CN102050706A - Method for serially producing dimethyl ether by dehydrating solid acid catalyzing methanol - Google Patents
Method for serially producing dimethyl ether by dehydrating solid acid catalyzing methanol Download PDFInfo
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- CN102050706A CN102050706A CN 201010123944 CN201010123944A CN102050706A CN 102050706 A CN102050706 A CN 102050706A CN 201010123944 CN201010123944 CN 201010123944 CN 201010123944 A CN201010123944 A CN 201010123944A CN 102050706 A CN102050706 A CN 102050706A
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Abstract
The invention discloses a method for serially producing dimethyl ether by dehydrating solid acid catalyzing methanol, comprising the steps of: filling solid acid catalysts in a reactor section by section; arranging an inert filler layer at the upper part of each catalyst bed; and contacting cold shock materials with the solid acid catalysts after the cold shock materials pass through the inert filler layers, wherein the reaction pressure is 0.2-4.0MPa, the reaction temperature is 120-400DEG C and the feeding airspeed is 0.1-20.0h<-1>. In the invention, the solid acid catalysts are filled section by section and the temperature of a gas-phase reaction catalyst bed is controlled in a set range by using the cold shock materials; and under the condition of obtaining higher methanol percent conversion, as the temperature of the catalyst beds is controlled evenly, the side reaction is reduced and the life of the catalysts is prolonged.
Description
Technical field
The present invention relates to a kind of method, particularly relate to a kind of reaction process that adopts 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 liquid-phase dehydration method to produce the earliest, and main drawback is that equipment corrosion is serious, operational condition is abominable, and environmental pollution is serious.At present, industrial main employing solid acid catalysis methanol gas-phase dehydration is produced dme.
U.S. Pat P6740783 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 gas is carried out dehydration reaction on molecular sieve catalyst.
Chinese patent CN 1036199A discloses a kind of method by the methanol production dme, methanol gas 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 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.
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%.
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.
The methanol gas phase dewatering preparing dimethy ether temperature of reaction is higher, is generally 220～380 ℃; And reaction process is an exothermic process, and 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 more: (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 solid acid catalysis methanol dehydration continuous production dme, the bed temperature that can control effectively in the dehydration reactor distributes.
For achieving the above object, the invention provides the method for solid acid catalysis methanol dehydration continuous production dme, solid acid catalyst is loaded in segmentation in reactor; The inert filler layer is equipped with on every section catalyst layer top; The cold shock material contacts with solid acid catalyst by behind the inert filler layer;
Reaction pressure is 0.2～4.0MPa, and temperature of reaction is 120～400 ℃, and the charging air speed is 0.1～20.0h
-1
Preferably reaction conditions is: reaction pressure 0.5～1.5MPa, temperature of reaction is 150～300 ℃, charging air speed 0.1～8.0h
-1
Wherein, described solid acid catalyst comprises that MCM-222, ZSM are any one or a few mixing in molecular sieve, USY, beta-molecular sieve, gama-alumina, the mordenite.
Wherein, described catalyst reactor bed is divided into 1～20 section, preferably is divided into 2～10 sections.
Wherein, described cold shock material is any one or a few the mixture in liquid methyl alcohol, dme, the water.
Wherein, described inert filler comprises structured packing or/and dumped packing, structured packing comprises grid packing, ripple packing, pulse filler etc., and dumped packing comprises that Raschig ring, Pall ring, cascade ring, Berl saddle, Intalox saddle, metal ring intalox are filled out, Ball-type packing.
The present invention is by segmentation filling solid acid catalyst, and the temperature of utilizing cold shock Material control gas-phase reaction beds is in a scope of setting.Obtaining under the condition of higher methanol transformation rate,, taking place, prolonging catalyst life thereby can reduce side reaction because reaction bed temperature control evenly.
Embodiment
The present invention relates in the presence of solid acid catalyst the gas-phase dehydration reaction that methyl alcohol carries out in fixed-bed reactor.Dehydration reaction is an exothermic process, and under approximate adiabatic situation, the temperature difference of reactor import and export can reach 150 ℃ or higher (and the initial temperature of gas-phase reaction is about 250 ℃).Particularly when operational condition was unstable, bigger fluctuation can take place in reaction bed temperature, and deep reaction very easily takes place, and caused hydrocarbon or low-carbon alkene to generate.Because a large amount of gaseous product generates and the release of heat, and reactor temperature and pressure are sharply risen, cause catalyzer to burn and bring serious threat to the security of equipment and system.Adopt the catalyst segments filling also by the inert filler Distribution Layer, injecting the method for cold shock material to beds can be simply, effective control catalyst bed temperature, and whole reaction bed temperature is comparatively even.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 is beneficial to the Dehydration of methanol forward and moves, and improves the equilibrium conversion of methyl alcohol.
The present invention relates to the reaction 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 1～20 section, the catalyzer of filling is a solid acid catalyst in the reactor, comprise that MCM-22, ZSM are molecular sieve, USY, beta-molecular sieve, gama-alumina, mordenite, or the mixing of its above-mentioned catalyzer, every layer of catalyzer top filling inert filler.Reactor operating condition: reaction pressure 0.2～4.0MPa, 120～400 ℃ of temperature of reaction, charging air speed 0.5～20.0h
-1Between, preferable operational condition: reaction pressure 0.5～1.5MPa, 150～300 ℃ of temperature of reaction, charging air speed 2.0～8.0h
-1Between.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 the cold shock material quickly falls in the scope of technique initialization bed temperature by inert filler injecting catalyst reactor.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 catalyst segments filling, and the cold shock material that injects is entered in the reactor catalyst bed after by the inert filler layer again; The cold shock material can be any one or a few the mixture in liquid methyl alcohol, dme, the water.
A kind of special situation be mixture with the thick methyl alcohol of liquid phase, dme and the water that after condensation, gas-liquid separation, obtains from the effusive material of Dehydration of methanol device as the cold shock material, can be directly with charging methyl alcohol as cold shock Material control catalyst bed reaction temperature.
Be comparative example with not stratified filling solid acid catalyst below, layering is loaded solid acid catalyst and for embodiment the present invention is described in detail, 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
3Mol ratio is 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, 550 ℃ 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, 550 ℃ roastings of 120 ℃ of dryings 2 hours, makes 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 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.
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.
Embodiment 1: the fixed bed dimethyl ether by methanol dehydration
Catalyzer, reactor, raw material are with comparative example 1.Divide four sections fillings with 2500 milliliters of catalyzer, 100 milliliters of Φ, 6 stainless steel Raschig ring fillers are all loaded on every section beds top, have four cold shock material decanting points on every layer of Raschig ring filler top.Temperature is that 125 ℃ liquid methanol (purity is 97.5% (weight)) was with air speed 0.102 hour
-1Suitably adjust the cold shock flow in the injecting reactor and according to bed temperature.
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%, 225.1 ℃ of bed temperature outs.
Embodiment 2: the fixed bed dimethyl ether by methanol dehydration
Catalyzer is a gamma-alumina catalyst, and reactor, methanol feedstock, cold shock material, inert filler, catalyzer loading amount 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.
Embodiment 3: fixing adiabatic reactor dimethyl ether by methanol dehydration
Catalyzer be D803C-III01 (commercial catalyst, DICP), catalyzer is that ZSM-5 and gama-alumina mixed by 50: 50; Reactor, methanol feedstock, cold shock material, inert filler, catalyzer loading amount are with embodiment 1.
190 ℃ of reactor inlet temperatures, reaction pressure (gauge pressure) 1.2MPa, methanol feeding air speed 2.5 hours
-1Condition under, methanol conversion is 77.6%, the dme selectivity is～100%, 230.6 ℃ of bed temperature outs.
Claims (7)
1. the method for solid acid catalysis methanol dehydration continuous production dme, solid acid catalyst is loaded in segmentation in reactor; The inert filler layer is equipped with on each beds top; The cold shock material contacts with solid acid catalyst by behind the inert filler layer;
Reaction pressure is 0.2～4.0MPa, and temperature of reaction is 120～400 ℃, and the charging air speed is 0.1～20.0h
-1
2. in accordance with the method for claim 1, wherein, described solid acid catalyst comprises that MCM-22, ZSM are any one or a few mixing in molecular sieve, USY, beta-molecular sieve, gama-alumina, the mordenite.
3. in accordance with the method for claim 1, wherein, solid acid catalyst is divided into 1～20 bed in the described reactor.
4. according to claim 1 or 3 described methods, wherein, solid acid catalyst is divided into 2～10 beds in the described reactor.
5. in accordance with the method for claim 1, wherein, described cold shock material is any one or a few the mixture in liquid methyl alcohol, dme, the water.
6. in accordance with the method for claim 1, wherein, described inert filler comprises structured packing or/and dumped packing.
7. in accordance with the method for claim 1, wherein, reaction pressure is 0.5～1.5MPa, and temperature of reaction is 150～300 ℃, charging air speed 0.1～8.0h
-1
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| CN 201010123944 CN102050706B (en) | 2009-11-04 | 2010-03-10 | Method for serially producing dimethyl ether by dehydrating solid acid catalyzing methanol |
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| CN200910237083.5 | 2009-11-04 | ||
| CN200910237083 | 2009-11-04 | ||
| CN 201010123944 CN102050706B (en) | 2009-11-04 | 2010-03-10 | Method for serially producing dimethyl ether by dehydrating solid acid catalyzing methanol |
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| CN102050706B CN102050706B (en) | 2013-04-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588104A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099676A1 (en) * | 1982-07-01 | 1984-02-01 | E.I. Du Pont De Nemours And Company | Catalytic preparation of dimethyl ether |
| CN2921008Y (en) * | 2006-07-20 | 2007-07-11 | 武汉三联节能环保工程有限公司 | Separating heat tube type dimethyl ether reactor |
| CN101108790A (en) * | 2006-12-04 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction |
-
2010
- 2010-03-10 CN CN 201010123944 patent/CN102050706B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099676A1 (en) * | 1982-07-01 | 1984-02-01 | E.I. Du Pont De Nemours And Company | Catalytic preparation of dimethyl ether |
| CN2921008Y (en) * | 2006-07-20 | 2007-07-11 | 武汉三联节能环保工程有限公司 | Separating heat tube type dimethyl ether reactor |
| CN101108790A (en) * | 2006-12-04 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method for manufacturing dimethyl ether with solid acid catalysis methanol dehydration reaction |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588104A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for catalyst used for preparation of dimethyl ether through dehydration of methanol |
| 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 |
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| CN102050706B (en) | 2013-04-03 |
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Effective date of registration: 20230113 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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