CN101125802A - Gas phase continuous production method for dimethyl ether from methanol - Google Patents
Gas phase continuous production method for dimethyl ether from methanol Download PDFInfo
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- CN101125802A CN101125802A CNA2006101443430A CN200610144343A CN101125802A CN 101125802 A CN101125802 A CN 101125802A CN A2006101443430 A CNA2006101443430 A CN A2006101443430A CN 200610144343 A CN200610144343 A CN 200610144343A CN 101125802 A CN101125802 A CN 101125802A
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Abstract
A method for producing dimethyl ether continuously through methanol vapor phase is carried out in a fluidized bed in the presence of solid-acid catalyst by methanol synthesis reaction (MSR); the operation condition of a reactor is that: reaction pressure is 0.1- 2.0MPa, reaction temperature is 120-400 DEG C and feeding airspeed is 0.5 -20.0h -1; solid-acid catalyst is a cation exchange resin, a ZSM-5 molecular sieve, a ZSM-35 molecular sieve, an MCM-22 molecular sieve, gamma-Alumina or a mixture of the catalysts. The invention is characterized by the controllability of uniform catalyst bed temperature during vapor-phase through methanol dehydration carried out in the fluidized reactor. Under the condition of higher methanol transformation rate and appropriate reaction temperature, side effect is decreased and the service life of catalyst is prolonged for the homogeneous control of the catalyst bed temperature.
Description
Technical field
The present invention relates to a kind of method of methanol vapor phase continuous production dme.
Background technology
Dme is a kind of broad-spectrum Chemicals and fuel substitute.Dme adopts the methanol dehydration method to produce the earliest, is reflected in the liquid phase and carries out, and main drawback is that equipment corrosion is serious, operational condition is abominable, and environmental pollution is serious.At present, the producing dimethyl ether by dehydrating methanol technology of industrial employing solid acid catalyst is main method and Future Development trend.
Disclose a kind of molecular sieve catalyst by the methanol production dme at U.S. Pat P6740783, 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 CN1036199A 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 a certain column plate of this tower as the sideline product extraction.
Chinese patent CN1125216 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, 190～380 ℃ of temperature of reaction, methanol conversion～78%.
Chinese patent Granted publication CN1073979C 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.
Methanol gas phase dewatering preparing dimethy ether can obtain purity and reach 99.9% dme, but temperature of reaction is higher, is generally 220～380 ℃; And reaction process also has certain requirement to the purity of methanol feedstock, 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.
Among the China utility model patent ZL94222811.1, a kind of gas-solid phase multiterminal cold shock formula method has been proposed, this method is by coming the control catalyst bed temperature to reactor catalyst bed injection cold air, because the Dehydration of methanol device is a strong exothermal reaction, cold air is not enough to reduce reaction bed temperature, therefore, under the temperature of reaction condition, be difficult to control bed temperature by this method.
Because the methanol gas phase dehydration reaction is the last one exothermic process, the beds temperature rise of adiabatic reactor reactor can reach nearly 100 ℃, even higher.The above invention is the general fixed-bed reactor that adopt following form in industrial implementation: (1) adiabatic reactor, (2) interior heat transfer reactor, (3) shell and tube reactor, the reactor of (4) gas phase cold shock, (5) gas phase quench reactor.In industrial production, there are problems such as the restive or temperature distributing disproportionation of reaction bed temperature, the industry that therefore is difficult to maximize is produced.
Summary of the invention
The object of the present invention is to provide a kind of method of methanol vapor phase continuous production dme.
For achieving the above object, the method for methanol vapor phase continuous production dme provided by the invention under the solid acid catalyst effect, is carried out in fluidized-bed by Dehydration of methanol;
Reactor operating condition: reaction pressure is 0.1-2.0MPa, and temperature of reaction is 120-400 ℃, and the charging air speed is 0.5-20.0 hour
-1Preferable reactor operating condition: reaction pressure is 0.3-1.5MPa, and temperature of reaction is 150-300 ℃, and the charging air speed is 2.0-8.0 hour
-1
Solid acid catalyst is the mixing of Zeo-karb, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, gama-alumina or its above-mentioned catalyzer.
Described method, wherein, fluidized-bed reactor comprises: circulating fluidized bed, riser tube fluidized-bed, dense phase fluidized bed, moving-burden bed reactor.
Described method, wherein, the size distribution of solid acid catalyst is in 10～150 micrometer ranges, and median size is 20～100 microns.
Characteristics of the present invention are to carry out in fluidizing reactor by methanol dehydration, can control the gas-phase reaction reaction bed temperature in the scope of homogeneous.Under condition of higher methanol transformation rate, under suitable reaction temperature, react, because reaction bed temperature control is evenly, take place thereby can reduce side reaction, prolong the purpose of catalyst life.
Catalytic conversion process involved in the present invention can be realized on fluidized-bed, riser tube, moving-burden bed reactor.Selecting preferably is dense phase fluidized bed.Raw material passes through beds continuously in reactive system, and catalyzer circulates between fluidized-bed reactor and revivifier continuously.Feed stream can and flow or adverse current with catalyzer.In the presence of solid acid catalyst, methyl alcohol carries out gas phase shape dehydration reaction and generates dme in fluidizing reactor.
The reaction of dimethyl ether by methanol dehydration is thermopositive reaction, and under approximate adiabatic situation, the temperature of reaction system raises gradually.Can cause that at fixed-bed reactor reaction bed temperature raises, the temperature difference that reactor is imported and exported is (and the initial temperature of gas-phase reaction is about 200 ℃) or higher more than 150 ℃.By adopt fluidizing reactor can be simply, effective control catalyst bed temperature.Whole reaction bed temperature is comparatively all even lower, thereby the selectivity of dme is high, near 100%; Be subjected to the low more equilibrium conversion of thermopositive reaction, temperature of Equilibrium limit high more because the reaction of dimethyl ether by methanol dehydration is one simultaneously, low temperature also helps the Dehydration of methanol forward and moves, and improves conversion of methanol.
In above-mentioned fluidized-bed reaction technology, the size distribution of catalyzer is in 10～150 micrometer ranges, and median size is 20～100 microns.Catalyzer suspends or fluidisation in reaction mass usually.Raw material adds in the bottom of reaction bed, also can add carrier gas simultaneously, with the dividing potential drop that reduces reaction mass and help catalyst fluidization.Carrier gas can adopt water vapour or rare gas element, preferably adopts water vapour.Raw material and carrier gas mix in reactor with catalyzer makes its fluidisation, and is converted into the product dimethyl ether mixture under higher temperature of reaction and pressure, and catalyzer produces carbon distribution and part or all of inactivation after reacting.Gaseous reaction products flows out from reactor and enters tripping device, and decaying catalyst then flows out from reactor continuously and enters revivifier and regenerate.Decaying catalyst is carried device through gas earlier before entering revivifier, removes hydro carbons residual on the catalyzer with rare gas elementes such as water vapour.Carbon distribution is removed in burning in the oxygen-containing atmosphere of decaying catalyst in revivifier, obtains regeneration and heating, gets back to reactor then.For guaranteeing to obtain the product dimethyl ether of higher yields, the reaction conditions of above-mentioned fluidized-bed is in following ranges: temperature of reaction is 120～380 ℃, is preferably 150～300 ℃; Reaction pressure is 0.1～2.8MPa, is preferably 0.2～1.5MPa; Weight space velocity is 0.1～20 hour
-1, be preferably 1～10 hour
-1
At the solid acid catalyst that this process adopted can be that micropore size is the Si-Al zeolite of 0.3-0.6nm, the silicophosphate molecular sieve, and as ZSM-5, ZSM-11, SAPO-34, SAPO-11 etc., and their element modified product.Reaction conditions should guarantee the commentaries on classics selectivity of dme greater than 99.5%, and generation dme that can high conversion.Mixture can carry out in comprising various types of reactors such as moving-bed, fluidized-bed and riser tube with contacting of catalyzer, if adopt fluidized-bed and riser reactor, then the reaction zone planted agent comprises the device to continuous catalyst regenerating.
Optimized technical scheme of the present invention is to adopt circulating fluid bed reactor.
Embodiment
Be embodiments of the invention below, but the present invention is not limited to following examples.
Comparative example 1: fixing adiabatic reactor dimethyl ether by methanol dehydration
With MCM-22 zeolite powder (SiO
2/ Al
2O
3Be 26) even with SB powder (a kind of pseudo-boehmite of German import) by the mixed of 70: 30 (butt weight), add an amount of nitric acid and deionized water, extruded moulding, make the bar shaped sample of 1.6 millimeters of diameters, 120 ℃ of dryings 2 hours, 540 ℃ of roastings are 3 hours in muffle furnace, use the NH of 0.8M then
4NO
3The aqueous solution exchanges 3 times down for 85 ℃, uses deionized water wash 3 times, through 4 hours, 530 ℃ roastings of 120 ℃ of dryings 2 hours, breaks into the bar shaped catalyst of 2～3 millimeters long off with the fingers and thumb.
2500 milliliters of above-mentioned catalyzer are packed in the fixed bed adiabatic reactor of 37 millimeters of internal diameters, are that the industrial methanol of 97.5% (weight) is a reaction raw materials with purity, carry out the reaction of dimethyl ether by methanol dehydration.
205 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methanol feeding air speed 3 hours
-1Condition under, methanol conversion is 76.2%, the dme selectivity is 99.5%, 305 ℃ of bed temperature outs, bed top temperature point is 336.7 ℃, bed medial temperature 269.2.
Comparative example 2: fixing adiabatic reactor dimethyl ether by methanol dehydration
Catalyzer, reactor and methanol feedstock are with comparative example 1.
220 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methanol feeding air speed 3 hours
-1Condition under, methanol conversion is 85.2%, the dme selectivity is 98.9%, 330 ℃ of bed temperature outs, bed top temperature point is 356.7 ℃, bed medial temperature 287.3.
Embodiment 1: fixed fluidized bed dimethyl ether by methanol dehydration
Catalyzer, methyl alcohol are with comparative example 1.
Be reflected in the small-sized fluidized bed reaction unit and carry out.Reaction conditions is as follows: loaded catalyst is 300g, and the bed temperature of reaction is 241 ℃, and the methanol feeding air speed is 1.8 hours
-1, pressure is 0.6MPa.Reaction product adopts Varian CP-3800 gas-chromatography, Plot post and hydrogen flame detector analysis.Methanol conversion is 80.2%, and the dme selectivity is 99.99%.
Embodiment 2: the circulating fluidized bed dimethyl ether by methanol dehydration
Catalyzer is with comparative example 1.
Be reflected in the medium-sized circulating fluid bed reaction device and carry out.Reaction conditions is as follows: loaded catalyst is 5Kg, and the reactor reserve is 1.25Kg, and the catalyst recirculation amount is 0.6-1Kg/hr, and temperature of reaction is 235 ℃, and raw material adopts 80% methanol aqueous solution, and the methanol feeding air speed is 3.0 hours
-1, reaction pressure is 0.5MPa.Reaction product adopts Varian CP-3800 gas-chromatography, Plot post and hydrogen flame detector analysis.Methanol conversion is 80.9%, and the dme selectivity is～100%.
Claims (5)
1. the method for a methanol vapor phase continuous production dme under the solid acid catalyst effect, is carried out in fluidized-bed by Dehydration of methanol;
Reactor operating condition: reaction pressure is 0.1-2.0MPa, and temperature of reaction is 120-400 ℃, and the charging air speed is 0.5-20.0 hour
-1
Solid acid catalyst is the mixing of Zeo-karb, ZSM-5 molecular sieve, ZSM-35 molecular sieve, MCM-22 molecular sieve, gama-alumina or its above-mentioned catalyzer.
2. the method for claim 1, wherein fluidized-bed reactor comprises: circulating fluidized bed, riser tube fluidized-bed, dense phase fluidized bed, moving-burden bed reactor.
3. the method for claim 1, wherein reactor operating condition: reaction pressure is 0.3-1.5MPa, and temperature of reaction is 150-300 ℃, and the charging air speed is 2.0-8.0 hour
-1
4. method as claimed in claim 1 or 2, wherein, the size distribution of solid acid catalyst is in 10～150 micrometer ranges.
5. method as claimed in claim 4, wherein, the median size of solid acid catalyst is 20～100 microns.
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| CNA2006101443430A CN101125802A (en) | 2006-12-04 | 2006-12-04 | Gas phase continuous production method for dimethyl ether from methanol |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009117851A1 (en) * | 2008-03-26 | 2009-10-01 | 中国石油化工股份有限公司 | A process for producing dimethyl ether from methanol |
| CN101786009A (en) * | 2010-03-04 | 2010-07-28 | 西北化工研究院 | Preparation method of catalyst in preparation of dimethyl ether by methyl alcohol |
| RU2466980C2 (en) * | 2008-03-26 | 2012-11-20 | Чайна Петролеум & Кемикал Корпорейшн | Method of producing dimethyl ether from methanol |
| CN102875298A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for co-producing dimethyl ether and ethene by using methanol and ethanol as raw materials |
| CN102872772A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for co-producting dimethyl ether and ethene by using methanol and ethanol as raw materials |
| CN103508855A (en) * | 2013-03-26 | 2014-01-15 | 新能(张家港)能源有限公司 | Device and method for preparing dimethyl ether |
| CN104341270A (en) * | 2013-07-30 | 2015-02-11 | 泉州恒河化工有限公司 | Sodium methoxide and dimethyl ether combined production technology |
| CN116510771A (en) * | 2023-04-26 | 2023-08-01 | 哈尔滨师范大学 | Preparation method of catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of catalyst in preparation of dimethyl ether |
-
2006
- 2006-12-04 CN CNA2006101443430A patent/CN101125802A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8541630B2 (en) | 2008-03-26 | 2013-09-24 | China Petroleum & Chemical Corporation | Process for producing dimethyl ether from methanol |
| AU2008353375B2 (en) * | 2008-03-26 | 2014-03-20 | China Petroleum & Chemical Corporation | A process for producing dimethyl ether from methanol |
| US20110065963A1 (en) * | 2008-03-26 | 2011-03-17 | China Petroleum & Chemical Corporation | Process for producing dimethyl ether from methanol |
| WO2009117851A1 (en) * | 2008-03-26 | 2009-10-01 | 中国石油化工股份有限公司 | A process for producing dimethyl ether from methanol |
| RU2466980C2 (en) * | 2008-03-26 | 2012-11-20 | Чайна Петролеум & Кемикал Корпорейшн | Method of producing dimethyl ether from methanol |
| CN101786009B (en) * | 2010-03-04 | 2011-08-31 | 西北化工研究院 | Preparation method of catalyst in preparation of dimethyl ether by methyl alcohol |
| CN101786009A (en) * | 2010-03-04 | 2010-07-28 | 西北化工研究院 | Preparation method of catalyst in preparation of dimethyl ether by methyl alcohol |
| CN102872772A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for co-producting dimethyl ether and ethene by using methanol and ethanol as raw materials |
| CN102875298A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for co-producing dimethyl ether and ethene by using methanol and ethanol as raw materials |
| CN102875298B (en) * | 2011-07-12 | 2015-10-21 | 中国石油化工股份有限公司 | With the method that methyl alcohol and ethanol are raw material combined producing dimethyl ether and ethene |
| CN102872772B (en) * | 2011-07-12 | 2015-10-21 | 中国石油化工股份有限公司 | With the reaction unit that methyl alcohol and ethanol are raw material combined producing dimethyl ether and ethene |
| CN103508855A (en) * | 2013-03-26 | 2014-01-15 | 新能(张家港)能源有限公司 | Device and method for preparing dimethyl ether |
| CN104341270A (en) * | 2013-07-30 | 2015-02-11 | 泉州恒河化工有限公司 | Sodium methoxide and dimethyl ether combined production technology |
| CN116510771A (en) * | 2023-04-26 | 2023-08-01 | 哈尔滨师范大学 | Preparation method of catalyst for preparing dimethyl ether by low-temperature dehydration of high-water-content methanol and application of catalyst in preparation of dimethyl ether |
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