CN101108789A - Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction - Google Patents
Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction Download PDFInfo
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- CN101108789A CN101108789A CNA2006101443407A CN200610144340A CN101108789A CN 101108789 A CN101108789 A CN 101108789A CN A2006101443407 A CNA2006101443407 A CN A2006101443407A CN 200610144340 A CN200610144340 A CN 200610144340A CN 101108789 A CN101108789 A CN 101108789A
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Abstract
A method that the solid acid catalyzes the methanol to dehydrate and react to produce the dimethyl ether is provided, which adopts the sectional feeding control of the methanol or adjusts the bed temperature distribution in the dehydration reactor. The solid acid catalysts are the cation exchange resin, the ZSM-5 molecular sieve, the ZSM-35 molecular sieve, the MCM-22 molecular sieve, Gamma-alumina or the mixture of any of the above. The operation conditions of the reactor are that the reaction pressure is 0.2MPa to 4.0MPa, the reaction temperature is 120 DEG C. to 400 DEG C. and the feeding air speed is 0.5h-1 to 20h-1. The invention is characterized in that: the feeding amount of the methanol on different catalyst bed is adjusted to control the distribution of the methanol dehydration catalyst bed temperature. The dehydration is carried out under proper reaction temperature. Because the invention can control the catalyst bed temperature, thereby reducing the occurrence of the side-effects and prolonging the catalyst life.
Description
Technical field
The present invention relates to a kind of method, particularly relate to a kind of employing solid acid catalyst, the method for methanol gas phase dehydration continuous production dme by the methanol 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 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 a 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, 190～380 ℃ of temperature of reaction, methanol conversion～78%.
Chinese patent Granted publication 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.
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 ZL 94222811.1, 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 manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction.
For achieving the above object, the method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction provided by the invention adopts the control of methyl alcohol sectional feeding or regulates the interior bed temperature of dehydration reactor to distribute;
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 any catalyzer;
Reactor operating condition: reaction pressure is 0.2～4.0MPa, and temperature of reaction is 120～400 ℃, and the charging air speed is 0.5～20h
-1Preferred reactor operating condition: reaction pressure is 0.5～1.5MPa, and temperature of reaction is 150～300 ℃, and the charging air speed is 2.0～8.0h
-1
Described method, wherein, the methyl alcohol sectional feeding enters the mouth at beds.
Described method, wherein, the methyl alcohol sectional feeding enters the mouth between two beds.
Described method, wherein, methyl alcohol sectional feeding inlet number is 2～20.
Described method, wherein, methyl alcohol sectional feeding inlet number is 2～6.
Launch to say that characteristics of the present invention are to control by the methanol feeding amount of regulating the different catalysts bed distribution of methanol dehydration catalyst bed temperature.Under suitable temperature of reaction condition, carry out dehydration reaction, because can the control catalyst bed temperature, take place thereby can reduce side reaction, prolong the purpose of catalyst life.
The present invention relates in the presence of solid acid catalyst, methyl alcohol carries out the process that the gas-phase dehydration reaction generates dme in fixed-bed reactor.The reaction of dimethyl ether by methanol dehydration is thermopositive reaction, and under approximate adiabatic situation, the temperature of carrying out beds along with reaction raises gradually, and the vertex of general reaction bed temperature is at the middle hypomere of whole bed.The vertex of beds temperature rise in this adiabatic process can be at (and the initial temperature of gas-phase reaction be about 200 ℃) more than 250 ℃ or higher.Particularly when operational condition was unstable, bigger fluctuation can take place in temperature, and deep reaction very easily takes place, and caused low-carbon alkene and hydrocarbon to generate.Because a large amount of gaseous products generates and the release of heat, causes the rapid rising of reactor temperature and pressure, this can cause catalyzer to burn and the security of the equipment of giving and system brings serious threat.Method by adopting sectional feeding can be simply, effective control catalyst bed temperature.Because the sectional feeding of methyl alcohol, so the distribution of dehydration reaction release of heat also just changes with different, makes whole reaction bed temperature relatively evenly avoid very violent exothermic process appearance.
The present invention relates to the process of methanol production dme.Material benzenemethanol flowed out with reactor before entering reactor and enters dehydration reactor behind the reacted material heat-shift and carry out dehydration reaction, and the catalyst in reactor bed generally is divided into 2～6 sections, and the catalyzer of filling is a solid acid catalyst in the reactor; Solid acid catalyst comprises Zeo-karb, molecular sieve, gama-alumina, or the mixing of its above-mentioned catalyzer.Between reactor operating pressure: 0.2～4.0MPa, 120～400 ℃ of temperature of reaction, the charging air speed 0.5～20.0, between preferable operational condition: reaction pressure: 0.5～1.5MPa, 150～300 ℃ of temperature of reaction, the charging air speed 2.0～8.0, methanol feedstock enters in the reactor in the different catalysts bed sections.After reaction raw materials methyl alcohol entered reactor and begins reaction, a large amount of heats was emitted and can be caused reaction bed temperature to rise, and can make the bed temperature rise in the scope of technique initialization by controlling quantitative methyl alcohol material.Because it is even relatively that reaction bed temperature distributes, and can reduce the generation of side reaction and reduce the carbon distribution on the catalyzer, prolonged the life-span that catalyzer uses.
Optimized technical scheme of the present invention is the gaseous methanol material to be divided into different ratios inject in the fixed bed reactor catalyst bed; The gas-phase methanol material can be in any point, multiple spot injecting reactor in the middle of the beds or between any two beds among the present invention.
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, is broken into the bar shaped catalyst of 2～3 millimeters long.
2500 milliliters of above-mentioned catalyzer are packed in the fixed bed adiabatic reactor of 37 millimeters of internal diameter φ, the Thermal couple casing pipe of an external diameter φ 6 is arranged in the reactor; Catalyzer divides 3 sections fillings, and every section 800mm has the gas-phase methanol opening for feed on every section beds top.With purity is that the industrial methanol of 97.5% (weight) is a reaction raw materials, carries 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, gas-phase methanol enters into reactor from first opening for feed.Methanol conversion is 76.2%, and the dme selectivity is 99.5%, 305 ℃ of bed temperature outs, and 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, methanol feedstock and feeding manner are with comparative example 1.
220 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methanol feeding air speed 3 hours
-1Condition under, gas-phase methanol enters into reactor from first opening for feed.Methanol conversion is 85.2%, and the dme selectivity is 98.9%, 330 ℃ of bed temperature outs, and bed top temperature point is 356.7 ℃, bed medial temperature 287.3.
Embodiment 1: the fixed bed dimethyl ether by methanol dehydration
Catalyzer, reactor and methanol feedstock are with comparative example 1.Methanol feedstock is divided equally 3 section feedings.
205 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methanol feeding air speed 3 hours
-1Condition under, methanol conversion is 73.9.1%, the dme selectivity is 99.99%, 245 ℃ of bed temperature outs, bed top temperature point is 252.3 ℃, bed medial temperature 231.4.
Embodiment 2: the fixed bed dimethyl ether by methanol dehydration
Catalyzer, reactor and methanol feedstock are with comparative example 1.Methanol feedstock in 1.5: 1: 1.5 ratio respectively from first, second, third throat-fed.
225 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methyl alcohol combined feed total feed air speed 3 hours
-1Condition under, methanol conversion is 80.6%, the dme selectivity is 99.97%, 276 ℃ of bed temperature outs, bed top temperature point is 291.1 ℃, bed medial temperature 260.3.
Claims (6)
1. the method for a manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction adopts the control of methyl alcohol sectional feeding or regulates the interior bed temperature of dehydration reactor to distribute;
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 any catalyzer;
Reactor operating condition: reaction pressure is 0.2～4.0MPa, and temperature of reaction is 120～400 ℃, and the charging air speed is 0.5～20h
-1
2. the method for claim 1, wherein reactor operating condition: reaction pressure is 0.5～1.5MPa, and temperature of reaction is 150～300 ℃, and the charging air speed is 2.0～8.0h
-1
3. the method for claim 1, wherein the methyl alcohol sectional feeding enters the mouth at beds.
4. the method for claim 1, wherein the methyl alcohol sectional feeding enters the mouth between two beds.
5. the method for claim 1, wherein methyl alcohol sectional feeding inlet number is 2～20.
6. the method for claim 1, wherein methyl alcohol sectional feeding inlet number is 2～6.
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| CNA2006101443407A CN101108789A (en) | 2006-12-04 | 2006-12-04 | Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction |
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| CNA2006101443407A CN101108789A (en) | 2006-12-04 | 2006-12-04 | Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452907A (en) * | 2010-10-25 | 2012-05-16 | 榆林学院 | Method for producing dimethyl ether by catalyzing distilled methanol dehydration reaction |
| CN103357433A (en) * | 2013-06-28 | 2013-10-23 | 浙江工业大学 | Carbon-nitrogen hybrid material of lamellar structure and application thereof |
| 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 |
| CN103896768A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate |
| WO2016086361A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing nano-zsm-5 zeolite |
-
2006
- 2006-12-04 CN CNA2006101443407A patent/CN101108789A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452907A (en) * | 2010-10-25 | 2012-05-16 | 榆林学院 | Method for producing dimethyl ether by catalyzing distilled methanol dehydration reaction |
| CN103896768A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for preparing methyl acetate |
| WO2014101898A1 (en) * | 2012-12-25 | 2014-07-03 | 中国科学院大连化学物理研究所 | Process for preparing methyl acetate |
| CN103896768B (en) * | 2012-12-25 | 2016-03-09 | 中国科学院大连化学物理研究所 | A kind of method preparing methyl acetate |
| 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 |
| CN103357433A (en) * | 2013-06-28 | 2013-10-23 | 浙江工业大学 | Carbon-nitrogen hybrid material of lamellar structure and application thereof |
| CN103357433B (en) * | 2013-06-28 | 2015-04-22 | 浙江工业大学 | Carbon-nitrogen hybrid material of lamellar structure and application thereof |
| WO2016086361A1 (en) * | 2014-12-02 | 2016-06-09 | 中国科学院大连化学物理研究所 | Method for synthesizing nano-zsm-5 zeolite |
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