CN101219937B - Device for producing dimethyl ether with methanol dehydration - Google Patents
Device for producing dimethyl ether with methanol dehydration Download PDFInfo
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- CN101219937B CN101219937B CN2008100592757A CN200810059275A CN101219937B CN 101219937 B CN101219937 B CN 101219937B CN 2008100592757 A CN2008100592757 A CN 2008100592757A CN 200810059275 A CN200810059275 A CN 200810059275A CN 101219937 B CN101219937 B CN 101219937B
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- dimethyl ether
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Abstract
The invention relates to a device for producing dimethyl ether by methanol dehydration, which is characterized in that a methanol raw material tube (A) is preheated by a methanol preheater (2) and then is connected with an inlet of an evaporation tower (4); a gas phase outlet of the evaporation tower (4) passes through a gas heat exchanger (3) to connect with an inlet of a reactor (7);an outlet of the reactor (7) passes through a distillation column reboiler (10) to exchange heat and then is connected with the gas heat exchanger (3) and cooled, then passes through the methanol preheater (2) and a crude dimethyl ether preheater (5) to be connected with a crude dimethyl ether tank (9), then passes through the crude dimethyl ether preheater (5) from the outlet of the crude dimethyl ether tank (9) to be connected with an inlet of a distillation column (11). A gas phase outlet at the top of the distillation column (11) is connected with a dimethyl ether reflux tank (14); an outlet of the dimethyl ether reflux tank (14) passes through a pump (16) and is divided into two paths, one of which is taken as a product outlet. A gas phase outlet at the top of a methanol recovery tower (12) passes through the pipe to tie back an outlet pipe of the evaporation tower (4). The device has the advantages of simple process, convenient production and operation; the fuel dimethyl ether reaction heat can replace steam for heating a dimethyl ether reboiler; the grade of steam pressure requirement is low, the reaction heat can be recycled completely and the consumption of the steam is less.
Description
Technical field
The present invention relates to a kind of device of producing dme, especially refer to produce the device of dme with methanol gas phase dehydration.
Background technology
Dme is called for short DME, chemical formula CH
3OCH
3, it is a kind of colourless, oxygenatedchemicals that slight ether fragrance is arranged, is widely used as narcotic, aerosol, refrigeration agent and various organic synthesis raw material in chemical industry and pharmaceutical industries always.
Dme can directly be used as motor spirit and domestic fuel, because oil price constantly soars, dme has become focus as coal for the alternative petroleum products of the fuel on basis.Dme in conjunction with the national conditions of the many coals of the oil-poor weak breath of China's energy, makes used for dimethyl ether quite vast in the prospect in clean fuel market with resources advantage and environmental protection characteristic.Dme is described as " green product of 21 century " abroad, then is called as " s-generation civil liquid fuel " at home.
For a long time, because production cost and selling price are too high, dme is difficult to apply as the energy except that field of fine chemical is applied.Along with the new breakthrough of China on the dme production technology, some expert advice China should greatly develop and promote the cleaning new energy dme, as replenishing and substituting to petroleum resources, utilize the coal resources of China's abundant fundamentally to solve the national energy security problem, and realize the leap that China's energy technology is caught up with and surpassed the world's advanced levels.Because dme has the incomparable advantage of other fuel substitute, if the price of dme drops to the level that can compete mutually with diesel oil, will become the main alternative fuel of diesel oil, gasoline and liquefied gas, have market outlook difficult to the appraisal.
The exploitation dme also has crucial meaning to China environmental protection.Coal directly burns, and discharges a large amount of sulfide, oxynitride, flue dust and carbonic acid gas, and this is the present primary pollution source of China.And dme itself contains oxygen, and sufficient combustion is not analysed charcoal, no raffinate.
The production method of dme:
The production method of existing dme has two kinds of one-step method from syngas, methanol dehydration two-step approachs; And the methanol dehydration method is divided into methanol vapor phase catalytic dehydration and liquid-phase catalysis evaporation.
One-step method from syngas is produced the technology of dme:
So-called single stage method is meant with the synthetic gas to be raw material, and methyl alcohol is synthetic in same reactor carries out on dual-function catalyst simultaneously with the methanol dehydration two-step reaction.In the reaction process, because the reaction synergistic effect, methyl alcohol is once generation, carry out dehydration reaction and change into dme at once, broken through the thermodynamics equilibrium limit of simple methyl alcohol in synthetic, increased the reaction impellent, made when the simple methyl alcohol of CO transformation efficiency is synthetic much higher.
The one-step method from syngas preparing dimethy ether is to be raw material with coal, Sweet natural gas, residual oil, is the operational path of exploitation competitively in the world in recent years, has characteristics such as flow process is short, cost is low, remarkable in economical benefits.U.S. APC, Japanese NKK company begin research and development from phase early 1990s, have finished commerical test, make significant progress.Domestic Zhejiang University builds up 1500t/a worker's trial assembly the end of the nineties in Hubei Tian Li company and puts, and Dalian materialization institute, Shanxi coalification institute, East China University of Science etc. also possessed some special knowledge to this at Chongqing 3000t/a pilot plant in 2003 in Tsing-Hua University.
It is new technical field that one-step method from syngas is produced dme, and the research institution of lot of domestic and foreign and patent merchant extremely pay close attention to this technology, but the industrialization project is few, does not still have the ton device both at home and abroad.
The subject matter of one-step method from syngas has: 1) product is single, can only produce dme, and methanol output is the 1-10% of dme output, can not regulate the ratio of methyl alcohol and two kinds of products of dme.
2) the use problem of catalyzer
The synthetic catalyst of DME adopts the synthetic and methanol dehydration agent be combined into of methyl alcohol, very responsive to the toxic substance in the synthetic gas (S, CI), the purification precision of synthetic gas directly has influence on the life-span of synthetic catalyst, all will influence the DMG activity of such catalysts greatly to the deleterious medium of catalyst for methanol, because dimethyl ether synthetic catalyst is very expensive, the length in its life-span directly has influence on the production cost of DMG.With the coal be the synthetic gas that makes of raw material except that S, the toxic substances such as CL, AS iron carbonyl of trace are arranged, enter and must be removed before synthetic.
3) raw material availability is low
The ratio of dme and CO is 1: 1 (molecular ratio) in reaction product, as water or CO are arranged in the raw material
2, CO in the reaction product in the reaction product then
2Concentration (volumetric molar concentration) will be above the concentration (volumetric molar concentration) of dme, and the carbonic acid gas utility value is very low.Therefore, in the target product dme, the raw material availability of one-step method from syngas is very low.
4) reactor efficiency is low
Synthesizing methanol, CO conversion, methanol dehydration are thermopositive reaction, total reaction heat effect very big (58.8kcal/molDME), and thermal insulation warming reaches 500-1050 ℃.As can not effectively removing heat, then the catalytic active center of synthesizing methanol is with destroyed and cause inactivation.Thereby must use the heat exchange type reactor.And no matter be fixed bed or slurry attitude bed, because reactor efficiency is low, maximizing all has certain problem.
The domestic and international dimethyl ether by methanol dehydration state of the art
Because the one-step method from syngas preparing dimethy ether is in through engineering approaches, particularly maximize to use on the device and also have more risk, therefore producing the dme technology under the present case adopts methanol dehydration law technology route more suitable, companies such as Japanese Toyo Engineering Corporation (TEC) and Dupont are abroad arranged, domestic perfect through improvement about ten years, Technology is also quite ripe.As singly building the DME device, to invest lowly, the construction period is also short.The dme production technology is mainly as follows both at home and abroad:
(1) Dupont gas-phase dehydration method
E.I.Du Pont Company's technology adopts insulation fix bed dehydration reactor, synthesis pressure 1.13MPa, and the turnover reaction bed temperature is respectively 270 ℃, 380 ℃, methanol conversion 70%.Dme rectifying and Methanol Recovery pressure are respectively: 1MPa, normal pressure, reclaim back methyl alcohol and deliver to the recycling of methyl alcohol basin.This technology Production Flow Chart is the typical case comparatively.Reactor adopts fixed bed, and the temperature difference is big, and methanol conversion is low, by product generates many; The utilization of Heat of Reaction rate is not high, and reaction mass advances the preceding water cooler temperature of dme rectifying tower more than 160 ℃, and consumption of cooling-water is big.Press the superheated vapour heating during gas heater needs before the reactor, the steam consumption height.
(2) Japanese Toyo Engineering Corporation gas-phase dehydration method
Existing at home 100,000 tons of/year devices of the said firm put into operation, industrial scale is domestic present maximum, reactor is established 3-4 section thermal insulation layer, intersegmental employing inlet tower gas is as the heat-eliminating medium heat exchange, flow process has been done partly to optimize on heat balance, but limit by the reactor pattern, utilization of Heat of Reaction is abundant not enough.
(3) compound sour dehydration technique
Sulfuric acid process is carried out technological improvement, add phosphoric acid in reactor, change the relative composition of reactor evaporation material, the continuous production of implement device has solved the emission problem of reactor mineral acid.
The advantage of liquid phase method is that temperature of reaction is low, because Dehydration of methanol is thermopositive reaction, temperature of reaction is low more, and equilibrium conversion is high more, so the per pass conversion of its methyl alcohol in reactor reaches more than 90% than vapor phase process height.
The shortcoming of liquid phase method: product purity is low, ton product power consumption height; Equipment material requires high, and investment is big.Reactor volume is big, and device maximization difficulty is big, and 10,000 tons of device reaction device diameters are more than 4 meters.
(4) Xian Jin methanol gas phase dehydration method
By domestic Southwest Chemical Research and Design Institute exploitation, it also is one of domestic unit that carries out the DME production technology research the earliest, it is with methyl alcohol vaporization and the ingenious combination of Methanol Recovery in the DME flow process, can reduce steam and cooling-water consumption, existing at home at present several covers put into operation, but dehydration reactor adopts thermal insulation or cold shock formula structure, and methanol conversion is low, unit scale is generally less, the no practical experience of reactor maximization.
Summary of the invention
Technical problem to be solved by this invention is that a kind of device with producing dimethyl ether by dehydrating methanol is provided at above-mentioned prior art present situation, have that flow process is simple, production operation is convenient, the alternative steam of reaction heat of producing fuel grade dimethyl ether is used for the heating of dme reboiler, the vapor pressure class requirement is low and the reaction heat recovery is abundant, the advantage that steam consumption is low.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the device of this usefulness producing dimethyl ether by dehydrating methanol, include distillation tower and reactor, it is characterized in that: the methanol feedstock pipe is through the import of the pre-hot joining gasification of methanol preheater tower, gasification tower gaseous phase outlet connects Reactor inlet through gas heat exchanger, heat exchange connects gas heat exchanger and is cooled reactor outlet through the distillation tower reboiler successively, pass through methanol preheater more successively, thick dme preheater, connect thick dme jar, connect the distillation tower import from thick dme jar outlet through thick dme preheater, distillation tower top gaseous phase outlet, connect the dme return tank, the outlet of dme return tank is divided into two-way through pump, one the tunnel as products export, another road tieback distillation tower refluxing opening, liquid phase outlet in distillation tower bottom connects the methanol distillation column import, Methanol Recovery top of tower gaseous phase outlet by in the deferent tieback gasification tower outlet conduit with its interflow.
As improvement, the mother tube before its import of described methanol preheater is provided with the condensed heat transfer fluid device.
Improve, the deferent between described thick dme preheater and the thick dme jar is provided with thick dme condenser again.
Improve, deferent is provided with distillation column condenser between described distillation tower gaseous phase outlet and the dme return tank again.
Improve, the inlet temperature of described its methanol feedstock of reactor is 200～220 ℃ again, and the temperature out of reactor recovery tower is 300～350 ℃.
Compared with prior art, the invention has the advantages that:
(1) flow process is simple, and production operation is convenient;
Flow process mainly comprises methyl alcohol vaporization, dme distillation and Methanol Recovery, simple to operate, production process controls easily, if any methanol distillation column, the first alcohol and water that DME (promptly referring to dme) distillation tower comes out can deliver to also that methyl alcohol is synthetic to carry out Methanol Recovery, increases operation rate.
(2) inlet temperature of stabilizer is low, tower exit temperature is high, produces the alternative steam of reaction heat of fuel grade dimethyl ether, is used for the heating of dme distillation tower reboiler, and the vapor pressure class requirement is low.Reactor inlet temperatures 200-220 ℃, than low many of cold shock, heat insulation-type reactor, and the reactor outlet temperature can be more than 300 ℃.Reactor outlet gas can be used for by-product earlier than higher-grade steam or be directly used in the heating of distillation Tata still, and then preheating dimethyl ether reactor inlet gas.Methyl alcohol vaporization, Methanol Recovery can adopt the 0.7MPa steam heating to get final product, and make the dme device need not the above elevated pressures steam of 1.0MPa.
(3) reaction heat reclaims fully, and steam consumption is low.
After dme reaction heat is used for the heating of distillation tower reboiler earlier, is used further to heating and goes into reactor methanol gas and preheating material methyl alcohol, the thick dme of distillation tower is gone in heating at last, makes full use of step by step according to heat quality height, reduces steam and cooling-water consumption.
Description of drawings
Fig. 1 is the structural representation of inventive embodiments.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
As shown in Figure 1, be the device of present embodiment with producing dimethyl ether by dehydrating methanol, include distillation tower 11 and reactor 7, methanol feedstock pipe A is through 4 imports of methanol preheater 2 pre-hot joining gasification towers, gasification tower 4 gaseous phase outlets connect reactor 7 imports through gas heat exchanger 3,10 heat exchange connect gas heat exchanger 3 and are cooled through the distillation tower reboiler successively in reactor 7 outlet, pass through methanol preheater 2 more successively, thick dme preheater 5, connect thick dme jar 9, connect distillation tower 11 imports from thick dme jar 9 outlets through thick dme preheater 5, distillation tower 11 top gaseous phase outlets, connect dme return tank 14,14 outlets of dme return tank are divided into two-way through pump 16, one the tunnel as products export, another road tieback distillation tower 11 refluxing openings, the outlet of distillation tower 11 bottom liquid phases connects methanol distillation column 12 imports, methanol distillation column 12 top gaseous phase outlets by in deferent tieback gasification tower 4 outlet conduits with its interflow.Mother tube before the import of methanol preheater 2 is provided with condensed heat transfer fluid device 1; And the deferent between thick dme preheater 5 and the thick dme jar 9 is provided with thick dme condenser 8, and deferent is provided with distillation column condenser 15 between distillation tower 11 gaseous phase outlets and the dme return tank 14.The inlet temperature of the methanol feedstock of reactor 7 is 200～220, and the temperature out of reactor 7 synthetic gas is 300～350 ℃.
Producing fuel grade dimethyl ether raw material that the product consumes by this device is:
Serial number name specification specification consumes
1 methyl alcohol refined methanol ton 1.42
2 water vapor 1.0MPa tons 1.35
3 recirculated cooling waters≤32 ℃ ton 120
4 electric 380/220V kwh 8.
Claims (5)
1. device with producing dimethyl ether by dehydrating methanol, include distillation tower (11) and reactor (7), it is characterized in that: methanol feedstock pipe (A) is through the import of the pre-hot joining gasification of methanol preheater (2) tower (4), gasification tower (4) gaseous phase outlet connects reactor (7) import through gas heat exchanger (3), reactor (7) outlet is passed through distillation tower reboiler (10) heat exchange successively and is connect gas heat exchanger (3) and be cooled, pass through methanol preheater (2) more successively, thick dme preheater (5), connect thick dme jar (9), connect distillation tower (11) import from thick dme jar (9) outlet through thick dme preheater (5), distillation tower (11) top gaseous phase outlet, connect dme return tank (14), dme return tank (14) outlet is divided into two-way through pump (16), one the tunnel as products export, another road tieback distillation tower (11) refluxing opening, liquid phase outlet in distillation tower (11) bottom connects methanol distillation column (12) import, methanol distillation column (12) top gaseous phase outlet by in deferent tieback gasification tower (4) outlet conduit with its interflow.
2. device according to claim 1 is characterized in that: the mother tube before its import of described methanol preheater (2) is provided with condensed heat transfer fluid device (1).
3. device according to claim 1 and 2 is characterized in that: the deferent between described thick dme preheater (5) and the thick dme jar (9) is provided with thick dme condenser (8).
4. device according to claim 3 is characterized in that: deferent is provided with distillation column condenser (15) between described distillation tower (11) gaseous phase outlet and the dme return tank (14).
5. device according to claim 4 is characterized in that: the inlet temperature of its methanol feedstock of described reactor (7) is 200～220 ℃, and the temperature out of reactor (7) synthetic gas is 300～350 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100592757A CN101219937B (en) | 2008-01-14 | 2008-01-14 | Device for producing dimethyl ether with methanol dehydration |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100592757A CN101219937B (en) | 2008-01-14 | 2008-01-14 | Device for producing dimethyl ether with methanol dehydration |
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| CN101219937A CN101219937A (en) | 2008-07-16 |
| CN101219937B true CN101219937B (en) | 2010-06-09 |
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| CN2008100592757A Expired - Fee Related CN101219937B (en) | 2008-01-14 | 2008-01-14 | Device for producing dimethyl ether with methanol dehydration |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012062B (en) * | 2012-12-20 | 2015-04-22 | 上海戊正工程技术有限公司 | Process for indirectly producing alcohol with synthetic gas and application of process |
| CN106045824B (en) * | 2016-07-28 | 2019-02-22 | 鹤壁宝发能源科技股份有限公司 | A kind of dimethyl ether production system and production technology with cogeneration |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0124078A1 (en) * | 1983-04-27 | 1984-11-07 | Mitsubishi Kasei Corporation | Process for the production of dimethyl ether useful as a propellant |
| CN1562927A (en) * | 2004-03-15 | 2005-01-12 | 四川天一科技股份有限公司 | Method for producing dimethyl ether from methanol |
| CN1919819A (en) * | 2006-07-21 | 2007-02-28 | 新奥新能(北京)科技有限公司 | Process for preparing dimethyl ether |
| US20070078285A1 (en) * | 2005-09-30 | 2007-04-05 | Battelle Memorial Institute | Dimethyl ether production from methanol and/or syngas |
| CN201180118Y (en) * | 2008-01-14 | 2009-01-14 | 宁波远东化工集团有限公司 | Device for producing dimethyl ether with methanol dehydration |
-
2008
- 2008-01-14 CN CN2008100592757A patent/CN101219937B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0124078A1 (en) * | 1983-04-27 | 1984-11-07 | Mitsubishi Kasei Corporation | Process for the production of dimethyl ether useful as a propellant |
| CN1562927A (en) * | 2004-03-15 | 2005-01-12 | 四川天一科技股份有限公司 | Method for producing dimethyl ether from methanol |
| US20070078285A1 (en) * | 2005-09-30 | 2007-04-05 | Battelle Memorial Institute | Dimethyl ether production from methanol and/or syngas |
| CN1919819A (en) * | 2006-07-21 | 2007-02-28 | 新奥新能(北京)科技有限公司 | Process for preparing dimethyl ether |
| CN201180118Y (en) * | 2008-01-14 | 2009-01-14 | 宁波远东化工集团有限公司 | Device for producing dimethyl ether with methanol dehydration |
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