CN101306984B - Process for preparing ethanediol by hydrating ethyleneoxide - Google Patents
Process for preparing ethanediol by hydrating ethyleneoxide Download PDFInfo
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- CN101306984B CN101306984B CN2007100407075A CN200710040707A CN101306984B CN 101306984 B CN101306984 B CN 101306984B CN 2007100407075 A CN2007100407075 A CN 2007100407075A CN 200710040707 A CN200710040707 A CN 200710040707A CN 101306984 B CN101306984 B CN 101306984B
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Abstract
The invention relates to a method for manufacturing glycol by epoxy ethane hydration. The method mainly solves the problems that in the prior art, heat is difficult to remove in strong heat emission, catalyzer is easy to break caused by chemical expansion swelling and thermal expansion, and resistance drops of vertical tubes are different. The method adopts the technical proposal comprising the following steps that: epoxy ethane and water are used as raw materials; nanometer carbon tube resin is used as a catalyzer; under the conditions of a reaction temperature of between 85 and 120 DEG C, areaction pressure of between 1.0 and 1.8 MPa and an airspeed of between 1 and 3 hours SUP<-1>, the raw materials in a liquid state form are contacted and reacted with the catalyzer outside the vertical tube in a uniform temperature liquid-solid phase catalysis reactor to generate glycol, wherein, the uniform temperature liquid-solid phase catalysis reactor mainly consists of a shell body (1) capable of bearing pressure, a flange (2), an end enclosure (3), an inverted U-shaped vertical tube (4), an inverted U-shaped vertical tube bearing plate (5), a U-shaped tube tilting prevention baffle (6), a ramiform distributor (7), a discal redistributor (8), a cooling or heating medium inlet (9), a cooling or heating medium outlet (10), a tube box clapboard (11), a liquid state reaction material inlet pipe (12) and a liquid state reaction material outlet pipe (13), thereby well solving the problems. The method can be used in industrial production for manufacturing the ethanol by the epoxy ethane hydration.
Description
Technical field
The present invention relates to the method for a kind of oxyethane and water direct hydration preparing ethylene glycol.
Background technology
The oxyethane direct hydration method is the unique method of current existing plant-scale production ethylene glycol, nearly all oxyethane factory coproduction ethylene glycol, or oxyethane all is converted into ethylene glycol, the shortcoming of this technology maximum is that energy consumption is big, the evaporation concentration long flow path, facility investment is big.
The direct hydration method technical process is as follows: roughly contain oxyethane 1～3% (mole) in the gas mixture that the ethylene oxide device oxidation system is come, after the water absorption is removed carbonic acid gas and a small amount of aldehyde type impurities with desorption system, replenish process recycled water the water ratio is transferred to 22～28: 1 (mole).The gained aqueous solution of ethylene oxide enters ethylene glycol reactor, 190～220 ℃, greater than 1.9MPa pressure under, reaction generates monoethylene glycol (abbreviated as MEG) (annotate and do not use catalyzer), and main by product is glycol ether (vehicle economy G) and triglycol (being called for short TEG).Reaction mixture roughly contains alcohol 15～20% (weight), and mol ratio is roughly MEG: DEG: TEG=100: 10: 1.Through the multiple-effect evaporation upgrading system, pure content is brought up to about 85% (weight).Obtain product MEG and byproduct DEG and TEG respectively by refining system at last.
Another kind of under catalyst action, shell and tube reactor by oxyethane and water direct hydration preparing ethylene glycol, see accompanying drawing 1, reactor mainly enters feed distributor (7) by being distributed to the tubulation dress nano-sized carbon pipe resin catalyzer direct hydration preparing ethylene glycol in pipe behind the divider by housing (1), flange (2), end socket (3), tubulation (4), tubulation supporting plate (5), catalyzer (6), feed distributor (7), raw material from bottom feed pipe (8).Because catalyzer is contained in the tubulation, and the loading capacity of each root tubulation inner catalyst is not quite similar, brought the bearing capacity difference of each root tubulation inner catalyst to cause the catalyzer in the local tubulation to lose activity in advance, and CNT (carbon nano-tube) resin catalyst chemical swelling of meeting and the as easy as rolling off a log fragmentation that causes catalyzer of chance thermal expansion, even tubulation breaks, and the consequence of being brought is that reaction conversion ratio descends, selectivity reduces, catalyst life shortens.
Summary of the invention
Technical problem to be solved by this invention is in the method for the oxyethane that exists in the prior art and the direct catalytic hydration preparing ethylene glycol of water, CNT (carbon nano-tube) resin catalyst chemical swelling of meeting and the as easy as rolling off a log fragmentation that causes catalyzer of chance thermal expansion during catalyzed reaction, and the loading capacity of each root tubulation inner catalyst is not quite similar, having brought the bearing capacity difference of each root tubulation inner catalyst to cause catalyzer in the local tubulation consequence of being brought that in advance loses activity is that reaction conversion ratio descends, selectivity reduces, the problem that catalyst life shortens provides a kind of method of new hydration of epoxy ethane to prepare ethandiol.This method has catalyzer and is difficult for fragmentation, catalytic activity height, the advantage of long service life.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of hydration of epoxy ethane to prepare ethandiol, with oxyethane and water is raw material, with the CNT (carbon nano-tube) resin is catalyzer, is that 85～120 ℃, reaction pressure are that 1.0～1.8MPa, air speed are 1～3 hour in temperature of reaction
-1Under the condition, raw material passes through samming liquid-solid phase catalyticreactor with liquid form, generate ethylene glycol with the catalyzer contact reacts that fills in the tubulation outside in the reactor, wherein used samming liquid-solid phase catalyticreactor, main by a housing (1) that can bear pressure, flange (2), end socket (3), inverted u-shaped tubulation (4), inverted u-shaped tubulation supporting plate (5), anti-U type pipe sloping baffle (6), dendritic divider (7), plate-like redistributor (8), cooling or heating medium import (9), cooling or heating medium outlet (10) and bobbin carriage dividing plate (11) are formed, the liquid reaction material is advanced by feed-pipe (12), discharge nozzle (13) goes out, wherein inverted u-shaped tubulation (4) is uniformly distributed on the tubulation supporting plate (5), between tubulation supporting plate (5) and lower cover (3), form a bobbin carriage, and be divided into cooling mutually or heating medium advances by bobbin carriage dividing plate (11), go out two casees; Be provided with dendritic divider (7) and plate-like redistributor (8) according to this in tubulation supporting plate (5) top; Dendritic divider (7) is made up of at least one material opening for feed (12), ring-like feed-pipe (14) and at least one dendritic pipe (17), offers aperture (15) on the wherein dendritic pipe, and dendritic pipe (17) is uniformly distributed on the ring-like feed-pipe (14); Be evenly distributed with the tubulation corresponding on the plate-like redistributor (8) and evenly offer a plurality of apertures (16) with tubulation supporting plate (5), wherein the percentage of open area of inverted u-shaped tubulation (4) on plate-like redistributor (8) is 20～45%, and aperture (16) is 1～10% at plate-like redistributor (8) percentage of open area.
In the technique scheme, reactor inverted u-shaped tubulation (4) preferred version is arranged with trilateral or quadrangle, and open section is fixing by inverted u-shaped tubulation supporting tube sheet (5).
Material is entered on the ring-like feed-pipe (14) by opening for feed (12) during reaction, and the distribution reaction mass by dendritic divider (7) and plate-like redistributor (8) enters beds and catalyzer with the piston flow form and fully contacts the back and go out reactor from discharge nozzle (13) then.
The present invention is used for the method for oxyethane and the direct catalytic hydration preparing ethylene glycol of water, when reaction, the beds footpath phase temperature difference is 3～10 ℃, the catalyzer rate of expansion reaches at 12～21% o'clock, because catalyzer places the tubulation outside, so catalyzer can not squeeze fragmentation, but employing fixed-bed column reactor, the beds footpath phase temperature difference is 5～18 ℃, the catalyzer rate of expansion reaches 2～5% o'clock catalyzer will be squeezed fragmentation, and tubulation inner catalyst resistance drop sharply increase causes activity to descend even can't run well.Adopt the method for the direct catalytic hydration preparing ethylene glycol of oxyethane of the present invention and water, its catalyst life can reach more than 8000 hours, had obtained better technical effect.
Description of drawings
Fig. 1 is the reactor synoptic diagram of prior art;
Fig. 2 is the synoptic diagram of oxyethane of the present invention and the direct catalytic hydration reaction for preparing glycol of water device;
Fig. 3 is the synoptic diagram of dendritic feed distributor (7) in oxyethane of the present invention and the direct catalytic hydration reaction for preparing glycol of the water device;
Fig. 4 is the synoptic diagram of plate-like redistributor (8) in oxyethane of the present invention and the direct catalytic hydration reaction for preparing glycol of the water device.
The reactor that the method for the direct catalysis hydration preparing ethylene glycol of oxirane of the present invention and water adopts, see Fig. 2, mainly comprise a housing (1) that can bear pressure, flange (2), end socket (3), inverted u-shaped tubulation (4), inverted u-shaped tubulation support plate (5), anti-U-shaped pipe sloping baffle (6), dendritic distributor (7) and plate-like redistributor (8), cooling or heat medium import (9), cooling or heat medium outlet (10) and bobbin carriage dividing plate (11), the liquid reaction material is advanced by feed pipe (12), discharge nozzle (13) goes out; Wherein inverted u-shaped tubulation (4) is uniformly distributed on the tubulation support plate (5), between tubulation support plate (5) and low head (3), form a bobbin carriage, and be divided into mutually cooling or heat medium enters (8), goes out (8) two casees by bobbin carriage dividing plate (11); Be provided with according to this dendritic distributor (7) and plate-like redistributor (8) in tubulation support plate (5) top; Dendritic distributor (7) has at least a material feeding mouth (12), ring-like feed pipe (14) and at least one dendritic pipe (17) to form, wherein offer aperture (15) on the dendritic pipe, 1～20 millimeter in aperture, dendritic pipe (17) are uniformly distributed on the ring-like feed pipe (14); Be evenly distributed with the tubulation corresponding with tubulation support plate (5) on the plate-like redistributor (8) and evenly offer a plurality of apertures (16), wherein the percent opening of inverted u-shaped tubulation (4) on plate-like redistributor (8) is 20～45%, aperture (16) is 1～10% at plate-like redistributor (8) percent opening, 1～10 millimeter in aperture. Reaction temperature is controlled by the temperature of regulating cooling or heat medium.
The present invention is the U-shaped pipe outside because catalyst is contained in, so increased the Catalyst packing coefficient, reaches more than 75%. And calandria type fixed bed reactor Catalyst packing coefficient is usually about 30%.
Reactor of the present invention is owing to remove heat or heating tube adopts U-shaped tubulation (4), and open section is fixing by inverted u-shaped tubulation support plate (5), and another section retractable has increased structural reliability.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
See Fig. 2 with a kind of samming liquid-solid phase catalytic reactor of the present invention, finish oxyethane and water catalysis direct hydration preparing ethylene glycol, 2.6 meters of reactor diameters, high 6.0 meters, the dress composite catalyst, synthesis pressure 0.7～2.0MPa, material composition: oxyethane and water, mol ratio 1: 8, inlet amount: 37.5 tons/hour, 90～120 ℃ of catalyzer hot(test)-spot temperatures, the temperature difference＜15 ℃ between the catalyzer hot(test)-spot temperature outside bed temperature and the U type pipe in the U type pipe.Catalyst life reached more than 8000 hours.
Under same operational condition, adopt calandria type fixed bed reactor to see Fig. 1, catalyzer is heated for a long time, expands in the tubulation, causes catalyzer to squeeze broken, shortening in work-ing life.See Fig. 2 with reactor of the present invention, because catalyzer is contained in the U type tubulation outside, catalyzer is heated for a long time, expands and also should not squeeze fragmentation, and catalyzer doubles above work-ing life.Adopt both technical data of same catalyst to see Table 1.
| Reactor types | Water/EO mol ratio | Temperature of reaction ℃ | Reaction pressure MPa | EO transformation efficiency % | EG selectivity % | Catalyst life hour |
| Homogeneous temperature type liquid-solid phase |
5～8? | 85～120? | 1.0～1.8? | 99.6? | 96.3? | 8000>? |
| Calandria type |
6～10? | 85～125? | 1.0～1.8? | 99.5? | 94.5? | 3000<? |
Annotate: EO is an oxyethane, and EG is an ethylene glycol.
In addition, under same annual production, with reactor of the present invention the catalyzer demolition, installation than calandria type fixed bed reactor to save time, laborsaving.
In addition, adopt oxyethane and the direct catalytic hydration reaction for preparing glycol of the water system of being used for of the present invention, the data of being gathered under the situation of differing temps, different pressures and air speed see Table 2.
| Temperature of reaction ℃ | Reaction pressure MPa | Water/EO mol ratio | Air speed hour -1 | EO transformation efficiency % | EG selectivity % |
| 90 | 1.2 | 8 | 1.2 | 99.58 | 97.64 |
| 90 | 1.2 | 8 | 1.5 | 99.40 | 97.60 |
| 90 | 1.2 | 8 | 3 | 99.32 | 96.54 |
| 100 | 1.3 | 8 | 1.5 | 99.62 | 97.56 |
| 100 | 1.3 | 6 | 1.5 | 99.54 | 96.31 |
| 100 | 1.3 | 5 | 1.5 | 99.53 | 94.32 |
| 105 | 1.3 | 6 | 2 | 99.63 | 95.8 |
| 105 | 1.3 | 5 | 2 | 99.57 | 94.1 |
| 105 | 1.3 | 5 | 2.5 | 99.51 | 93.8 |
From above data obtain temperature of reaction at 90～105 ℃, pressure at 1.2～1.3MPa, air speed hour
-1Between 1.2～2.5, reaction has fine EO transformation efficiency % and EG selectivity %.
Claims (2)
1. the method for a hydration of epoxy ethane to prepare ethandiol is a raw material with oxyethane and water, is catalyzer with the CNT (carbon nano-tube) resin, is that 85～120 ℃, reaction pressure are that 1.0～1.8MPa, air speed are 1～3 hour in temperature of reaction
-1Under the condition, raw material passes through samming liquid-solid phase catalyticreactor with liquid form, generate ethylene glycol with the catalyzer contact reacts that fills in the tubulation outside in the reactor, wherein used samming liquid-solid phase catalyticreactor, main by a housing (1) that can bear pressure, flange (2), end socket (3), inverted u-shaped tubulation (4), inverted u-shaped tubulation supporting plate (5), anti-U type pipe sloping baffle (6), dendritic divider (7), plate-like redistributor (8), cooling or heating medium import (9), cooling or heating medium outlet (10) and bobbin carriage dividing plate (11) are formed, the liquid reaction material is advanced by feed-pipe (12), discharge nozzle (13) goes out, wherein inverted u-shaped tubulation (4) is uniformly distributed on the tubulation supporting plate (5), between tubulation supporting plate (5) and lower cover (3), form a bobbin carriage, and be divided into cooling mutually or heating medium advances by bobbin carriage dividing plate (11), go out two casees; Be provided with dendritic divider (7) and plate-like redistributor (8) according to this in tubulation supporting plate (5) top; Dendritic divider (7) is made up of at least one material opening for feed (12), ring-like feed-pipe (14) and at least one dendritic pipe (17), offers aperture (15) on the wherein dendritic pipe, and dendritic pipe (17) is uniformly distributed on the ring-like feed-pipe (14); Be evenly distributed with the tubulation corresponding on the plate-like redistributor (8) and evenly offer a plurality of apertures (16) with tubulation supporting plate (5), wherein the percentage of open area of inverted u-shaped tubulation (4) on plate-like redistributor (8) is 20～45%, and aperture (16) is 1～10% at plate-like redistributor (8) percentage of open area.
2. the method for hydration of epoxy ethane to prepare ethandiol according to claim 1 is characterized in that reactor inverted u-shaped tubulation (4) with trilateral or quadrangle arrangement, and open section is fixing by inverted u-shaped tubulation supporting plate (5).
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| CN2007100407075A CN101306984B (en) | 2007-05-16 | 2007-05-16 | Process for preparing ethanediol by hydrating ethyleneoxide |
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| CN2007100407075A CN101306984B (en) | 2007-05-16 | 2007-05-16 | Process for preparing ethanediol by hydrating ethyleneoxide |
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| CN101306984B true CN101306984B (en) | 2011-02-09 |
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| CN102219642B (en) * | 2010-04-15 | 2013-12-04 | 中国石油化工股份有限公司 | Method for producing glycol by virtue of hydration of ethylene oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198429A (en) * | 1997-04-30 | 1998-11-11 | 三菱化学株式会社 | Process for producing alkylene glycol |
| CN1721385A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Process for producing alkylene glycol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198429A (en) * | 1997-04-30 | 1998-11-11 | 三菱化学株式会社 | Process for producing alkylene glycol |
| CN1721385A (en) * | 2004-07-12 | 2006-01-18 | 中国石油化工股份有限公司 | Process for producing alkylene glycol |
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