CN101066955A - Synthesis proces sof N-methyl morpholine - Google Patents
Synthesis proces sof N-methyl morpholine Download PDFInfo
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- CN101066955A CN101066955A CN 200710069194 CN200710069194A CN101066955A CN 101066955 A CN101066955 A CN 101066955A CN 200710069194 CN200710069194 CN 200710069194 CN 200710069194 A CN200710069194 A CN 200710069194A CN 101066955 A CN101066955 A CN 101066955A
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Abstract
The present invention discloses synthesis process of N-methyl morpholine. The mixture of morpholine and methanol as the material after being gasified is made to pass through fixed bed containing supported catalyst to produce amination reaction under hydrogen condition; and the resultant is condensed, collected, dewatered and rectified to obtain N-methyl morpholine. The supported catalyst is prepared with metal salt solution of at least two of copper salt, nickel salt, cobalt salt, palladium salt and platinum salt and carrier and has metal accounting for 33-41 wt%. The synthesis process of the present invention can produce N-methyl morpholine of high purity in the yield up to 85 %.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, particularly a kind of organic chemical industry's intermediate---the synthetic method of N-methylmorpholine.
Background technology
N-methylmorpholine is a kind of important organic chemical industry's intermediate, and it is a kind of excellent solvent, emulsifying agent, inhibiter, polyurethane foam catalyzer, also can be used as pesticide intermediate.It is the N-methylation method of raw material that its synthetic method mainly contains with the morpholine, with the diethanolamine be raw material the cyclization method, be the cyclization method of raw material and be synthetic method of raw material etc. with the ethylene dichloride with a diethyl acetal amine.These methods generally adopt metal catalyst to carry out catalysis, carry out under higher temperature and pressure.And the method for most convenient is that the employing morpholine is a raw material, directly selects for use different methylating reagents to carry out the N-methylation reaction.At present, mainly contain following several research report by morpholine as the method that raw material synthesizes N-methylmorpholine:
The USSR (Union of Soviet Socialist Republics) patent SU1 164 234 in (1) 1985 year has reported that with morpholine and methyl chloride be the feedstock production N-methylmorpholine, and yield is higher.It is methylating reagent that but this method is selected methyl chloride for use, and toxicity is bigger, and lower boiling needs steel cylinder to store inconvenient operation; Simultaneously the hydrogenchloride of Sheng Chenging can with raw material and product salify, consume big, unfriendly to environment;
(2) document Syn.Comm, 32 (3), 457～465 (2002), reported with formaldehyde, oxalic acid and morpholine to be the method for the synthetic N-methylmorpholine of raw material.This method per pass conversion height, reaction conditions gentleness are not used catalyzer, but emit carbonic acid gas isothermal chamber gas formaldehyde etc., and Atom economy is relatively poor, and the element waste is more, pollute big;
The U.S. Pat 585 949 in (3) 1985 years proposes to obtain N-methylmorpholine with methyl-sulfate and morpholine reaction, the reaction conversion ratio height, and raw material conveniently is easy to get.But methyl-sulfate toxicity is very big, and this technology is eliminated gradually now.
The German patent DE 2 205 597 in (4) 1973 years proposes, carry out alkylated reaction with morpholine and methyl alcohol, catalyzer is SiO2-H3PO4, the molar ratio of morpholine and methyl alcohol is 40: 60, with the flow velocity is the catalyst fluidized bed of the mixing steam feeding 200mL of 106g/h, react under 160 ℃ and can make 91% N-methylmorpholine, the morpholine transformation efficiency reaches 95%.This process using raw material cheap and easy to get, but the technical requirements of fluidized-bed process is higher, operation easier, intensity, wear resistance, particle diameter and life requirements to catalyzer in the industrial production are very high.Very not suitable for the be pilot fluidized-bed production that N-methylmorpholine is such.
Summary of the invention
The technical problem to be solved in the present invention provides that a kind of cost is low, yield is high, the synthetic method of easy industrialized N-methylmorpholine.
In order to solve the problems of the technologies described above, the invention provides a kind of synthetic method of N-methylmorpholine, be raw material with morpholine and methanol mixture, with behind the material gasification by containing the fixed bed of load catalyzer, under hydro condition, carry out amination reaction; After condensation, collect reactant, obtain N-methylmorpholine after dehydration, the rectifying again; This load Preparation of catalysts process is as follows:
Metal salt solution and carrier are made loaded catalyst, and metal accounts for 33%～41% of gross weight in the described loaded catalyst, and metal-salt is at least two kinds in mantoquita, nickel salt, cobalt salt, palladium salt and the platinum salt.
Improvement as the synthetic method of N-methylmorpholine of the present invention: methyl alcohol is 1～8: 1 with the ratio of the amount of substance of morpholine, raw material after the gasification carries out amination reaction with the air speed and the load catalyzer of 0.1～0.3g/h/mL load catalyzer, and reaction pressure is that 0.2～0.5Mpa, temperature are 140～200 ℃.
Further improvement as the synthetic method of N-methylmorpholine of the present invention: carrier is through the pretreated gama-alumina of phosphoric acid; Metal-salt is selected cobalt salt and nickel salt for use, in the loaded catalyst of gained cobalt account for gross weight 30%～31%, nickel accounts for 9%～10% of gross weight.
Further improvement as the synthetic method of N-methylmorpholine of the present invention: metal salt solution and carrier successively through behind 2 times dipping, drying, the calcination steps loaded catalyst.
Load Preparation of catalysts process is specific as follows:
1), the nitrate of each component proportionally is dissolved in the distilled water, is settled to desired concn,, the pretreated γ-Al2O3 of phosphoric acid is immersed in the solution that configures, flooded 36 hours with the ratio of 1.2mL solution/1g carrier; Filter, get filtrate and catalyzer;
2), with the catalyzer of step 1) gained under agitation condition in 60 ℃ of dry 2h, put into retort furnace then with 80 ℃, 150 ℃, 280 ℃ each roast 3h, then nature cooling;
3), with step 2) catalyzer of the gained filtrate of putting into the step 1) gained floods 24h, filter;
4), the catalyzer that step 3) filtered gained in 80 ℃ of dry 2h, is put into retort furnace with 150 ℃ of roast 2h, with 400～500 ℃ of roast 4h then under agitation condition; Then nature cooling, both required load catalyzer.
According to the method described above, the load catalyzer preferentially selected for use for the present invention of prepared following 3 kinds of load catalyzer (as shown in table 1).
Table 1
| The load catalyzer | Carrier | Active ingredient Wt% | Profile | Specific surface | ||
| Cu | Ni | Co | m 2g -1 | |||
| No. 1 | γ-Al 2O 3 | 18～20 | 14.5～16 | 0 | The cylinder grain of high 3～5mm diameter, 2～6mm | 201 |
| No. 2 | 18～20 | 0 | 17～18.5 | 197 | ||
| No. 3 | 0 | 9～10.5 | 29.5～31 | 189 | ||
The synthetic method of N-methylmorpholine of the present invention, the reaction conditions gentleness, production cost is low, and the equipment serialization is good, easy handling and realization industrialization.With the N-methylmorpholine that synthetic method of the present invention is produced, product purity is higher, and can reach 85% yield.
Embodiment
The synthetic method of embodiment 1, a kind of N-methylmorpholine, carry out following steps successively:
1), preparation load catalyzer:
A), with commercially available γ-Al
2O
3With concentration 10% H
3PO
4Solution handle to soak 30min at 40 ℃-60 ℃, leach drying again after, at 450 ℃ of roasting 3.5h, standby behind 700 ℃ of roasting 5h.
B), 79.0g Xiao Suangu and 26.4g nickelous nitrate solid (not containing crystal water) are dissolved in the 50mL distilled water, it is standby to make the 50mL metal salt solution.Ratio with 1.2mL metal salt solution/1.0g γ-Al2O3 carrier is immersed in the γ-Al2O3 after the above-mentioned processing in the solution that configures, and floods after 36 hours; Filter, get filtrate and catalyzer.
C), with the catalyzer of gained after the above-mentioned filtration under agitation in 60 ℃ of dry 2h, put into retort furnace with 80 ℃, 150 ℃, 280 ℃ each roast 3h, naturally cooling.
D), the catalyzer of the above-mentioned gained of cooling naturally immersed 24h in the filtrate of step b) gained, refilter.
E), with the catalyzer of step d) gained under agitation condition in 80 ℃ of dry 2h, then successively at retort furnace: 150 ℃ of roast 2h, 400～500 ℃ of roast 4h; Then nature cooling, both required granular load catalyzer, wherein contain Ni and be about 10% (W/W), contain Co and be about 30% (W/W), all the form with oxide compound exists.
2), 1: 3 morpholine of mol ratio and methanol mixed are placed in the head tank, the above-mentioned catalyzer of filling 80mL in the tubular reactor of capacity 100mL, facing hydrogen activation back adjusting heater voltage makes temperature of reaction be controlled at 170 ℃, with after the mixture in the head tank vaporization (200 ℃) through reactor head, enter reactor jointly with hydrogen and face the hydrogen amination, regulating hydrogen pressure makes reactor pressure remain on 0.3Mpa, raw material enters catalyst bed reaction with the air speed of 0.2g/h/mL catalyzer, product is through collecting with liquid form after the condensation, collects to analyze behind the product of q.s and separate.
3), the sample that gets collection carries out gas chromatographic analysis, product is in the 500mL flask, recovery methyl alcohol is taken off in distillation earlier, add again water-retaining agent dewater the back atmospheric distillation, the cut of collecting 115～116 ℃ is a product, and continuing to collect 128 ℃ of cuts is raw material, adds behind the methyl alcohol circulation once more and reacts.
It is 95% that the product that obtains carries out gas chromatographic analysis content, and product yield after a collection of raw material recycle (with respect to the molar yield of morpholine, down together) can reach 96%.
The synthetic method of embodiment 2, a kind of N-methylmorpholine:
In step 2) in, the mol ratio of morpholine and methyl alcohol made into 1: 6, and temperature of reaction is controlled at 140 ℃, regulates hydrogen pressure and makes reactor pressure remain on 0.5Mpa, and raw material enters catalyst bed reaction with the air speed of 0.3g/h/mL catalyzer.All the other are all with embodiment 1.
It is 95% that the product of gained carries out gas chromatographic analysis content, and product yield is 97% after a collection of raw material recycle.
The synthetic method of embodiment 3, a kind of N-methylmorpholine:
In step 2) in, the mol ratio of morpholine and methyl alcohol made into 1: 1, and temperature of reaction is controlled at 200 ℃, regulates hydrogen pressure and makes reactor pressure remain on 0.2Mpa, and raw material enters catalyst bed reaction with the air speed of 0.1g/h/mL catalyzer.All the other are all with embodiment 1.
It is 95% that the product of gained carries out gas chromatographic analysis content, and product yield is 90% after a collection of raw material recycle.
The synthetic method of embodiment 4, a kind of N-methylmorpholine, carry out following steps successively:
1), preparation load catalyzer:
A), with commercially available γ-Al
2O
3With concentration 10% H
3PO
4Solution handle to soak 30min at 40 ℃-60 ℃, leach drying again after, at 450 ℃ of roasting 3.5h, standby behind 700 ℃ of roasting 5h.
B), 40.9g cupric nitrate and 34.0g nickelous nitrate solid (not containing crystal water) are dissolved in the 50mL distilled water, it is standby to make the 50mL metal salt solution.Ratio with 1.2mL metal salt solution/1.0g γ-Al2O3 carrier is immersed in the γ-Al2O3 after the above-mentioned processing in the solution that configures, and floods after 36 hours; Filter, get filtrate and catalyzer.
C), with the catalyzer of gained after the above-mentioned filtration under agitation in 60 ℃ of dry 2h, put into retort furnace with 80 ℃, 150 ℃, 280 ℃ each roast 3h, naturally cooling.
D), the catalyzer of the above-mentioned gained of cooling naturally immersed 24h in the filtrate of step b) gained, refilter.
E), with the catalyzer of step d) gained under agitation condition in 80 ℃ of dry 2h, then successively at retort furnace: 150 ℃ of roast 2h, 400～500 ℃ of roast 4h; Then nature cooling, both required granular load catalyzer, wherein contain Cu and be about 19% (W/W), contain Ni and be about 15% (W/W), all the form with oxide compound exists.
All the other steps are with embodiment 1.It is 95% that the product that gets carries out gas chromatographic analysis content, and product yield is 86% after a collection of raw material recycle.
The synthetic method of embodiment 5, a kind of N-methylmorpholine, carry out following steps successively:
1), preparation load catalyzer:
A), with commercially available γ-Al
2O
3With concentration 10% H
3PO
4Solution handle to soak 30min at 40 ℃-60 ℃, leach drying again after, at 450 ℃ of roasting 3.5h, standby behind 700 ℃ of roasting 5h.
B), 43.8g cupric nitrate and 43.6g Xiao Suangu solid (not containing crystal water) are dissolved in the 50mL distilled water, it is standby to make the 50mL metal salt solution.Ratio with 1.2mL metal salt solution/1.0g γ-Al2O3 carrier is immersed in the γ-Al2O3 after the above-mentioned processing in the solution that configures, and floods after 36 hours; Filter, get filtrate and catalyzer.
C), with the catalyzer of gained after the above-mentioned filtration under agitation in 60 ℃ of dry 2h, put into retort furnace with 80 ℃, 150 ℃, 280 ℃ each roast 3h, naturally cooling.
D), the catalyzer of the above-mentioned gained of cooling naturally immersed 24h in the filtrate of step b) gained, refilter.
E), with the catalyzer of step d) gained under agitation condition in 80 ℃ of dry 2h, then successively at retort furnace: 150 ℃ of roast 2h, 400～500 ℃ of roast 4h; Then nature cooling, both required granular load catalyzer, wherein contain Cu and be about 19% (W/W), contain Co and be about 18% (W/W), all the form with oxide compound exists.
All the other steps are with embodiment 1.It is 95% that the product that gets carries out gas chromatographic analysis content, and product yield is 90% after a collection of raw material recycle.
At last, it is also to be noted that what more than enumerate only is several specific exampless of the present invention.Obviously, the invention is not restricted to above example, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1, a kind of synthetic method of N-methylmorpholine is characterized in that: with morpholine and methanol mixture is raw material, with behind the material gasification by containing the fixed bed of load catalyzer, under hydro condition, carry out amination reaction; After condensation, collect reactant, obtain N-methylmorpholine after dehydration, the rectifying again; Described load Preparation of catalysts process is as follows:
Metal salt solution and carrier are made loaded catalyst, and metal accounts for 33%～41% of gross weight in the described loaded catalyst, and metal-salt is at least two kinds in mantoquita, nickel salt, cobalt salt, palladium salt and the platinum salt.
2, the synthetic method of N-methylmorpholine according to claim 1, it is characterized in that: methyl alcohol is 1～8: 1 with the ratio of the amount of substance of morpholine, raw material after the gasification carries out amination reaction with the air speed and the load catalyzer of 0.1～0.3g/h/mL load catalyzer, and reaction pressure is that 0.2～0.5Mpa, temperature are 140～200 ℃.
3, the synthetic method of N-methylmorpholine according to claim 2 is characterized in that: described carrier is through the pretreated gama-alumina of phosphoric acid; Metal-salt is selected cobalt salt and nickel salt for use, in the loaded catalyst of gained cobalt account for gross weight 29.5%～31%, nickel accounts for 9%～10.5% of gross weight.
4, according to the synthetic method of claim 2 or 3 described N-methylmorpholines, it is characterized in that: metal salt solution and carrier successively through behind 2 times dipping, drying, the calcination steps loaded catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229582A (en) * | 2011-04-15 | 2011-11-02 | 浙江建业化工股份有限公司 | Method for synthesizing 4-cyclohexyl morpholine |
| CN104130210A (en) * | 2014-07-01 | 2014-11-05 | 浙江建业化工股份有限公司 | Preparation method for N-methylmorpholine |
| CN106279064A (en) * | 2016-08-05 | 2017-01-04 | 西南化工研究设计院有限公司 | A kind of synthesis technique of N methyl morpholine |
| CN110627743A (en) * | 2019-09-20 | 2019-12-31 | 四川鸿鹏新材料有限公司 | Method for preparing morpholine and monoethylamine by using N-ethyl morpholine |
| CN110713469A (en) * | 2019-09-26 | 2020-01-21 | 宿州亿帆药业有限公司 | Synthesis process of tridemorph |
| CN110773175A (en) * | 2019-11-07 | 2020-02-11 | 江苏美思德化学股份有限公司 | Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine |
| CN111675677A (en) * | 2020-07-13 | 2020-09-18 | 江苏富比亚化学品有限公司 | Synthesis process of N-methylmorpholine |
| CN112851598A (en) * | 2021-01-27 | 2021-05-28 | 安徽昊源化工集团有限公司 | Continuous production method for synthesizing N-methylmorpholine by catalysis of morpholine and methanol |
-
2007
- 2007-06-05 CN CNB2007100691940A patent/CN100545152C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229582A (en) * | 2011-04-15 | 2011-11-02 | 浙江建业化工股份有限公司 | Method for synthesizing 4-cyclohexyl morpholine |
| CN102229582B (en) * | 2011-04-15 | 2013-09-18 | 浙江建业化工股份有限公司 | Method for synthesizing 4-cyclohexyl morpholine |
| CN104130210A (en) * | 2014-07-01 | 2014-11-05 | 浙江建业化工股份有限公司 | Preparation method for N-methylmorpholine |
| CN104130210B (en) * | 2014-07-01 | 2016-01-20 | 浙江建业化工股份有限公司 | The preparation method of N-methylmorpholine |
| CN106279064A (en) * | 2016-08-05 | 2017-01-04 | 西南化工研究设计院有限公司 | A kind of synthesis technique of N methyl morpholine |
| CN110627743A (en) * | 2019-09-20 | 2019-12-31 | 四川鸿鹏新材料有限公司 | Method for preparing morpholine and monoethylamine by using N-ethyl morpholine |
| CN110627743B (en) * | 2019-09-20 | 2023-06-02 | 四川鸿鹏新材料有限公司 | Method for preparing morpholine and monoethylamine by using N-ethylmorpholine |
| CN110713469A (en) * | 2019-09-26 | 2020-01-21 | 宿州亿帆药业有限公司 | Synthesis process of tridemorph |
| CN110773175A (en) * | 2019-11-07 | 2020-02-11 | 江苏美思德化学股份有限公司 | Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine |
| CN111675677A (en) * | 2020-07-13 | 2020-09-18 | 江苏富比亚化学品有限公司 | Synthesis process of N-methylmorpholine |
| CN112851598A (en) * | 2021-01-27 | 2021-05-28 | 安徽昊源化工集团有限公司 | Continuous production method for synthesizing N-methylmorpholine by catalysis of morpholine and methanol |
| CN112851598B (en) * | 2021-01-27 | 2024-01-23 | 安徽昊源化工集团有限公司 | Continuous production method for synthesizing N-methylmorpholine by using morpholine and methanol as catalyst |
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