CN1079391C - Preparation of N-alkyl naphthylamines - Google Patents
Preparation of N-alkyl naphthylamines Download PDFInfo
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- CN1079391C CN1079391C CN97119109A CN97119109A CN1079391C CN 1079391 C CN1079391 C CN 1079391C CN 97119109 A CN97119109 A CN 97119109A CN 97119109 A CN97119109 A CN 97119109A CN 1079391 C CN1079391 C CN 1079391C
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- naphthylamine
- reaction
- alpha
- naphthylamines
- alkyl
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Abstract
In the present invention, alcohol with alkyl or naphthenic radicals react with naphthylamine; then under the existence of a solid metallic oxide catalyst, a dehydrogenation ammonification reaction occurs to synthesize N-alkyl naphthylamine compounds. The present invention has no corrosion and pollution during the reaction process, is simple in the refining process of products, reduces links of the production technology, lowers consumption, and solves the problems of the previous technology in the aspects.
Description
The invention relates to a kind of novel method of preparation N-alkyl naphthylamines, it is raw material that present method adopts naphthylamines and alcohol, in the presence of a kind of solid metal oxide catalyst, carries out dehydration reaction, with synthetic N-alkyl naphthylamines.
These compounds are intermediates of the important dyestuff of a class, pigment, rubber ingredients.Can be used for again synthetic pesticide, medicine etc.,
The production of early stage N-alkyl naphthylamines, be that employing hydrochloric ether and naphthylamines are that raw material carries out condensation reaction, be reflected in the autoclave and carry out, operating process intermittently, the acid that produces is serious to equipment corrosion, the subsequent processes complexity of reaction product, and side reaction is many, raw material consumption is big, and product yield is low.
According to German patent DE 2509040 introductions, adopt the reaction of 1 (2)-naphthols and methylamine or ethamine, with the carboxylic acid is catalyzer, in autoclave, 200 ℃ are reacted 30 hours synthetic N-methyl (or ethyl) naphthylamines down, owing to adopted weak acid catalysis, reduced corrosion, but fundamentally do not solved etching problem like this.Equally in the product purification process, still need carry out alkali neutralization, washing removing catalyzer carboxylic acid wherein, and speed of response to be too slow to reaction product, the reaction times is long partially.
German Patent 2544504 and 2549957 is introduced, and adopting naphthylamines and Fatty Alcohol(C12-C14 and C12-C18) is raw material, and perhaps naphthols and aliphatic amide are raw material, and under the triple phenoxyl phosphine catalyst, at 200-230 ℃, reaction is 10 hours in the autoclave, with synthetic relevant N-alkyl naphthylamines.According to German patent DE 2918023, adopting naphthylamines and Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol is raw material, at POCl again
3Under the catalysis, at 289 ℃, reaction contains the alpha-naphthylamine of 30w%, N-ethyl-alpha-naphthylamine of 52w% and the N of 6w%, N-diethyl-alpha-naphthylamine with the amine of synthetic monoalkyl and two alkyl in the autoclave of 6.0MPa in the thick liquid of acquisition.These two kinds of processing methodes, all adopting autoclave is reactor, periodical operation, though to some improvement of catalyzer, do not exceed acid catalyzed scope, under reaction conditions, catalyzer forms caustic soln with the water that reaction produces, and still equipment is constituted corrosion.And most of processes all will carry out alkali neutralization to reactant, and washing is to remove catalyzer wherein.
Method of the present invention is that to contain CuO 10-50w%, ZnO 70-10w% the rest is Al
2O
3Metal oxide be catalyzer, in the presence of hydrogen, in fixed bed successive reactor or in the high pressure tank reactor, be raw material with naphthylamines and alcohol, the dehydrogenation aminating reaction takes place, synthetic N-alkyl naphthylamines.
Catalyst system therefor of the present invention can be conventional CuO-ZnO-Al
2O
3Catalyzer can obtain by conventional preparation method, as: with the powder of CuO-ZnO and the pseudo-boehmite mixing moulding of peptization, drying, roasting again.
Among the present invention, so-called N-alkyl amine compound has following general formula:
Wherein: R
1Represent H, methyl or ethyl.
R
2Represent C
1～C
10Alkyl or C
4～C
10Cycloalkyl.
R
3Represent methylidene or ethyl.
The naphthylamines class raw material that adopts can be alpha-naphthylamine, beta-naphthylamine, methyl-alpha-naphthylamine, methyl-beta-naphthylamine, or N-methyl-α (β)-naphthylamines, N-ethyl-α (β)-naphthylamines, and optimal raw material is alpha-naphthylamine and beta-naphthylamine.
In theory, all Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol can be as alkylating raw materials.But be suitable for raw polyol of the present invention can be C
1-C
10Fatty Alcohol(C12-C14 and C12-C18) or C
4-C
10Alicyclic ring alcohol, with C
1-C
4Fatty Alcohol(C12-C14 and C12-C18) and C
5-C
8Alicyclic ring alcohol optimum.
Based on reaction process of the present invention, can in fixed bed successive reactor, carry out, also can in the high pressure tank reactor, carry out, be reflected under the hydrogen stream or nitrogen gas stream under carry out, also can not face hydrogen or face nitrogen, but best under hydrogen stream, to carry out, because can keep the permanent activity of catalyzer like this.
Before using, must at first carry out reduction activation based on catalyzer of the present invention, make copper oxide reduction wherein, can play katalysis like this it.
Can carry out between 200～350 ℃ of the temperature based on reaction of the present invention, be the best with 250～350 ℃.
The pressure of reaction can be between normal pressure～10.0MPa, and the hydrogen dividing potential drop is 0.0～10.0MPa.With the charging naphthylamines, when normal pressure, be gas phase, at this moment Fan Ying transformation efficiency is higher, but catalyst activity reduction is very fast.Under the condition of pressurization, naphthylamines is a liquid phase, though the transformation efficiency of reaction is low slightly, catalyst activity reduction is slow, and the life-span is long.Too high pressure can cause the hydrogenation of naphthalene nucleus again, and side reaction increases, so optimal pressure is normal pressure～5.0MPa.
The ratio range of reaction feed can change in a very wide scope, and the mol ratio of alcohol and naphthylamines can be 0.5～20: between 1, the ratio range of the best is 1: 1～5: 1.
The air speed of reaction feed, in mixture, volume space velocity is at 0.1～10.0h during the liquid of charging
-1Between, with 0.2～5.0h
-1Between be best.
The primary process that realizes the inventive method can be described as:
One. fixed bed continous way: naphthylamines that proportioning is good and corresponding alcohol, through volume pump, and after mixing, squeezes in the feed preheater hydrogen, enter after the heating in the fixed bed cartridge reactor that catalyzer is housed, under certain temperature and pressure, react, reactant is after cooling off, isolating hydrogen, acquisition one contains the mixture of N-alkylnaphthalene amine product and unreacting material, directly this mixture is distilled the acquisition product, after unconverted raw material steams, loop back and continue reaction in the reactor.
Two. the autoclave formula: naphthylamines that proportioning is good and relevant alcohol, add in the autoclave, and catalyst fines added in the lump, the reactor that closes feeds hydrogen, be heated to temperature of reaction after, stirring reaction 8～10 hours.Reaction finishes, and after the cooling, after reacting liquid filtering fell catalyzer, distillation obtained product.
The advantage of the inventive method is, has changed the catalysis method that adopts acid and acidic cpd in technological process, has fundamentally solved the equipment corrosion problem.And reaction process takes operate continuously, is easy to automatic control, the selectivity height of product, and consumption of raw materials is low; Reaction product can get product by straight run distillation without aftertreatment, has reduced the generation of sewage, and problem of environmental pollution is not outstanding.This of Cai Yonging type catalyzer is base metal in addition, and is cheap.
Example 1
Adopting ethanol and alpha-naphthylamine is the synthetic N-ethyl-alpha-naphthylamine of raw material.Proportion of raw materials (mole) is an ethanol: alpha-naphthylamine=1.2: 1.
At an internal diameter is in the tubular fixed-bed reactor of 14mm, and the granularity of packing into 8～20 purposes contain CuO35w%, ZnO 45w%, Al
2O
3The catalyzer 30ml of 20w% squeezes into mixing raw material to this reactor continuously by certain air speed, and feeds hydrogen simultaneously, carries out gas-phase reaction under normal pressure, certain temperature.Enter a gas-liquid separator after the reaction product cooling, isolate hydrogen after, obtain the reactant of liquid, through gas chromatographic analysis, calculate the selectivity of the transformation efficiency and the product N-ethyl-alpha-naphthylamine of alpha-naphthylamine.The results are shown in Table 1.
Table 1
| Temperature, ℃ | Air speed, h -1 | The transformation efficiency of alpha-naphthylamine, w% | The selectivity of N-ethyl-alpha-naphthylamine, w% | N, the selectivity of N-diethyl-alpha-naphthylamine, w% |
| 290 300 310 320 290 | 1.0 0.5 2.0 3.0 | 76.5 80.3 84.7 89.7 78.6 67.5 58.9 | 92.5 92.3 90.8 88.7 90.6 93.4 95.3 | 2.2 2.5 3.4 5.6 6.5 1.6 0.7 |
Example 2
Adopting ethanol and alpha-naphthylamine is the synthetic N-ethyl-alpha-naphthylamine of raw material.Proportion of raw materials (mole) is an ethanol: alpha-naphthylamine=1.8: 1.
In the reactive system identical with example one, packing into contains CuO 20w%, ZnO 60w%, Al
2O
3The catalyzer 30ml of 20w%.Be reflected under the 2.0MPa hydrogen pressure and carry out, alpha-naphthylamine at this moment is liquid phase under reaction conditions.
At 2.0MPa, 290 ℃, charging air speed 0.4h
-1Under the condition, through 720 hours continuous operation, the selectivity of the transformation efficiency of alpha-naphthylamine and N-ethyl-alpha-naphthylamine was not fallen as follows.The results are shown in Table 2.
Table 2
| Temperature, ℃ | Air speed, h -1 | The transformation efficiency of alpha-naphthylamine, w% | The selectivity of N-ethyl-alpha-naphthylamine, w% | N, the selectivity of N-diethyl-α-naphthylamines, w% |
| 250 270 290 310 290 | 0.4 0.2 1.0 1.5 | 22.8 37.2 54.6 60.1 59.3 41.9 29.7 | 92.8 91.3 90.4 87.3 87.5 92.1 93.2 | 3.2 3.9 4.5 6.2 5.3 2.7 1.8 |
Example 3
Adopting alpha-naphthylamine and methyl alcohol is raw material, synthetic N-methyl-alpha-naphthylamine, and proportion of raw materials (mole) is a methyl alcohol: alpha-naphthylamine=1.5: 1.
In the reactive system identical with example one, packing into contains CuO 45w%, ZnO 30w%, Al
2O
3The catalyzer 30ml of 15w%.Volume space velocity 0.2h when mixing raw material is pressed liquid
-1Squeeze into reactor,, react under 290 ℃ of conditions at the 2.0MPa hydrogen pressure, the cooled product of reaction by analysis, the transformation efficiency that calculates alpha-naphthylamine is 42.3w%, the selectivity that obtains N-methyl-alpha-naphthylamine is 94.0w%, N, the selectivity of N-dimethyl-is 2.0w%.
Example 4
Adopting alpha-naphthylamine and n-propyl alcohol is raw material, synthetic N-n-propyl-alpha-naphthylamine, and proportion of raw materials (mole) is a n-propyl alcohol: alpha-naphthylamine=2.0: 1.
In the reactive system identical with example one, packing into contains CuO 35w%, ZnO 45w%, Al
2O
3The catalyzer 30ml of 20w%.Volume space velocity 0.4h when mixing raw material is pressed liquid
-1Squeeze into reactor,, react under 290 ℃ of conditions at the 2.0MPa hydrogen pressure, the cooled product of reaction by analysis, the transformation efficiency that calculates alpha-naphthylamine is 46.6w%, the selectivity that obtains N-n-propyl-alpha-naphthylamine is 95.3w%, N, the selectivity of N-di-alpha-naphthylamine is 2.0w%.
Example 5
Adopting alpha-naphthylamine and Virahol is raw material, synthetic N-sec.-propyl-alpha-naphthylamine, and proportion of raw materials (mole) is a Virahol: alpha-naphthylamine=2.5: 1.
In the reactive system identical with example one, packing into contains CuO 20w%, ZnO 55w%, Al
2O
3The catalyzer 30ml of 25w%.Volume space velocity 0.4h when mixing raw material is pressed liquid
-1Squeeze into reactor,, react under 290 ℃ of conditions at the 2.0MPa hydrogen pressure, the cooled product of reaction by analysis, the transformation efficiency that calculates alpha-naphthylamine is 39.7w%, the selectivity that obtains N-sec.-propyl-alpha-naphthylamine is 97.6w%, N is not arranged, and N-di-isopropyl-alpha-naphthylamine is detected.
Example 6
Adopting alpha-naphthylamine and propyl carbinol is raw material, synthetic N-normal-butyl-alpha-naphthylamine, and proportion of raw materials (mole) is a propyl carbinol: alpha-naphthylamine=2.0: 1.
In the reactive system identical with example one, packing into contains CuO 35w%, ZnO 40w%, Al
2O
3The catalyzer 30ml of 25w%.Volume space velocity 0.4h when mixing raw material is pressed liquid
-1Squeeze into reactor,, react under 290 ℃ of conditions at the 2.0MPa hydrogen pressure, the cooled product of reaction by analysis, the transformation efficiency that calculates alpha-naphthylamine is 39.7w%, the selectivity that obtains N-normal-butyl-alpha-naphthylamine is 97.3w%, no N, N-di-n-butyl-alpha-naphthylamine is detected.
Example 7
Adopting alpha-naphthylamine and hexalin is raw material, synthetic N-cyclohexyl-alpha-naphthylamine, and proportion of raw materials (mole) is a cyclic group alcohol: alpha-naphthylamine=2.0: 1.
In the reactive system identical with example one, packing into contains CuO 45w%, ZnO 40w%, Al
2O
3The catalyzer of 15w%.Volume space velocity 0.2h when mixing raw material is pressed liquid
-1Squeeze into reactor,, react under 290 ℃ of conditions at the 2.0MPa hydrogen pressure, the cooled product of reaction by analysis, the transformation efficiency that calculates alpha-naphthylamine is 32.5w%, the selectivity that obtains N-cyclohexyl-alpha-naphthylamine is 98.4w%, no N, N-dicyclohexyl-alpha-naphthylamine is detected.
Example 8
Adopting beta-naphthylamine and ethanol is raw material, synthetic N-ethyl-beta-naphthylamine, and proportion of raw materials (mole) is an ethanol: beta-naphthylamine=1.5: 1.
In the reactive system identical with example one, packing into contains CuO 35w%, ZnO 25w%, Al
2O
3The catalyzer of 40w%.Volume space velocity 0.4h when mixing raw material is pressed liquid
-1Squeeze into reactor,, react under 290 ℃ of conditions at the 2.0MPa hydrogen pressure, the cooled product of reaction by analysis, the transformation efficiency that calculates beta-naphthylamine is 64.4w%, the selectivity that obtains N-ethyl-beta-naphthylamine is 87.4w%, N, the selectivity of N-diethyl-beta-naphthylamine is 9.2w%.
Example 9
With mol ratio is ethanol: the ethanol and the alpha-naphthylamine mixture 200g of alpha-naphthylamine=1.5: 1, add in the autoclave of 1000ml, and pack into after the catalyzer 50g pulverizing with embodiment 3 and press in the still, feed hydrogen to reactor, be heated to 280 ℃, pressure reaches 8.0MPa, stir after 8 hours, cooling bleeds off hydrogen pressure, filter out catalyst fines, reaction solution is analyzed, and the transformation efficiency that calculates alpha-naphthylamine is 85.0w%, and the selectivity of N-ethyl methyl naphthylamine is 62.3w%, N, the selectivity of N-diethyl methyl naphthylamine is 8.4w%.
Claims (8)
1. the preparation method of a N-alkyl naphthylamines has following general formula with the alkyl naphthylamines of this method preparation:
Wherein: R
1Represent H, methyl or ethyl;
R
2Represent C
1～C
10Alkyl or C
4～C
10Cycloalkyl;
R
3Represent methylidene or ethyl; It is characterized in that with alcohol naphthylamines and alkyl or cycloalkyl be raw material, the mole proportioning of raw alcohol and naphthylamines is 0.5: 1～20: 1, contains CuO 10～50 weight % after reduction activation, and ZnO 70～10 weight % the rest is Al
2O
3Metal oxide catalyst exist down, under 200～350 ℃, 0.0～10.0MPa hydrogen pressure, carry out chemical reaction.
2. method according to claim 1 is characterized in that being reflected in the tank reactor and carries out, and the reaction times is 8～10 hours.
3. method according to claim 1 is characterized in that being reflected in the continuous fixed-bed reactor and carries out, and volume space velocity is 0.1～10.0h during the liquid of charging
-1
4. method according to claim 1, reaction is carried out in the presence of hydrogen.
5. method according to claim 1, the temperature that reaction is carried out is between 250～350 ℃.
6. method according to claim 1, the pressure that reaction is carried out is between normal pressure～5.0MPa.
7. method according to claim 1, when carrying out successive reaction in fixed-bed reactor, volume space velocity is at 0.2～5.0h during the liquid of mixing raw material charging
-1Between.
8. method according to claim 1, the mole proportioning of used raw alcohol and naphthylamines is between 1: 1～5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119109A CN1079391C (en) | 1997-10-09 | 1997-10-09 | Preparation of N-alkyl naphthylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119109A CN1079391C (en) | 1997-10-09 | 1997-10-09 | Preparation of N-alkyl naphthylamines |
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| Publication Number | Publication Date |
|---|---|
| CN1214338A CN1214338A (en) | 1999-04-21 |
| CN1079391C true CN1079391C (en) | 2002-02-20 |
Family
ID=5175194
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97119109A Expired - Fee Related CN1079391C (en) | 1997-10-09 | 1997-10-09 | Preparation of N-alkyl naphthylamines |
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| Country | Link |
|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU644526A1 (en) * | 1976-06-09 | 1979-01-30 | Предприятие П/Я А-7850 | Catalyst for alkylation of aromatic amines with alcohols |
| HUT44479A (en) * | 1985-11-10 | 1988-03-28 | Nitroil Vegyipari Termeloe Fej | Process for selective n-alkylization of aromatic amins |
| JPS6391351A (en) * | 1986-10-06 | 1988-04-22 | Mitsui Petrochem Ind Ltd | Production of n-alkylated aromatic amines |
-
1997
- 1997-10-09 CN CN97119109A patent/CN1079391C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU644526A1 (en) * | 1976-06-09 | 1979-01-30 | Предприятие П/Я А-7850 | Catalyst for alkylation of aromatic amines with alcohols |
| HUT44479A (en) * | 1985-11-10 | 1988-03-28 | Nitroil Vegyipari Termeloe Fej | Process for selective n-alkylization of aromatic amins |
| JPS6391351A (en) * | 1986-10-06 | 1988-04-22 | Mitsui Petrochem Ind Ltd | Production of n-alkylated aromatic amines |
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| Publication number | Publication date |
|---|---|
| CN1214338A (en) | 1999-04-21 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
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Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
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