CN1194257A - Novel pulpous bed dimethyl ether synthesizing reaction technology and apparatus - Google Patents
Novel pulpous bed dimethyl ether synthesizing reaction technology and apparatus Download PDFInfo
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- CN1194257A CN1194257A CN98101430A CN98101430A CN1194257A CN 1194257 A CN1194257 A CN 1194257A CN 98101430 A CN98101430 A CN 98101430A CN 98101430 A CN98101430 A CN 98101430A CN 1194257 A CN1194257 A CN 1194257A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
Through optimizing operation pressure and temperature in synthesizing reactor and leading in specific inert solvent, triphase pulpous bed reaction system with double-function granular catalyst and synthetic gas is formed in reactor, in which the intermediate product methanol is in near-critical state while the end product dimethyl ether is in far supercritical state so as to be separated from the gas-phase synthetic gas and the liquid- phase water produced and to suppress effectively two reverse reactions and raise single path conversion ratio of synthetic gas and single path yield of dimethyl ether. Leading in inert solvent is favourable to lead-out of reaction heat and raise of dimethyl ether yield.
Description
The present invention relates to a kind of reaction process and corresponding apparatus thereof of three phase slurry bed dimethyl ether synthesizing.
The three phase slurry bed bioreactor is known for a long time reactor, being used for dimethyl ether synthesizing reaction is adopted by forefathers, usually the copper base dual-function catalyst that adopts can make the per pass conversion of synthetic gas bring up to about 30～50% by the coupling of two reversible reaction devices.
The purpose of this invention is to provide a kind of reaction process that reaches the novel pulpous bed dimethyl ether synthesizing that improves synthetic gas per pass conversion and dme once through yield by the preferred reaction operational condition.
Another object of the present invention provides the used equipment of an above-mentioned reaction process of cover.
Novel pulpous bed dimethyl ether synthesizing reaction technology of the present invention is in the three phase slurry bed bioreactor, makes synthetic gas (H
2, CO, CO
2) under the effect of dual-function catalyst, two reversible reactions take place, i.e. the reversible reaction of reversible reaction of synthetic mesophase product methyl alcohol and synthetic final product dme; Particularly by control operation temperature, pressure and introducing inert solvent, make intermediate product methyl alcohol be in nearly criticality, and the final product dme is in supercritical state far away, thereby, reach the purpose that more effectively suppresses two reversed reactions with the synthetic gas that is in gas phase and separating with the generation water that is in liquid phase.Described operation pressure is P=7.8～10.0MPa, described operation temperature T=450～512.6K, described inert solvent ether and alcohol, (3～5 carbon) ketone, (3～4 carbon) ester, aromatic hydrocarbons and derivative thereof that to be hexane contain 5～8 carbon to the straight chain or the cycloalkanes stable hydrocarbon of decane.The median size dp=50 of described dual-function catalyst～500 μ m, density p p=500～2000g/cm
3
The characteristic of the material that body series is related sees Table 1.
Table 1, reaction system property list
| System component | Emergent pressure MPa | Critical temperature K | Phase in reaction system |
| Granules of catalyst | ????/ | ??/ | ????S |
| ??H 2 | ????1.28 | ??33.2 | ????G |
| ??CO | ????3.45 | ??132.9 | The nearly criticality of G |
| ??CH 8OH | ????7.99 | ??512.6 | Nearly criticality |
| ??H 2O | ????21.82 | ??647.3 | The L supercritical state |
| ??CH 3OCH 3 | ????5.2 | ??402.0 | Supercritical state |
| Solvent | ????＞8. | ??＞515 | ????L |
| The state of reaction system | ????7.8～10.0 | ??450～512.6 | ????G-L-S |
Inert solvent (Tc＞512.6K of the present invention, Pc＞10.MPa) does not influence activity of such catalysts and selectivity in the catalyzed reaction of synthesizing methanol and dme, require itself and methyl alcohol and dme that alap mutual solubility is arranged, be liquid phase under the working pressure temperature of reaction system, this solvent can be own propyl ether, positive isopropyl ether, ethanol, propyl alcohol, positive isopropylcarbinol, acetone, butanone, diethyl ketone, formic acid second fat, ethyl acetate, benzene, methyl-phenoxide, phenyl ether.
The determined operation condition of the present invention, the firstth, the methyl alcohol (Tc=512.6K that the first step reversible reaction is generated, Pc=7.99MPa) be in nearly criticality, at this moment (Tc＞512.6K, Pc＞10.0MPa) have good intermiscibility for methyl alcohol and liquid phase solvent, and mainly remain in liquid phase, unreacted synthetic gas [H2 (Tc=33.2K, P=1.28MPa), CO (Tc=132.9K, P=3.45MPa)] still be in gas phase, thereby reach the purpose that suppresses the synthesizing methanol reversed reaction; The secondth, make dme (Tc=402K, P=5.2MPa) be in supercritical state far away, preferentially enter gas phase, make another product water (Tc=647.3K of dehydration reaction, Pc=21.82MPa) still locate liquid phase, thereby suppress dme synthetic reversed reaction speed, reach the purpose that improves synthetic gas transformation efficiency to 60%～100%.
The present invention is by the working pressure and the temperature of preferred building-up reactions, and introduce specific inert solvent and difunctional finely grained catalyst and synthetic gas forms three phase slurry bed bioreactor (1), the introducing of inert solvent is except that helping the drawing of reaction heat, and can make the methyl alcohol that is in nearly criticality and solvent that good intermiscibility (under normal condition this intermiscibility may seldom) is arranged, make methyl alcohol preferentially remain in liquid phase like this, and methyl alcohol is in further dehydration reaction, constantly be consumed because of generating dme, thereby reach the purpose that suppresses the synthesizing methanol reversed reaction; The dme that generates is overcritical strong attitude far away under the operation pressure and temp of setting, because unreacted synthetic gas (H
2, CO, CO
2) gas propose effect and make dme break away from reaction system and remain in gas phase; The water that reaction generates will remain in the liquid phase suspended dispersed in solvent, can help suppressing the reversed reaction of dme like this, and the one way yield of dimethyl ether is increased substantially.Referring to reaction system principle schematic 2.
Novel pulpous bed dimethyl ether synthesizing reaction technology equipment used of the present invention comprises three phase slurry bed bioreactor (1), first cooling tower (6), dme gasifier (8), dme drainer (14) and recycle compressor (7), strainer (15), variable valve (16); Described three-phase slurry reactor comprises that tank body, tank body are from being disposed with synthetic gas import, micropore sparger (2), inner member (10), water-cooled tube (3), vortex-flow and defrosting device (9) and reaction gas outlet down.
Described micropore sparger (2) adopts the metal sintered or wire netting agglomerated material of microporous type, and micro-pore diameter d=5～50 μ m is so that bubble mean diameter d-in the three-phase bed
PB=0.1～1.5mm can improve gas holdup and the gas residence time and the gas-liquid two-phase mass transfer surfaces of system greatly, thereby has improved macroscopical speed of reaction.
Described whirlwind-type mist eliminator (9) can reduce solvent and catalyzer and is entrained with reactor.The vortex-flow and defrosting device can be single rotation center or many rotation centers (being applicable to large-scale plant), and percentage of open area is 80～98%, and blade angle can change between 30 °～60 °, also can adopt built-in cyclonic separator group to replace the vortex-flow and defrosting device.
Described inner member adopts built-in structured packing formula (10), percentage of open area is 85-98%, so that bubble at the diameter of axle of reactor to being evenly distributed, and help the coalescence that prevents that bubble is possible, reach and pulverize bubble (if bubble is excessive) once more, the effect of inner member, also be to promote reactor inside diameter to mixing, and axial back-mixing in the inhibited reaction device, favourable axially setting up concentration gradient to improve transformation efficiency, very big at reactor diameter, and when wishing to reduce the structure of reactor complexity and being convenient to the reactor maintenance, also inner member can be set, reactor still can have good usefulness.
Be provided with cooling tube in the described reactor, to shift out reaction heat.
The sepn process of dme of the present invention and water and raw material, solvent, catalyzer and the intermediate product recycle system have following characteristics:
The product of drawing from reactor head is mainly not reacted H
2, CO, CO
2Solvent and catalyzer that resultant dme and part carry secretly out.At first at first water cooler (6) internal cooling, temperature drops to 385 ± 5K from 450～512.6K to this system, and pressure remains unchanged substantially, at this moment mixes and removes H in the system
2, CO, CO
2Still remain outside the gas phase, all dme, methyl alcohol, solvent are liquid phase, thereby gas phase separation, and utilize again with fresh synthesis gas mixing Returning reactor by recycle compressor.
Table 2, state parameter table
| Service temperature | Working pressure | ||
| The reactor internal state | 450k～512.6k | ?7.8～10MPa | |
| First water cooler internal state | 385±5K | ?7.8～10MPa | |
| Dme vaporizer internal state | 348～369K | ?2.0～3.0MPa | |
| Dme condenser internal state | 318±20K | ?2.0～3.0MPa |
Just the liquid phase in the water cooler (6) may contain little amount of catalyst, falls in the bottom slurry attitude material, by the gravity Returning reactor through sedimentation; Just the supernatant liquid (including dme, methyl alcohol, water and solvent etc.) in the water cooler (6) enters dme gasifier (8) by the throttling valve decompression, makes pressure drop to 2.0～3.0MPa; At this moment dme will gasify, and its gasification temperature will be corresponding to about 348～369K; At this moment in order to improve the heat utilization efficiency of system, the heat of gasification effect of dme will be used for cooling off the resultant of reaction material.Heat transfer process will have 20～40 ℃ the temperature difference to utilize between first water cooler (6) and dme gasifier (8).The first water cooler (6) of reaction product can be independently (to see accompanying drawing 1) respectively with dme gasifier (8), also can be (the seeing accompanying drawing 2) of combined type, is provided with a large amount of heat transfer areas between the latter's two devices, helps the utilization of energy like this.
Dme in the gasifier (8) will constantly gasify, and enter condenser (14), and the pressure in the condenser is roughly identical with gasifier (8); Water coolant is adopted in condensation, and (water temp 293 ± 5K), condensed dme product will be under 2.0～3.0MPa pressure, at room temperature will be liquid-phase product.
Table 3, dme saturation vapour pressure
| T(℃) | ?20.8 | ?45.5 | ?75.7 | ?96.0 | ?112.5 |
| ?P(MPa) | ?0.5 | ?1.0 | ?2.0 | ?3.0 | ?4.0 |
Just water cooler (6), dme gasifier (8) all can be the shell and tube heat-exchanger rig with dme condenser (14), also can adopt coil pipe type, built-up type.
Dme gasifier water byproduct will layering be separated out (solubleness of dme is approximately about 3.7% in 18 ℃ of following water) from solvent and dme, water layer can be discharged from base of evaporator; Discharging is because dme differs more than 120 ℃ with water boiling point reclaim the dme of remaining stripping again in withdrawer after, and this sepn process is easily capable, and does not have pollution problem.
Liquid phase in the dme gasifier consists of not evaporable methyl ether of solvent and a part, can use by recycle pump pressurization back Returning reactor.Behind the solvent process filter (15) that returns, can partly be used for the periodic flushing gas distributor, prevent that the micropore sparger from being stopped up by catalyst fines, and make the pressure falling-rising height of sparger.
Novel pulpous bed dimethyl ether synthesizing reaction technology equipment used of the present invention is scientific and reasonable, simple to operation, advantageously cooperates a whole set of process for synthesis of dimethyl ether, reaches the purpose that suppresses two reversed reactions and improve synthetic gas per pass conversion and yield of dimethyl ether.
Further specify the present invention below in conjunction with drawings and Examples;
Accompanying drawing 1 is a novel pulpous bed dimethyl ether synthesizing reaction technology general flow chart of the present invention.
Accompanying drawing 2 is the general flow chart of combined type for first cooling tower and dme gasifier in the novel pulpous bed dimethyl ether synthesizing reaction technology of the present invention.
Accompanying drawing 3 is the structural representation of inner member in the three-phase slurry reactor.
Accompanying drawing 4 is a reaction system principle schematic in the three-phase slurry reactor.
Wherein label 1 is a three-phase slurry reactor, and 2 is the micropore sparger, and 3 is water-cooled tube, 4 is reducing valve, and 5 is back pressure valve, and 6 is first cooling tower, 7 is recycle compressor, and 8 is the dme gasifier, and 9 is the vortex-flow and defrosting device, 10 is inner member, and 11 is the catalyst pulp circulation tube, and 12 are gasifier outlet down, 13 is the gasifier upper outlet, and 14 is the dme drainer, and 15 is strainer, 16 is variable valve, and 17 is the gasifier middle outlet, and 18 is heating tube.
Shown in the state parameter in A district be T=512.6～450k, P=78～100atm,
The state parameter in B district is T=385 ± 5k, P=78～100atm,
The state parameter in C district is T=348～369k, P=20～30atm,
The state parameter in D district is T=318 ± 20k, P=20～30atm;
Solvent is a solvent.
Novel pulpous bed dimethyl ether synthesizing reaction technology of the present invention is in the three phase slurry bed bioreactor, makes synthetic gas (H
2, CO, CO
2) under the effect of copper base dual-function catalyst, two reversible reactions take place, i.e. the reversible reaction of reversible reaction of synthetic mesophase product methyl alcohol and synthetic final product dme; Particularly by control operation temperature, pressure and introducing inert solvent, make intermediate product methyl alcohol be in nearly criticality, and the final product dme is in supercritical state far away, thereby, reach the purpose that more effectively suppresses two reversed reactions with the synthetic gas that is in gas phase and separating with the generation water that is in liquid phase.Described operation pressure is P=8.5MPa, and described operation temperature T=490K, described inert solvent are propyl alcohol.Copper base dual-function catalyst, median size are 300 μ m, and density p is 1000g/cm
3
The equipment that this technology adopted comprises three phase slurry bed bioreactor (1) shown in accompanying drawing 1,3,4, first cooling tower (6), dme gasifier (8), dme drainer (14) and recycle compressor (7), strainer (15), variable valve (16); Described three-phase slurry reactor comprises that tank body, tank body are from being disposed with synthetic gas import, micropore sparger (2), inner member (10), water-cooled tube (3), vortex-flow and defrosting device (9) and reaction gas outlet down.
Just the Partial Liquid Phase in the water cooler 6 (contains CH
3OCH
3, solvent, catalyzer etc.) rely on gravity partly to circulate to enter reactor so that the catalyzer of carrying secretly can Returning reactor, after the liquid phase decompression of all the other clarification parts, enter the dme gasifier;
In the gasifier 8, be provided with three outlets, outlet at bottom 12 is used for get rid of generating water, and top exit 13 is used for drawing the dme after the gasification, and centre exit 17 is used for drawing circulating solvent; The dme condenser that is adopted is a pressurized vessel, in be provided with cooling tube, adopt the room temperature water cooling, and to obtain pressure be 2.0～3.0MPa, help carrying and use for liquid-phase product under the room temperature.
The solvent of drawing from dme vaporizer centre exit 17, through direct Returning reactor after the recycle pump pressurization, after also can regularly filtering through strainer, send reactor preceding 1 bottom, the micropore sparger 2 that is used for the backwash reactor, because trickle granules of catalyst stops up sparger, make its pressure fall rising to prevent.
Claims (10)
1, a kind of novel pulpous bed dimethyl ether synthesizing reaction technology is characterized in that novel pulpous bed dimethyl ether synthesizing reaction technology of the present invention is in the three phase slurry bed bioreactor, makes synthetic gas (H
2, CO, CO
2) under the effect of dual-function catalyst, two reversible reactions take place, i.e. the reversible reaction of reversible reaction of synthetic mesophase product methyl alcohol and synthetic final product dme; Particularly by control operation temperature, pressure and introducing inert solvent, make intermediate product methyl alcohol be in nearly criticality, and the final product dme is in supercritical state far away, thereby, reach the purpose that more effectively suppresses two reversed reactions with the synthetic gas that is in gas phase and separating with the generation water that is in liquid phase.Described operation pressure is P=7.8～10.0MPa, described operation temperature T=450～512.6K, described inert solvent are straight chain or cycloalkanes stable hydrocarbon, the ether that contains 5～8 carbon and alcohol, (3～5 carbon) ketone, (3～4 carbon) ester, aromatic hydrocarbons and the derivative thereof of hexane to decane.
2, reaction process as claimed in claim 1 is characterized in that the median size dp=50～500 μ m of described dual-function catalyst, density p p=500～2000g/cm
3
3, the equipment used as the reaction process of one of claim 1-2, it is characterized in that, comprise three phase slurry bed bioreactor (1), first cooling tower (6), dme gasifier (8), dme drainer (14) and recycle compressor (7), strainer (15), variable valve (16); Described three-phase slurry reactor comprises that tank body, tank body are from being disposed with synthetic gas import, micropore sparger (2), inner body spare (10), water-cooled tube (3), vortex-flow and defrosting device (9) and reaction gas outlet down.
4, equipment as claimed in claim 3 is characterized in that described inner member adopts built-in structured packing formula (10), and percentage of open area is 85-98%.
5, equipment as claimed in claim 3 is characterized in that described micropore sparger (2) adopts the metal sintered or wire netting agglomerated material of microporous type, and micro-pore diameter d=5～50 μ m is so that bubble mean diameter d in the three-phase bed
PB=0.1～1.5mm.
6, equipment as claimed in claim 3 is characterized in that described whirlwind-type mist eliminator (9) is single rotation center or many rotation centers (being applicable to large-scale plant), and percentage of open area is 80～98%, and blade angle can change between 30 °～60 °.
7, equipment as claimed in claim 6 is characterized in that adopting built-in cyclonic separator group to replace the vortex-flow and defrosting device.
8, equipment as claimed in claim 3, the first water cooler (6) that it is characterized in that reaction product and dme gasifier (8) are respectively independently or combined type, are provided with a large amount of heat transfer areas between the latter's two devices.
9, equipment as claimed in claim 3 is characterized in that just water cooler (6), dme gasifier (8) are the shell and tube heat-exchanger rig or adopt coil pipe type, built-up type with dme condenser (14).
10, equipment as claimed in claim 3 is characterized in that also being connected with withdrawer with dme gasifier bottom, the dme of remnants in the recyclable water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101430A CN1194257A (en) | 1998-04-24 | 1998-04-24 | Novel pulpous bed dimethyl ether synthesizing reaction technology and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98101430A CN1194257A (en) | 1998-04-24 | 1998-04-24 | Novel pulpous bed dimethyl ether synthesizing reaction technology and apparatus |
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| Publication Number | Publication Date |
|---|---|
| CN1194257A true CN1194257A (en) | 1998-09-30 |
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ID=5216691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98101430A Pending CN1194257A (en) | 1998-04-24 | 1998-04-24 | Novel pulpous bed dimethyl ether synthesizing reaction technology and apparatus |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100439310C (en) * | 2003-03-05 | 2008-12-03 | 乔治洛德方法研究和开发液化空气有限公司 | Process and apparatus for the production of dimethyl ether |
| CN101372446B (en) * | 2007-08-23 | 2014-05-28 | 赫多特普索化工设备公司 | Process for the preparation of dimethyl ether |
-
1998
- 1998-04-24 CN CN98101430A patent/CN1194257A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100439310C (en) * | 2003-03-05 | 2008-12-03 | 乔治洛德方法研究和开发液化空气有限公司 | Process and apparatus for the production of dimethyl ether |
| CN101372446B (en) * | 2007-08-23 | 2014-05-28 | 赫多特普索化工设备公司 | Process for the preparation of dimethyl ether |
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