CN103113233A - Production method for preparing chlorinated aniline via chlorination of nitrobenzene hydrogenation by utilizing solvent-free process - Google Patents
Production method for preparing chlorinated aniline via chlorination of nitrobenzene hydrogenation by utilizing solvent-free process Download PDFInfo
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Abstract
The invention belongs to the production field of catalytic hydrogenation, and particularly discloses a production method for preparing chlorinated aniline via the chlorination of nitrobenzene hydrogenation by utilizing a solvent-free process. Chlorinated nitrobenzene is used as a raw material. The method is characterized in that under the existence of a catalyst and an aiding agent, the chlorinated nitrobenzene reacts with hydrogen at the temperature of 80 to 100 DEG C and under the pressure of 0.3 to 2.5 MPa, wherein a solvent is not added; and after the reaction is finished, the water diversion treatment is carried out, thereby obtaining the chlorinated aniline. The catalyst containing 1% of Pt/C precious metal is developed independently, wherein the adding amount of the catalyst accounts for 0.05% to 20% of that of the chlorinated nitrobenzene as the raw material. The aiding agent is a mixture of ethanol amine and pyridine, wherein the adding amount of the aiding agent accounts for 0.01% to 10% of that of the chlorinated nitrobenzene as the raw material. For the obtained o-chloroaniline, the chromatographic purity is above 99.5%, and the dechlorination quantity can be controlled within 0.1%. For the obtained 2,5-dichloroaniline, the chromatographic purity is above 99%, and the dechlorination quantity can be controlled within 0.1%. For the obtained 3,4-dichloroaniline, the chromatographic purity is above 99%, and the dechlorination quantity can be controlled within 0.1%.
Description
Technical field
The invention belongs to the shortening production field, disclose especially the production method of the standby chloro aminobenzen of a kind of solventless method chloronitrobenzene Hydrogenation.
Background technology
Chloro aminobenzen is the important fine-chemical intermediate of a class, in fields such as medicine, agricultural chemicals, dyestuff and daily-use chemical industries, purposes is widely arranged.Ortho-Chloro aniline is the glacial dye color base, also can be used as the diazo component of azoic dyestuff, for the production of erie black, acid blue and organic color lake permanent yellow R, permanent bordeaux FR, the husky yellow HR of the Chinese etc.And the two chloroanilines of the linking agent methyl that can be used for producing medicine, agricultural chemicals, urethane resin; 2,5 one dichlorphenamide bulk powders are important medicine and pesticide intermediates, are mainly used to the synthetic pesticide dicamba 98, also can be used for making glacial dye Fast Scarlet G and nitrogen fertilizer potentiating agent; 3, the 4-dichlorphenamide bulk powder is widely used in the weedicides such as synthetic methoxydiuron, Diuron Tech, swep and azoic dyestuff etc., also to produce fungistat 3,4, the raw material of 4 '-trichlorocarbanilide is important intermediate and the biological activity intermediate of Multiple Pesticides, medicine, dyestuff, pigment, fine chemical product.The production technique commonly used of the standby chloro aminobenzen of chloronitrobenzene Hydrogenation has iron powder reducing method, sodium sulfide reducing method and shortening method.Although iron powder reducing method technology maturation, raw material is easy to get, and technique is simple, but the labour protection condition is poor, the environmental pollution that iron mud causes is serious, is listed in and orders superseded backward production technique by " industry restructuring guidance list (basis in 2011) " of the National Development and Reform Commission.The sodium sulfide reducing method is also a kind of comparatively common reducing process, and this technological reaction mild condition be easy to control, but cost is higher, and wastewater flow rate is large, and damage ratio is more serious.In the kinds of processes route of synthetic chloro aminobenzen, catalytic hydrogenation process is because process is simple, advantages of environment protection receives much concern, and is the production technique of a green.But, the chloro aminobenzen catalytic hydrogenation process exists this difficult problem of hydrogenolysis dechlorination, causes equipment corrosion and product purity to descend, and selects suitable auxiliary agent can effectively reduce dechlorination, improve the content of principal product, this is also that domestic and international researchist is in research emphasis and the difficult point in this field.Traditional technology mostly adopts Raney's nickel catalyst, low-molecular-weight the first and second alcohol are solvent, add appropriate anti-dechlorination auxiliary agent, the more difficult control of this kind technique dechlorination, Raney-Ni uses dangerous, and need desolvation in industrial production, operation is more, and the product solvent has loss, and energy consumption is high,, have influence on holistic cost.
Summary of the invention
The present invention is directed to the deficiency that exists in existing production technique,, adopt solvent-free production process, chloronitrobenzene under catalyzer and auxiliary agent exist, under 80-100 ℃ and 0.3-2.5MPa with hydrogen reaction,, after completing, catalyzer is leached, minute water obtains chloro aminobenzen.Wherein said catalyzer is the 1%Pt/C noble metal catalyst of independent research, and the consumption of catalyzer is the 0.05%-20% of raw material chloronitrobenzene quality; Described auxiliary agent is following two kinds of mixtures: thanomin, pyridine, the consumption of auxiliary agent are the 0.01%-10% of raw material chloronitrobenzene quality; Gained Ortho-Chloro aniline chromatographic purity is more than 99.5%, and the dechlorination amount can be controlled in 0.1%; Gained 2,5-dichlorphenamide bulk powder chromatographic purity is more than 99%, and the dechlorination amount can be controlled in 0.1%; Gained 3,4-DCA chromatographic purity is more than 99%, and the dechlorination amount can be controlled in 0.1%.
The method of the standby chloro aminobenzen of the said chloronitrobenzene Hydrogenation of the present invention, its feature comprise following some:
(1) solvent-free reaction only adds raw material, catalyzer and auxiliary agent in reduction kettle, logical hydrogen heats up and carries out reduction reaction, reacts to fall to generate water in complete minute and namely get product;
(2) the 1%Pt/C noble metal catalyst of independent research coordinates thanomin and pyridine to use, and dechlorination is low, dechlorination rate≤0.1%, and reusable edible, the low interpolation, height is applied mechanically, and cost is low;
(3) reaction conditions is gentle, and temperature 80-100 ℃, pressure 0.3-2.5MPA can complete reaction in the left and right;
(4) reaction yield is high, and cost is low, and no waste discharge has alleviated environmental stress.
The present invention need not solvent distillation, has significantly reduced production cost and equipment investment; The 1%Pt/C noble metal catalyst of independent research coordinates suitable auxiliary agent thanomin and pyridine, has successfully realized low interpolation, and height is applied mechanically, and cost is low; The products obtained therefrom quality is high, and yield is high, and cost is low, produces and stablizes, and no waste discharge has alleviated environmental stress.
Embodiment
The present invention will be further elaborated below by specific embodiment, should be understood that, following explanation is only in order to explain the present invention, its content not to be limited.
Following embodiment is take our company's laboratory equipment as example, elaborate technological process of the present invention, main raw material used is: o-chloronitrobenzene (technical grade, 99%), 2,5-dichloronitrobenzene (technical grade, 99%), 3,4-dichloronitrobenzene (technical grade, 99%), hydrogen (technical grade, 99.9%), 1%Pt/C noble metal catalyst (self-control), thanomin (technical grade), pyridine (technical grade); Major equipment used is: reduction kettle (1L), vacuum filtration device (1000ml), separating funnel (1000ml).
The present invention's catalyzer used is the metal platinum catalyzer that loads on gac, and the preparation method is:
1, take 10 gram platinum powder equivalent sodium platinichlorides (Platinic chloride), be dissolved in the polysulfide aqueous solution, be incubated 60 ℃ stand-by.
2, take 1.1kg coal activated carbon (water content≤10%), the nitric acid treatment with 10% is cleaned to neutral in 70 ℃ of condition activation 20 hours, pH value 6.5, and suction filtration forms filter cake, and is stand-by.
3, add in adsorption barrel 1, be incubated 60 ℃, the gac filter cake that activation is good adds constant temperature absorption 10 hours, and is stand-by.
4, will adsorb good gac suction filtration, washing adds filter cake in reduction kettle, drips 10% formaldehyde 200ml reduction in 50 ℃, drips 60 ℃ of insulations 3 hours, takes out filtering and washing to neutral, gets final product without chlorion with the Silver Nitrate qualitative detection.
Embodiment 1
with o-chloronitrobenzene 400g, 1%Pt/C noble metal catalyst 3 grams (self-control), join in the 1L autoclave, the enclosed high pressure still, open the hydrogen valve, pass into hydrogen in autoclave, stir temperature reaction, temperature of reaction is controlled 80-100 ℃, reaction pressure is controlled 0.3-2.5MPA, 700 rev/mins of reaction speed settings, till reaction is not extremely inhaled hydrogen, close the hydrogen valve, cooling rear opening high pressure still, discharging, add in separating funnel after filtration, tell the water that reaction generates, oil phase is Ortho-Chloro aniline, be 97.22% through gas chromatographic analysis purity, dechlorination amount 1.9%, between oil phase pH value 4-5.
Embodiment 2
with o-chloronitrobenzene 400g, 1%Pt/C noble metal catalyst 3 grams (self-control), thanomin 0.7 gram, join in the 1L autoclave, the enclosed high pressure still, open the hydrogen valve, pass into hydrogen in autoclave, stir temperature reaction, temperature of reaction is controlled 80-100 ℃, reaction pressure is controlled 0.3-2.5MPA, 700 rev/mins of reaction speed settings, till reaction is not extremely inhaled hydrogen, close the hydrogen valve, cooling rear opening high pressure still, discharging, add in separating funnel after filtration, tell the water that reaction generates, oil phase is Ortho-Chloro aniline, be 98.87% through gas chromatographic analysis purity, dechlorination amount 0.7%, between oil phase pH value 5-6.
Embodiment 3
with o-chloronitrobenzene 400g, 1%Pt/C noble metal catalyst 3 grams (self-control), pyridine 2ml, join in the 1L autoclave, the enclosed high pressure still, open the hydrogen valve, pass into hydrogen in autoclave, stir temperature reaction, temperature of reaction is controlled 80-100 ℃, reaction pressure is controlled 0.3-2.5MPA, 700 rev/mins of reaction speed settings, till reaction is not extremely inhaled hydrogen, close the hydrogen valve, cooling rear opening high pressure still, discharging, add in separating funnel after filtration, tell the water that reaction generates, oil phase is Ortho-Chloro aniline, be 98.72% through gas chromatographic analysis purity, dechlorination amount 0.9%, between oil phase pH value 5-6.
Embodiment 4
with o-chloronitrobenzene 400g, 1%Pt/C noble metal catalyst 3 grams (self-control), thanomin 0.7 gram, pyridine 2ml joins in the 1L autoclave, the enclosed high pressure still, open the hydrogen valve, pass into hydrogen in autoclave, stir temperature reaction, temperature of reaction is controlled 80-100 ℃, reaction pressure is controlled 0.3-2.5MPA, 700 rev/mins of reaction speed settings, till reaction is not extremely inhaled hydrogen, close the hydrogen valve, cooling rear opening high pressure still, discharging, add in separating funnel after filtration, tell the water that reaction generates, oil phase is Ortho-Chloro aniline, be 99.73% through gas chromatographic analysis purity.Reaction is applied mechanically to 20 still catalyzer and is still had activity.Reacting balance, quality is high, and the additional amount of catalyzer is few.React front 10 quality of lot situations as follows.
| Sequence number | Catalyzer | Pyridine | Thanomin | Purity | Dechlorination | Starting material |
| 1 | 3g | 2ml | 0.7 | 99.73% | 0.05% | Nothing |
| 2 | 1g | 2ml | 0.7 | 99.71% | 0.06% | Nothing |
| 3 | 0.8g | 2ml | 0.7 | 99.85% | 0.04% | Nothing |
| 4 | 0.5g | 2ml | 0.7 | 99.66% | 0.1% | Nothing |
| 5 | 0.5g | 2ml | 0.7 | 99.65% | 0.1% | Nothing |
| 6 | 0.5g | 2ml | 0.7 | 99.72% | 0.06% | Nothing |
| 7 | 0.5g | 2ml | 0.7 | 99.83% | 0.04% | Nothing |
| 8 | 0.5g | 2ml | 0.7 | 99.62% | 0.1% | Nothing |
| 9 | 0.5g | 2ml | 0.7 | 99.65% | 0.1% | Nothing |
| 10 | 0.5g | 2ml | 0.7 | 99.81% | 0.06% | Nothing |
Embodiment 5
with 2, 5-dichloronitrobenzene 400g, 1%Pt/C noble metal catalyst 4 grams (self-control), thanomin 0.7 gram, pyridine 2ml joins in the 1L autoclave, the enclosed high pressure still, open the hydrogen valve, pass into hydrogen in autoclave, stir temperature reaction, temperature of reaction is controlled 80-100 ℃, reaction pressure is controlled 0.3-2.5MPA, 700 rev/mins of reaction speed settings, till reaction is not extremely inhaled hydrogen, close the hydrogen valve, cooling rear opening high pressure still, discharging, add in separating funnel after filtration, tell the water that reaction generates, oil phase is 2, the 5-dichlorphenamide bulk powder, be 99.30% through gas chromatographic analysis purity.Reaction is applied mechanically to 20 still catalyzer and is still had activity.Reacting balance, quality is high, and the additional amount of catalyzer is few.React front 10 quality of lot situations as follows.
| Sequence number | Catalyzer | Pyridine | Thanomin | Purity | Dechlorination | Starting material |
| 1 | 4g | 4ml | 0.7 | 99.30% | 0.1% | Nothing |
| 2 | 1g | 4ml | 0.7 | 99.45% | 0.08% | Nothing |
| 3 | 0.8g | 4ml | 0.7 | 99.42% | 0.09% | Nothing |
| 4 | 0.5g | 4ml | 0.7 | 99.31% | 0.1% | Nothing |
| 5 | 0.5g | 4ml | 0.7 | 99.35% | 0.1% | Nothing |
| 6 | 0.5g | 4ml | 0.7 | 99.52% | 0.06% | Nothing |
| 7 | 0.5g | 4ml | 0.7 | 99.59% | 0.04% | Nothing |
| 8 | 0.5g | 4ml | 0.7 | 99.34% | 0.1% | Nothing |
| 9 | 0.5g | 4ml | 0.7 | 99.32% | 0.1% | Nothing |
| 10 | 0.5g | 4ml | 0.7 | 99.47% | 0.06% | Nothing |
Embodiment 6
with 3, 4-dichloronitrobenzene 400g, 1%Pt/C noble metal catalyst 4 grams (self-control), thanomin 0.7 gram, pyridine 2ml joins in the 1L autoclave, the enclosed high pressure still, open the hydrogen valve, pass into hydrogen in autoclave, stir temperature reaction, temperature of reaction is controlled 80-100 ℃, reaction pressure is controlled 0.3-2.5MPA, 700 rev/mins of reaction speed settings, till reaction is not extremely inhaled hydrogen, close the hydrogen valve, cooling rear opening high pressure still, discharging, add in separating funnel after filtration, tell the water that reaction generates, oil phase is 3, the 4-dichlorphenamide bulk powder, be 99.45% through gas chromatographic analysis purity.Reaction is applied mechanically to 20 still catalyzer and is still had activity.Reacting balance, quality is high, and the additional amount of catalyzer is few.React front 10 quality of lot situations as follows.
| Sequence number | Catalyzer | Pyridine | Thanomin | Purity | Dechlorination | Starting material |
| 1 | 4g | 3ml | 0.7 | 99.45% | 0.1% | Nothing |
| 2 | 1g | 3ml | 0.7 | 99.55% | 0.08% | Nothing |
| 3 | 0.8g | 3ml | 0.7 | 99.56% | 0.09% | Nothing |
| 4 | 0.5g | 3ml | 0.7 | 99.42% | 0.1% | Nothing |
| 5 | 0.5g | 3ml | 0.7 | 99.39% | 0.1% | Nothing |
| 6 | 0.5g | 3ml | 0.7 | 99.60% | 0.06% | Nothing |
| 7 | 0.5g | 3ml | 0.7 | 99.62% | 0.04% | Nothing |
| 8 | 0.5g | 3ml | 0.7 | 99.39% | 0.1% | Nothing |
| 9 | 0.5g | 3ml | 0.7 | 99.85% | 0.1% | Nothing |
| 10 | 0.5g | 3ml | 0.7 | 99.91% | 0.06% | Nothing |
Embodiment 7
O-chloronitrobenzene 400g, 1% platinum-carbon 3 g (purchased), 0.7 g ethanolamine, 2ml of pyridine was added to the 1L autoclave, the autoclave was closed, the valve opening of hydrogen to the hydrogen introduced into the autoclave, heated with stirring reaction, the reaction temperature 80-100 ℃, reaction pressure control 0.3-2.5MPA,? reaction speed setting 700 rev / min, until the hydrogen absorption reaction until no hydrogen absorbing slower rate than in Example 4, a long reaction time.Close the hydrogen valve, cooling rear opening high pressure still, discharging adds after filtration in separating funnel, tells the water that reaction generates, and oil phase is Ortho-Chloro aniline, is 96.53% through gas chromatographic analysis purity, and dechlorination amount 2.1% is between oil phase pH value 3-4.
Embodiment 8
2,5 - dichloro-nitrobenzene 400g, 1% 4 g of platinum carbon (purchased), 0.7 g ethanolamine, 2ml of pyridine was added to the 1L autoclave, the autoclave was closed, the valve opening of hydrogen, introduced into the autoclave hydrogen, the reaction temperature with stirring, the reaction temperature control 80-100 ℃, reaction pressure control 0.3-2.5MPA,? reaction speed setting 700 rev / min, until the hydrogen absorption reaction until no hydrogen absorbing slower rate than in Example 5, and the reaction time long.Close the hydrogen valve, cooling rear opening high pressure still, discharging adds after filtration in separating funnel, tells the water that reaction generates, and oil phase is 3,4-DCA, is 94.73% through gas chromatographic analysis purity, and dechlorination amount 3.6% is between oil phase pH value 2-3.
Embodiment 9
3,4 - dichloro-nitrobenzene 400g, 1% 4 g of platinum carbon (purchased), 0.7 g ethanolamine, 2ml of pyridine was added to the 1L autoclave, the autoclave was closed, the valve opening of hydrogen, introduced into the autoclave hydrogen, the reaction temperature with stirring, the reaction temperature control 80-100 ℃, reaction pressure control 0.3-2.5MPA,? reaction speed setting 700 rev / min, until the hydrogen absorption reaction until no hydrogen absorption speed slower than the embodiment of Example 6, the reaction time long.Close the hydrogen valve, cooling rear opening high pressure still, discharging adds after filtration in separating funnel, tells the water that reaction generates, and oil phase is 3,4-DCA, is 94.63% through gas chromatographic analysis purity, and dechlorination amount 2.7% is between oil phase pH value 2-3.
Claims (9)
1. the production method of the standby chloro aminobenzen of a solventless method chloronitrobenzene Hydrogenation, take chloronitrobenzene as raw material, it is characterized in that: chloronitrobenzene is under catalyzer and auxiliary agent existence, under 80-100 ℃ and 0.3-2.5MPa with hydrogen reaction, do not add solvent, complete Hou Fenshui and obtain chloro aminobenzen.
2. the production method of chloro aminobenzen as claimed in claim 1, it is characterized in that: described catalyzer is the 1%Pt/C noble metal catalyst of independent research, and the consumption of catalyzer is the 0.05%-20% of raw material chloronitrobenzene quality.
3. the production method of chloro aminobenzen as claimed in claim 1, it is characterized in that: described auxiliary agent is following two kinds of mixtures: thanomin, pyridine, the consumption of auxiliary agent are the 0.1%-10% of raw material chloronitrobenzene quality.
4. the production method of chloro aminobenzen as claimed in claim 1, it is characterized in that: temperature of reaction is 80 ℃-100 ℃.
5. the production method of chloro aminobenzen as claimed in claim 1, it is characterized in that: reaction pressure is 0.3-2.5MPa.
6. as the production method of the described chloro aminobenzen of claim 1-5, it is characterized in that: chloronitrobenzene, hydrogen, catalyzer, auxiliary agent enter reactor, do not add any solvent reaction.
7. as the production method of the described chloro aminobenzen of claim 1-5, it is characterized in that: gained Ortho-Chloro aniline chromatographic purity is more than 99.5%, and the dechlorination amount can be controlled in 0.1%.
8. as the production method of the described chloro aminobenzen of claim 1-5, it is characterized in that: gained 2,5-dichlorphenamide bulk powder chromatographic purity is more than 99%, and the dechlorination amount can be controlled in 0.1%.
9. as the production method of the described chloro aminobenzen of claim 1-5, it is characterized in that: gained 3,4-DCA chromatographic purity is more than 99%, and the dechlorination amount can be controlled in 0.1%.
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| CN103333075A (en) * | 2013-07-11 | 2013-10-02 | 江苏扬农化工集团有限公司 | Production method of 2,5-dichloroaniline |
| CN103387498A (en) * | 2013-07-20 | 2013-11-13 | 王一如 | Method and device for producing o-chloroaniline without solvent |
| CN103467308A (en) * | 2013-09-18 | 2013-12-25 | 葫芦岛天启晟业化工有限公司 | Method for producing 2,5-dichloroaniline without anti-dechlorinating agent |
| CN103497112A (en) * | 2013-09-18 | 2014-01-08 | 葫芦岛天启晟业化工有限公司 | Method for preparing p-chloroaniline without adding organic solvent |
| CN103524357A (en) * | 2013-09-18 | 2014-01-22 | 葫芦岛天启晟业化工有限公司 | Parachloroaniline production method without using anti-dechlorination agent |
| CN103896804A (en) * | 2014-04-28 | 2014-07-02 | 西安凯立化工有限公司 | Method for preparing 2, 5-diamino cyanophenyl through liquid phase catalytic hydrogenation |
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| CN103333075A (en) * | 2013-07-11 | 2013-10-02 | 江苏扬农化工集团有限公司 | Production method of 2,5-dichloroaniline |
| CN103387498A (en) * | 2013-07-20 | 2013-11-13 | 王一如 | Method and device for producing o-chloroaniline without solvent |
| CN103467308B (en) * | 2013-09-18 | 2015-08-12 | 葫芦岛天启晟业化工有限公司 | Anti-dechlorinating agent is not used to produce the method for 2,5-dichlorphenamide bulk powder |
| CN103524357A (en) * | 2013-09-18 | 2014-01-22 | 葫芦岛天启晟业化工有限公司 | Parachloroaniline production method without using anti-dechlorination agent |
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