CN100371333C - Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material - Google Patents
Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material Download PDFInfo
- Publication number
- CN100371333C CN100371333C CNB2006100168188A CN200610016818A CN100371333C CN 100371333 C CN100371333 C CN 100371333C CN B2006100168188 A CNB2006100168188 A CN B2006100168188A CN 200610016818 A CN200610016818 A CN 200610016818A CN 100371333 C CN100371333 C CN 100371333C
- Authority
- CN
- China
- Prior art keywords
- morpholine
- ethylmorpholine
- reaction
- hydrogen
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for producing morpholine and ethylamine, which adopts N-ethyl morpholine of a byproduct of a morpholine device as raw material. Under the existence of hydrogen and a Ni-MgO/Al2 O3 catalyst, the raw material is continuously added from the top of a fixed bed reactor after gasified, and products can collect liquid phase products by condensation and separation; the reaction pressure is 0.2 to 1.0MPa, and the reaction temperature is 190 to 260 DEG C; the N-ethyl morpholine airspeed is 0.12 to 0.18h<-1>; the high diameter ratio of the reactor is 6 to 1; the molar ratio of N-ethyl morpholine is 50-120 to 1; and the molar ratio of liquid ammonia and N-ethyl morpholine is 8-14 to 1. The method adopts N-ethyl morpholine of a byproduct produced by morpholine to produce morpholine and ethylamine, and N-ethyl morpholine of small purpose and low additional value can be fully and reasonably utilized; morpholine and ethylamine of high value are produced; and the environment pollution of oxynitrides generated by adopting N-ethyl morpholine as fuels is avoided.
Description
Technical field:
The present invention relates to a kind of method of utilizing morpholine device byproduct N-ethylmorpholine to prepare fine chemical material morpholine and monoethylamine simultaneously.
Background technology
Morpholine is a kind of important Organic Chemicals, is mainly used in to produce rubber accelerator, vulcanizing agent, medicine, agricultural chemicals, inhibiter, petrochemical complex auxiliary agent and chemical polishing agent etc.
Monoethylamine also is a kind of important Organic Chemicals, is mainly used in agricultural chemicals, medicine, dyestuff and Rubber processing etc.
Adopt the production equipment of glycol ether-liquefied ammonia explained hereafter morpholine all can produce a certain amount of N-methylmorpholine and N-ethylmorpholine byproduct at present, wherein N-methylmorpholine is the higher fine chemical product of a kind of added value, and the purposes of N-ethylmorpholine is very little, have price but no buyers, the oil that can only act as a fuel is sold, added value is very low, also produces the nitrogen oxides pollution thing during burning.The present invention carries out reverse ammonia with N-ethylmorpholine exactly and separates morpholine that generating value is higher and monoethylamine.
By glycol ether-liquid ammonia material route synthesize morpholine is technology open already and that generally adopt, and under the condition of hydrogen and catalyzer existence, glycol ether, liquid ammonia material obtain morpholine through gas-solid or the solid inhomogeneous reaction of gas-liquid.Reaction equation is as follows:
Synthesis technique report about morpholine is a lot.Research institute of Jilin Petrochemical company adopts Ni-Cu/ wilkinite or Ni-Cu/Al
2O
3For catalyzer and continuous vapor phase process fixed bed reaction technology, be raw material with glycol ether and liquefied ammonia, the yield of morpholine is 70～77%, this technology is domestic mature and reliable the most and the generally technology of employing at present.Patent ZL890100687 of Fushun Petrochemical Research Institute and CN88107491.8 adopt Ni-Cu-Zn/Al
2O
3(or chromic oxide) is catalyzer and liquid phase method fixed bed reaction technology, and glycol ether and liquefied ammonia are raw material, and the morpholine yield is 66%.Research Inst. of Petroleum Processing, SINOPEC patent CN87105893, CN87105893 and CN87105833 adopt Ni-Cu-Cr-Re/Al
2O
3Catalyzer and liquid phase method fixed bed reaction technology are raw material with glycol ether and liquefied ammonia, and the yield of morpholine is 80～93%; With glycol ether, methyl alcohol and liquefied ammonia is raw material, and the yield of N-methylmorpholine is 66%, and the yield of morpholine is 23%.
U.S. Pat 3151113 adopts Ni-Cu-Cr catalyzer and high pressure batch reactor, is raw material with glycol ether, Fatty Alcohol(C12-C14 and C12-C18) and liquefied ammonia, liquid phase method synthesis of alkyl morpholine.Japanese Patent JP 58-225078 adopts Ni-Cu-Cr-Re/ α-Al
2O
3Catalyzer and high pressure batch reactor are raw material with glycol ether and liquefied ammonia, the liquid phase method synthesize morpholine.
The present invention is a raw material with N-ethylmorpholine and liquefied ammonia, adopts fixed-bed reactor and vapor phase process operating procedure, at hydrogen and Ni-MgO/Al
2O
3Catalyzer exists down, separates through continuous ammonia and obtains morpholine and two kinds of products of monoethylamine simultaneously.Reaction equation is as follows:
The side reaction of this process is few under appropriate condition, only just a small amount of scission reaction can take place when temperature is higher, generates methylmorpholine and methane.
Summary of the invention
The objective of the invention is to utilize morpholine produce in byproduct N-ethylmorpholine and liquefied ammonia be raw material, adopt fixed-bed reactor and vapor phase process operating procedure, at hydrogen with Ni-MgO/Al
2O
3Catalyzer exists down, separates through continuous ammonia and obtains morpholine and two kinds of products of monoethylamine simultaneously.
The objective of the invention is to realize by the following technical solutions:
A kind of is the method for raw material production morpholine and monoethylamine with morpholine byproduct N-ethylmorpholine, it is characterized in that: with Ni-MgO/Al
2O
3Catalyzer is put into fixed-bed reactor, under 380 ℃, with hydrogen reducing 8 hours, hydrogen flowing quantity was 30ml/mlCatmin, is cooled to 220 ℃, again with N-ethylmorpholine and liquefied ammonia mixture with hydrogen after gasification, add from the fixed-bed reactor top continuously, carry out gas and solid heterogeneous reaction, reaction product is through condensation and gas-liquid separation, obtain the thick product of liquid phase, gas phase is emptying after absorbing; Its reaction pressure is 0.2～1.0MPa, and temperature of reaction is 190～260 ℃, and the N-ethylmorpholine air speed is 0.12～0.18h
-1(catalyzer that is meant unit volume is the volumetric flow rate of needed N-ethylmorpholine per hour), the reactor aspect ratio is not less than 6 to 1; The mol ratio of hydrogen and N-ethylmorpholine is 50～120: 1, and the mol ratio of liquefied ammonia and N-ethylmorpholine is 8～14: 1.
Above-mentioned method is characterized in that: reaction pressure is 0.3～0.6MPa, and temperature of reaction is 210～240 ℃, and the N-ethylmorpholine air speed is 0.14～0.16h-1.
Above-mentioned method is characterized in that: the mol ratio of hydrogen and N-ethylmorpholine is 80～100: 1, and the mol ratio of liquefied ammonia and N-ethylmorpholine is 9～10: 1.
The present invention compared with prior art has following positive effect:
(1) the present invention utilizes morpholine production equipment byproduct N-ethylmorpholine to prepare fine chemical material morpholine and monoethylamine simultaneously, make the purposes that produces when producing morpholine very little, have price but no buyers, the N-ethylmorpholine that value added is very low is used adequately reasonably, and produces to be worth higher fine chemical material morpholine and monoethylamine;
Produce oxynitrides and contaminate environment when (2) having avoided N-ethylmorpholine to act as a fuel.
(3) technology is simpler, and is easy to control.
The reaction unit that the present invention adopts is the Tianjin W3050 micro-reaction equipment of power scientific instrument company limited earlier, and gasifier and reactor are integrated, and top is gasifier, and inner φ 2 * 2 metal Dixon ring fillers of filling are of a size of φ 20 * 280; The bottom is a fixed-bed micro-reactor, is of a size of φ 14 * 220, and the efficient loading amount is 20cm
3
Embodiment:
Embodiment 1
With φ 3.2 cloverleaf pattern Ni-MgO/Al
2O
3Sieve is got 20～30 purposes part as catalyzer behind the break-up of catalyst.Measure in the reaction of packing into after catalyzer after the above-mentioned processing of 10ml and the broken porcelain ring of 10ml 20～30 purposes mix.And under 380 ℃ of conditions, use hydrogen reducing 8 hours, hydrogen flowing quantity is controlled at 50ml/min.Cool to 220 ℃ then, N-ethylmorpholine and liquefied ammonia joined in proportion be made into raw material in the material-compound tank, raw material gasifies in constant-flux pump joins the mixing tank on gasifier top continuously with in the vaporizer that together enters into reactor top after hydrogen from hydrogen gas cylinder mixes, gaseous phase materials passes through the beds of microreactor continuously, reactant enters gas-liquid separator through condenser condenses, liquid phase is thick product, gas phase emptying after back pressure valve and absorption tower absorption.Its reaction conditions is: reaction pressure is 0.4MPa, and temperature of reaction is 220 ℃, and the N-ethylmorpholine air speed is 0.14h
-1, the reactor aspect ratio is not less than 6 to 1; The mol ratio of hydrogen and N-ethylmorpholine is 100: 1, and the mol ratio of liquefied ammonia and N-ethylmorpholine is 10: 1.Reaction result is as follows: the N-ethylmorpholine transformation efficiency is 42.7% (mol%), and the morpholine yield is 42.6% (mol%).
The present invention used catalyzer be that Jilin permanent rising sun Chemical Industry Science Co., Ltd produces, main technical details: nickel oxide content 〉=20% (wt%), content of magnesia 〉=3% (wt%), all the other are alumina supporter, mean pore size 12nm (pore size distribution 8～18nm is not less than 70%), specific surface area 140～160m2/g, bulk density 0.74, carrier diameter 3.2mm.
Example 2～12
Operation steps according to example 1 is operated, and example 2～12 reaction results see Table 1.
Table 1 is implemented 2～12 processing condition and reaction result thereof
| Routine number | Temperature ℃ | Pressure MPa | NEML air speed h -1 | H 2∶NEML | NH 3∶NEML | NEML transformation efficiency % | Morpholine yield % |
| Example 2 | 190 | 0.2 | 0.12 | 120 | 14 | 20.4 | 20.1 |
| Example 3 | 210 | 0.8 | 0.12 | 100 | 14 | 22.6 | 22.6 |
| Example 4 | 220 | 1.0 | 0.14 | 50 | 10 | 27.4 | 34.4 |
| Example 5 | 230 | 0.6 | 0.16 | 80 | 9 | 41.9 | 41.7 |
| Example 6 | 240 | 0.6 | 0.14 | 100 | 10 | 44.1 | 44.0 |
| Example 7 | 250 | 0.8 | 0.15 | 130 | 12 | 46.5 | 45.6 |
| Example 8 | 260 | 1.0 | 0.18 | 90 | 8 | 52.2 | 49.3 |
| Example 9 | 240 | 0.3 | 0.15 | 100 | 9 | 46.8 | 46.7 |
| Example 10 | 220 | 0.6 | 0.14 | 90 | 10 | 40.9 | 40.8 |
| Example 11 | 230 | 0.5 | 0.16 | 90 | 9 | 43.7 | 43.4 |
| Example 12 | 240 | 0.4 | 0.16 | 90 | 10 | 46.4 | 46.1 |
Annotate: NEML represents N-ethylmorpholine.The methylmorpholine by product that high temperature generates down can make the refining complicated of product.
NH in the above-mentioned table
3: NEM is meant the mol ratio of liquefied ammonia and N-ethylmorpholine, H
2: NEML is H
2Mol ratio with N-ethylmorpholine; Described NEML transformation efficiency and morpholine yield are molar percentage (mol%).More than the yield of monoethylamine of each embodiment identical with the yield of morpholine.
Claims (3)
1. one kind is the method for raw material production morpholine and monoethylamine with morpholine device byproduct N-ethylmorpholine, it is characterized in that: with Ni-MgO/Al
2O
3Catalyzer is put in the fixed-bed reactor, uses hydrogen reducing 8 hours down at 380 ℃, and hydrogen flowing quantity is 30ml/mlCatmin; Be cooled to 220 ℃ then, again with N-ethylmorpholine and liquefied ammonia mixture with hydrogen after gasification, add from the fixed-bed reactor top continuously, carry out gas and solid heterogeneous reaction, reaction product obtains the thick product of liquid phase through condensation and gas-liquid separation, and gas phase is through absorbing emptying; Its reaction pressure is 0.2～1.0MPa, and temperature of reaction is 190～260 ℃, and the N-ethylmorpholine air speed is 0.12～0.18h
-1, the reactor aspect ratio is not less than 6 to 1; The mol ratio of hydrogen and N-ethylmorpholine is 50～120: 1, and the mol ratio of liquefied ammonia and N-ethylmorpholine is 8～14: 1.
2. method according to claim 1 is characterized in that: reaction pressure is 0.3～0.6MPa, and temperature of reaction is 210～240 ℃, and the N-ethylmorpholine air speed is 0.14～0.16h
-1
3. method according to claim 1 is characterized in that: the mol ratio of hydrogen and N-ethylmorpholine is 80～100: 1, and the mol ratio of liquefied ammonia and N-ethylmorpholine is 9～10: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100168188A CN100371333C (en) | 2006-04-26 | 2006-04-26 | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100168188A CN100371333C (en) | 2006-04-26 | 2006-04-26 | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1830971A CN1830971A (en) | 2006-09-13 |
| CN100371333C true CN100371333C (en) | 2008-02-27 |
Family
ID=36993491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100168188A Expired - Fee Related CN100371333C (en) | 2006-04-26 | 2006-04-26 | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100371333C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002019A (en) * | 2010-10-18 | 2011-04-06 | 吉林化工学院 | Method for removing ethylene glycol monomethyl ether impurity in coarse product of morpholine device |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3151113A (en) * | 1962-02-19 | 1964-09-29 | Jefferson Chem Co Inc | Nu-alkyl morpholine production |
| JPS58225078A (en) * | 1982-06-25 | 1983-12-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for preparation of morpholine |
| CN1031699A (en) * | 1987-08-31 | 1989-03-15 | 中国石油化工总公司石油化工科学研究院 | The manufacture method of morpholinium compound (II) |
| CN1042539A (en) * | 1988-11-07 | 1990-05-30 | 中国石油化工总公司 | The catalyzer of synthesize morpholine and derivative thereof and method for making |
| CN1339434A (en) * | 2001-09-07 | 2002-03-13 | 天津大学 | Process for extracting N-methyl morpholine and N-ethyl morpholine in morpholine waste water |
-
2006
- 2006-04-26 CN CNB2006100168188A patent/CN100371333C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3151113A (en) * | 1962-02-19 | 1964-09-29 | Jefferson Chem Co Inc | Nu-alkyl morpholine production |
| JPS58225078A (en) * | 1982-06-25 | 1983-12-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for preparation of morpholine |
| CN1031699A (en) * | 1987-08-31 | 1989-03-15 | 中国石油化工总公司石油化工科学研究院 | The manufacture method of morpholinium compound (II) |
| CN1042539A (en) * | 1988-11-07 | 1990-05-30 | 中国石油化工总公司 | The catalyzer of synthesize morpholine and derivative thereof and method for making |
| CN1339434A (en) * | 2001-09-07 | 2002-03-13 | 天津大学 | Process for extracting N-methyl morpholine and N-ethyl morpholine in morpholine waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1830971A (en) | 2006-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102838116B (en) | Method for preparing carbon monoxide from coke oven gas and carbon dioxide | |
| CN104628508B (en) | A kind of taking coal and natural gas as raw material is through system and the technique of synthesis gas alkene processed | |
| KR101882813B1 (en) | A plasma tri-reformer | |
| CN107001177A (en) | The manufacture method of butadiene manufacture system and butadiene | |
| CN102464570B (en) | The series production method of a kind of alcohols or mixed alcohols and methanation hydro carbons | |
| AU2011240710B2 (en) | Method for preparing oxalate from carbon monoxide by gaseous phase method | |
| TW200427676A (en) | Method of improving the operation of a manufacturing process | |
| CN103333073A (en) | Process for preparing N,N-dimethyl-1,3-propane diamine through continuous method | |
| CN100371333C (en) | Method for producing marpholine and monoethylamine using by-products N-ethylamine from morpholine prodn. installation as raw material | |
| CN101619025A (en) | Continuous preparation method for n-pentylamine | |
| CN114015472A (en) | Reverse water-gas shift reaction and coal-to-methanol process coupling water electrolysis hydrogen production | |
| CN101215213B (en) | Overcritical Fischer-Tropsck synthesis method | |
| CN108212204A (en) | A kind of microwave radiation technology methane directly prepares the catalyst and Catalytic processes of higher olefins | |
| CN103421561A (en) | Synthesis gas methanation reaction method | |
| CN112194566A (en) | Device and process for synthesizing methanol based on carbon dioxide hydrogenation | |
| CN204509155U (en) | A kind of with coal and Sweet natural gas for raw material is through the system of synthetic gas alkene | |
| CN101134707B (en) | One-step method for preparing exo-tetrahydrodicyclopentadiene | |
| CN104262173A (en) | Method for synthesizing diglycolamine from diglycol by virtue of low-pressure process | |
| Xie et al. | Influence of different microstructures of cobalt on the catalytic activity for amination of ethylene glycol: comparison of HCP cobalt and FCC cobalt | |
| CN106040253A (en) | Preparation method and application of primaquine-terminated polyether catalyst prepared through static bed catalytic hydrogenation | |
| RU2515477C2 (en) | Method of obtaining hydrogen | |
| Dongmei et al. | Steam reforming of dimethyl ether over coupled catalysts of CuO-ZnO-Al2O3-ZrO2 and solid-acid catalyst | |
| CN214456841U (en) | Device for producing hydrogen by using waste biomass carbon | |
| CN104513679A (en) | New technology for preparing natural gas through coke-oven gas methanation | |
| CN110015940B (en) | Method for preparing toluene and methane by oxidative dehydrogenation of methylcyclohexane under carbon dioxide atmosphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080227 |