CN1331833C - Process for preparing dimethyl ether - Google Patents
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- CN1331833C CN1331833C CNB2005100407818A CN200510040781A CN1331833C CN 1331833 C CN1331833 C CN 1331833C CN B2005100407818 A CNB2005100407818 A CN B2005100407818A CN 200510040781 A CN200510040781 A CN 200510040781A CN 1331833 C CN1331833 C CN 1331833C
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- dimethyl ether
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- methyl alcohol
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Abstract
The present invention discloses a process for preparing dimethyl ether. Purified methanol synthesis gas enters a methanol synthesis reactor for methanol synthesis, and coarse methanol condensate is obtained via condensation cooling from methanol containing reaction gas. The coarse methanol condensate is flashed to certain pressure, the heat energy and the pressure energy of a methanol synthesis system are furthest reserved, and the coarse methanol and non-condensable gas containing methanol saturated air are sent to a dimethyl ether synthesis procedure; after being gasified, the coarse methanol liquid is sent to a methanol dehydration reactor so as to prepare coarse dimethyl ether, and the coarse dimethyl ether is processed via a rectifying tower so as to obtain the dimethyl ether. The synthesis processes of the methanol and the dimethyl ether are directly connected for optimizing configuration and integration, so the inner energy and materials of the system can be recycled and used, and entire energy use rate and product yield are increased. The present invention is an improvement and the increase of the existing dimethyl ether production methods, and the process can effectively decrease the production energy consumption and the cost of products and can increase the market competitiveness of products.
Description
Technical field
The present invention relates to a kind of processing method of producing dme.
Technical background
Dme is a kind of rising Chemicals.It is as industrial chemicals, except that being used for aerosol industry, alternative Chlorofluorocarbons (CFCs) uses to reduce the destruction of aerosol to atmospheric ozone layer as the sprays carrier, still produce the intermediate of synthetic gasoline and alkene, alternative traditional production route of producing gasoline and alkene by oil.A kind of especially ideal clean fuel of dme is the diesel oil substitute of mass consumption, can be used as the LPG that domestic fuel replaces large consumption again.For the raw material production fuel grade dimethyl ether replaces LPG, to reducing the pressure of the current a large amount of imported L PG of China, reduce drain of foreign exchange with the coal, have great significance, its potential market also is very huge.
Dimethylether industrial production basic line all belongs to Dehydration of methanol, but owing to the differences such as starting raw material, dehydration catalyst and synthetic tower type that adopt have different processing methodes, mainly contains the branch of single stage method and two-step approach.
Patent CN1172468A discloses the preparation method of fuel grade dimethyl ether, patent CN1285340A discloses synthetic gas dimethyl ether synthesis method in three-phase slurry bed, patent CN1413974A propose a kind of in combination cot the method for catalytic synthesising dimethyl ether, patent CN1413973A discloses the integrated technology process of synthetic gas one-step synthesis dme in the reactive system that slurry bed and fixed bed two combination of reactors form.The single stage method dimethyl ether synthesis that is proposed all is to be starting raw material with the synthetic gas, and in the presence of the dual-function catalyst that has the synthetic and methanol dehydration of methyl alcohol concurrently, one goes on foot and changes into dme.Though this method has improved the per pass conversion of synthetic gas, technical process is shortened, and equipment reduces, and energy consumption is low, and the dme selectivity is low, and product cost is just a little less than two-step approach.In nearest pilot scale process, expose the shortcoming of present insoluble single stage method again, do not match, cause catalyst life shorter as the optimum temperature range of two kinds of catalyzer; The dme boiling point is low to make itself and synthetic gas sepn process complicated, the dme loss greatly, the cost height; The methyl alcohol of by-product 10%～15% can not be directly used in circulation, changes into dme as need and must set up methanol dehydration and vapourizing unit.These shortcoming have been offset its superiority in reaction, and as seen, it is technical still very unripe that single stage method is produced dme, and there is certain problem in the stability in use of catalyzer, so far not industrialization as yet.
Patent CN1322704 proposes complex and dewatering and catalyzing process to produce dimethyl ether, and the industrial methanol with 98% is that raw material adopts the compound acid of liquid as catalyzer, carries out Dehydration of methanol and produces dme.Though this method improves to some extent to traditional methanol liquid-phase dehydration preparing dimethy ether method, but still it is strong not break away from acid system corrodibility, the intermediate product methyl-hydrogen-sulfate monomethyl-sulfate is poisonous and in case deal with improperly and have contaminate environment even jeopardize problem such as personnel safety.In addition, this method also can't be adapted to scale operation.
Patent CN1510021A has reported the method for thick methanol dehydration dimethyl ether-preparing, and patent CN1125216A has proposed gas-phase methanol dewatering preparing dimethy ether technology.They are to be raw material with 72～99.9% methyl alcohol, adopt vapor phase process to carry out the gas-phase dehydration reaction in fixed-bed reactor and produce dme.Patent CN1180064A dimethyl ether production method is to adopt homemade new catalyst in 100～125 ℃, carries out dehydration reaction under 0～0.05MPa and produces dme.Patent CN1510021A carries out dimethyl ether preparation by dehydrating in the presence of the hydrophobic zeolite catalyzer.Patent CN1125216A adopts γ-Al
2O
3, compound solid-acid such as aluminosilicate crystallization is catalyzer.Described method all is starting raw material with methyl alcohol, but use the catalyzer of different performance, they are current production methods that are widely used in industrial being commonly referred to as " two-step approach ", it is subjected to the restriction of methyl alcohol market, production owing to dme separates with methyl alcohol product installation again, energy consumption is higher, products production cost height, and economy is relatively poor also to be difficult to adapt to scale operation.
Summary of the invention
In order to overcome above-mentioned defective, the invention provides a kind of technology of producing dme, this technology can effectively reduce products production energy consumption and cost, improves the competitiveness of product in market.
The present invention for the technical scheme that solves its technical problem and adopt is: (pressure 4.0～12.0MPa) enters methanol sythesis reactor, and to carry out methyl alcohol synthetic, and methyl alcohol is synthetic can to adopt any methanol sythesis reactor for the methyl methanol syngas after the purification.Fresh synthesis gas compressed or directly with the circulation gas merging of coming out by circulator, also can take virgin gas and circulation gas to unite to enter methanol sythesis reactor after the compression to carry out building-up reactions.The reacted reaction gas that contains methyl alcohol is through recovery of heat and two sections condensation coolings, and controlling two sections condensation cooling system pressure is 3.5～11.0MPa, and temperature is 30～120 ℃.Isolate liquid through separator respectively after two sections condensation coolings, this liquid is through flash distillation (dropping to required pressure), and flashing tower pressure is 0.5～1.5MPa, and thick methanol condensed liquid that is obtained and the flashed vapour that contains the methyl alcohol saturated air are delivered to the dme operation respectively.The non-condensable gas that contains unreacting gas (methyl methanol syngas) that separator was told after two sections condensations were cooled off is most of to return methanol sythesis reactor through the circulator pressurization, and small portion is discharged as off-gas, can be used as the also recyclable hydrogen of fuel.
The thick methanol condensed liquid that is obtained after the flash distillation enters the methanol gasifying separation column through tundish, gasification separation column working pressure is 0.5～1.5MPa, in this tower, make thick methanol condensed liquid all gasification tell moisture grade of institute and send into the flashed vapour that dme synthesis reactor and introduction simultaneously contain methyl alcohol behind the impurity.Gas after Dehydration of methanol is by telling thick dme phlegma after heat exchange, the condensation cooling.The uncooled gas that contains saturated dme and methanol steam absorbs through thick methanol wash, reclaims useful dme and methyl alcohol, and washing absorbs tail gas and methyl alcohol synthetic off-gas merges, and recyclable hydrogen also can be made fuel and use; Resulting thick dme and absorption liquid are sent into rectifying tower in the lump.Dme synthesis pressure 1.0～1.5MPa, 190～300 ℃ of service temperatures adopt industrial any dehydration catalyst commonly used.
The invention has the beneficial effects as follows:
The present invention is that a kind of system optimization of synthesis process for dimethyl ether is integrated, directly is connected with synthesis process for dimethyl ether by methyl alcohol and produces dme.This processing method had both been avoided shortcomings such as the dual-function catalyst life-span weak point, product separation difficulty of single stage method, be not subjected to the restriction in methyl alcohol market again, and can fully recycle energy and useful material in the methanol production process, realize methyl alcohol, dme production integration, thereby reduce products production energy consumption and cost, improve the competitiveness of product in market.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment:
By technical process of the present invention, adopting young bituminous coal is raw material, multi-nozzle opposed type coal water slurry pressurized gasifier, and chilling process carries out gas making.Coal-water fluid concentration is 60%～62% (m); Vapor pressure 5.5～6.5MPa, 1400～1450 ℃ of gasification temperatures.
The raw gas that gasification produces makes through purifying methods such as sulfur-resisting transformation, MNHD desulfurization, decarburizations and meets the synthetic synthetic gas that requires of methyl alcohol.In air cooling-water-cooled built-up type methanol sythesis reactor, synthesizing methanol under 4.5～12.0MPa pressure.The reaction gas that contains methyl alcohol is through recovery of heat and two sections condensation coolings, and condensation cooling system pressure is 3.5～11.0MPa, and temperature is 30～120 ℃.Phlegma gets thick methanol condensed liquid after the process flash separation again, flashing tower pressure is 0.5～1.5Mpa.Isolating thick methanol condensed liquid enters the methanol gasifying separation column through tundish, and gasification separation column working pressure is 0.5～1.5MPa.Send into the dme synthesis procedure after the thick methanol condensed liquid gasification, under 1.0～1.5MPa, 190～300 ℃, obtain product dimethyl ether by dehydration catalyst.Thick dme liquid is sent into chemical industry efficient, energy-saving rectifying tower commonly used.Rectifying tower working pressure 0.8～1.5MPa requires its turndown ratio more greatly, makes it not only can satisfy dimethyl ether with high purity production needs but also can produce the fuel grade dimethyl ether that contains a certain amount of methyl alcohol.
Claims (6)
1. technology of producing dme, it is characterized in that: the methyl methanol syngas after the purification enters methanol sythesis reactor, and to carry out methyl alcohol synthetic, get thick methyl alcohol, the reaction gas that contains methyl alcohol after the reaction is through recovery of heat, again through condensation cooling, flash distillation, acquisition contains the flashed vapour and the thick methanol condensed liquid of methyl alcohol saturated air, its thick methanol condensed liquid is delivered to the dme synthesis procedure in the lump with the flashed vapour that contains the methyl alcohol saturated air, thick methanol condensed liquid enters the Dehydration of methanol device and makes thick dme after gasification, thick dme makes product through rectifying tower.
2. the technology of producing dme according to claim 1, it is characterized in that: contain of the phlegma again flash distillation of the reaction gas of methyl alcohol by two sections condensation cooling back acquisitions, the thick methanol condensed liquid of flash distillation gained is directly sent into the dme technological process with the flashed vapour that contains the methyl alcohol saturated air, and methanol synthesizing process directly is connected with synthesis process for dimethyl ether.
3. the technology of producing dme according to claim 1 and 2 is characterized in that: the condensation cooling divides two sections, and two sections condensation cooling system pressure are 3.5～11.0MPa, and temperature is 30～120 ℃.
4. the technology of producing dme according to claim 1 and 2 is characterized in that: the thick methanol condensed liquid that the condensation cooling separation is told is through flash separation, and flashing tower pressure is 0.5～1.5MPa.
5. the technology of producing dme according to claim 1 is characterized in that: thick methanol condensed liquid obtains through the gasification separation column and meets the synthetic gaseous methanol that requires of dme, gasification separation column working pressure 0.5～1.5MPa.
6. the technology of producing dme according to claim 1 is characterized in that: the dme synthesis pressure is 1.0～1.5Mpa, and temperature is 190～300 degrees centigrade.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100407818A CN1331833C (en) | 2005-06-23 | 2005-06-23 | Process for preparing dimethyl ether |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100407818A CN1331833C (en) | 2005-06-23 | 2005-06-23 | Process for preparing dimethyl ether |
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| CN1803748A CN1803748A (en) | 2006-07-19 |
| CN1331833C true CN1331833C (en) | 2007-08-15 |
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| CNB2005100407818A Expired - Fee Related CN1331833C (en) | 2005-06-23 | 2005-06-23 | Process for preparing dimethyl ether |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172934B (en) * | 2006-12-05 | 2010-12-29 | 褚雅志 | Device and method for co-production or single production of refined methanol with rough methanol |
| CN105218326A (en) * | 2014-06-28 | 2016-01-06 | 孙立 | A kind of method of dimethyl ether synthesis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172468A (en) * | 1995-02-03 | 1998-02-04 | 霍尔多.托普瑟公司 | Preparation of fuel grade dimethyl ether |
| CN1548411A (en) * | 2003-05-21 | 2004-11-24 | 中国石油化工集团公司 | Separation method of dimethyl ether prepared with synthetic gas through one-step process |
-
2005
- 2005-06-23 CN CNB2005100407818A patent/CN1331833C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172468A (en) * | 1995-02-03 | 1998-02-04 | 霍尔多.托普瑟公司 | Preparation of fuel grade dimethyl ether |
| CN1548411A (en) * | 2003-05-21 | 2004-11-24 | 中国石油化工集团公司 | Separation method of dimethyl ether prepared with synthetic gas through one-step process |
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