CN101108790B - 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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Abstract
A method that the solid acid catalyzes the methanol to dehydrate and react to produce the dimethyl ether is provided. Under the condition that the solid acid catalyst exists, the liquid state materials are adopted as the chill materials to control the catalyst bed temperature distribution. The reaction conditions are that the reaction pressure is 0.2MPa to 4.0 MPa, the reaction temperature is 120 DEG C. to 400 DEG C. and the feeding air speed is 0.5 to 20.0. 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 the above. The invention can make the bed temperature rapidly lower in the range set by the process via filling the cold-shocking materials. Because the catalyst bed temperature is distributed evenly, the invention greatly reduces the occurrence of the side-effects and the carbon deposit on the catalysts and prolongs the service life of the catalysts.
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, introduced a kind of gas-solid phase multiterminal cold shock formula method, 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., in the Dehydration of methanol process, distribute according to the present invention by the bed temperature in the method control dehydration reactor that adopts the liquid phase cold shock.
For achieving the above object, the method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction provided by the invention in the presence of solid acid catalyst, adopts liquid material to distribute as chilling Material control reaction bed temperature;
Reactor condition: reaction pressure 0.2～4.0MPa, 120～400 ℃ of temperature of reaction, charging air speed 0.5～20.0; Preferable reactor condition: reaction pressure 0.5～1.5MPa, 150～300 ℃ of temperature of reaction, charging air speed 2.0～8.0h
-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 is characterized in that, liquid material in beds difference injecting reactor, 1～10 of each beds decanting point, preferably each beds decanting point is 3～6.
In other words, characteristics of the present invention are to adopt liquid raw material as the cold shock material, control the gas-phase reaction reaction bed temperature in a scope of setting by the evaporation heat absorption of liquid phase material.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.
The present invention relates in the presence of solid acid catalyst, methyl alcohol carries out the process that gas phase shape dehydration reaction generates dme in fixed-bed reactor.The reaction of dimethyl ether by methanol dehydration is thermopositive reaction, under approximate adiabatic situation, carries out with reaction, and the temperature of reaction system raises gradually, and the temperature difference that reactor is imported and exported is more than 150 ℃ or higher (and the initial temperature of gas-phase reaction is about 200 ℃).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.By adopt inject the method for liquid phase material to beds can be simply, effective control catalyst bed temperature., therefore overcome gaseous phase materials cold shock poor effect and the temperature of beds is in the scope of may command and permission because its evaporative process absorbs a large amount of heats as liquid phase cold shock material.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 the equilibrium conversion of methyl alcohol.
The present invention relates to the process of methanol production dme.Material benzenemethanol enters dehydration reactor and carries out dehydration reaction before entering reactor with behind the material heat-shift of outflow reactor, the catalyst in reactor bed generally is divided into 1～6 section, the catalyzer of filling is a solid acid catalyst in the reactor, comprise Zeo-karb, ZSM-5, ZSM-35, MCM-22, gama-alumina, or the mixing of its above-mentioned catalyzer.Between reactor operating condition: reaction pressure 0.2-4.0MPa, temperature of reaction 120-400 ℃, charging air speed 0.5-20.0, between preferable operational condition: reaction pressure 0.5-1.5MPa, temperature of reaction 150-300 ℃, charging air speed 2.0-8.0.Liquid cold shock material is at catalyzer difference injecting catalyst bed, and each beds decanting point 1-10, preferably 3-6 is individual.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 by injecting the cold shock material bed temperature is quickly fallen in the scope of technique initialization.Because reaction bed temperature is evenly distributed, and greatly reduces the generation of side reaction and has reduced the carbon distribution on the catalyzer, prolonged the life-span that catalyzer uses.
Optimized technical scheme of the present invention is that liquid material is directly injected in the fixed bed reactor catalyst bed; Liquid phase material can be a reaction raw materials methyl alcohol, also can be dme, water or other.Liquid material can be in any one point in the middle of the beds or multiple spot injecting reactor among the present invention.
A kind of special situation be with the thick methyl alcohol of the liquid phase that after condensation, gas-liquid separation, obtains from the effusive material of Dehydration of methanol device-dme mixture as the cold shock material, can be directly with charging methyl alcohol as cold shock Material control catalyst bed reaction temperature.
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: the fixed bed dimethyl ether by methanol dehydration
Catalyzer is with comparative example 1.2500 milliliters of catalyzer are packed in the fixed-bed reactor of 37 millimeters of internal diameters, axially have four cold shock material decanting points along the reactor catalyst bed sections.Temperature is that 125 ℃ liquid methanol (purity is 97.5% (weight)) was with air speed 0.102 hour
-1Divide equally in the injecting reactor.
210 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methanol feeding air speed 3 hours
-1Condition under, methanol conversion is 75.1%, the dme selectivity is～100%, 220 ℃ of bed temperature outs, bed top temperature point is 225.1 ℃, bed medial temperature 215.6.
Embodiment 2: the fixed bed dimethyl ether by methanol dehydration
Catalyzer, reactor, methanol feedstock, cold shock material are with embodiment 1.
225 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.1MPa, methanol feeding air speed 3 hours
-1Condition under, methanol conversion is 86.2%, the dme selectivity is 99.99%, 237 ℃ of bed temperature outs, bed top temperature point is 241.0 ℃, bed medial temperature 232.2.
Comparative example 3: fixing adiabatic reactor dimethyl ether by methanol dehydration
Catalyzer DHC-803-2 (commercial catalyst, chemical plant in the Ji, Cangzhou), reactor and methanol feedstock are with comparative example 1.
130 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.0MPa, methanol feeding air speed 2.0 hours
-1Condition under, methanol conversion is 65.5%, the dme selectivity is 99.1%, 185 ℃ of bed temperature outs, bed top temperature point is 190.2 ℃, bed medial temperature 159.8.
Embodiment 3: the fixed bed dimethyl ether by methanol dehydration
Catalyzer, reactor and methanol feedstock are with comparative example 3.
140 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.0MPa, methanol feeding air speed 2.0 hours
-1Condition under, methanol conversion is 66.1%, the dme selectivity is～100%, 145.0 ℃ of bed temperature outs, bed top temperature point is 150.2 ℃, 142.1 ℃ of bed medial temperatures.
Claims (4)
1. the method for a manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction in the presence of solid acid catalyst, adopts liquid material to distribute as chilling Material control reaction bed temperature;
Reactor condition: reaction pressure 0.2～4.0MPa, 120～400 ℃ of temperature of reaction, charging air speed 0.5～20.0h
-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 liquid material is methyl alcohol or dme.
2. the method for claim 1 is characterized in that, reactor condition: reaction pressure 0.5～1.5MPa, 150～300 ℃ of temperature of reaction, charging air speed 2.0～8.0h
-1
3. the method for claim 1 is characterized in that, liquid material in beds difference injecting reactor, 1～10 of each beds decanting point.
4. as claim 1 or 3 described methods, it is characterized in that each beds decanting point is 3～6.
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| CN200610144341A CN101108790B (en) | 2006-12-04 | 2006-12-04 | Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction |
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| CN101108790B true CN101108790B (en) | 2010-05-12 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102050706B (en) * | 2009-11-04 | 2013-04-03 | 中国科学院大连化学物理研究所 | Method for serially producing dimethyl ether by dehydrating solid acid catalyzing methanol |
| TWI485130B (en) * | 2010-05-21 | 2015-05-21 | Dalian Chemical Physics Inst | Method for continuously producing dimethyl ether by solid acid catalyzed dehydration of methanol |
| CN102153451B (en) * | 2011-01-28 | 2014-01-22 | 凯瑞化工股份有限公司 | Method for producing ether by dehydrating alcohol |
| 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 |
| CN109351288A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A kind of technique controlling the temperature rise of alkylation reactor bed |
| CN109351289A (en) * | 2018-10-18 | 2019-02-19 | 中石化广州工程有限公司 | A method of control alkylation reactor bed temperature rise |
| CN114149308A (en) * | 2021-12-13 | 2022-03-08 | 杭州可菲克化学有限公司 | Method for preparing beta-naphthyl methyl ether |
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Effective date of registration: 20230118 Address after: 116085 909c, Huangpu Road, high tech park, Dalian City, Liaoning Province Patentee after: Section in extension(Dalian)Energy science and technology LLC Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |
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