CN102029130B - Device and method for preparing dimethyl ether - Google Patents
Device and method for preparing dimethyl ether Download PDFInfo
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- CN102029130B CN102029130B CN201010527563.8A CN201010527563A CN102029130B CN 102029130 B CN102029130 B CN 102029130B CN 201010527563 A CN201010527563 A CN 201010527563A CN 102029130 B CN102029130 B CN 102029130B
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Abstract
The invention belongs to the field of chemical engineering, and relates to a device for preparing dimethyl ether and a method for preparing the dimethyl ether by utilizing the device. The device for preparing the dimethyl ether comprises a slurry reactor and a heat exchanger, wherein the heat exchanger is arranged outside the reactor; the upper part of the heat exchanger is provided with a steam pocket; the upper pipe layer of the heat exchanger is equal to or lower than a liquid level of a heat carrier in the reactor, and the bottom of the heat exchanger is higher than that of the reactor; one end of a heat carrier outlet pipe is connected with the middle of the reactor, while the other end is connected with the upper pipe layer of the heat exchanger; the connecting part of the heat carrier outlet pipe and the reactor is lower than the liquid level of the heat carrier in the reactor; one end of a heat carrier inlet pipe is connected with the bottom of the heat exchanger, while the other end is connected with the lower part of the reactor; and the connecting part of the heat carrier inlet pipe and the reactor is higher than a gas distributor in the reactor. The device increase the effective reaction volume of the reactor, can produce the dimethyl ether on a large scale, ensures bed temperature, avoids temperature runaway of the bed, and improves conversion rate and dimethyl ether selectivity.
Description
Technical field
The invention belongs to chemical field, relate to a kind of preparation facilities of dimethyl ether and utilize this device to prepare the method for dimethyl ether.
Background technology
Dimethyl ether purposes is extensive: similar to liquefied petroleum gas, can be used as domestic fuel; There is higher Cetane number, can be used as the substitute of motor vehicle fuel.Dimethyl ether or important industrial chemicals, be widely used in the fields such as chemical industry, pharmacy, agricultural chemicals, daily use chemicals.Due to dimethyl ether, the scholar of various countries and company have carried out extensive research to the synthesis technique of dimethyl ether, catalyst.
At present the synthetic method of dimethyl ether has two kinds: (1) two-step process, i.e. and the first synthesizing methanol of synthesis gas, methyl alcohol is dewatering preparing dimethy ether technique again; (2) one-step technology, i.e. direct synthesis of dimethyl ether from synthesis gas.One-step technology can be broken the restriction of thermodynamical equilibrium, has improved the conversion per pass of carbon monoxide, reduces production costs, and production that can heavy industrialization, has broad application prospects.
One-step method from syngas preparing dimethy ether technology key is dimethyl ether reactor, many patents disclose the content of this reactor, for example Chinese patent: CN1382676, CN1593740, CN1194257, CN1600412, CN1327874, CN1259509, European patent EP 0409086 (A1), Japan Patent JP10192689, JP09301907, JP09309850, US Patent No. 2004151640 (A1), US6132690, US6562306, US5218003 etc.
There is following problem in the reactor of synthesis of dimethyl ether with synthesis gas one-step at present: (1) is for fixed bed reactors, the thermal discharge of one-step method from syngas preparing dimethy ether is very large, heat cannot be removed in time, be caused catalytic bed excess Temperature, cause normal operating to carry out; (2) for gas-liquid-solid catalytic reactor, existence due to heat carrier, can keep bed reaction temperature, the heat that has solved one-step method from syngas preparing dimethy ether shifts out problem, can prevent that bed temperature is too high, but heat exchanger is arranged in reactor, structure of reactor is complicated, the catalytic amount of unit reaction volume filling is few, and device is difficult to large-scale; (3) gas-solid catalytic reactor, due to the wearing and tearing of catalyst, catalyst loss is very fast, and operating cost is high, and heat of reaction is removed by gas sensible heat, reacts easy temperature runaway.
Summary of the invention
The object of this invention is to provide a kind of novel device of preparing dimethyl ether and utilize this device to prepare the method for dimethyl ether, by external heat exchanger is set, effectively solve in prior art because heat exchanger is arranged on that the complex structure, the manufacturing cost that cause in reactor effective reacting volume high, reactor is little, device is difficult to maximize, the easy temperature runaway of reaction temperature and the shortcoming such as catalyst loss is large.
The device of preparing dimethyl ether of the present invention comprises slurry-phase reactor (abbreviation reactor) and heat exchanger, and wherein heat exchanger is arranged on outside reactor, and heat exchanger top is provided with drum; Heat exchanger upper tube layer (being the space between upper perforated plate and heat exchanger upper cover) put down in or lower than reactor in heat carrier liquid level, heat exchanger bottom is higher than reactor bottom; Heat carrier flows out manages one end coupled reaction device middle part, and the other end connects the upper tube layer of heat exchanger, and heat carrier flows out the junction of pipe and reactor lower than heat carrier liquid level in reactor; Heat carrier flows into the bottom that pipe one end connects heat exchanger, other end coupled reaction device bottom, and heat carrier flows into manages with the junction of reactor higher than the gas distributor in reactor.
As preferred embodiment, 1-10 group heat carrier can be set between reactor and heat exchanger and flow into pipe and heat carrier outflow pipe, be preferably 4 groups.
As preferred embodiment, the diameter that heat carrier flows into pipe and heat carrier outflow pipe is 200mm-500mm.
As preferred embodiment, the top exit place that device of the present invention is also included in reactor is provided with gas-liquid-solid separator.
For further effectively utilizing catalyst, as preferred embodiment, in reactor of the present invention, be also provided with circular cone and lower circular cone, upper circular cone and lower circular cone are the silk screens that perforate varies in size, perforate is evenly distributed on the conical surface.Wherein, upper circular cone flows out the junction of pipe and reactor lower than heat carrier; Lower circular cone flows into the junction of pipe and reactor higher than heat carrier.Lower circular cone is fixed on apart from 1/3 of reactor bottom to be sentenced down, is preferably the 1/4-1/3 place apart from reactor bottom; Upper circular cone is fixed on the 2/5-4/5 place apart from reactor bottom, is preferably the 2/5-3/5 place apart from reactor bottom.Lower circular cone opening diameter is 0.125-2.0mm, is preferably 0.15-0.2mm; Upper circular cone opening diameter is 0.1-1.0mm, is preferably 0.12-0.15mm; The percent opening of upper and lower circular cone is 50-99%, is preferably 80-95%.The effect of upper and lower circular cone is to guarantee that catalyst is evenly distributed in heat carrier, by the different silk screen of opening diameter, make large granular catalyst be distributed in the bottom of reaction bed, catalyst particle is distributed in the top of reaction bed, prevent that catalyst granules from entering into heat exchanger simultaneously, effectively utilize catalyst, thereby reach, improved optionally object of output and dimethyl ether.
As preferred embodiment, device of the present invention is also included in the pump that is provided for forcing heat carrier circulation on the pipeline that heat carrier flows into pipe.
As preferred embodiment, heat exchanger of the present invention is water cooling heat exchanger.
As preferred embodiment, reactor middle part is apart from 1/4～1/3 place, reactor the top.
As preferred embodiment, a reactor can arrange a plurality of heat exchangers around, is preferably 1.
The present invention further provides a kind of method of using device of the present invention to prepare dimethyl ether, the method is removed heat when preparing dimethyl ether, by producing 3.0-4.0MPa middle pressure steam in the drum on heat exchanger top, heat is shifted out to system.
The catalyst that the present invention uses can be the synthetic copper-based catalysts of industrial methanol and methanol dehydration γ-Al
2o
3the catalyst of catalyst mechanical mixture can be also with HZSM molecular sieve or γ-Al
2o
3for the compound bifunctional catalyst of carrier, particularly with Cu-Based Catalysts for Methanol Synthesis and the methanol dehydration γ-Al with low temperature active
2o
3the catalyst of catalyst mechanical mixture is best.
While utilizing device of the present invention to react, the inert heat carrier using enters in heat exchanger tube because density contrast flows out pipe by heat carrier, after heat transferring medium indirect heat exchange in heat exchanger, heat carrier through heat exchanger bottom flows into pipe and enters in reactor, thereby form heat carrier circulation, the steam that reaction heat is produced by the heat transferring medium isothermal evaporation in heat exchanger is removed.
Usefulness of the present invention is: heat exchanger is arranged on outside reactor, has increased the effective reacting volume of reactor, can realize large-scale production; Structure of reactor is simple, easy to manufacture, and equipment investment cost is low; At reactor outlet, gas-liquid-solid separator is set, has avoided that exit gas is liquid-solid to be carried secretly; The production capacity that has improved device, has reasonably reclaimed energy, has reduced production cost; This device has been removed reaction heat in reaction, has kept normal reaction temperature, has guaranteed the continuity of producing, and has improved the selective of product yield and dimethyl ether; Prevent because of the too high catalysqt deactivation that causes of local catalyst temperature, thereby extended life-span of catalyst.
Accompanying drawing explanation
Fig. 1 is dimethyl ether preparation facilities schematic diagram of the present invention;
Fig. 2 is water cooling heat exchanger upper perforated plate schematic diagram.
The specific embodiment
In conjunction with the specific embodiment and accompanying drawing explanation the present invention, but the present invention is not limited to the specific embodiment below.
As depicted in figs. 1 and 2, the device for the preparation of dimethyl ether provided by the invention, comprises slurry-phase reactor 101 and water cooling heat exchanger 102, and water cooling heat exchanger 102 is arranged on outside reactor 101.Wherein 1 is raw material gas inlet, and 2 is gas distributor, and 3 is cylindrical shell, 4 is lower circular cone, and 5 is upper circular cone, and 6 is manhole, 7 is gas-liquid-solid separator, and 8 is reaction gas outlet, and 9 is drum, 10 is vapor uptake, and 11 is down-comer, and 12 manage for heat carrier flows out, 13 for fresh catalyst adds entrance, and 14 is water cooling heat exchanger upper perforated plate, and 15 is water cooling heat exchanger cylindrical shell, 16 is tubulation, and 17 is lower perforated plate, and 18 manage for heat carrier flows into.Water cooling heat exchanger 102 upper tube layers are lower than heat carrier height in reactor 101, and water cooling heat exchanger 102 bottoms are higher than reactor 101 bottoms; Heat carrier flows out manages distance reactor 1/3 place, the top of 12 difference coupled reaction devices 101 and the upper tube layer of water cooling heat exchanger 102, and the junction of heat carrier outflow pipe 12 and reactor 101 is arranged in the upper and lower circle of reactor 101 heat carrier liquid levels and bores on 5; Heat carrier flows into bottom and reactor 101 bottoms that pipe 18 connects respectively water cooling heat exchanger 102, and the junction that heat carrier flows into pipe 18 and reactor 101 is arranged under the upper and lower circular cone 4 of gas distributor 2 of reactor 101.
In the preparation process of dimethyl ether, synthesis gas enters gas distributor 2 by the raw material gas inlet 1 of reactor 101 bottoms, has hundreds of to several thousand apertures of opening on gas distributor 2 downwards.Synthesis gas enters into after reactor 101, from the bottom of reactor 101, upwards flows, and reacts being suspended on the catalyst of heat carrier.The temperature of the heat carrier in reactor 101 is greater than the temperature of water cooling heat exchanger 102, and heat carrier, because of temperature difference, forms heat carrier density contrast, so heat carrier flows out by heat carrier the upper tube layer that pipe 12 flows to water cooling heat exchanger 102 by reactor 101.Heat carrier flows in the tubulation 16 of water cooling heat exchanger 102 by water cooling heat exchanger upper perforated plate 14.Cooling water flows to the bottom of water cooling heat exchanger 102 by the down-comer 11 of drum 9 belows, enter the cylindrical shell 3 of water cooling heat exchanger 102.Outside tubulation 16, cooling water and heat carrier indirect heat exchange, produce middle pressure steam, and the heat of heat carrier is removed, and middle pressure steam enters drum 9 by the vapor uptake 10 of water cooling heat exchanger 102.Cooled heat carrier flows into pipe 18 in water cooling heat exchanger 102 bottoms by heat carrier and flows back to reactor 101, forms circulation.In reactor 101, reacted gas is through gas-liquid-solid separator 7, and for example, after spiral gas-liquid-solid separator separation, gas exports 8 by reaction gas and enters into next workshop section.
Example 1: produce 100000 tons of one-step method dimethyl ether synthesis slurry bed reactors per year, reactor size: internal diameter is 3.0m, height is 18m.68 tons of inert heat carrier paraffin oils are housed, industrial methanol synthetic catalyst (CuZnAl catalyst) and methanol dehydration catalyst (γ-Al in reactor
2o
3catalyst) in 1: 1 ratio, mix, form 34.46 tons of difunctional fine granularity catalyst, catalyst grain size is 80-120 order (Catalyst Production manufacturer is southwestern chemical research institute).The temperature of reaction is 240 ℃, and pressure is 6.0MPa, and air speed is 1.2L/ (gh), and synthesis gas composition is: by volume, and 65.77% H
2, 32.84% CO, 1.39% CO
2.Finally, the conversion ratio of CO is 80%, dimethyl ether be selectively 87%, CO
2be selectively 1%, C
2above is selectively 0.01%.
Comparative example 1: under identical reaction condition, adopt common inside with the bubbling bed reactor of heat exchanger, the internal diameter of reactor is 3.2m, height is 20m, the conversion ratio of CO is 75%, dimethyl ether be selectively 85%, CO
2be selectively 2%, C
2above is selectively 0.02%.
Example 2: produce 100000 tons of one-step method dimethyl ether synthesis slurry bed reactors per year, reactor size: internal diameter is 3.0m, height is 18m.68 tons of inert heat carrier paraffin oils are housed, industrial methanol synthetic catalyst (CuZnAl catalyst) and methanol dehydration catalyst (γ-Al in reactor
2o
3catalyst) in 1: 1 ratio, mix, form 34.46 tons of difunctional fine granularity catalyst, catalyst grain size is 80-120 order (Catalyst Production manufacturer is southwestern chemical research institute).Reaction temperature is 260 ℃, and pressure is 6.0MPa, and air speed is 1.2L/ (gh), and synthesis gas composition is: by volume, and 65.77% H
2, 32.84% CO, 1.39% CO
2.Finally, the conversion ratio of CO is 83%, dimethyl ether be selectively 89%, CO
2be selectively 1.2%, C
2above is selectively 0.01%.
Comparative example 2: under identical reaction condition, adopt common inside with the bubbling bed reactor of heat exchanger, the internal diameter of reactor is 3.2m, height is 20m, the conversion ratio of CO is 75.5%, dimethyl ether be selectively 80%, CO
2be selectively 4%, C
2above is selectively 0.04%.
Claims (10)
1. a device of preparing dimethyl ether, comprises slurry-phase reactor and heat exchanger, and wherein, heat exchanger is arranged on outside reactor, and heat exchanger top is provided with drum; Heat exchanger upper tube layer put down in or lower than reactor in heat carrier liquid level, heat exchanger bottom is higher than reactor bottom; Heat carrier flows out manages one end coupled reaction device middle part, and the other end connects the upper tube layer of heat exchanger, and heat carrier flows out the junction of pipe and reactor lower than heat carrier liquid level in reactor; Heat carrier flows into the bottom that pipe one end connects heat exchanger, other end coupled reaction device bottom, and heat carrier flows into manages with the junction of reactor higher than the gas distributor in reactor;
In reactor, be provided with circular cone and lower circular cone, upper circular cone flows out the junction of pipe and reactor lower than heat carrier, and lower circular cone flows into the junction of pipe and reactor higher than heat carrier; And by the different silk screen of opening diameter, making large granular catalyst be distributed in the bottom of reaction bed, catalyst particle is distributed in the top of reaction bed;
Lower circular cone opening diameter is 0.125-2.0mm; Upper circular cone opening diameter is 0.1-1.0mm; The percent opening of upper and lower circular cone is 50-99%.
2. device according to claim 1, is characterized in that, 1-10 group heat carrier is set between reactor and heat exchanger and flows into pipe and heat carrier outflow pipe.
3. device according to claim 2, is characterized in that, the diameter that heat carrier flows into pipe and heat carrier outflow pipe is 200mm-500mm.
4. device according to claim 1, is characterized in that, reactor head exit is provided with gas-liquid-solid separator.
5. device according to claim 1, is characterized in that, lower circular cone is fixed on apart from 1/3 of reactor bottom to be sentenced down; Upper circular cone is fixed on the 2/5-4/5 place apart from reactor bottom.
6. device according to claim 5, is characterized in that, lower circular cone is fixed on the 1/4-1/3 place apart from reactor bottom; Upper circular cone is fixed on the 2/5-3/5 place apart from reactor bottom.
7. device according to claim 1, is characterized in that, lower circular cone opening diameter is 0.15-0.2mm; Upper circular cone opening diameter is 0.12-0.15mm; The percent opening of upper and lower circular cone is 80-95%.
8. device according to claim 1, is characterized in that, is provided for forcing the pump of heat carrier circulation on the pipeline of heat carrier inflow pipe.
9. a method of preparing dimethyl ether, right to use requires 1～8 device described in any one.
10. method according to claim 9, is characterized in that, when preparing dimethyl ether, heat is removed, and by producing 3.0-4.0MPa middle pressure steam in the drum on heat exchanger top, heat is shifted out to system.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010527563.8A CN102029130B (en) | 2010-10-27 | 2010-10-27 | Device and method for preparing dimethyl ether |
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|---|---|---|---|
| CN201010527563.8A CN102029130B (en) | 2010-10-27 | 2010-10-27 | Device and method for preparing dimethyl ether |
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| CN102029130B true CN102029130B (en) | 2014-11-05 |
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| CN102319553B (en) * | 2011-08-30 | 2014-01-29 | 神华集团有限责任公司 | Dimethyl ether synthesis reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218003A (en) * | 1988-01-14 | 1993-06-08 | Air Products And Chemicals, Inc. | Liquid phase process for dimethyl ether synthesis |
| CN1285340A (en) * | 2000-08-31 | 2001-02-28 | 中国石油化工股份有限公司 | Process for synthesizing dimethyl ether in three-phase slurry bed |
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- 2010-10-27 CN CN201010527563.8A patent/CN102029130B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218003A (en) * | 1988-01-14 | 1993-06-08 | Air Products And Chemicals, Inc. | Liquid phase process for dimethyl ether synthesis |
| CN1285340A (en) * | 2000-08-31 | 2001-02-28 | 中国石油化工股份有限公司 | Process for synthesizing dimethyl ether in three-phase slurry bed |
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