CN100513374C - Method for preparing dimethyl ether by dehydration of methanol - Google Patents
Method for preparing dimethyl ether by dehydration of methanol Download PDFInfo
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- CN100513374C CN100513374C CNB2007100642357A CN200710064235A CN100513374C CN 100513374 C CN100513374 C CN 100513374C CN B2007100642357 A CNB2007100642357 A CN B2007100642357A CN 200710064235 A CN200710064235 A CN 200710064235A CN 100513374 C CN100513374 C CN 100513374C
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Abstract
The invention discloses a manufacturing method of dimethyl ether hydrated by carbinol, which comprises the following steps: introducing raw material with carbinol into catalytic distilling tower; hydrating at least partial carbinol to produce dimethyl ether and water; guiding partial steam from the top of catalytic distilling tower into autoclave of second distilling tower; using liquid-phased material in the second distilling tower as reflux liquid to lead into top of catalytic distilling tower; obtaining the mass with dimethyl ether as main component of top of second distilling tower; introducing liquid-phased mass of catalytic distilling tower into the third distilling tower; obtaining the mass with carbinol as main component of third distilling tower to lead into top of catalytic distilling tower or autoclave of second distilling tower; draining water mass as main component from the autoclave of third distilling tower.
Description
Technical field
The present invention relates to a kind of method by the methanol production dme, specifically, the present invention relates in the presence of a kind of solid acid catalyst, make methyl alcohol in catalytic distillation tower, carry out dehydration reaction and produce the method for dme with separating and combining with the distillation tower of a simplification and a conventional distillation tower.
Background technology
Dme is a kind of broad-spectrum Chemicals, can be synthesized by methanol dehydration and one-step method from syngas to make.The methanol dehydration method adopts sulfuric acid to make catalyzer the earliest, is reflected in the liquid phase and carries out, and main drawback is that equipment corrosion and environmental pollution are serious.In the present industrial production, adopt the method for the methanol gas phase dehydration production dme of solid acid catalyst to become main production method.
U.S. Pat P 5684213 discloses a kind of by C
1-3Alcohol is produced the catalytic distillation method of corresponding dialkyl ether.Adopt the catalytic distillation tower of internal diameter 25.4mm, high 7.62m, conversion zone is located at the high 4.57m in middle part, the filling mordenite catalyst, rectifying section and stripping section filling material, with the methyl alcohol of purity more than 99% is raw material, under the condition of 600psi, 350-400 ℉ and hydrogen existence, can obtain the dme of purity more than 99.9% from cat head.
U.S. Pat P 6740783 discloses a kind of molecular sieve catalyst by the methanol production dme, and the proton on the molecular sieve catalyst is substituted by metal or amine, and methanol vapor is carried out dehydration reaction on molecular sieve catalyst.
Chinese patent CN 1036199A discloses a kind of method by the methanol production dme, methanol vapor is carried out dehydration reaction containing on the gamma-alumina catalyst of a small amount of silicon-dioxide, dewatered product is sent into rectifying tower and is carried out rectifying, pure Dimethyl ether and impurity respectively on certain column plate of this tower as the sideline product extraction.
Chinese patent CN 1125216 discloses a kind of method by the methanol production dme, the methyl alcohol of content 72-99.9% is after the gasification knockout tower is removed high boiling material and impurity, in multistage chilling-type reactor, carry out the gas phase catalysis dehydration reaction, employing contains gama-alumina and aluminosilicate crystalline composite solid-acid catalyst, temperature of reaction 190-380 ℃, methanol conversion-78%.
Chinese patent CN 1322704 discloses a kind of method by the methanol production dme, the compound acid of liquid that employing is made up of sulfuric acid and phosphoric acid is catalyzer, the azeotropism of sulfuric acid and water when having destroyed single sulfuric acid and being catalyzer, when having overcome single sulfuric acid and being catalyzer moisture be difficult for steaming, the big shortcoming of acidity in the gas phase, reduced the equipment corrosion problem.Methanol vapor contacts with the liquid complex acid catalyst under the reaction pressure of 130-180 ℃ temperature of reaction and 0-0.03 MPa carries out dehydration reaction, the gasification of in reactor, carrying out reaction mixture simultaneously with catalyst separating.
Chinese patent notification number CN 1073979C discloses a kind of method from methanol production and recovery dme, be about to unreacted methanol and crystal's cut from the time with circulating reaction, the mol ratio of water and methyl alcohol is 0.8-1 in the recycle stock, can significantly reduce the load that reclaims the unreacted methanol still-process, also can contain the water of 3-10% (weight) in the fresh methanol raw material, keep the methanol conversion more than 76% simultaneously.
Chinese patent CN 1111231 discloses the method that a kind of catalytic distillation prepares dme.Catalytic distillation tower is made up of reactor and rectifying tower, the sulfuric acid that concentration is housed is 20-98% (weight) in the reactor is as catalyzer, methyl alcohol is in the rectifying tower position charging of the 5th theoretical plate number at the most, under the reaction pressure of 100-150 ℃ temperature of reaction and absolute pressure 0.05-0.15 MPa, carry out dehydration reaction, the by product methyl-hydrogen-sulfate monomethyl-sulfate, heavy constituent such as methyl-sulfate are toward the enrichment of tower bottom, and in reactor, continue to form chemical equilibrium with the methyl alcohol reaction, the light constituent dme, unreacted methanol and water are toward the top enrichment of tower, thereby suppressed the generation of by product, improved the selectivity of dme, the per pass conversion of methyl alcohol is 69-78%.
Chinese patent notification number CN 1043739C, 1047105C, 1085647C and Chinese patent publication number CN 1199038 etc. disclose the Catalyst And Method that is converted into dme by synthetic gas, the composite catalyst that adopts industrial catalst for synthesis of methanol and acidic components catalyst mix to make, temperature of reaction 200-400 ℃, reaction pressure 2-5 MPa, the carbon monoxide transformation efficiency can reach 90%, and the dme selectivity is more than 90%.
In above invention, use liquid acid such as sulfuric acid can bring equipment corrosion and problem of environmental pollution as catalyzer, then be difficult to obtain highly purified dme product by direct synthesis of dimethyl ether from synthesis gas.Adopt solid acid catalyst can obtain purity and reach 99.9% dme by methanol gas phase dewatering preparing dimethy ether, but temperature of reaction is higher, be generally 200-380 ℃, about per pass conversion 70-80%, purity to methanol feedstock also has certain requirement, can cause per pass conversion to descend when methyl alcohol reaction raw materials water content is higher inevitably, and higher temperature of reaction stable unfavorable to catalyzer.Disclosed catalytic distillation method, because reaction was finished in a catalytic distillation tower with separating fully of product, relative volatility under High Temperature High Pressure between each component is less, thereby stage number that need be more, facility investment is higher, and the manipulation require of catalytic distillation tower takes into account the requirement of methanol content in reaction condition optimization and product dme purity, the waste water simultaneously, and turndown ratio is less.
Summary of the invention
The object of the present invention is to provide a kind of method of producing dme by methyl alcohol through dehydration reaction, make methyl alcohol in comprising three distillation towers of a catalytic distillation tower, carry out dehydration reaction, carry out the fractionation by distillation of dme, methyl alcohol, water simultaneously and produce dme, can reduce facility investment and process cost greatly.
For achieving the above object, method of producing dme through dehydration reaction provided by the invention by methyl alcohol, this method may further comprise the steps:
A) raw material that will contain methyl alcohol is incorporated in the conversion zone of a catalytic distillation tower, makes at least a portion methyl alcohol generate dme and water and make dme in the cat head enrichment and water enrichment in the tower still through dehydration reaction therein;
Described catalytic distillation tower comprises a tower still, a stripping section, a conversion zone, and wherein filling comprises the catalytic distillation structure of solid acid catalyst in the conversion zone, or is arranged alternately distillation tower tray and beds;
B) the steam part of catalytic distillation column overhead is introduced directly into the tower still of second distillation tower, and rest part is flowed through and entered the tower still of second distillation tower behind the tower still reboiler of the 3rd distillation tower;
Wherein said second distillation tower is made up of a tower still, a rectifying section and an overhead condensation return channel;
The 3rd distillation tower is made up of a tower still, a stripping section, a rectifying section and an overhead condensation return channel, and their working pressure all is lower than catalytic distillation tower;
C) liquid phase material in second distillation Tata still is incorporated into the cat head of catalytic distillation tower as phegma, obtains the material that main ingredient is a dme from the cat head of second distillation tower;
D) liquid phase material of catalytic distillation Tata still is incorporated into the 3rd distillation tower, obtain the tower still that main ingredient is the material of methyl alcohol and the cat head that is introduced into catalytic distillation tower or second distillation tower from the cat head of the 3rd distillation tower, discharging main ingredient from the tower still of the 3rd distillation tower is the material of water.
Described method wherein, is provided with the high distillation filler of 1-2 piece tower tray or 0.1-1 rice on the catalytic distillation tower conversion zone.
Described method, wherein, the raw material that contains methyl alcohol is incorporated into the tower still of second distillation tower, enters catalytic distillation tower with wherein liquid phase material from cat head.
Described method, wherein, the raw material that contains methyl alcohol is incorporated in the 3rd distillation tower.
Described method, wherein, the raw material that contains methyl alcohol is incorporated in the stripping section of catalytic distillation tower.
Described method, wherein, contain be incorporated in the catalytic distillation tower after the liquid phase material heat exchange of the raw material of methyl alcohol and catalytic distillation Tata still or the tower still of second distillation tower or the 3rd distillation tower in.
Described method, wherein, the raw material that contains methyl alcohol is the thick methyl alcohol material of liquid phase that effusive material obtains through condensation and gas-liquid separation from methanol synthesis reactor when synthesizing methanol.
Described method wherein, is drawn side line from being positioned at second rectifying section below the distillation tower overhead condenser, is mainly contained the logistics of dme.
Described method, wherein, the tower still of second distillation tower is provided with two reboilers, and one is heating medium with the catalytic distillation tower overhead vapours, and another is a heating medium with other thermal source.
Described method, wherein, the feed volume air speed that contains methanol feedstock is 0.2-10 ml methanol/milliliter catalyzer hour;
The operational condition of catalytic distillation tower is: pressure is 0.8-5.0MPa, trim the top of column liquid and be incorporated into the weight rate sum that contains methanol feedstock in the catalytic distillation tower and the ratio of the weight rate of second distillation tower cat head and/or side line extraction material is 0.5-5;
The operational condition of second distillation tower is: pressure is 0.5-1.5MPa, and reflux ratio is 0.2-5;
The operational condition of the 3rd distillation tower is: pressure is 0.005-0.9MPa, and reflux ratio is 0.2-10.
Method of the present invention is carried out the fractionation by distillation of the dehydration reaction of methyl alcohol and reaction product dme, water simultaneously in a catalytic rectifying tower, in being lower than the distillation tower of catalytic distillation tower, the working pressure of a simplification carries out the further fractionation by distillation of dme to obtain qualified dme product, with the further fractionation by distillation of carrying out water in the conventional distillation tower that is lower than catalytic distillation tower at a working pressure to obtain enough low, the waste water that can discharger of methanol content, with reduction facility investment and energy consumption, thereby cause of the present invention finishing.
Description of drawings
Fig. 1 is the block diagram of one embodiment of this invention.
Embodiment
The raw material that the present invention will contain methyl alcohol is incorporated into the catalytic distillation tower from a certain position of cat head or conversion zone or stripping section, make at least a portion methyl alcohol generate dme and water through dehydration reaction therein, carry out making separating of methyl alcohol, water and dme dme in the cat head enrichment and water enrichment in the tower still simultaneously; Said catalytic distillation tower comprises a tower still, a stripping section, a conversion zone from the bottom up successively, wherein filling comprises the catalytic distillation structure of solid acid catalyst in the conversion zone, or is arranged alternately distillation tower tray and beds or adopts other catalyst loading patterns.
The composition of catalytic distillation tower overhead vapours mainly is methyl alcohol, dme and less water, and its part is introduced directly into the tower still of second distillation tower, and as the vapor phase stream of this tower, and its tower still need not be provided with reboiler; Simultaneously flow through a tower still reboiler of the 3rd distillation tower of the rest part of catalytic distillation tower overhead vapours produces the tower still that enters second distillation tower behind the required heat of steam for it provides.Wherein said second distillation tower that distillation tower is a simplification, form by a tower still, a rectifying section and an overhead condensation return channel, do not establish stripping section, working pressure is lower than catalytic distillation tower, should satisfy the requirement as heat-eliminating medium of overhead condenser employing water coolant and/or air simultaneously.
The dme product is from the cat head extraction of second distillation tower; Or draw the side line extraction from a certain position of rectifying section, to reduce the content of non-condensable gases such as nitrogen, oxygen in the dme product.Nitrogen, oxygen derive from dissolved little air in the methanol feedstock.Liquid phase material in second distillation Tata still is incorporated into the cat head of catalytic distillation tower as phegma.Because the temperature of this tower bottoms is lower than the temperature of catalytic distillation column overhead, and 1-2 piece tower tray or the high distillation filler of 0.1-1 rice can be set on the catalytic distillation tower conversion zone, so that tower bottoms obtains sufficient preheating, enters conversion zone then and reacts.
Reaction mixture in the catalytic distillation tower is through the centrifugation of stripping section, the content of methyl alcohol is that the content of 5～90 weight %, dme is lower than 1 weight % in the tower still material that obtains, and it is incorporated into the 3rd distillation tower carries out the further separation of first alcohol and water from the appropriate location.Catalytic distillation Tata still material temperature is higher than the service temperature of the 3rd distillation tower, the decompression of this strand material can be made its part vaporization and reduce temperature, directly enters the 3rd distillation tower then and carries out fractionation by distillation.Also can enter the 3rd distillation tower to make full use of its heat with decompression after the raw material heat exchange that contains methyl alcohol.
Obtaining main ingredient from the cat head of the 3rd distillation tower is the material of methyl alcohol and the conversion zone that is introduced into catalytic distillation tower or in the tower still of second distillation tower, and its methanol content is 80-99 weight %; Discharging main ingredient from the tower still of the 3rd distillation tower is the material of water, and wherein the content of methyl alcohol should be enough low, as be lower than 0.5 weight %.The 3rd distillation tower is the distillation tower of a routine, form by a tower still, a stripping section, a rectifying section and an overhead condensation return channel, working pressure is lower than catalytic distillation tower, can adopt a little more than atmospheric pressure operation, also can under high slightly pressure, operate with the diameter that reduces tower, the investment that reduces tower.Wherein a kind of situation of pressurized operation is to make tower top temperature be higher than 100 ℃, utilizes overhead vapours condensation liberated heat to produce low pressure water vapor, thereby saves energy consumption.In any case, should make its tower still temperature lower more than 20 ℃, be used for separating of methyl alcohol and water so that utilize the contained heat of catalytic distillation tower overhead vapours to produce steam than the temperature of catalytic distillation tower overhead vapours.The tower still of the 3rd distillation tower can be provided with second reboiler, uses other thermal source heating, so that this tower reaches desired separating effect.
The feed volume air speed that contains methanol feedstock is 0.2-10 ml methanol/(milliliter catalyzer hour); The operational condition of catalytic distillation tower is: pressure is 0.8-5.0MPa (gauge pressure), trim the top of column liquid and be incorporated into the weight rate sum that contains methanol feedstock in the catalytic distillation tower and the ratio of the weight rate of second distillation tower cat head extraction material is 0.5-5; The operational condition of second distillation tower is: pressure is 0.5-1.5MPa (gauge pressure), and reflux ratio is 0.2-5; The operational condition of the 3rd distillation tower is: pressure is 0.005-0.9MPa (gauge pressure), and reflux ratio is 0.2-10.
Material in the catalytic distillation tower is mainly methyl alcohol, dme and water, and wherein the volatility of dme is the highest, and the volatility of water is minimum.Thereby reaction product dme and water under distillment respectively to cat head and the enrichment of tower still, overhead vapor stream enters in second lower distillation tower of working pressure and isolates the dme product from cat head, and discharge from the tower still and mainly to contain the backflow material of the material of methyl alcohol as catalytic distillation tower, wherein methanol content is generally more than 70 weight %, make in conversion zone, to remain higher methanol concentration, keep higher Dehydration of methanol speed.
In catalytic distillation tower, catalyzer is surrounded by liquid reaction mixture, is reflected under liquid phase or the vapour-liquid admixture to carry out.Because the boiling point of dme is significantly less than the first alcohol and water, thereby dme is enriched in the gas phase under the gas-liquid mixed state, the concentration of dme is very low in the catalyst surface reaction mixture.Because the hydro carbons by product that the carbon distribution on the catalyst surface mainly comes free dme to generate, dme is enriched in gas phase, slowed down the carbon distribution speed of catalyzer greatly, and liquid phase material has certain dissolving souring to the carbon distribution precursor of catalyst surface, thereby can prolong life of catalyst greatly.
Adopt another advantage of catalytic distillation reaction method to be, the reaction heat of Dehydration of methanol be directly used in material in the tower rectifying separation, be fully utilized, and eliminated " focus " that occurs because of exothermic heat of reaction in the general fixed bed reaction method.
As everyone knows, it is closely related to reach the relative volatility of required number of theoretical plate of predetermined separating effect and component to be separated in distillation tower.Raise with temperature, dme all obviously reduces with respect to the relative volatility of methyl alcohol and the methyl alcohol relative volatility with respect to water.For example 40 ℃, 80 ℃ and 120 ℃ of following dme are respectively 25.2,12.5 and 7.5,100 ℃ and 200 ℃ of following methyl alcohol with respect to the relative volatility of methyl alcohol and are respectively 3.5 and 2.6 with respect to the relative volatility of water.Thereby the required number of theoretical plate of the fractionation by distillation of carrying out dme, first alcohol and water in the lower distillation tower of pressure is less, and lower working pressure also reduced the requirement to the distillation tower wall thickness, thereby can reduce facility investment.Because dme is much higher than the relative volatility of methyl alcohol with respect to water with respect to the relative volatility of methyl alcohol, the required number of theoretical plate of second distillation tower is than the 3rd distillation tower much less, therefore the tower still reboiler of the 3rd distillation tower of a part of catalytic distillation tower overhead vapours being flowed through produces the tower still that enters second distillation tower behind the required heat of steam again for it provides, though second distillation tower operated under lower reflux ratio, but only need increase a spot of column plate and can satisfy isolating requirement, and the 3rd distillation tower operated under higher reflux ratio, more column plate can be reduced, thereby total facility investment can be reduced.
Technology of the present invention also has the big advantage of turndown ratio.The operational condition of catalytic distillation tower needs to satisfy simultaneously reaction and isolating requirement, and both often are difficult to take into account.Among the present invention, the operational condition of catalytic distillation tower can satisfy the requirement of reaction as far as possible, and the operational condition of adjusting second and the 3rd distillation tower simultaneously guarantees that the content of methyl alcohol in the purity of dme product and the drainage water reaches controlling index, thereby turndown ratio is big.
The content of methyl alcohol can be 5-99.99 weight % in the raw material.Methanol content is 80 weight % when above, can be from a certain position charging of catalytic distillation tower conversion zone, also can be, or enter the tower still of second distillation tower from the cat head charging of catalytic distillation tower, and enter catalytic distillation tower with wherein liquid phase material from cat head.Methanol content is 85 weight % when following, can be from a certain position charging of catalytic distillation tower stripping section, or enter the 3rd distillation tower from correct position.When entering the 3rd distillation tower,, two bursts of materials merging can be entered the 3rd distillation tower if the composition of material benzenemethanol content and catalytic distillation Tata still material is close; If it is more different that their composition has, should enter the 3rd distillation tower from different positions respectively.
A kind of special situation is the charging as catalytic distillation tower of effusive material obtains after condensation and gas-liquid separation the reactor with from synthesizing methanol time the thick methyl alcohol material of liquid phase, can save the required rectifying tower of purification methyl alcohol in the existing process for methanol production like this, reduce investment outlay more and process cost, reduce production costs.
Said solid acid catalyst can be an acidic cation-exchange resin among the present invention, contains catalyzer, the aluminium oxide catalyst of molecular sieve or contains heteropolyacid or the catalyzer of heteropolyacid salt.
Said molecular sieve can be one or more mixture, particularly MCM-22, ZSM-5, SAPO-34 or the β zeolite in ZSM-5, ZSM-11, ZSM-22, ZSM-23, Y, mordenite, β zeolite, MCM-22, MCM-41, MCM-56, MCM-49, SAPO-5, SAPO-11, the SAPO-34 equimolecular sieve.For convenience of industrial application, can be with molecular sieve and suitable binding agent kneading and compacting, wherein the content of molecular sieve is that the content of 50-95% (butt weight), binding agent is 5-50% (butt weight).Binding agent adopts aluminum oxide usually.
When adopting acidic cation-exchange resin to be catalyzer,, generally do not answer 170 ℃ of superelevation because the resin catalyst non-refractory should make the conversion zone temperature not be higher than the maximum operation (service) temperature that the resin catalyst that adopts is allowed.
By the following examples and in conjunction with the accompanying drawings the present invention is described in detail, but the present invention is not limited to following examples, the mark in the accompanying drawing is respectively:
1-contains the raw material of methyl alcohol; The 2-catalytic distillation tower; The conversion zone of 3-catalytic distillation tower; The stripping section of 4-ization distillation tower; The tower still reboiler of 5-catalytic distillation tower; Second distillation tower of 6-; The overhead condenser of second distillation tower of 7-; The return tank of top of the tower of second distillation tower of 8-; The 3rd distillation tower of 9-; The overhead condenser of the 3rd distillation tower of 10-; The return tank of top of the tower of the 3rd distillation tower of 11-; The tower still reboiler of the 3rd distillation tower of 12-; Second tower still reboiler of the 3rd distillation tower of 13-; The 14-dme; 15-water.
Embodiment 1
The catalytic distillation dimethyl ether by methanol dehydration
Catalytic distillation tower comprises overhead condensation return channel, rectifying section, conversion zone, stripping section and tower still.50 millimeters of body of the tower internal diameters, 0.97 meter of conversion zone virtual height is packed into wherein after 364 milliliters of catalyzer and 5 * 5 millimeters stainless steel Dixon rings of 1360 milliliters of Φ are mixed; Rectifying section and stripping section virtual height are 0.57 meter, filling Φ 3 * 3 millimeters stainless steel Dixon rings, and the tower still heats with resistance furnace, is that the industrial methanol of 99.96 weight % is a reaction raw materials with purity.
Catalyzer was the bar shaped particle of 2 millimeters of diameters, long 5-10 millimeter, and its active ingredient is HZSM-5, and the sial molecular ratio is 38, contains the alumina binder of 20 weight %, through 550 ℃ of steam-treated 2 hours.
From conversion zone down 8 centimeters chargings of upper end, at 1.09 liters/hour of inlet amounies, catalytic distillation tower working pressure is 2.6MPa, 170 ℃ of feeding temperatures, 186 ℃ of conversion zone medial temperatures, trim the top of column than being under 4.2 the operational condition, methanol conversion is 51.2%, and the dme selectivity is 100%; The cat head load is 448 Grams Per Hours, and material consists of dme 71.0 weight %, methyl alcohol 27.7 weight %, water 1.3 weight %; Conversion zone top vapor-phase material consists of dme 0.8 weight %, methyl alcohol 97.2 weight %, water 2.0 weight %; Tower still load is 417 Grams Per Hours, and material consists of methyl alcohol 71.7 weight %, water 28.3 weight %, and dme does not detect.
From conversion zone down 8 centimeters chargings of upper end, at 1.09 liters/hour of inlet amounies, catalytic distillation tower working pressure is 2.5MPa, 170 ℃ of feeding temperatures, 179 ℃ of conversion zone medial temperatures, trim the top of column than being under 2.0 the operational condition, methanol conversion is 48.1%, and the dme selectivity is 100%; The cat head load is 404 Grams Per Hours, and material consists of dme 73.6 weight %, methyl alcohol 26.2 weight %, water 0.2 weight %; Conversion zone top vapor-phase material consists of dme 1.2 weight %, methyl alcohol 95.3 weight %, water 3.5 weight %; Tower still load is 460 Grams Per Hours, and material consists of methyl alcohol 74.7 weight %, water 25.3 weight %, and dme does not detect.
From conversion zone down 8 centimeters chargings of upper end, at 1.09 liters/hour of inlet amounies, catalytic distillation tower working pressure is 1.8MPa, 160 ℃ of feeding temperatures, 166 ℃ of conversion zone medial temperatures, trim the top of column than being under 6.2 the operational condition, methanol conversion is 21.0%, and the dme selectivity is 100%; The cat head load is 530 Grams Per Hours, and material consists of dme 31.4 weight %, methyl alcohol 68.4 weight %, water 0.2 weight %; Conversion zone top vapor-phase material consists of dme 0.6 weight %, methyl alcohol 97.6 weight %, water 1.8 weight %; Tower still load is 334 Grams Per Hours, and material consists of methyl alcohol 80.8 weight %, water 19.2 weight %, and dme does not detect.
From conversion zone down 8 centimeters chargings of upper end, at 0.72 liter/hour of inlet amount, catalytic distillation tower working pressure is 2.3MPa, 165 ℃ of feeding temperatures, 181 ℃ of conversion zone medial temperatures, trim the top of column than being under 4.6 the operational condition, methanol conversion is 85.7%, and the dme selectivity is 100%; The cat head load is 347 Grams Per Hours, and material consists of dme 99.9 weight %, methyl alcohol 0.1 weight %, and water does not detect; Conversion zone top vapor-phase material consists of dme 5.8 weight %, methyl alcohol 91.1 weight %, water 3.1 weight %; Tower still load is 220 Grams Per Hours, and material consists of dme 1.2 weight %, methyl alcohol 36.8 weight %, water 62.0 weight %.
The up 6.7 centimeters chargings from the conversion zone lower end, at 1.09 liters/hour of inlet amounies, catalytic distillation tower working pressure is 2.5MPa, 170 ℃ of feeding temperatures, 180 ℃ of conversion zone medial temperatures, trim the top of column than being under 3.6 the operational condition, methanol conversion is 50.8%, and the dme selectivity is 100%; The cat head load is 355 Grams Per Hours, and material consists of dme 88.3 weight %, methyl alcohol 11.4 weight %, water 0.3 weight %; Conversion zone top vapor-phase material consists of dme 4.5 weight %, methyl alcohol 94.7 weight %, water 0.8 weight %; Tower still load is 503 Grams Per Hours, and material consists of methyl alcohol 75.9 weight %, water 24.1 weight %, and dme does not detect.
Claims (10)
1, a kind of method of producing dme through dehydration reaction by methyl alcohol, this method may further comprise the steps:
A) raw material that will contain methyl alcohol is incorporated in the conversion zone of a catalytic distillation tower, makes at least a portion methyl alcohol generate dme and water and make dme in the cat head enrichment and water enrichment in the tower still through dehydration reaction therein;
Described catalytic distillation tower comprises a tower still, a stripping section, a conversion zone, and wherein filling comprises the catalytic distillation structure of solid acid catalyst in the conversion zone, or is arranged alternately distillation tower tray and beds;
B) the steam part of catalytic distillation column overhead is introduced directly into the tower still of second distillation tower, and rest part is flowed through and entered the tower still of second distillation tower behind the tower still reboiler of the 3rd distillation tower;
Wherein said second distillation tower is made up of a tower still, a rectifying section and an overhead condensation return channel;
The 3rd distillation tower is made up of a tower still, a stripping section, a rectifying section and an overhead condensation return channel, and their working pressure all is lower than catalytic distillation tower;
C) liquid phase material in second distillation Tata still is incorporated into the cat head of catalytic distillation tower as phegma, obtains the material that main ingredient is a dme from the cat head of second distillation tower;
D) liquid phase material of catalytic distillation Tata still is incorporated into the 3rd distillation tower, obtain the tower still that main ingredient is the material of methyl alcohol and the cat head that is introduced into catalytic distillation tower or second distillation tower from the cat head of the 3rd distillation tower, discharging main ingredient from the tower still of the 3rd distillation tower is the material of water.
2, the method for claim 1, wherein on the catalytic distillation tower conversion zone 1-2 piece tower tray or the high distillation filler of 0.1-1 rice are set.
3, the raw material that the method for claim 1, wherein contains methyl alcohol is incorporated into the tower still of second distillation tower, enters catalytic distillation tower with wherein liquid phase material from cat head.
4, the raw material that the method for claim 1, wherein contains methyl alcohol is incorporated in the 3rd distillation tower.
5, the raw material that the method for claim 1, wherein contains methyl alcohol is incorporated in the stripping section of catalytic distillation tower.
6, as each described method of claim 1-5, wherein, contain be incorporated in the catalytic distillation tower after the liquid phase material heat exchange of the raw material of methyl alcohol and catalytic distillation Tata still or the tower still of second distillation tower or the 3rd distillation tower in.
7, as each described method of claim 1-5, wherein, the raw material that contains methyl alcohol is the thick methyl alcohol material of liquid phase that effusive material obtains through condensation and gas-liquid separation from methanol synthesis reactor when synthesizing methanol.
8, the method for claim 1, wherein draw side line, mainly contained the logistics of dme from being positioned at second rectifying section below the distillation tower overhead condenser.
9, as claim 1,3 or 6 described methods, wherein, the tower still of the 3rd distillation tower is provided with two reboilers, and one is heating medium with the catalytic distillation tower overhead vapours, and another is a heating medium with other thermal source.
10, the feed volume air speed that the method for claim 1, wherein contains methanol feedstock is 0.2-10 ml methanol/milliliter catalyzer hour;
The operational condition of catalytic distillation tower is: pressure is 0.8-5.0MPa, trim the top of column liquid and be incorporated into the weight rate sum that contains methanol feedstock in the catalytic distillation tower and the ratio of the weight rate of second distillation tower cat head and/or side line extraction material is 0.5-5;
The operational condition of second distillation tower is: pressure is 0.5-1.5MPa, and reflux ratio is 0.2-5;
The operational condition of the 3rd distillation tower is: pressure is 0.005-0.9MPa, and reflux ratio is 0.2-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100642357A CN100513374C (en) | 2007-03-07 | 2007-03-07 | Method for preparing dimethyl ether by dehydration of methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100642357A CN100513374C (en) | 2007-03-07 | 2007-03-07 | Method for preparing dimethyl ether by dehydration of methanol |
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| CN100513374C true CN100513374C (en) | 2009-07-15 |
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| CN101550065B (en) * | 2008-04-02 | 2013-01-09 | 惠生工程（中国）有限公司 | Energy-saving and water-saving type high-low pressure double-tower process for preparing dimethyl ether by rectifying methanol |
| CN101475452B (en) * | 2008-10-31 | 2013-09-04 | 中国石油化工股份有限公司 | Method for producing dimethyl ether by catalyst distillation |
| CN106478383B (en) | 2015-08-28 | 2019-07-09 | 中国石油化工股份有限公司 | The method and consersion unit of preparing dimethyl ether from methanol and the method and system of methanol-to-olefins |
Citations (4)
| 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 |
| CN1036199A (en) * | 1986-11-18 | 1989-10-11 | 莱茵河褐煤动力燃料联合有限公司 | Produce the method for pure Dimethyl ether |
| CN1814579A (en) * | 2006-02-24 | 2006-08-09 | 杨奇申 | Production method for combined producing dimethyl ether from nitrogen fertilizer plant or methanol plant |
| WO2007014534A1 (en) * | 2005-08-04 | 2007-02-08 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process for synthesis of dimethyl ether by catalytic distillation from methanol |
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| 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 |
| CN1036199A (en) * | 1986-11-18 | 1989-10-11 | 莱茵河褐煤动力燃料联合有限公司 | Produce the method for pure Dimethyl ether |
| WO2007014534A1 (en) * | 2005-08-04 | 2007-02-08 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Process for synthesis of dimethyl ether by catalytic distillation from methanol |
| CN1814579A (en) * | 2006-02-24 | 2006-08-09 | 杨奇申 | Production method for combined producing dimethyl ether from nitrogen fertilizer plant or methanol plant |
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