CN106083650A - A kind of preparation method of efficient power-saving environmental protection N ethyl n cyanoethyl aniline - Google Patents
A kind of preparation method of efficient power-saving environmental protection N ethyl n cyanoethyl aniline Download PDFInfo
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- CN106083650A CN106083650A CN201610410538.9A CN201610410538A CN106083650A CN 106083650 A CN106083650 A CN 106083650A CN 201610410538 A CN201610410538 A CN 201610410538A CN 106083650 A CN106083650 A CN 106083650A
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- WYRNRZQRKCXPLA-UHFFFAOYSA-N 3-(n-ethylanilino)propanenitrile Chemical compound N#CCCN(CC)C1=CC=CC=C1 WYRNRZQRKCXPLA-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000007613 environmental effect Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 194
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 167
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 239000012043 crude product Substances 0.000 claims abstract description 84
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000654 additive Substances 0.000 claims abstract description 71
- 230000000996 additive effect Effects 0.000 claims abstract description 71
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 68
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011592 zinc chloride Substances 0.000 claims abstract description 34
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 34
- 238000004821 distillation Methods 0.000 claims abstract description 30
- 210000005252 bulbus oculi Anatomy 0.000 claims abstract description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 22
- 238000003825 pressing Methods 0.000 claims abstract description 9
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims description 214
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 153
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- 238000010438 heat treatment Methods 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 51
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 51
- 230000003068 static effect Effects 0.000 claims description 42
- -1 compound rare-earth Chemical class 0.000 claims description 39
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 34
- 230000003472 neutralizing effect Effects 0.000 claims description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 29
- 238000009835 boiling Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- FENJKTQEFUPECW-UHFFFAOYSA-N 3-anilinopropanenitrile Chemical compound N#CCCNC1=CC=CC=C1 FENJKTQEFUPECW-UHFFFAOYSA-N 0.000 claims description 15
- 230000009471 action Effects 0.000 claims description 15
- 238000009413 insulation Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 230000000630 rising effect Effects 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 14
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 8
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 8
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 8
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 8
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 8
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 13
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000002075 main ingredient Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 7
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 150000002828 nitro derivatives Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- Chemical Kinetics & Catalysis (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is the preparation method of efficient power-saving environmental protection N ethyl n cyanoethyl aniline, it is pressed in including, neutralizes reaction, rectification additive reaction and distillation, in be pressed into, in pressing reactor in ethanol, aniline and the first catalyst being put into, first catalyst is mixed by weight 5:1 2 with copper chromium by phosphorus oxychloride, and reaction obtains rectification after N MEA crude product after terminating；In additive reaction, putting in additive reaction still by N MEA and propylene eyeball and the second catalyst, the second catalyst is mixed by weight 6:2 with copper chromium by zinc chloride, and reaction terminates to obtain distillation after N ethyl n cyanoethyl aniline crude product.The present invention can further improve the reaction selectivity of N ethyl n cyanoethyl aniline；While reducing utilization of energy and shortening the response time, separately improve again the selectivity of N ethyl n cyanoethyl aniline.
Description
Technical field
The present invention relates to the preparation method of N-ethylaniline, a kind of efficient power-saving environmental protection N-ethyl n-cyanogen
The preparation method of MEA.
Background technology
N-ethylaniline be azo dye and kiton colors important centre stop, it may also be used for rubber chemicals, explosive,
The intermediate of the fine chemicals such as photographic material.
In prior art, the preparation technology of N-ethylaniline is mainly: reaction, by aniline with ethanol at catalyst, pressure
Effect under, generate N-ethylaniline and N, N-diethylaniline, the selection of catalyst can use hydrochloric acid, sulphuric acid, phosphorus oxychloride
Deng compound, reaction temperature at 230-250 DEG C, gauge pressure 3-4.5MPa, about 10 hours response time, in the product obtained,
Aniline content 28-31%, N-ethylaniline content 58-60%, N, N-diethylbenzene amine content 8-10%.Rectification, rectification tower reactor system
System vacuum 0.1MPa, collects the first fraction aniline, recovery according to temperature difference, and the second fraction is N-MEA,
3rd fraction is N, N-diethylaniline.For the technical problem that above N-MEA selectivity is low, prior art carries
Go out, catalyst is made into any two composition in phosphorus oxychloride, Phosphorous chloride., phosphorus pentachloride, Phosphorous chloride. and mineral acid
Binary catalyst, under the conditions of equivalent responses, in the product obtained, aniline content 26%, N-ethylaniline content 68%, N,
N-diethylbenzene amine content 5-6%, can improve about 10% by practical N-ethylaniline selectivity；But, N-ethylaniline selectivity is the most not
It is the highest, and the whole response time is longer, about need about 10 hours, have much room for improvement.N-ethyl n-cyanoethyl aniline by
N-ethylaniline and propylene eyeball react under catalyst action and prepare, in prior art, for N-ethyl n-cyanoethyl aniline system
Standby catalyst is zinc chloride, or is urged by two kinds of binary formed any in aluminum chloride, zinc chloride, glacial acetic acid, hydroquinone
Changing, the reaction selectivity using both catalyst ns-ethyl n-cyanoethyl aniline is not the most the highest, and the former is about about 90% years old, after
Person is about about 92%, and the whole response time is longer, about needs about 12 hours, haves much room for improvement.
Summary of the invention
The technical problem to be solved is:
Improve the reaction selectivity of N-ethylaniline the most further；
While reducing utilization of energy and shortening the response time, the most how to improve again the reaction selectivity of N-ethylaniline；
Improve the reaction selectivity of N-ethyl n-cyanoethyl aniline the most further；
The most how reduce utilization of energy and shorten N-ethyl n-cyanoethyl aniline response time the most do not reduce simultaneously N-ethyl n-
The reaction selectivity of cyanoethyl aniline.
The present invention solves the technical scheme of above technical problem:
The preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, comprises the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:1-2 with copper chromium, with 2-2.5 hour, middle pressure reactor temperature is risen to 150 ± 5 DEG C, pressure
Rising to 1.7-1.8Mpa, then stop heating, due to exothermic heat of reaction, in 1-1.5 hour, middle pressure reactor temperature rises to voluntarily
300 ± 5 DEG C, pressure rises to 27-28MPa, treats that temperature is down to 195-210 DEG C subsequently, and pressure is down to heat-insulation pressure keeping during 25-28MPa
Reacting reaction in 2-2.5 hour to terminate, reaction terminates rear discharging to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: putting into liquid caustic soda in reactor to neutralizing and stir 5-7 minute, pH value is more than 12 in neutralizing reactor
Time, stopping static 11-13 minute of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs
Mixing 5-7 minute, static 11-13 minute, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed, with 30-35 minute by additive reaction still by weight 6:1-2 with copper chromium by zinc chloride
Interior temperature rises to 65-67 DEG C, and due to exothermic heat of reaction, within 35-37 minute, additive reaction temperature in the kettle rises to 89-91 DEG C voluntarily, pressure
Rising to 0.09-0.1MPa, keep temperature 89-91 DEG C, pressure 0.09-0.1MPa reacts reaction in 8-9 hour to be terminated, then limit stirring
Limit adds liquid caustic soda (liquid caustic soda content more than 30%) and is neutralized, and after having added liquid caustic soda static 10-12 minute, obtains N-ethyl n-cyanogen
MEA crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
The present invention in be pressed into, use and first urged by what phosphorus oxychloride and copper chromium 5:1-2 by weight mixed
Agent, N-ethylaniline selectivity reaches about 75%, and middle phosphorus oxychloride single catalyst can realize reaction compared to existing technology
Selectivity improves about 15%；The binary being made up of phosphorus oxychloride and Phosphorous chloride. or mineral acid in compared to existing technology urges the agent can
The selectivity realizing reaction improves about 5%；And copper chromium is for being a kind of environment-friendly materials, can avoid increasing use Phosphorous chloride. and
Mineral acid, serves good environment protecting while reducing cost.It addition, during the present invention is pressed into, use zone heating,
First with 2-2.5 hour, middle pressure reactor temperature is risen to 150 ± 5 DEG C, then utilize exothermic heat of reaction to make temperature at 1-1.5 hour
Rise to 300 ± 5 DEG C voluntarily, within 2-2.5 hour, i.e. complete reaction with 195-210 DEG C of reaction；And existing the most in the art it is generally required to
230-240 DEG C is reacted about 10 hours, and compared to existing technology, the application reaction temperature is low, utilizes id reaction heat release at high temperature
Duan Fanying, reacted total used time within 7 hours, shortened the response time while reducing utilization of energy, improve production effect
Rate；It addition, by zone heating, MEA selectivity reaches about 80%, can additionally improve the selectivity about 5% of reaction,
Obtain beyond thought technique effect.
The present invention in be pressed into and rectification add and neutralize reaction, add in liquid caustic soda (liquid caustic soda content more than 30%)
The purpose of no effuent discharge is reached after with.
In order to improve the selectivity of N-ethylaniline further, it is found by the applicant that return in alcohol water thick possibly together with N-ethylaniline
Product, through analyzing, the Main Ingredients and Appearance returning alcohol water has: ethanol about 10%, water about 70%, and N-ethylaniline crude product about 20% is existing
Technology does not carry out rectification to returning alcohol water, and the present invention by be pressed in the alcohol water that returns be put into receiving slit and be collected, and
It is entered together with N-ethylaniline crude product subliming by heating in rectifying still, the N-ethylaniline in alcohol water can be reclaimed back, enter
One step improves the selectivity of N-ethylaniline.
In additive reaction of the present invention, use the second catalyst mixed by weight 6:1-2 by zinc chloride with copper chromium,
The reaction selectivity of N-ethyl n-cyanoethyl aniline reaches about 95%, and middle zinc chloride single catalyst can be real compared to existing technology
The selectivity now reacted improves about 5%；By by aluminum chloride, zinc chloride, glacial acetic acid, hydroquinone in compared to existing technology
The binary catalyst of any two kinds of compositions can realize the selectivity of reaction and improve about 3%；And copper chromium is for being a kind of environment-friendly materials, fall
Good environment protecting is served while low cost.It addition, in additive reaction of the present invention, use zone heating, use 30-35
Minute additive reaction temperature in the kettle being risen to 65-67 DEG C, due to exothermic heat of reaction, 35-37 minute additive reaction temperature in the kettle is voluntarily
Rising to 89-91 DEG C, then heat-insulation pressure keeping reacts reaction in 8-9 hour and terminates, and existing the most in the art it is generally required to 85-95 DEG C of reaction
About 12 hours, compared to existing technology, the application utilized id reaction heat release to react in high temperature section, reacts total used time little 10.5
Time within, shorten the response time while reducing utilization of energy, improve production efficiency.
The technical scheme that the present invention limits further is:
The preparation method of aforesaid efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, has wherein been also added with in the first catalyst
Compound rare-earth, the addition of described compound rare-earth is the 5-7% of phosphorus oxychloride and copper chromium gross weight, the quality of described compound rare-earth
Percent composition is: cerium: 2-4%, neodymium: 17-19%, gadolinium: 7-9%, lutecium: 1-3%, dysprosium: 2-4%, praseodymium: 7-9%, holmium: 9-11%, erbium: 5-
7%, surplus is lanthanum.The present invention is by increasing compound rare-earth in the first catalyst, and MEA selectivity reaches about 85%, than
Use the first catalyst that phosphorus oxychloride and copper chromium combine under the conditions of equivalent responses, the selectivity about 5% of reaction can be improved,
Obtain beyond thought technique effect.
Accompanying drawing explanation
Fig. 1 is the process chart being pressed into reaction in the present invention.
Fig. 2 is the process chart of additive reaction of the present invention.
Detailed description of the invention
Embodiment 1
The present embodiment is the preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, technological process such as Fig. 1 and
Shown in Fig. 2, mainly comprise the steps that
(i) be pressed in: press in reactor during ethanol, aniline and the first catalyst are put into, the first catalyst by phosphorus oxychloride with
Copper chromium mixes by weight 5:1, and aniline content more than 99.96% witch's nitro compounds exists, and during ethanol 20 DEG C, ethanol density is more than
95 DEG C, phosphorus oxychloride content more than 99.3%, charge ratio: ethanol 550kg, aniline 1600kg, the first catalyst 35kg(high pressure
Volume 3500 liter)；With 2 hours, middle pressure reactor temperature being risen to 150 DEG C, pressure rises to 1.7Mpa, then stops heating,
Due to exothermic heat of reaction, in 1 hour, middle pressure reactor temperature rises to 300 DEG C voluntarily, and pressure rises to 27MPa, treats that temperature drops subsequently
To 195 DEG C, when pressure is down to 25MPa, heat-insulation pressure keeping reacts reaction in 2 hours and terminates, and reaction terminates rear discharging to neutralizing reactor,
Return alcohol water and be put into receiving slit.
(ii) reaction is neutralized: putting into liquid caustic soda in reactor to neutralizing and stir 5 minutes, pH value is more than 12 in neutralizing reactor
Time, stopping static 11 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water stirring 5
Minute, static 11 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
Through analyzing, crude product Main Ingredients and Appearance has: ethanol 0.2%, water 0.8%, aniline 15%, N-ethylaniline 79%, N-N-diethylbenzene
Amine 5%；
Return alcohol water Main Ingredients and Appearance to have: ethanol about 10%, water about 70%, N-ethylaniline crude product about 20%.
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still, according to the boiling point of its composition with N-ethylaniline crude product
Difference is separated ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline one by one through rectification tower body；It is specially
Temperature collects aniline less than 135 DEG C, and temperature collects N-ethylaniline at 145 DEG C, and temperature collects N, N-diethylbenzene at 150 DEG C
Amine；
(iv) additive reaction: the pure N-ethylaniline that (iii) 4500 steps are obtained and 2750 propylene eyeball propylene eyeballs and 290
Two catalyst put in 8,000 liter additive reaction stills, and the second catalyst is mixed by weight 6:1 with copper chromium by zinc chloride,
With 30 minutes, additive reaction temperature in the kettle being risen to 65 DEG C, due to exothermic heat of reaction, within 35 minutes, additive reaction temperature in the kettle rises voluntarily
To 89 DEG C, pressure rises to 0.09MPa, keeps temperature 89 DEG C, and pressure 0.09MPa reacts reaction in 8 hours to be terminated, the most while stirring
Add 60 liquid caustic soda (liquid caustic soda content more than 30%) to be neutralized, after having added liquid caustic soda static 10 minutes, obtain N-ethyl n-cyanogen second
Base aniline crude product；
Through analyzing, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 95%, acrylonitrile
About 1.0%, ethyl about 4.0%；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated；Specifically, in vacuum 0.1MPa, temperature is less than 180 DEG C, collects low boilers, temperature
Rise to 185-190 DEG C and collect main evaporating for N-ethyl n-cyanoethyl aniline, through analyzing, N-ethyl n-cyanoethyl aniline content
More than 99.3%, acrylonitrile about 0.05%, within N-ethylaniline 0.5%.
Embodiment 2
The present embodiment is the preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, technological process such as Fig. 1 and
Shown in Fig. 2, mainly comprise the steps that
(i) be pressed in: press in reactor during ethanol, aniline and the first catalyst are put into, the first catalyst by phosphorus oxychloride with
Copper chromium mixes by weight 5:1.5, and aniline content more than 99.96% witch's nitro compounds exists, and during ethanol 20 DEG C, ethanol density is big
In 95 DEG C, phosphorus oxychloride content more than 99.3%, charge ratio: ethanol 550kg, aniline 1600kg, the first catalyst 35kg(are high
Pressure-volume amasss 3500 liters)；With 2.2 hours, middle pressure reactor temperature being risen to 145 DEG C, pressure rises to 1.7Mpa, then stops
Heating, due to exothermic heat of reaction, in 1.2 hours, middle pressure reactor temperature rises to 295 DEG C voluntarily, and pressure rises to 27MPa, treats subsequently
Temperature is down to 200 DEG C, and when pressure is down to 26MPa, heat-insulation pressure keeping reacts 2.2 hours to react and terminates, and reaction terminates rear discharging to neutralizing
Reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 6 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 12 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 6 points
Clock, static 12 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
Through analyzing, crude product Main Ingredients and Appearance has: ethanol 0.6%, water 0.7%, aniline 14%, N-ethylaniline 80%, N-N-diethylbenzene
Amine 5%；
Return alcohol water Main Ingredients and Appearance to have: ethanol about 10%, water about 70%, N-ethylaniline crude product about 20%.
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still, according to the boiling point of its composition with N-ethylaniline crude product
Difference is separated ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline one by one through rectification tower body；It is specially
Temperature collects aniline less than 135 DEG C, and temperature collects N-ethylaniline at 145 DEG C, and temperature collects N, N-diethylbenzene at 150 DEG C
Amine；
(iv) additive reaction: the pure N-ethylaniline that (iii) 4500 steps are obtained and 2750 propylene eyeball propylene eyeballs and 290
Two catalyst put in 8,000 liter additive reaction stills, the second catalyst mixed with copper chromium 6:1.5 by weight by zinc chloride and
Becoming, with 33 minutes, additive reaction temperature in the kettle is risen to 66 DEG C, due to exothermic heat of reaction, 36 minutes additive reaction temperature in the kettle are voluntarily
Rising to 90 DEG C, pressure rises to 0.095MPa, keeps temperature 90 DEG C, and pressure 0.095MPa reacts reaction in 8.5 hours to be terminated, then limit
Stirring limit adds liquid caustic soda (liquid caustic soda content more than 30%) and is neutralized, and after having added liquid caustic soda static 11 minutes, obtains N-ethyl n-cyanogen
MEA crude product；
Through analyzing, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 95%, acrylonitrile
About 1.0%, ethyl about 4.0%；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated；Specifically, in vacuum 0.1MPa, temperature is less than 180 DEG C, collects low boilers, temperature
Rise to 185-190 DEG C and collect main evaporating for N-ethyl n-cyanoethyl aniline, through analyzing, N-ethyl n-cyanoethyl aniline content
More than 99.3%, acrylonitrile about 0.05%, within N-ethylaniline 0.5%.
Embodiment 3
The present embodiment is the preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, technological process such as Fig. 1 and
Shown in Fig. 2, mainly comprise the steps that
(i) be pressed in: press in reactor during ethanol, aniline and the first catalyst are put into, the first catalyst by phosphorus oxychloride with
Copper chromium mixes by weight 5:2, and aniline content more than 99.96% witch's nitro compounds exists, and during ethanol 20 DEG C, ethanol density is more than
95 DEG C, phosphorus oxychloride content more than 99.3%, charge ratio: ethanol 550kg, aniline 1600kg, the first catalyst 35kg(high pressure
Volume 3500 liter)；With 2.5 hours, middle pressure reactor temperature being risen to 155 DEG C, pressure rises to 1.8Mpa, then stops adding
Heat, due to exothermic heat of reaction, in 1.5 hours, middle pressure reactor temperature rises to 305 DEG C voluntarily, and pressure rises to 28MPa, treats temperature subsequently
Degree is down to 210 DEG C, and when pressure is down to 28MPa, heat-insulation pressure keeping reacts 2 hours to react and terminates, and reaction terminates rear discharging to neutralizing reaction
Still, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 7 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 13 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 7 points
Clock, static 13 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
Through analyzing, crude product Main Ingredients and Appearance has: ethanol 0.4%, water 0.6%, aniline 12%, N-ethylaniline 81%, N-N-diethylbenzene
Amine 6%；
Return alcohol water Main Ingredients and Appearance to have: ethanol about 10%, water about 70%, N-ethylaniline crude product about 20%.
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still, according to the boiling point of its composition with N-ethylaniline crude product
Difference is separated ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline one by one through rectification tower body；It is specially
Temperature collects aniline less than 135 DEG C, and temperature collects N-ethylaniline at 145 DEG C, and temperature collects N, N-diethylbenzene at 150 DEG C
Amine；
(iv) additive reaction: the pure N-ethylaniline that (iii) 4500 steps are obtained and 2750 propylene eyeball propylene eyeballs and 290
Two catalyst put in 8,000 liter additive reaction stills, and the second catalyst is mixed by weight 6:2 with copper chromium by zinc chloride,
With 35 minutes, additive reaction temperature in the kettle being risen to 67 DEG C, due to exothermic heat of reaction, within 37 minutes, additive reaction temperature in the kettle rises voluntarily
To 91 DEG C, pressure rises to 0.1MPa, keeps temperature 91 DEG C, and pressure 0.1MPa reacts reaction in 9 hours to be terminated, and adds the most while stirring
Enter liquid caustic soda (liquid caustic soda content more than 30%) to be neutralized, after having added liquid caustic soda static 12 minutes, obtain N-ethyl n-cyanoethyl aniline
Crude product；
Through analyzing, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 95%, acrylonitrile
About 1.0%, ethyl about 4.0%；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated；Specifically, in vacuum 0.1MPa, temperature is less than 180 DEG C, collects low boilers, temperature
Rise to 185-190 DEG C and collect main evaporating for N-ethyl n-cyanoethyl aniline, through analyzing, N-ethyl n-cyanoethyl aniline content
More than 99.3%, acrylonitrile about 0.05%, within N-ethylaniline 0.5%.
Embodiment 4
The present embodiment is the preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, technological process such as Fig. 1 and
Shown in Fig. 2, mainly comprise the steps that
(i) be pressed in: press in reactor during ethanol, aniline and the first catalyst are put into, the first catalyst by phosphorus oxychloride with
Copper chromium mixes by weight 5:1, has been also added with compound rare-earth in the first catalyst, and the addition of compound rare-earth is trichlorine oxygen
Phosphorus and the 5% of copper chromium gross weight, the mass percent component of compound rare-earth is: cerium: 2%, neodymium: 17%, gadolinium: 7%, lutecium: 1%, dysprosium: 2%,
Praseodymium: 7%, holmium: 9%, erbium: 5%, surplus is lanthanum；Aniline content more than 99.96% witch's nitro compounds exists, ethanol density during ethanol 20 DEG C
More than 95 DEG C, phosphorus oxychloride content more than 99.3%, charge ratio: ethanol 550kg, aniline 1600kg, the first catalyst 35kg
(high pressure volume 3500 liter)；With 2 hours, middle pressure reactor temperature being risen to 150 DEG C, pressure rises to 1.7Mpa, then stops
Heating, due to exothermic heat of reaction, in 1 hour, middle pressure reactor temperature rises to 300 DEG C voluntarily, and pressure rises to 27MPa, treats temperature subsequently
Degree is down to 195 DEG C, and when pressure is down to 25MPa, heat-insulation pressure keeping reacts 2 hours to react and terminates, and reaction terminates rear discharging to neutralizing reaction
Still, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 5 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 11 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 5 points
Clock, static 11 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
Through analyzing, crude product Main Ingredients and Appearance has: ethanol 0.2%, water 0.8%, aniline 9%, N-ethylaniline 84%, N-N-diethylaniline
6%；
Return alcohol water Main Ingredients and Appearance to have: ethanol about 10%, water about 70%, N-ethylaniline crude product about 20%.
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still, according to the boiling point of its composition with N-ethylaniline crude product
Difference is separated ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline one by one through rectification tower body；It is specially
Temperature collects aniline less than 135 DEG C, and temperature collects N-ethylaniline at 145 DEG C, and temperature collects N, N-diethylbenzene at 150 DEG C
Amine；
(iv) additive reaction: the pure N-ethylaniline that (iii) 4500 steps are obtained and 2750 propylene eyeball propylene eyeballs and 290
Two catalyst put in 8,000 liter additive reaction stills, and the second catalyst is mixed by weight 6:1 with copper chromium by zinc chloride,
With 30 minutes, additive reaction temperature in the kettle being risen to 65 DEG C, due to exothermic heat of reaction, within 35 minutes, additive reaction temperature in the kettle rises voluntarily
To 89 DEG C, pressure rises to 0.09MPa, keeps temperature 89 DEG C, and pressure 0.09MPa reacts reaction in 8 hours to be terminated, the most while stirring
Add liquid caustic soda (liquid caustic soda content more than 30%) to be neutralized, after having added liquid caustic soda static 10 minutes, obtain N-ethyl n-cyanoethyl benzene
Amine crude product；
Through analyzing, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 95%, acrylonitrile
About 1.0%, ethyl about 4.0%；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated；Specifically, in vacuum 0.1MPa, temperature is less than 180 DEG C, collects low boilers, temperature
Rise to 185-190 DEG C and collect main evaporating for N-ethyl n-cyanoethyl aniline, through analyzing, N-ethyl n-cyanoethyl aniline content
More than 99.3%, acrylonitrile about 0.05%, within N-ethylaniline 0.5%.
Embodiment 5
The present embodiment is the preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, technological process such as Fig. 1 and
Shown in Fig. 2, mainly comprise the steps that
(i) be pressed in: press in reactor during ethanol, aniline and the first catalyst are put into, the first catalyst by phosphorus oxychloride with
Copper chromium mixes by weight 5:1.5, has been also added with compound rare-earth in the first catalyst, and the addition of compound rare-earth is trichlorine
Oxygen phosphorus and the 6% of copper chromium gross weight, the mass percent component of compound rare-earth is: cerium: 3%, neodymium: 18%, gadolinium: 8%, lutecium: 2%, dysprosium:
3%, praseodymium: 8%, holmium: 10%, erbium: 6%, surplus is lanthanum；Aniline content more than 99.96% witch's nitro compounds exists, ethanol during ethanol 20 DEG C
Density is more than 95 DEG C, phosphorus oxychloride content more than 99.3%, charge ratio: ethanol 550kg, aniline 1600kg, the first catalyst
35kg(high pressure volume 3500 liter)；With 2.2 hours, middle pressure reactor temperature being risen to 145 DEG C, pressure rises to 1.7Mpa, so
Rear stopping is heated, and due to exothermic heat of reaction, in 1.2 hours, middle pressure reactor temperature rises to 295 DEG C voluntarily, and pressure rises to 27MPa,
Treating that temperature is down to 200 DEG C subsequently, when pressure is down to 26MPa, heat-insulation pressure keeping reacts 2.2 hours to react and terminates, and reaction terminates rear discharging
To neutralizing reactor, return alcohol water and be put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 6 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 12 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 6 points
Clock, static 12 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
Through analyzing, crude product Main Ingredients and Appearance has: ethanol 0.2%, water 0.3%, aniline 9%, N-ethylaniline 85%, N-N-diethylaniline
5.5%；
Return alcohol water Main Ingredients and Appearance to have: ethanol about 10%, water about 70%, N-ethylaniline crude product about 20%.
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still, according to the boiling point of its composition with N-ethylaniline crude product
Difference is separated ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline one by one through rectification tower body；It is specially
Temperature collects aniline less than 135 DEG C, and temperature collects N-ethylaniline at 145 DEG C, and temperature collects N, N-diethylbenzene at 150 DEG C
Amine；
(iv) additive reaction: the pure N-ethylaniline that (iii) 4500 steps are obtained and 2750 propylene eyeball propylene eyeballs and 290
Two catalyst put in 8,000 liter additive reaction stills, the second catalyst mixed with copper chromium 6:1.5 by weight by zinc chloride and
Becoming, with 33 minutes, additive reaction temperature in the kettle is risen to 66 DEG C, due to exothermic heat of reaction, 36 minutes additive reaction temperature in the kettle are voluntarily
Rising to 90 DEG C, pressure rises to 0.095MPa, keeps temperature 90 DEG C, and pressure 0.095MPa reacts reaction in 8.5 hours to be terminated, then limit
Stirring limit adds liquid caustic soda (liquid caustic soda content more than 30%) and is neutralized, and after having added liquid caustic soda static 11 minutes, obtains N-ethyl n-cyanogen
MEA crude product；
Through analyzing, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 95%, acrylonitrile
About 1.0%, ethyl about 4.0%；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated；Specifically, in vacuum 0.1MPa, temperature is less than 180 DEG C, collects low boilers, temperature
Rise to 185-190 DEG C and collect main evaporating for N-ethyl n-cyanoethyl aniline, through analyzing, N-ethyl n-cyanoethyl aniline content
More than 99.3%, acrylonitrile about 0.05%, within N-ethylaniline 0.5%.
Embodiment 6
The present embodiment is the preparation method of a kind of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, technological process such as Fig. 1 and
Shown in Fig. 2, mainly comprise the steps that
(i) be pressed in: press in reactor during ethanol, aniline and the first catalyst are put into, the first catalyst by phosphorus oxychloride with
Copper chromium mixes by weight 5:2, has been also added with compound rare-earth in the first catalyst, and the addition of compound rare-earth is trichlorine oxygen
Phosphorus and the 7% of copper chromium gross weight, the mass percent component of compound rare-earth is: cerium: 4%, neodymium: 19%, gadolinium: 9%, lutecium: 3%, dysprosium:
4%, praseodymium: 9%, holmium: 11%, erbium: 7%, surplus is lanthanum；Aniline content more than 99.96% witch's nitro compounds exists, ethanol during ethanol 20 DEG C
Density is more than 95 DEG C, phosphorus oxychloride content more than 99.3%, charge ratio: ethanol 550kg, aniline 1600kg, the first catalyst
35kg(high pressure volume 3500 liter)；With 2 hours, middle pressure reactor temperature being risen to 155 DEG C, pressure rises to 1.8Mpa, then
Stopping heating, due to exothermic heat of reaction, in 1.5 hours, middle pressure reactor temperature rises to 305 DEG C voluntarily, and pressure rises to 28MPa, with
After treat that temperature is down to 210 DEG C, when pressure is down to 28MPa heat-insulation pressure keeping react 2.5 hours reaction terminate, reaction terminate rear discharging extremely
Neutralize reactor, return alcohol water and be put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 7 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 13 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 7 points
Clock, static 13 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
Through analyzing, crude product Main Ingredients and Appearance has: ethanol 0.4%, water 0.6%, aniline 8%, N-ethylaniline 86%, N-N-diethylaniline
5%；
Return alcohol water Main Ingredients and Appearance to have: ethanol about 10%, water about 70%, N-ethylaniline crude product about 20%.
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still, according to the boiling point of its composition with N-ethylaniline crude product
Difference is separated ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline one by one through rectification tower body；It is specially
Temperature collects aniline less than 135 DEG C, and temperature collects N-ethylaniline at 145 DEG C, and temperature collects N, N-diethylbenzene at 150 DEG C
Amine；
(iv) additive reaction: the pure N-ethylaniline that (iii) 4500 steps are obtained and 2750 propylene eyeball propylene eyeballs and 290
Two catalyst put in 8,000 liter additive reaction stills, and the second catalyst is mixed by weight 6:2 with copper chromium by zinc chloride,
With 35 minutes, additive reaction temperature in the kettle being risen to 67 DEG C, due to exothermic heat of reaction, within 37 minutes, additive reaction temperature in the kettle rises voluntarily
To 91 DEG C, pressure rises to 0.1MPa, keeps temperature 91 DEG C, and pressure 0.1MPa reacts reaction in 9 hours to be terminated, and adds the most while stirring
Enter liquid caustic soda (liquid caustic soda content more than 30%) to be neutralized, after having added liquid caustic soda static 12 minutes, obtain N-ethyl n-cyanoethyl aniline
Crude product；
Through analyzing, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 95%, acrylonitrile
About 1.0%, ethyl about 4.0%；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated；Specifically, in vacuum 0.1MPa, temperature is less than 180 DEG C, collects low boilers, temperature
Rise to 185-190 DEG C and collect main evaporating for N-ethyl n-cyanoethyl aniline, through analyzing, N-ethyl n-cyanoethyl aniline content
More than 99.3%, acrylonitrile about 0.05%, within N-ethylaniline 0.5%.
Comparative example 1
The first catalyst that this comparative example uses is phosphorus oxychloride, in be pressed into time, directly rise slow for middle pressure temperature of reaction kettle
To 230-240 DEG C, required 10 hours are reacted.
Through analyzing, N-ethylaniline crude product Main Ingredients and Appearance has: ethanol 0.2-0.4%, water 0.3-0.8%, aniline 28-32%, N-
MEA 60-63%, N-N-diethylaniline 5-6%；N-ethylaniline selectivity is about 60%.
The second catalyst that comparative example uses is zinc chloride, reacts about 12 hours at 85-95 DEG C in additive reaction, through dividing
Analysis, N-ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 90%, acrylonitrile about 1.0%,
Ethyl about 8.0%；N-ethyl n-cyanoethyl aniline selectivity is about 90%.
Comparative example 2
This comparative example use the first catalyst be to be urged agent by phosphorus oxychloride with the binary that Phosphorous chloride. or mineral acid form, in
When being pressed into, directly rise to 230-240 DEG C by slow for middle pressure temperature of reaction kettle, reacted required 10 hours.
Through analyzing, N-ethylaniline crude product Main Ingredients and Appearance has: ethanol 0.2-0.4%, water 0.3-0.8%, aniline 24-28%, N-
MEA 66-70%, N-N-diethylaniline 5-6%.N-ethylaniline selectivity is about 70%；
The second catalyst that comparative example uses is to be formed by aluminum chloride, zinc chloride, glacial acetic acid, hydroquinone any two kinds
Binary catalyst, reacts about 12 hours at 85-95 DEG C in additive reaction, and through analyzing, N-ethyl n-cyanoethyl aniline crude product is main
Composition has: N-ethyl n-cyanoethyl aniline about 92%, acrylonitrile about 1.0%, ethyl about 6.0%；N-ethyl n-cyanoethyl benzene
Amine selectivity is about 92%.
Comparative example 3
This comparative example and embodiment 1 use raw material with, in be pressed into difference and be, directly rise to slow for middle pressure temperature of reaction kettle
230-240 DEG C, required 10 hours are reacted.
Through analyzing, N-ethylaniline crude product Main Ingredients and Appearance has: ethanol 0.2-0.4%, water 0.3-0.8%, aniline 18-20%, N-
MEA 74-76%, N-N-diethylaniline 4-5%；N-ethylaniline selectivity reaches about 75%.
Additive reaction difference is, does not use zone heating, directly reacts about 12 hours at 85-95 DEG C, through analyzing, and N-
Ethyl n-cyanoethyl aniline crude product Main Ingredients and Appearance has: N-ethyl n-cyanoethyl aniline about 93%, acrylonitrile about 1.0%, ethyl
About 5.0%；N-ethyl n-cyanoethyl aniline selectivity is about 93%.
Following table is to be pressed in the embodiment of the present invention and comparative example reaction selectivity contrast table:
Table 1:
| First catalyst | In be pressed into heating condition | Deadline | N-ethylaniline selectivity | |
| Comparative example 1 | Phosphorus oxychloride | 230-240℃ | 10 hours | 60% |
| Comparative example 2 | Phosphorus oxychloride+Phosphorous chloride. | 230-240℃ | 10 hours | 70% |
| Comparative example 3 | Phosphorus oxychloride+copper chromium | 230-240℃ | 10 hours | 75% |
| Embodiment 1 | Phosphorus oxychloride+copper chromium | Zone heating | 5 hours 32 points | 79% |
| Embodiment 2 | Phosphorus oxychloride+copper chromium | Zone heating | 6 hours 12 points | 80% |
| Embodiment 3 | Phosphorus oxychloride+copper chromium | Zone heating | 6 hours 40 points | 81% |
| Embodiment 4 | Phosphorus oxychloride+copper chromium+compound rare-earth | Zone heating | 5 hours 32 points | 84% |
| Embodiment 5 | Phosphorus oxychloride+copper chromium+compound rare-earth | Zone heating | 6 hours 12 points | 85% |
| Embodiment 6 | Phosphorus oxychloride+copper chromium+compound rare-earth | Zone heating | 6 hours 40 points | 86% |
Table 2 below is embodiment of the present invention additive reaction and comparative example reaction selectivity contrast table:
Table 2
| Second catalyst | Additive reaction heating condition | Complete the response time | N-ethylaniline selectivity | |
| Comparative example 1 | Zinc chloride | 85-95℃ | 12 hours | 90% |
| Comparative example 2 | Aluminum chloride+zinc chloride | 85-95℃ | 12 hours | 92% |
| Comparative example 3 | Zinc chloride+copper chromium | 85-95℃ | 12 hours | 93% |
| Embodiment 1 | Zinc chloride+copper chromium | Zone heating | 9 hours 15 points | 95% |
| Embodiment 2 | Zinc chloride+copper chromium | Zone heating | 9 hours 50 points | 95% |
| Embodiment 3 | Zinc chloride+copper chromium | Zone heating | 10 hours 24 points | 95% |
| Embodiment 4 | Zinc chloride+copper chromium | Zone heating | 9 hours 15 points | 95% |
| Embodiment 5 | Zinc chloride+copper chromium | Zone heating | 9 hours 50 points | 95% |
| Embodiment 6 | Zinc chloride+copper chromium | Zone heating | 10 hours 24 points | 95% |
From upper table 1, the present invention in be pressed into, use and mixed with copper chromium 5:1-2 by weight by phosphorus oxychloride
The first catalyst, N-ethylaniline selectivity reaches about 75%, compared to existing technology in phosphorus oxychloride single catalyst can be real
The selectivity now reacted improves about 15%；Two be made up of phosphorus oxychloride and Phosphorous chloride. or mineral acid in compared to existing technology
The selectivity that unit urges agent can realize reaction improves about 5%；And copper chromium is for being a kind of environment-friendly materials, plays while reducing cost
Good environment protecting.It addition, during the present invention is pressed into, use zone heating, react total used time within 7 hours,
And existing in the art it is generally required to react about 10 hours at 230-240 DEG C, compared to existing technology, the application reaction temperature is low,
Utilize id reaction heat release to react in high temperature section, shorten the response time while reducing utilization of energy, improve production efficiency；
It addition, by zone heating, MEA selectivity reaches about 80%, can additionally improve the selectivity about 5% of reaction.This
Bright by increasing compound rare-earth in the first catalyst, MEA selectivity reaches about 85%, and ratio uses phosphorus oxychloride and copper
First catalyst of chromium combination, under the conditions of equivalent responses, can improve the selectivity about 5% of reaction, it is thus achieved that beyond thought
Technique effect.
As shown in Table 2, in additive reaction of the present invention, use the second catalyst mixed by zinc chloride and copper chromium, N-
The reaction selectivity of ethyl n-cyanoethyl aniline reaches about 95%, and middle zinc chloride single catalyst can realize compared to existing technology
The selectivity of reaction improves about 5%；Appointed by by aluminum chloride, zinc chloride, glacial acetic acid, hydroquinone in compared to existing technology
Two kinds of binary catalysts formed of anticipating can realize the selectivity of reaction and improve about 3%.It addition, in additive reaction of the present invention, use and divide
Duan Jiare, reacted total used time within 10.5 hours, with and existing the most in the art it is generally required to left 85-95 DEG C of reaction 12 hours
The right side, compared to existing technology, the application utilizes id reaction heat release to react in high temperature section, shortens anti-while reducing utilization of energy
Between Ying Shi, improve production efficiency, the reaction selectivity of N-ethyl n-cyanoethyl aniline also will not reduce.
In addition to the implementation, the present invention can also have other embodiments.All employing equivalents or equivalent transformation shape
The technical scheme become, all falls within the protection domain of application claims.
Claims (8)
1. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline, it is characterised in that: comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:1-2 with copper chromium, with 2-2.5 hour, middle pressure reactor temperature is risen to 150 ± 5 DEG C, pressure
Rising to 1.7-1.8Mpa, then stop heating, due to exothermic heat of reaction, in 1-1.5 hour, middle pressure reactor temperature rises to voluntarily
300 ± 5 DEG C, pressure rises to 27-28MPa, treats that temperature is down to 195-210 DEG C subsequently, and pressure is down to heat-insulation pressure keeping during 25-28MPa
Reacting reaction in 2-2.5 hour to terminate, reaction terminates rear discharging to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: putting into liquid caustic soda in reactor to neutralizing and stir 5-7 minute, pH value is more than 12 in neutralizing reactor
Time, stopping static 11-13 minute of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs
Mixing 5-7 minute, static 11-13 minute, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed, with 30-35 minute by additive reaction still by weight 6:1-2 with copper chromium by zinc chloride
Interior temperature rises to 65-67 DEG C, and due to exothermic heat of reaction, within 35-37 minute, additive reaction temperature in the kettle rises to 89-91 DEG C voluntarily, pressure
Rising to 0.09-0.1MPa, keep temperature 89-91 DEG C, pressure 0.09-0.1MPa reacts reaction in 8-9 hour to be terminated, then limit stirring
Limit adds liquid caustic soda and is neutralized, and after having added liquid caustic soda static 10-12 minute, obtains N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
2. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 1, it is characterised in that:
Being also added with compound rare-earth in described first catalyst, the addition of described compound rare-earth is phosphorus oxychloride and copper chromium gross weight
5-7%, the mass percent component of described compound rare-earth is: cerium: 2-4%, neodymium: 17-19%, gadolinium: 7-9%, lutecium: 1-3%, dysprosium: 2-
4%, praseodymium: 7-9%, holmium: 9-11%, erbium: 5-7%, surplus is lanthanum.
3. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 1, it is characterised in that:
Comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:1 with copper chromium, with 2 hours, middle pressure reactor temperature is risen to 150 DEG C, and pressure rises to
1.7Mpa, then stops heating, and due to exothermic heat of reaction, in 1 hour, middle pressure reactor temperature rises to 300 DEG C voluntarily, pressure liter
To 27MPa, treating that temperature is down to 195 DEG C subsequently, when pressure is down to 25MPa, heat-insulation pressure keeping reacts 2 hours to react and terminates, and reaction terminates
Rear discharging, to neutralizing reactor, is returned alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 5 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 11 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 5 points
Clock, static 11 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed, with 30 minutes by additive reaction temperature in the kettle by weight 6:1 with copper chromium by zinc chloride
Rising to 65 DEG C, due to exothermic heat of reaction, within 35 minutes, additive reaction temperature in the kettle rises to 89 DEG C voluntarily, and pressure rises to 0.09MPa, keeps
Temperature 89 DEG C, pressure 0.09MPa reacts reaction in 8 hours to be terminated, and adds liquid caustic soda the most while stirring and is neutralized, after having added liquid caustic soda
Static 10 minutes, obtain N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
4. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 1, it is characterised in that:
Comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:1.5 with copper chromium, with 2.2 hours, middle pressure reactor temperature is risen to 145 DEG C, and pressure rises to
1.7Mpa, then stops heating, and due to exothermic heat of reaction, in 1.2 hours, middle pressure reactor temperature rises to 295 DEG C voluntarily, pressure
Rising to 27MPa, treat that temperature is down to 200 DEG C subsequently, when pressure is down to 26MPa, heat-insulation pressure keeping reacts 2.2 hours to react and terminates, reaction
After end, discharging is to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 6 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 12 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 6 points
Clock, static 12 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed by weight 6:1.5 with copper chromium by zinc chloride, with 33 minutes by temperature in additive reaction still
Degree rises to 66 DEG C, and due to exothermic heat of reaction, within 36 minutes, additive reaction temperature in the kettle rises to 90 DEG C voluntarily, and pressure rises to 0.095MPa,
Keeping temperature 90 DEG C, pressure 0.095MPa reacts reaction in 8.5 hours to be terminated, and adds liquid caustic soda the most while stirring and is neutralized, adds
After good liquid caustic soda static 11 minutes, obtain N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
5. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 1, it is characterised in that:
Comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:2 with copper chromium, with 2.5 hours, middle pressure reactor temperature is risen to 155 DEG C, and pressure rises to
1.8Mpa, then stops heating, and due to exothermic heat of reaction, in 1.5 hours, middle pressure reactor temperature rises to 305 DEG C voluntarily, pressure
Rising to 28MPa, treat that temperature is down to 210 DEG C subsequently, when pressure is down to 28MPa, heat-insulation pressure keeping reacts 2.5 hours to react and terminates, reaction
After end, discharging is to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 7 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 13 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 7 points
Clock, static 13 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed, with 35 minutes by additive reaction temperature in the kettle by weight 6:2 with copper chromium by zinc chloride
Rising to 67 DEG C, due to exothermic heat of reaction, within 37 minutes, additive reaction temperature in the kettle rises to 91 DEG C voluntarily, and pressure rises to 0.1MPa, keeps
Temperature 91 DEG C, pressure 0.1MPa reacts reaction in 9 hours to be terminated, and adds liquid caustic soda the most while stirring and is neutralized, after having added liquid caustic soda
Static 12 minutes, obtain N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
6. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 2, it is characterised in that:
Comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:1 with copper chromium, has been also added with compound rare-earth, adding of described compound rare-earth in described first catalyst
Enter that amount is phosphorus oxychloride and copper chromium gross weight 5%, the mass percent component of described compound rare-earth is: cerium: 2%, neodymium: 17%,
Gadolinium: 7%, lutecium: 1%, dysprosium: 2%, praseodymium: 7%, holmium: 9%, erbium: 5%, surplus is lanthanum；With 2 hours, middle pressure reactor temperature is risen to 150
DEG C, pressure rises to 1.7Mpa, then stops heating, and due to exothermic heat of reaction, in 1 hour, middle pressure reactor temperature rises to voluntarily
300 DEG C, pressure rises to 27MPa, treats that temperature is down to 195 DEG C subsequently, and pressure is down to heat-insulation pressure keeping during 25MPa and is reacted reaction in 2 hours
Terminating, reaction terminates rear discharging to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 5 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 11 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 5 points
Clock, static 11 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed, with 30 minutes by additive reaction temperature in the kettle by weight 6:1 with copper chromium by zinc chloride
Rising to 65 DEG C, due to exothermic heat of reaction, within 35 minutes, additive reaction temperature in the kettle rises to 89 DEG C voluntarily, and pressure rises to 0.09MPa, keeps
Temperature 89 DEG C, pressure 0.09MPa reacts reaction in 8 hours to be terminated, and adds liquid caustic soda the most while stirring and is neutralized, after having added liquid caustic soda
Static 10 minutes, obtain N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
7. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 2, it is characterised in that:
Comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:1.5 with copper chromium, has been also added with compound rare-earth in described first catalyst, described compound rare-earth
Addition is the 6% of phosphorus oxychloride and copper chromium gross weight, and the mass percent component of described compound rare-earth is: cerium: 3%, neodymium: 18%,
Gadolinium: 8%, lutecium: 2%, dysprosium: 3%, praseodymium: 8%, holmium: 10%, erbium: 6%, surplus is lanthanum；With 2.2 hours, middle pressure reactor temperature is risen to
145 DEG C, pressure rises to 1.7Mpa, then stops heating, and due to exothermic heat of reaction, in 1.2 hours, middle pressure reactor temperature is voluntarily
Rising to 295 DEG C, pressure rises to 27MPa, treats that temperature is down to 200 DEG C subsequently, and when pressure is down to 26MPa, to react 2.2 little for heat-insulation pressure keeping
Shi Fanying terminates, and reaction terminates rear discharging to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 6 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 12 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 6 points
Clock, static 12 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed by weight 6:1.5 with copper chromium by zinc chloride, with 33 minutes by temperature in additive reaction still
Degree rises to 66 DEG C, and due to exothermic heat of reaction, within 36 minutes, additive reaction temperature in the kettle rises to 90 DEG C voluntarily, and pressure rises to 0.095MPa,
Keeping temperature 90 DEG C, pressure 0.095MPa reacts reaction in 8.5 hours to be terminated, and adds liquid caustic soda the most while stirring and is neutralized, adds
After good liquid caustic soda static 11 minutes, obtain N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
8. the preparation method of efficient power-saving environmental protection N-ethyl n-cyanoethyl aniline as claimed in claim 2, it is characterised in that:
Comprise the following steps:
(i) it is pressed in: in pressing reactor in ethanol, aniline and the first catalyst being put into, described first catalyst is by trichlorine oxygen
Phosphorus mixes by weight 5:2 with copper chromium, has been also added with compound rare-earth, adding of described compound rare-earth in described first catalyst
Enter that amount is phosphorus oxychloride and copper chromium gross weight 7%, the mass percent component of described compound rare-earth is: cerium: 4%, neodymium: 19%,
Gadolinium: 9%, lutecium: 3%, dysprosium: 4%, praseodymium: 9%, holmium: 11%, erbium: 7%, surplus is lanthanum；With 2.5 hours by middle pressure reactor temperature liter
To 155 DEG C, pressure rises to 1.8Mpa, then stops heating, and due to exothermic heat of reaction, in 1.5 hours, middle pressure reactor temperature is certainly
Row rises to 305 DEG C, and pressure rises to 28MPa, treats that temperature is down to 210 DEG C subsequently, and pressure is down to heat-insulation pressure keeping reaction 2.5 during 28MPa
Hour reaction terminates, and reaction terminates rear discharging to neutralizing reactor, returns alcohol water and is put into receiving slit；
(ii) reaction is neutralized: liquid caustic soda put into by reactor to neutralizing and stirs 7 minutes, when in neutralization reactor, pH value is more than 12,
Stopping static 13 minutes of stirring, put to wastewater disposal basin from bottom by lower floor's float, upper strata oil content adds clear water and stirs 7 points
Clock, static 13 minutes, then be layered, oil reservoir is put to N-ethylaniline crude product groove；
(iii) rectification: incite somebody to action back alcohol water and enter subliming by heating in rectifying still with N-ethylaniline crude product, the boiling point according to its composition is different
Through rectification tower body, ethanol, water, aniline, N-ethylaniline, N, N-diethylaniline are separated one by one；
(iv) additive reaction: the pure N-ethylaniline (iii) obtained by step is put into additive reaction still with propylene eyeball and the second catalyst
In, described second catalyst is mixed, with 35 minutes by additive reaction temperature in the kettle by weight 6:2 with copper chromium by zinc chloride
Rising to 67 DEG C, due to exothermic heat of reaction, within 37 minutes, additive reaction temperature in the kettle rises to 91 DEG C voluntarily, and pressure rises to 0.1MPa, keeps
Temperature 91 DEG C, pressure 0.1MPa reacts reaction in 9 hours to be terminated, and adds liquid caustic soda the most while stirring and is neutralized, after having added liquid caustic soda
Static 12 minutes, obtain N-ethyl n-cyanoethyl aniline crude product；
(v) distillation: enter in distillating still by N-ethyl n-cyanoethyl aniline crude product, through heating distillation, makes low boiling refuse and N-second
Base N-cyanoethyl aniline is separated.
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