CN103962144A - Catalyst for synthesizing morpholine by gas-solid phase catalysis and preparation method thereof - Google Patents
Catalyst for synthesizing morpholine by gas-solid phase catalysis and preparation method thereof Download PDFInfo
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- CN103962144A CN103962144A CN201410186330.4A CN201410186330A CN103962144A CN 103962144 A CN103962144 A CN 103962144A CN 201410186330 A CN201410186330 A CN 201410186330A CN 103962144 A CN103962144 A CN 103962144A
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Abstract
The invention relates to a catalyst for synthesizing morpholine by gas-solid phase catalysis and a preparation method thereof. The catalyst is characterized in that Al2O3 bobbles are used as carriers for loading Cu, Ni, Zn and Mg active components. The preparation method comprises the following steps: roasting the carriers with the required amount at the temperature of 600-900 DEG C for 3-6 hours to obtain a preroasting carrier; carrying out ultrasonic immersion on the preroasting carrier in Cu, Ni, Zn and Mg nitrite solution at the temperature of 40-80 DEG C, filtering and drying; roasting the dried substance at the temperature of 350-600 DEG C for 3-5 hours and naturally cooling to room temperature and obtaining the catalyst for synthesizing the morpholine by the gas-solid phase catalysis. The prepared catalyst is evaluated; the conversion rate of diglycolamine is 87-99.9 percent and the selectivity of the morpholine is 85-91 percent. The catalyst has the advantages that nitrogen gas is used to replace part of hydrogen gas and can be directly used to synthesize ammonia tail gas; in addition, the production safety can be improved.
Description
Technical field
The invention belongs to catalyst preparation technology, field of fine chemical in Chemical Engineering and Technology, particularly relate to a kind of Catalysts and its preparation method of diethylene glycol (DEG) gas and solid phase catalyzing ammonia solution cyclisation method synthesize morpholine.
Background technology
Morpholine is important fine chemical product raw material, has a wide range of applications in fields such as agricultural chemicals, medicine, dyestuff and rubber.The synthetic main method of morpholine is diethylene glycol (DEG) catalysis ammonia solution cyclisation method at present, and generation efficiency is low, energy consumption is high.Reduce the synthetic energy consumption of morpholine and cost, need to prepare function admirable, be applicable to the catalyst of different process route and raw material route.Diethylene glycol (DEG) catalysis ammonia solution cyclisation method synthesize morpholine process route has intermittently synthesis technique and the continuous synthesis technique of gas-solid catalysis of gas-liquid-solid three-phase catalysis, because the continuous synthesis technique of gas-solid catalysis has, catalyst consumption is few, production efficiency advantages of higher, is current domestic main morpholine synthesis technique.But there is the deficiencies such as selective concentration not high enough and charging diethylene glycol (DEG) is low in the continuous synthetic catalyst of gas-solid at present, has increased to a certain extent the difficulty of producing.For example Chinese patent [application (patent) number] the 200410010816.9 continuous synthesize morpholine catalyst of disclosed a kind of diethylene glycol (DEG) ammonification and techniques thereof, although employing pellet catalyst, but dipping effect is good not, the catalyst obtaining only just obtains higher morpholine yield in the time that raw material diethylene glycol (DEG) concentration is lower, and production efficiency is low.The synthetic raw material of morpholine is diethylene glycol (DEG), ammonia and hydrogen, does not openly report that useful nitrogen replaces the situation of hydrogen partial.
Summary of the invention
The inventor after research and testing, taking Ni-Cu-Zn-Mg as active component, Al
2o
3bead is in the catalyst preparation process of carrier impregnation synthesize morpholine, adopts ultrasonic wave dipping, prepares a kind of gas and solid phase catalyzing synthesize morpholine catalyst that floods that efficiency is high, catalytic performance good, can replace with part nitrogen hydrogen.
The catalyst of synthesize morpholine of the present invention is with Al
2o
3for carrier, taking Ni, Cu, Zn and Mg as active constituent, the Al that its preparation method is is 1～4mm diameter
2o
3bead is roasting 3～6h at 600～900 DEG C, and cool to room temperature obtains pre-activated carrier, adds by Cu: Ni: Zn: Mg=1: 0.40～1.00: 0.30～0.90: 0.10～0.20 mole of proportioning compound concentration is 1～5molL
-1nitrate mixed solution, at 40～80 DEG C with ultrasonic power dipping 30～200min of 100～500W; Then filter out bead, by bead after dry at 100～130 DEG C at 350～600 DEG C of roasting 3～5h, naturally cool to room temperature and obtain these four kinds of active component quality of Ni, Cu, Zn and Mg and account for the catalyst of the gas and solid phase catalyzing synthesize morpholine of carrier quality 10～30%.
The synthesize morpholine catalyst that the present invention prepares is filled in gas-solid and fixes bed bioreactor, after hydrogen reducing activation, is that 180～250 DEG C, pressure are that 1.3～2.5MPa, diethylene glycol (DEG) liquid air speed are 0.1～0.3h in temperature
-1, ammonia: (hydrogen+nitrogen): diethylene glycol (DEG)=3～10: 20～30: 1 and hydrogen: nitrogen=1: while use for 0～6 time, diethylene glycol (DEG) conversion ratio is 87.7%～99.9%, morpholine be selectively 85%～91%.
Compare with current synthesize morpholine gas and solid phase catalyzing agent, employing ultrasonic wave dipping, not only dip time can shorten more than 5 times, and can make the active component content of catalyst and specific area increase, thereby increase the activity of catalyst, its raw material can use nitrogen to replace hydrogen partial, consists of hydrogen: nitrogen: ammonia=3: 1: 0.1～0.3 tail gas thereby can directly use synthetic ammonia to discharge.
Detailed description of the invention
Embodiment mono-
The Al that is 1.5mm by diameter
2o
3bead is roasting 4h at 750 DEG C, and cool to room temperature obtains pre-activated carrier; Add by Cu: Ni: Zn: Mg=1: 0.69: 0.55: 0.14 mole of proportioning compound concentration is 2.6molL
-1nitrate mixed solution, in 60 DEG C of water-baths dipping 5h; Then filter out bead, by bead after dry at 105 DEG C at 500 DEG C of roasting 4h, naturally cool to room temperature and obtain the catalyst of conventional impregnating gas solid catalysis synthesize morpholine.If adopt ultrasonic wave dipping, impregnation steps changes the ultrasonic power dipping 120min with 245W at 60 DEG C into, and other conditions are all identical with the condition of above-mentioned conventional dipping, obtain ultrasonic immersing catalyst.The active component of catalyst adopts ICP to measure, and what specific surface adopted is that specific surface area analysis instrument is measured, and the results are shown in Table 1.
Conventional impregnated catalyst and ultrasonic immersing catalyst, after hydrogen reducing activation, are that 230 DEG C, pressure are 1.7MPa, diethylene glycol (DEG) liquid air speed 0.2h in temperature respectively
-1, ammonia: (hydrogen+nitrogen): alcohol ratio is 5: 25: 1 and hydrogen: nitrogen=1: synthesize morpholine under 2 condition, its reaction conversion ratio and selectively in table 2.
Embodiment bis-
The Al that is 2mm diameter
2o
3bead is roasting 4.5h at 750 DEG C, and cool to room temperature obtains pre-activated carrier, adds by Cu: Ni: Zn: Mg=1: 0.69: 0.55: 0.14 mole of proportioning compound concentration is 2.6molL
-1nitrate mixed solution, the ultrasonic power dipping 120min with 140W, 175W, 245W and 315W respectively at 65 DEG C; Then filter out bead, by bead after dry at 110 DEG C at 500 DEG C of roasting 4h, naturally cool to room temperature and obtain the catalyst of 4 kinds of ultrasonic power gas and solid phase catalyzing synthesize morpholines.These 4 kinds of catalyst respectively after hydrogen reducing activation, are that 230 DEG C, pressure are 1.7MPa, diethylene glycol (DEG) liquid air speed 0.2h in temperature
-1, ammonia: (hydrogen+nitrogen): diethylene glycol (DEG)=5: 25: 1 and hydrogen: nitrogen=1: while use for 2 times, its its reaction conversion ratio of diethylene glycol (DEG) conversion ratio and selectively in table 2.
Embodiment tri-
The Al that is 2mm diameter
2o
3bead is roasting 4.5h at 750 DEG C, and cool to room temperature obtains pre-activated carrier, adds by Cu: Ni: Zn: Mg=1: 0.69: 0.55: 0.14 mole of proportioning compound concentration is 2.6molL
-1nitrate mixed solution, under 65 DEG C and 245W ultrasonic power, flood respectively 30min, 60min, 90min, 120min and 150min; Then filter out bead, by bead after dry at 110 DEG C at 500 DEG C of roasting 4h, naturally cool to room temperature and obtain the catalyst of the gas and solid phase catalyzing synthesize morpholine of 4 kinds of dip times.These 4 kinds of catalyst respectively after hydrogen reducing activation, are that 230 DEG C, pressure are 1.7MPa, diethylene glycol (DEG) liquid air speed 0.2h in temperature
-1, ammonia: (hydrogen+nitrogen): diethylene glycol (DEG)=5: 25: 1 and hydrogen: nitrogen=1: while use for 2 times, its its reaction conversion ratio of diethylene glycol (DEG) conversion ratio and selectively in table 2.
Embodiment tetra-
The Al that is 2mm diameter
2o
3bead is roasting 5h at 700 DEG C, and cool to room temperature obtains pre-activated carrier, adds by Cu: Ni: Zn: Mg=1: 0.69: 0.55: 0.14 mole of proportioning compound concentration is 2.8molL
-1nitrate mixed solution, in 60 DEG C, 245W ultrasonic power dipping 120min; Then filter out bead, by bead after dry at 110 DEG C at 500 DEG C of roasting 4h, naturally cool to room temperature and obtain the catalyst of 4 kinds of ultrasonic power gas and solid phase catalyzing synthesize morpholines.Catalyst, after hydrogen reducing activation, is that 230 DEG C, pressure are 1.7MPa, diethylene glycol (DEG) liquid air speed 0.2h in temperature
-1, ammonia: (hydrogen+nitrogen): diethylene glycol (DEG) is respectively 3: 25: 1,5: 25: 1,7: 25: 1,9: 25: 1, hydrogen: nitrogen=1: while use for 3 times, its its reaction conversion ratio of diethylene glycol (DEG) conversion ratio and selectively in table 2.
Embodiment five
The Al that is 2mm diameter
2o
3bead is roasting 5h at 700 DEG C, and cool to room temperature obtains pre-activated carrier, adds by Cu: Ni: Zn: Mg=1: 0.69: 0.55: 0.14 mole of proportioning compound concentration is 2.8molL
-1nitrate mixed solution, in 60 DEG C, 245W ultrasonic power dipping 120min; Then filter out bead, by bead after dry at 110 DEG C at 500 DEG C of roasting 4h, naturally cool to room temperature and obtain the catalyst of 4 kinds of ultrasonic power gas and solid phase catalyzing synthesize morpholines.Catalyst, after hydrogen reducing activation, is that 230 DEG C, pressure are 1.7MPa, diethylene glycol (DEG) liquid air speed 0.2h in temperature
-1, ammonia: (hydrogen+nitrogen): diethylene glycol (DEG) is 5: 25: 1, hydrogen: nitrogen is respectively 1: 0,1: 2,1: 4 and 1: 6 time while using, its its reaction conversion ratio of diethylene glycol (DEG) conversion ratio and selectively in table 2.
Table 1
Table 2
Claims (2)
1. a preparation method for gas and solid phase catalyzing synthesize morpholine catalyst is with Al
2o
3bead is carrier, and taking Ni, Cu, Zn and tetra-kinds of elements of Mg as active constituent, concrete preparation method is as follows: the Al that is 1～4mm diameter
2o
3bead is roasting 3～6h at 600～900 DEG C, after cool to room temperature, adds by Cu: Ni: Zn: Mg=1: 0.40～1.00: 0.30～0.90: the concentration of 0.10～0.20 mole of proportioning preparation is 1～5mol.L
-1nitrate mixed solution, at 40～80 DEG C with ultrasonic power dipping 30～200min of 100～500W; After dipping finishes, filter out bead, bead is dry at 100～130 DEG C, and then roasting 3～5h at 350～600 DEG C, naturally cools to room temperature and obtains described catalyst.
2. the catalyst that preparation method according to claim 1 obtains, its condition using on the fixed bed reactors of synthesize morpholine is as follows: temperature is that 180～250 DEG C, pressure are that 1.3～2.5MPa, diethylene glycol (DEG) liquid air speed are 0.1～0.3h
-1, raw material proportioning ammonia: (hydrogen+nitrogen): diethylene glycol (DEG) is 3～10: 20～30: 1, Qi Zhongqing: nitrogen is 1: 0～6.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503516A (en) * | 2018-12-26 | 2019-03-22 | 高化学（江苏）化工新材料有限责任公司 | A kind of preparation method of double morpholine Anaesthetie Ethers |
| CN110586110A (en) * | 2019-10-09 | 2019-12-20 | 四川鸿鹏新材料有限公司 | Supported catalyst for preparing morpholine from diethylene glycol and preparation method thereof |
| CN113578372A (en) * | 2021-08-31 | 2021-11-02 | 滨州中科催化技术有限公司 | Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof |
| CN116178306A (en) * | 2021-11-29 | 2023-05-30 | 安徽昊源化工集团有限公司 | Morpholine synthesis process |
| CN117417262A (en) * | 2023-10-19 | 2024-01-19 | 山东达民化工股份有限公司 | Preparation method of diglycolamine |
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| CN1915497A (en) * | 2006-08-21 | 2007-02-21 | 广西大学 | Catalyst for synthesizing morphine through diethylene glycol ammoniation, and preparation method |
| JP2008019176A (en) * | 2006-07-11 | 2008-01-31 | Ihi Corp | Method for synthesizing methanol and dimethyl ether |
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2014
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| JP2008019176A (en) * | 2006-07-11 | 2008-01-31 | Ihi Corp | Method for synthesizing methanol and dimethyl ether |
| CN1915497A (en) * | 2006-08-21 | 2007-02-21 | 广西大学 | Catalyst for synthesizing morphine through diethylene glycol ammoniation, and preparation method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503516A (en) * | 2018-12-26 | 2019-03-22 | 高化学（江苏）化工新材料有限责任公司 | A kind of preparation method of double morpholine Anaesthetie Ethers |
| CN110586110A (en) * | 2019-10-09 | 2019-12-20 | 四川鸿鹏新材料有限公司 | Supported catalyst for preparing morpholine from diethylene glycol and preparation method thereof |
| CN113578372A (en) * | 2021-08-31 | 2021-11-02 | 滨州中科催化技术有限公司 | Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof |
| CN113578372B (en) * | 2021-08-31 | 2023-07-07 | 安徽昊源化工集团有限公司 | Catalyst for synthesizing morpholine from diethylene glycol and preparation method thereof |
| CN116178306A (en) * | 2021-11-29 | 2023-05-30 | 安徽昊源化工集团有限公司 | Morpholine synthesis process |
| CN117417262A (en) * | 2023-10-19 | 2024-01-19 | 山东达民化工股份有限公司 | Preparation method of diglycolamine |
| CN117417262B (en) * | 2023-10-19 | 2024-03-29 | 山东达民化工股份有限公司 | Preparation method of diglycolamine |
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Application publication date: 20140806 |