p-Nitromethoxybenzene to prepare the method for Para-Anisidine.This technique is with compared with sodium sulphite reducing process, and product cost can reduce by 1500 yuan/about t, lacks the nearly 3.5t/t of waste discharge simultaneously.In the process, when catalyst levels 1%, temperature of reaction 140 DEG C, reaction pressure 4MPa, reaction times 3h, yield can reach more than 96%.But, not only severe reaction conditions in this technique, and the highest yield of Para-Anisidine is also only 96.4%, product purity 99.38%, still can not reach industry requirement.
Yuan Zhongyi etc. are at document 5: " backbone ruthenium nickel carbon selectivity shortening prepares Para-Anisidine ", fine chemistry industry, 23rd volume the 5th phase, in 2006 5 months, disclose with skeletal isomerzation is catalyzer, p-Nitromethoxybenzene liquid phase selective hydrogenation is to prepare Para-Anisidine, but target product selectivity only reaches 99.4%, needs further isolation andpurification still can obtain the sterling of target product.This research group is also in Chinese patent CN1775353, disclose the backbone ruthenium catalyzer of promotor that one comprises main catalyst ruthenium and is made up of Al, Ni, M (Fe, Mn, Mo or Cr) and C, adopt the hydrogenation reaction of this backbone ruthenium catalyzer, 4g p-Nitromethoxybenzene 100% can be made to be converted into Para-Anisidine, and the yield of this product is 99%.
Applicant in this case discloses a kind of synthetic method of alkoxyl aniline in Chinese patent CN101492379, and the method is that raw material passes through under catalysts conditions, add hydrogen reaction generation alkoxyl aniline by alkoxyl nitrobenzene.In the disclosure in this patent in disclosed embodiment 2, by 100g p-Nitromethoxybenzene, 1gRaneyNi, 100mL methyl alcohol joins in reactor, and passes into hydrogen in 80 DEG C and react, until reaction no longer inhale hydrogen after half an hour stop.The method, compared to other prior art before, has obtained larger lifting in selectivity and yield.But the method is only can implement in the lab, when being scaled up to industrial production, the Para-Anisidine of highly selective (high purity), high yield can not be obtained at all.Especially, even if in laboratory scale, the kind of catalyzer and consumption, the kind of solvent and the difference of the factor such as consumption, temperature and pressure, all can cause the fluctuation of selectivity and yield, is difficult to reach high yield and highly selective simultaneously.By embodiment 1,2,3,7 disclosed in this patent, this impact can be found out.Such as, embodiment 1 is compared with embodiment 2, and be only that Ni content reduces, methyl alcohol reduces, and pressure and temp reduces, then the transformation efficiency in embodiment 1 is then reduced to 82% by 100%, and selectivity rises to 100% by 99.5%.Again such as, embodiment 7 is compared with embodiment 2, and be only that pressure and temp rises, then the transformation efficiency in embodiment 7 still can keep 100%, and selectivity drops to 90% by 99.5%.At least, disclosing from this patent, this method is also unstable in laboratory scale, and can not expect the Para-Anisidine that how just can reach and obtain highly selective, high yield simultaneously.
In sum, prior art fails to realize in industrial scale so far, highly selective, prepares the method for Para-Anisidine with high yield.
Summary of the invention
The object of the present invention is to provide a kind of take into account highly selective, high yield and clean can with the preparation method of the Para-Anisidine of industrial-scale production, the method can solve the many disadvantages existed in prior art substantially.
The preparation method of Para-Anisidine provided by the invention, under Ternary Amorphous Alloy alloy catalyst exists, with intermittent type hydrogenation, hydrogenation is carried out to p-Nitromethoxybenzene liquid phase, thus can obtain selectivity up to more than 99.7% Para-Anisidine, the reaction conditions of this preparation method is gentle, solvent, catalyzer can be recycled, and are easy to suitability for industrialized production.
The preparation method of Para-Anisidine provided by the invention, comprises following step:
1) feed intake: be that the ratio of 100:0.2 ~ 2:80 ~ 100 adds in reactor with mass ratio by p-Nitromethoxybenzene, catalyzer and methyl alcohol, form mixed solution;
Wherein, described catalyzer is Ni-Mo-B (wherein the weight percent of Ni, Mo, B is respectively 95.0wt%, 3.0wt% and 2.0wt%) or Ni-Co-P (wherein the weight percent of Ni, Co, P is respectively 95.0wt%, 3.0wt% and 2.0wt%);
2) deoxygenation: pass into nitrogen with the air in replacement reaction kettle; Then, hydrogen is passed into the nitrogen in replacement reaction kettle;
3) intermittent type hydrogenation: be replaced, passes into hydrogen to 0.8 ~ 1.8MPa, stirs mixed solution in reactor, carries out hydrogenation reaction; In reaction process, controlling temperature of reaction is 80 ~ 120 DEG C, and keeps the hydrogen pressure in reactor to be 0.8 ~ 1.8MPa;
Detection mixed solution per hour once; When the content (removal solvent) recording the p-Nitromethoxybenzene in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content (removal solvent) recording the p-Nitromethoxybenzene in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal solvent) all lower than 0.1% time, close hydrogen valve, stop hydrogenation;
4) cooling discharge: reduce stirring velocity and lower the temperature with water coolant, when temperature is down to 30 ~ 50 DEG C, stop stirring, extrude the material on upper strata after leaving standstill, the material of lower floor is mainly catalyzer;
5) purified product: by step 4) material on upper strata that extrudes enters method separation tower and isolates methyl alcohol, isolated methyl alcohol uses as solvent cycle when preparing Para-Anisidine next time, this is eliminated the material after methyl alcohol and boil off moisture through thin-film evaporator, obtain required Para-Anisidine.
In an embodiment of the invention, step 2) in deoxygenation emptying again to 0.5MPa for passing into nitrogen, repeat 3 ~ 5 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 3 ~ 5 times to remove the nitrogen in reactor.
In an embodiment of the invention, step 3) in pass into hydrogen to 0.8 ~ 1.8MPa, preferably 1.0 ~ 1.6MPa.
In an embodiment of the invention, step 3) stirring velocity be 60 ~ 300rpm, preferably 80 ~ 160rpm.
In an embodiment of the invention, step 3) temperature of reaction be 80 ~ 120 DEG C, preferably 90 ~ 100 DEG C.
In an embodiment of the invention, step 4) middle reduction stirring velocity to 30 ~ 60rpm.
In an embodiment of the invention, step 4) in the Matter Transfer of lower floor use, enter in the preparation flow of Para-Anisidine next time.In an embodiment of the invention, by step 4) the material of lower floor add p-Nitromethoxybenzene, methyl alcohol, and supplement input catalyzer, to meet the mass ratio of p-Nitromethoxybenzene, total catalyzer and inert organic solvents for 100:0.2 ~ 2:80 ~ 100, then repeating step 2)-step 5), recycling of catalyzer can be realized.
In an embodiment of the invention, step 5) in the condition of method separation tower separation of methanol be: knockout tower column bottom temperature is 80 ~ 130 DEG C, and tower top temperature is 50 ~ 100 DEG C; Preferably, column bottom temperature is 90 ~ 120 DEG C, and tower top temperature is 60 ~ 80 DEG C.
In an embodiment of the invention, step 5) in boil off moisture at thin-film evaporator condition be: 0.09 ~-0.1MPa, 90 ~ 130 DEG C, preferably 100 ~ 120 DEG C.
Method of the present invention utilizes specific ternary alloy Ni-Mo-B or Ni-Co-P as catalyzer, carries out hydro-reduction, thus obtain Para-Anisidine with intermittent type hydrogenation method to p-Nitromethoxybenzene liquid phase.Compared with prior art, the advantage of method of the present invention is:
(1) using commercially available ternary alloy as catalyzer, namely can obtain than selectivity higher when using Raney-Ni, Pd-C or skeletal isomerzation catalyzer in prior art and transformation efficiency;
(2) the shortening method of prior art is all with " no longer consuming hydrogen " for standard terminates catalytic hydrogenating reduction reaction, therefore is not very accurate to the terminal point control of reaction, thus is difficult to high yield and/or highly selective prepares Para-Anisidine.And the present invention is by the content to nitrosobenzene methyl ether, hydrazobenzene and zinin in monitoring reaction mixture, thus the accurate control realized reaction end, hydrogenation reduction of the present invention therefore can be made to have the feature of high conversion, highly selective (up to more than 99.7%) simultaneously;
(3) hydrogen reduction of the present invention adopts cheap hydrogen to be raw material, through a step shortening synthesis Para-Anisidine; And solvent, catalyzer can be recycled, and are easy to industrialization, because this reducing production cost;
(4) in hydrogen reduction of the present invention, by product is water, there is no other waste water and dregs or waste gas, therefore makes the generation avoiding the three wastes in whole building-up process, is environment amenable green reaction;
(5) the present invention is after intermittent type hydrogenation step, the Para-Anisidine that purity is more than 99.7% can be obtained, therefore make follow-up purification step (aftertreatment) become simple, more highly purified Para-Anisidine product can be obtained by means of only simple rectifying.
Therefore, method of the present invention not only avoid sodium sulfide reducing and causes sulfur-containing waste water to the pollution of environment, possesses again the advantages such as high yield, highly selective and low by product simultaneously, is easy to realize technical scaleization and produces.
Embodiment
Embodiment 1
6000kg p-Nitromethoxybenzene, 120kg catalyst n i-Mo-B (wherein the weight percent of Ni, Mo, B is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 7500L methyl alcohol are added in 16000L reactor, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 5 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 5 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.2MPa, open steam valve and reactor is heated up, when temperature rises to 80 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 80rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 80 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.2MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 30rpm, lower the temperature with water coolant; When temperature is down to 30 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 120 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 50 DEG C, and then under 0.06MPa, 90 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 4756kg, its transformation efficiency 100%, yield is 98.6%, selectivity 99.8%, the purity 99.8% of Para-Anisidine.
Embodiment 2
3000kg p-Nitromethoxybenzene, 6kg catalyst n i-Mo-B (wherein the weight percent of Ni, Mo, B is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 3030L methyl alcohol are added embodiment 1 to be left in the 16000L reactor of catalyzer, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 3 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 3 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.0MPa, open steam valve and reactor is heated up, when temperature rises to 90 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 120rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 90 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.0MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 40rpm, lower the temperature with water coolant; When temperature is down to 45 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 130 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 80 DEG C, and then under 0.08MPa, 130 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 2385kg, its transformation efficiency 100%, yield is 98.9%, selectivity 99.7%, the purity 99.7% of Para-Anisidine.
Embodiment 3
6000kg p-Nitromethoxybenzene, 12kg catalyst n i-Mo-B (wherein the weight percent of Ni, Mo, B is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 7000L methyl alcohol are added embodiment 2 to be left in the 16000L reactor of catalyzer, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 4 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 4 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.6MPa, open steam valve and reactor is heated up, when temperature rises to 100 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 160rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 90 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.6MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 60rpm, lower the temperature with water coolant; When temperature is down to 50 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 90 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 50 DEG C, and then under 0.06MPa, 90 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 4776kg, its transformation efficiency 100%, yield is 99.0%, selectivity 99.9%, the purity 99.9% of Para-Anisidine.
Embodiment 4
3000kg p-Nitromethoxybenzene, 6kg catalyst n i-Mo-B (wherein the weight percent of Ni, Mo, B is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 3600L methyl alcohol are added embodiment 3 to be left in the 16000L reactor of catalyzer, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 4 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 4 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 0.8MPa, open steam valve and reactor is heated up, when temperature rises to 120 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 100rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 90 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 0.8MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 50rpm, lower the temperature with water coolant; When temperature is down to 40 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 130 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 80 DEG C, and then under 0.08MPa, 130 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 2383kg, its transformation efficiency 100%, yield is 98.8%, selectivity 99.7%, the purity 99.7% of Para-Anisidine.
Embodiment 5
6000kg p-Nitromethoxybenzene, 100kg catalyst n i-Co-P (wherein the weight percent of Ni, Co, P is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 7500L methyl alcohol are added in 16000L reactor, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 5 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 5 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.0MPa, open steam valve and reactor is heated up, when temperature rises to 95 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 120rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 95 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.0MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 30rpm, lower the temperature with water coolant; When temperature is down to 30 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 80 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 70 DEG C, and then under 0.01MPa, 100 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 4771kg, its transformation efficiency 100%, yield is 98.9%, selectivity 99.9%, the purity 99.9% of Para-Anisidine.
Embodiment 6
3000kg p-Nitromethoxybenzene, 6kg catalyst n i-Co-P (wherein the weight percent of Ni, Co, P is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 3300L methyl alcohol are added embodiment 5 to be left in the 16000L reactor of catalyzer, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 3 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 3 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.5MPa, open steam valve and reactor is heated up, when temperature rises to 80 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 140rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 80 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.5MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 50rpm, lower the temperature with water coolant; When temperature is down to 50 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 130 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 100 DEG C, and then under 0.01MPa, 120 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 2390kg, its transformation efficiency 100%, yield is 99.1%, selectivity 99.7%, the purity 99.7% of Para-Anisidine.
Embodiment 7
6000kg p-Nitromethoxybenzene, 12kg catalyst n i-Co-P (wherein the weight percent of Ni, Co, P is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 6060L methyl alcohol are added embodiment 6 to be left in the 16000L reactor of catalyzer, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 4 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 4 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.6MPa, open steam valve and reactor is heated up, when temperature rises to 100 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 80rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 100 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.6MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 40rpm, lower the temperature with water coolant; When temperature is down to 40 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 90 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 60 DEG C, and then under 0.02MPa, 110 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 4776kg, its transformation efficiency 100%, yield is 99.0%, selectivity 99.8%, the purity 99.8% of Para-Anisidine.
Embodiment 8
3000kg p-Nitromethoxybenzene, 6kg catalyst n i-Co-P (wherein the weight percent of Ni, Co, P is respectively 95.0wt%, 3.0wt% and 2.0wt%) and 3600L methyl alcohol are added embodiment 7 to be left in the 16000L reactor of catalyzer, forms mixed solution.
Pass into nitrogen to reactor emptying again to 0.5MPa, repeat 4 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 4 times to remove the nitrogen in reactor.
Be replaced, in reactor, pass into hydrogen to 1.2MPa, open steam valve and reactor is heated up, when temperature rises to 110 DEG C, steam off valve.Open reactor agitator (slowly being raised speed by frequency transformer) to stir mixed solution with the stirring velocity of 150rpm, carry out hydrogenation reaction; In reaction process, controlling temperature of reaction is 110 ± 1 DEG C, and keeps the hydrogen pressure in reactor to be 1.2MPa.
In reaction process, detection mixed solution per hour once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content of the p-Nitromethoxybenzene recording (removal methanol content) in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until in mixed solution the content to nitrosobenzene methyl ether, hydrazobenzene and zinin of (removal methanol content) all lower than 0.1% time, close hydrogen valve, stop hydrogenation.
Reduce stirring velocity to 30rpm, lower the temperature with water coolant; When temperature is down to 60 DEG C, stop stirring, extrude the material on upper strata after leaving standstill half an hour, lower floor is mainly catalyzer, stays in reactor, for hydrogenation next time.
The upper materials of extrusion is entered method separation tower, it is 110 DEG C at column bottom temperature, tower top temperature is isolate methyl alcohol under the condition of 80 DEG C, and then under 0.01MPa, 120 DEG C of conditions, boil off moisture through thin-film evaporator, obtain Para-Anisidine 2381kg, its transformation efficiency 100%, yield is 98.7%, selectivity 99.7%, the purity 99.7% of Para-Anisidine.
Comparative example 1
The synthetic method of the alkoxyl aniline disclosed in Chinese patent CN101492379 according to applicant in this case, compares experiment.
According to the reaction conditions of the embodiment 2 in CN101492379, scaled up the technical scale to the application, that is: by 3000kg p-Nitromethoxybenzene, 30kgRaneyNi, 3000L methyl alcohol joins in reactor, and pass into hydrogen (setting pressure is 1.5Mpa) in 80 DEG C and react, until reaction no longer inhale hydrogen after half an hour stop.After reaction terminates, by autoclave quenching to room temperature, filtration catalizer, gets filtrate and carries out gas chromatographic analysis, finds far away less than its result when laboratory scale (100g para-nitrotoluene).At laboratory stage (disclosed in patent CN101492379), p-Nitromethoxybenzene transformation efficiency 100%, Para-Anisidine selectivity 99.5% can be obtained; And after the technical scale being amplified to 3000kg p-Nitromethoxybenzene, to the analysis display of reaction filtrate, transformation efficiency only has 99.0%, Para-Anisidine selectivity 96.5%, the purity 96.5% of Para-Anisidine, therefore, such product purity is obviously the demand that can not meet downstream raw materials for production far away, must carry out purifying technique further again.
By comparison, material rate and this comparative example 1 of the embodiment of the present application 6 are comparatively close, but this embodiment finally obtains Para-Anisidine 2390kg, its transformation efficiency 100%, yield is 99.1%, selectivity 99.7%, the purity 99.7% of Para-Anisidine, meet the demand to raw material when downstream produces completely, can directly use.Be appreciated that, this excellent effect of the present invention is commercially available ternary alloy Ni-Co-P (the wherein Ni owing to have employed through selecting especially, Co, the weight percent of P is respectively 95.0wt%, 3.0wt% and 2.0wt%) as catalyzer, and to pass through in monitoring reaction mixture nitrosobenzene methyl ether, the content standard of being used as of hydrazobenzene and zinin terminates catalytic hydrogenation reaction, thus than in comparative example 1 with " no longer consuming hydrogen " for standard can control reaction end more accurately, therefore high selectivity and transformation efficiency can be obtained in plant-scale reaction simultaneously.
Comparative example 2
According to being catalyzer with skeletal isomerzation disclosed in Chinese patent CN1775353, p-Nitromethoxybenzene liquid phase selective hydrogenation is to prepare the method for Para-Anisidine, its processing condition are scaled up the technical scale to the application, that is: the backbone ruthenium catalyzer after 4000kg p-Nitromethoxybenzene, 20000 liters of tetrahydrofuran (THF)s, 100kg being activated, then hydrogen is passed into and slowly reacting by heating still is warming up to 70 degree, keep system pressure, assaying reaction liquid after 2 hours.
In lab scale stage (magnitude of 4g p-Nitromethoxybenzene), Chinese patent CN1775353 can obtain transformation efficiency 100% and yield is 99%.But after the technical scale being amplified to 4000kg p-Nitromethoxybenzene, to the analysis display of reaction filtrate, transformation efficiency only has 99.0%, and the purity 97.0% of Para-Anisidine, yield is only 96.0%.The purity of this product is obviously the demand that can not meet downstream raw materials for production far away, must carry out purifying technique further again.
The result of above-mentioned each comparative example all demonstrates, compared to prior art fail so far to realize on a commercial scale highly selective, prepare Para-Anisidine with high yield, the preparation method of Para-Anisidine of the present invention can take into account high conversion, highly selective really at industrial scale simultaneously, and the industry preparation therefore for Para-Anisidine has profound significance.
Claims (10)
1. a preparation method for Para-Anisidine, comprises following step:
1) feed intake: be that the ratio of 100:0.2 ~ 2:80 ~ 100 adds in reactor with mass ratio by p-Nitromethoxybenzene, catalyzer and methyl alcohol, form mixed solution;
Wherein, described catalyzer is Ni-Mo-B, and wherein the weight percent of Ni, Mo, B is respectively 95.0wt%, 3.0wt% and 2.0wt%; Or described catalyzer is Ni-Co-P, and wherein the weight percent of Ni, Co, P is respectively 95.0wt%, 3.0wt% and 2.0wt%;
2) deoxygenation: pass into nitrogen with the air in replacement reaction kettle; Then, hydrogen is passed into the nitrogen in replacement reaction kettle;
3) intermittent type hydrogenation: be replaced, passes into hydrogen to 0.8 ~ 1.8MPa, stirs mixed solution in reactor, carries out hydrogenation reaction; In reaction process, controlling temperature of reaction is 80 ~ 120 DEG C, and keeps the hydrogen pressure in reactor to be 0.8 ~ 1.8MPa;
Detection mixed solution per hour once; When the content recording the p-Nitromethoxybenzene in mixed solution drops to 20%, change every 0.5 hour into and detect mixed solution once; When the content recording the p-Nitromethoxybenzene in mixed solution drops to 5%, change every 10 minutes into and detect mixed solution once; Until the content to nitrosobenzene methyl ether, hydrazobenzene and zinin in mixed solution all lower than 0.1% time, close hydrogen valve, stop hydrogenation;
4) cooling discharge: reduce stirring velocity and lower the temperature with water coolant, when temperature is down to 30 ~ 50 DEG C, stop stirring, extrude the material on upper strata after leaving standstill, the material of lower floor is mainly catalyzer;
5) purified product: by step 4) material on upper strata that extrudes enters method separation tower and isolates methyl alcohol, isolated methyl alcohol uses as solvent cycle when preparing Para-Anisidine next time, this is eliminated the material after methyl alcohol and boil off moisture through thin-film evaporator, obtain required Para-Anisidine.
2. the deoxygenation the preparation method of Para-Anisidine according to claim 1, wherein: step 2) is emptying again to 0.5MPa for passing into nitrogen, repeats 3 ~ 5 times to remove the air in reactor; Then, pass into hydrogen emptying again to 0.5MPa, repeat 3 ~ 5 times to remove the nitrogen in reactor.
3. the preparation method of Para-Anisidine according to claim 1, wherein: step 3), pass into hydrogen to 1.0 ~ 1.6MPa.
4. the stirring velocity preparation method of Para-Anisidine according to claim 1, wherein: step 3) is 60 ~ 300rpm
5. the stirring velocity preparation method of Para-Anisidine according to claim 1, wherein: step 3) is 80 ~ 160rpm.
6. the temperature of reaction preparation method of Para-Anisidine according to claim 1, wherein: step 3) is 90 ~ 100 DEG C.
7. the preparation method of Para-Anisidine according to claim 1, wherein: step 4) middle reduction stirring velocity to 30 ~ 60rpm.
8. the Matter Transfer of the lower floor the preparation method of Para-Anisidine according to claim 1, wherein: step 4) uses, and enters in the preparation flow of Para-Anisidine next time.
9. the preparation method of Para-Anisidine according to claim 1, wherein: step 5) in the condition of method separation tower separation of methanol be: knockout tower column bottom temperature is 80 ~ 130 DEG C, and tower top temperature is 50 ~ 100 DEG C.
10. the condition boiling off moisture at thin-film evaporator the preparation method of Para-Anisidine according to claim 1, wherein: step 5) is: 0.09 ~-0.1MPa, 90 ~ 130 DEG C.
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