CN104059686A - Device, reactor and method for preparing gasoline from dimethyl ether - Google Patents
Device, reactor and method for preparing gasoline from dimethyl ether Download PDFInfo
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- CN104059686A CN104059686A CN201310086183.9A CN201310086183A CN104059686A CN 104059686 A CN104059686 A CN 104059686A CN 201310086183 A CN201310086183 A CN 201310086183A CN 104059686 A CN104059686 A CN 104059686A
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Abstract
The invention discloses a device, a reactor and a method for preparing gasoline from dimethyl ether. The device comprises a reactor, wherein the reactor comprises a tube housing provided with a heat transfer medium inlet, a heat transfer medium outlet, a catalyst feeding port, and a catalyst discharging port, and a heat transfer medium circulating distributor is disposed inside the tube housing and is connected with the heat transfer medium inlet; the device also comprises a heat exchanger, wherein the heat exchanger is provided with a heat exchange inlet, a heat exchange outlet, a cold water inlet and a hot water outlet, the cold water inlet is connected with a cold water pump for supplying cooling water, and the heat exchange inlet is connected with the heat transfer medium outlet; the device further comprises a heater, wherein the heating comprises a medium inlet and a medium outlet, and the medium inlet is connected with the heat exchange outlet; the device additionally comprises a reflux pump, wherein an inlet of the reflux pump is connected with the medium outlet, and an outlet of the reflux pump is connected with the heat transfer medium inlet on the reactor. The beneficial effects of the invention are that: catalyst caking is avoided, regeneration of the catalyst is not necessary, and continuous generation is realized.
Description
[technical field]
The present invention relates to methyl alcohol or dme technique for preparing gasoline field, device, reactor and the method for especially a kind of dme gasoline processed.
[background technology]
Dme process of gasoline processed refers to dme makes raw material, and ether water ratio according to a certain ratio, under certain temperature, pressure and air speed, is converted into the hydro carbons oil product below C11 under the effect such as dehydration, oligomeric isomeric by specific catalyzer.
Because world's coal reserves are more than many many of oil and natural gas, therefore from coal preparing synthetic gas, methyl alcohol and dme, the finally research of gasoline processed once came into one's own abroad.The method of the ZSM-5 type synthetic zeolite catalyst of wherein especially succeeding in developing with Mobil company is the most striking.The gasoline knock resistance that this method makes is good, do not have the components such as conventional sulfur in gasoline, chlorine, and chemical constitution is very similar to conventional gasoline.
The reactor that existing MTG commercial run route adopts can be divided into three, enters classical fixed-bed reactor method technique, the industry of fluidized-bed reactor method and multi-tubular reactor method technique.All there is in various degree coking in the reactor of these three techniques, so that catalyst activity do not reach requirement, and this is to need to shut down, and the catalyzer in reactor is regenerated, and after regeneration, just can reproduce.And the life cycle of catalyzer is short, be only 22-100 days, stop and regenerate with regard to needs.Regeneration frequently can make the activity decreased of catalyzer, when serious, can make catalyzer scrap.
Methanol conversion technique for preparing gasoline is relatively simple, but still exist at reactor, catalyzer is coking regenerates with needing, and all there is no so far the breakthrough of principle, cannot industrialization.
[summary of the invention]
The object of the invention is to effectively overcome the deficiency of above-mentioned technology, device, reactor and the method for a kind of dme gasoline processed is provided, can avoid the transformation efficiency of the coking and dimethyl ether conversion gasoline of catalyzer and the problem that productive rate reduces.
Technical scheme of the present invention is achieved in that the device of a kind of dme gasoline processed, and it comprises
One reactor, comprise shell, described shell is provided with heat-transfer medium input aperture, heat-transfer medium delivery port, catalyzer adds entrance and catalyzer unloads outlet, described shell inside is provided with the heat-transfer medium loop distribution device being connected with described heat-transfer medium input aperture, described shell bottom is provided with dme and passes into mouth, the respond gas outlet of the top of shell;
One heat exchanger, has heat exchange entrance, heat exchange outlet, cold water inlet and hot water outlet, and described cold water inlet connection one provides the water supply pump of water coolant, and described heat exchange entrance is connected with the heat-transfer medium delivery port on described reactor;
One well heater, has a medium import and a media outlet, and described medium import is connected with the heat exchange outlet on described heat exchanger;
One reflux pump, the entrance of described reflux pump is connected with the media outlet on described well heater, and described backflow pump outlet is connected with the heat-transfer medium input aperture on described reactor.
Described shell is established sieve tray in top, is provided with sieve tray in described reactor lower part; Described catalyzer adds entrance and is arranged at the below of described upper sieve tray, and described catalyzer unloads outlet and be arranged at the top of described lower sieve tray; Described heat-transfer medium input aperture and heat-transfer medium delivery port are arranged at the top of described upper sieve tray; Described dme passes into a mouthful below that is arranged at described lower sieve tray.
Described heat-transfer medium loop distribution device comprises multiple heat-transfer mediums sparger that circulates, and described multiple heat-transfer mediums sparger that circulates is longitudinally distributed between described upper sieve tray and lower sieve tray.
In described shell bottom, be provided with one and pass into described dme the gas of dimethyl ether sparger that mouth is connected.
A kind of reactor, it comprises shell, described shell is provided with heat-transfer medium input aperture, heat-transfer medium delivery port, catalyzer adds entrance and catalyzer unloads outlet, described shell inside is provided with the heat-transfer medium loop distribution device being connected with described heat-transfer medium input aperture, described shell bottom is provided with dme and passes into mouth, the respond gas outlet of the top of shell.
Described shell is established sieve tray in top, is provided with sieve tray in described reactor lower part; Described catalyzer adds entrance and is arranged at the below of described upper sieve tray, and described catalyzer unloads outlet and be arranged at the top of described lower sieve tray; Described heat-transfer medium input aperture and heat-transfer medium delivery port are arranged at the top of described upper sieve tray; Described dme passes into a mouthful below that is arranged at described lower sieve tray.
Described heat-transfer medium loop distribution device comprises multiple heat-transfer mediums sparger that circulates, and described multiple heat-transfer mediums sparger that circulates is longitudinally distributed between described upper sieve tray and lower sieve tray.
In described shell bottom, be provided with one and pass into described dme the gas of dimethyl ether sparger that mouth is connected.
A method of utilizing the device gasoline processed of described dme gasoline processed, comprises step:
S1, by well heater, the inertia heat-transfer medium of well heater inside is heated, while being heated to certain temperature, start reflux pump the inertia heat-transfer medium in well heater is delivered in reactor, so that the catalyzer in reactor is soaked in described inertia heat-transfer medium;
S2, utilize well heater to carry out circulating-heating to the inertia heat-transfer medium in reactor, inside reactor inertia heat-transfer medium temperature is raise, in the time of excess Temperature, stop heating and pass through water supply pump and heat exchanger cooling, so that inside reactor temperature is controlled at 380 DEG C～410 DEG C;
S3, pass into mouth by the dme of reactor lower part and pass into the high-temperature steam of dme and water, dme high-temperature steam fully contacts with the catalyzer in described reactor, react and generate the product as leading taking hydrocarbons and water, export and derive and form gasolene ingredient after gas-liquid separation by reaction gas described.
Described inertia heat-transfer medium is inertia thermal oil.
Beneficial effect of the present invention is: one, in method of the present invention, the catalyzer of the solid particulate in reactor is soaked in inertia heat-transfer medium, make catalyzer uniformly transfer heat, inertia heat-transfer medium does not participate in reaction, in reactor, cannot provide generation carbon black, tar, the condition of coke, generate the surface that does not also adhere to catalyzer once have ready conditions, transfer in cooling separator through the reaction gas outlet on reactor top with air-flow, because whole reaction process is continuous, catalyzer can not need regeneration because of coking deactivation, the transformation efficiency of dme is up to 99%, reach the object that industrialization generates continuously, two, in the present invention reacting appliance standby the ability of dimethyl ether conversion gasoline, and can be for methanol conversion gasoline, or methanol conversion dme, can carry out easily production interchange, factory also can adjust the product mix according to the market requirement, the reactor of three, producing gasoline with respect to other, processing unit obviously reduces, and plant investment reduces, and floor space reduces, and plant energy consumption reduces, four, with respect to the reactor of other methanol conversion gasoline or MTG methanol conversion gasoline, more easily control the temperature in reactor, make temperature of reaction relatively constant, can shift out rapidly the amount of heat in chemical reaction process, suppress the carbon black producing because of excess Temperature, five, the thermal oil in this reaction process is inertia, can Yin Wendu and decompose, thermal oil and catalyzer have no side effect, reactor also can not reduce because the impact of thermal oil makes the transformation efficiency of dimethyl ether conversion gasoline and productive rate, reaction has no side effect to thermal oil thing for gasoline or hydrocarbon gas, and thermal oil is uniform heat conduction, heat exchange, decarburization, presses down burnt specific function in reactor.
[brief description of the drawings]
Fig. 1 is the structural representation of reactor in the present invention;
Fig. 2 is the structural representation of the device of dme gasoline processed in the present invention;
In figure: shell 1; Catalyzer adds entrance 2; Catalyzer unloads outlet 3; Heat-transfer medium input aperture 4; Heat-transfer medium delivery port 5; Heat-transfer medium loop distribution device 6; The heat-transfer medium sparger 61 that circulates; Dme passes into mouth 7; Reaction gas outlet 8; Gas of dimethyl ether sparger 9; Catalyzer 10; Thermal oil 11; Heat exchanger 12; Heat exchange entrance 13; Heat exchange outlet 14; Cold water inlet 15; Hot water outlet 16; Water supply pump 17; Well heater 18; Media outlet 19; Medium import 20; Reflux pump 21; Repairing mouth 22.
[embodiment]
Below in conjunction with drawings and Examples, the invention will be further described.
Shown in Fig. 1, the invention provides a kind of reactor, it comprises shell 1, described shell 1 is provided with heat-transfer medium input aperture 4, heat-transfer medium delivery port 5, catalyzer adds entrance 2 and catalyzer unloads outlet 3, wherein, heat-transfer medium input aperture 4 for passing into heat-transfer medium in reactor cavity, heat-transfer medium delivery port 5 is for discharging inside reactor heat-transfer medium, and catalyzer adds entrance 2 for add catalyzer 10 in reactor cavity, catalyzer unloads outlet 3 for catalyzer 10 is discharged, described shell 1 inside is provided with the heat-transfer medium loop distribution device 6 being connected with described heat-transfer medium input aperture 4, heat-transfer medium can enter from heat-transfer medium input aperture 4 heat-transfer medium loop distribution device 6, enter to uniformly in reactor cavity through heat-transfer medium circle distributor, described shell 1 bottom is provided with dme and passes into mouth 7, for to the high-temperature steam that passes into dme and water in the reactor of catalyzer 10 is housed, the gas outlet 8 that responds of the top of shell 1, be used for collecting dme and the reacted product of catalyzer 10 (hydrocarbons etc.).
In addition, described shell is established sieve tray in 1 top, is provided with sieve tray in described reactor lower part; Described catalyzer adds entrance 2 and is arranged at the below of described upper sieve tray, and described catalyzer unloads outlet 3 and be arranged at the top of described lower sieve tray, so, forms region and be convenient to splendid attire pellet type catalyst 10 between upper sieve tray and lower sieve tray; Described heat-transfer medium input aperture 4 and heat-transfer medium delivery port 5 are arranged at the top of described upper sieve tray, are convenient to input and the discharge of heat-transfer medium; Described dme passes into mouthfuls 7 belows that are arranged at described lower sieve tray, and the dme passing into and the high-temperature steam of water can pass catalyzer 10 from the bottom to top, fully contact with catalyzer 10 is surperficial.
Further, described heat-transfer medium loop distribution device 6 comprises multiple heat-transfer mediums sparger 61 that circulates, described multiple heat-transfer medium sparger 61 that circulates is longitudinally distributed between described upper sieve tray and lower sieve tray, so, is convenient to heat-transfer medium and is distributed in uniformly in whole reactor cavity.In described shell 1 bottom, be provided with one and pass into mouthful 7 gas of dimethyl ether spargers 9 that are connected with described dme, the dme steam that is conducive to pass into is uniformly distributed in reactor cavity.
Further, on shell 1, be also provided with the temperature detection mouth for detection of inside reactor temperature, by the temperature of the detection reaction device inside such as temperature sensor, then temperature signal be passed to external control system, so that control.
Shown in Fig. 2, the invention provides the device of a kind of dme gasoline processed, be reactor shown in Fig. 1 and specifically apply, it comprises a reactor, a heat exchanger 12, a well heater 18 and a reflux pump 21, wherein, reactor is the reactor shown in Fig. 1, and its structure is not repeated, heat exchanger 12 has heat exchange entrance 13, heat exchange outlet 14, cold water inlet 15 and hot water outlet 16, well heater 18 has a medium import 20, one media outlet 19 and a repairing mouth 22, described heat exchange entrance 13 is connected with the heat-transfer medium delivery port 5 on described reactor, heat-transfer medium in reactor can be delivered to heat-transfer medium in heat exchanger 12 by heat-transfer medium delivery port 5, described heat exchange outlet 14 is connected with medium import 20 on described well heater 18, heat-transfer medium in heat exchanger 12 can export 14 by heat exchange and be delivered in well heater 18, utilize well heater 18 to heat heat-transfer medium, repairing mouth 22 on well heater 18 can be the interior supplementary heat-transfer medium of well heater 18, described cold water inlet 15 connects a water supply pump 17 that water coolant is provided, water supply pump 17 provides cold water for heat exchanger 12, utilize the heat-transfer medium in cold water and heat exchanger 12 to carry out thermal exchange, so that heat-transfer medium temperature reduces, discharged by hot water outlet 16 and become hot water after the heat of cold water absorption heat-transfer medium, reach heat exchange object, the entrance of described reflux pump 21 is connected with the media outlet 19 on described well heater 18, the outlet of described reflux pump 21 is connected with the heat-transfer medium input aperture 4 on described reactor, so form heat-transfer medium circulation loop, reflux pump 21 provides power for heat-transfer medium circulation loop, heat-transfer medium in well heater 18 can be delivered to inside reactor by thermal medium input aperture by media outlet 19.
The method of utilizing said apparatus to prepare gasoline specifically comprises step:
S1, add entrance 2 by the catalyzer on reactor and upwards add catalyzer 10 in the region between sieve tray and lower sieve tray, general, this catalyzer 10 is ZSM-5 Type Zeolites agent, by well heater 18, the inertia heat-transfer medium of well heater 18 inside is heated, while being heated to certain temperature (being generally 300 DEG C), start reflux pump 21 the inertia heat-transfer medium in well heater 18 is delivered in reactor, so that the catalyzer 10 in reactor is soaked in described inertia heat-transfer medium; General, this inertia heat-transfer medium adopts inertia thermal oil 11;
S2, by well heater 18, the inertia heat-transfer medium in reactor is carried out to circulating-heating, inside reactor inertia heat-transfer medium temperature is raise, reach design temperature, this design temperature is temperature of reaction, and this temperature is controlled at 380 DEG C～410 DEG C, concrete circulating-heating process is as follows: the high temperature heat conductive oil 11 after heating is delivered in reactor by reflux pump 21, inner low temperature thermal oil 11 is back to again heat exchanger 12, now, because the temperature of thermal oil 11 does not also reach design temperature, therefore, now water supply pump 17 is not worked, low temperature thermal oil 11 in heat exchanger 12 is without heat exchange, directly entering well heater 18 heats again, temperature is further raise, thermal oil 11 after heating, again be recycled and deliver to reactor, so realize circulating-heating, when temperature reaches after design temperature, well heater 18 cuts out automatically, stop heating, whole process is by the temperature sensor detected temperatures signal on reactor, temperature signal is transferred to Controlling System, Controlling System realizes well heater 18, heat exchanger 12 and reflux pump 21 etc. are controlled automatically.
S3, pass into mouthfuls 7 high-temperature steams that pass into dme and water by the dme of reactor lower part, dme high-temperature steam fully contacts with the catalyzer 10 in described reactor, react and generate the product as leading taking hydrocarbons and water, in this step, dimethyl ether conversion gasoline reactor becomes dimethyl ether conversion the strong exothermal reaction of hydro carbons and water in the process that transforms gasoline under normal temperature of reaction:
CH
3OCH
3→(-CH
2-)n+H
2O；
Its reaction process resultant:
Dimethyl ether conversion gasoline be strong exothermal reaction, in the time that temperature of reaction is too high, the water supply pump 17 connecting on heat exchanger 12 starts, the thermal oil 11 of autoreactor is cooling in working cycle in the future, reaction heat is shifted out rapidly, in the time reaching normal temps, water supply pump 17 stops, so just ensure the constant of temperature of reaction, temperature in reaction process is constant under setting, avoid causing thermal oil 11 to decompose because excess Temperature produces, because catalyzer 10 in dimethyl ether conversion gasoline is because being immersed in thermal oil 11, and homo(io)thermism, cannot produce under normal circumstances tar, coke etc.
But, in this process, dme starts to occur slow decomposition in the time of 250 DEG C, generates CH2O+CH4, in the time of 350 DEG C, concentration of formaldehyde has reached maximum value, the oxygen level of dme own is high by 34.8%, belongs under oxygen enrichment state, if in this process in reactor, temperature is unstable, when temperature of reaction rises to higher than 430 DEG C, arrived the natural temperature of formaldehyde, induce reaction thing in reactor from however produce carbon black;
Meanwhile, formaldehyde nature generates high temperature and causes the burning of methane at inside reactor, a large amount of carbon black of having emitted a large amount of heat generations:
CH
4+O
2→C+2H
2O
Therefore, catalyzer 10 temperature in the reactor of dimethyl ether conversion gasoline must be less than 415 degrees Celsius, avoid excess Temperature to cause the burning of formaldehyde nature and methane and generate a large amount of carbon blacks, and the temperature of reactor is evenly controlled extremely important.
Reaction process is C
2-C
5condensation, cyclisation, further generate hydro carbons and C that molecular weight is higher
6above aromatic hydrocarbon, paraffinic hydrocarbons etc., finally form C
2-C
11hydrocarbon mixture and a part of tar and coke; In prior art, ZSM-5 molecular sieve all can produce a part of tar so that slowly coking, cause catalyzer 10 life cycles short, be 22 days just because of coking need regeneration, this is the own characteristic of dimethyl ether conversion gasoline, experiment and research find that dimethyl ether conversion gasoline reactor has produced two carbon kinds in application process, the one, and carbon black, because the high heat of high temperature generates; The 2nd, ZSM-5 molecular sieve changes into and generates in gasoline process.The major cause of catalyzer 10 inactivations when carbon deposit, in the fixed-bed reactor of filling live catalyst 10, first carbon deposit and inactivation of bed top catalyzer 10, and move down gradually, until complete deactivation.
But, suppose that in the present invention, temperature is unstable, there is coke production, but, in reaction process, catalyzer 10 is because being soaked in thermal oil 11, coke cannot glue attached catalyst 10 surfaces, charcoal separates with catalyzer 10, charcoal and separating of oil, charcoal is also cooled to gas-liquid separator outward with air-flow to reactor, therefore whole reaction process, can suppress carbon black by the control of temperature, the generation of tar and coke, in reaction process, reactant does not produce and reacts with inertia thermal oil 11, can be in the scope of temperature of reaction and decompose yet, the transformation efficiency of dme is up to 99%, there is coke etc. even if generate, also can not adsorb with catalyzer 10, but directly discharge, do not affect catalyzer 10 activity, catalyzer 10 does not need regeneration, reach the object that industrialization generates continuously.
Described above is only preferred embodiment of the present invention, and above-mentioned specific embodiment is not limitation of the present invention.In technological thought category of the present invention, can there is various distortion and amendment, retouching that all those of ordinary skill in the art make according to above description, revise or be equal to replacement, all belong to the scope that the present invention protects.
Claims (10)
1. a device for dme gasoline processed, is characterized in that: it comprises
One reactor, comprise shell, described shell is provided with heat-transfer medium input aperture, heat-transfer medium delivery port, catalyzer adds entrance and catalyzer unloads outlet, described shell inside is provided with the heat-transfer medium loop distribution device being connected with described heat-transfer medium input aperture, described shell bottom is provided with dme and passes into mouth, the respond gas outlet of the top of shell;
One heat exchanger, has heat exchange entrance, heat exchange outlet, cold water inlet and hot water outlet, and described cold water inlet connection one provides the water supply pump of water coolant, and described heat exchange entrance is connected with the heat-transfer medium delivery port on described reactor;
One well heater, has a medium import and a media outlet, and described medium import is connected with the heat exchange outlet on described heat exchanger;
One reflux pump, the entrance of described reflux pump is connected with the media outlet on described well heater, and described backflow pump outlet is connected with the heat-transfer medium input aperture on described reactor.
2. the device of dme according to claim 1 gasoline processed, is characterized in that: described shell is established sieve tray in top, is provided with sieve tray in described reactor lower part; Described catalyzer adds entrance and is arranged at the below of described upper sieve tray, and described catalyzer unloads outlet and be arranged at the top of described lower sieve tray; Described heat-transfer medium input aperture and heat-transfer medium delivery port are arranged at the top of described upper sieve tray; Described dme passes into a mouthful below that is arranged at described lower sieve tray.
3. the device of dme according to claim 1 gasoline processed, it is characterized in that: described heat-transfer medium loop distribution device comprises multiple heat-transfer mediums sparger that circulates, described multiple heat-transfer mediums sparger that circulates is longitudinally distributed between described upper sieve tray and lower sieve tray.
4. the device of dme according to claim 1 gasoline processed, is characterized in that: in described shell bottom, be provided with one and pass into described dme the gas of dimethyl ether sparger that mouth is connected.
5. a reactor, it is characterized in that: it comprises shell, described shell is provided with heat-transfer medium input aperture, heat-transfer medium delivery port, catalyzer adds entrance and catalyzer unloads outlet, described shell inside is provided with the heat-transfer medium loop distribution device being connected with described heat-transfer medium input aperture, described shell bottom is provided with dme and passes into mouth, the respond gas outlet of the top of shell.
6. reactor according to claim 5, is characterized in that: described shell is established sieve tray in top, is provided with sieve tray in described reactor lower part; Described catalyzer adds entrance and is arranged at the below of described upper sieve tray, and described catalyzer unloads outlet and be arranged at the top of described lower sieve tray; Described heat-transfer medium input aperture and heat-transfer medium delivery port are arranged at the top of described upper sieve tray; Described dme passes into a mouthful below that is arranged at described lower sieve tray.
7. reactor according to claim 5, is characterized in that: described heat-transfer medium loop distribution device comprises multiple heat-transfer mediums sparger that circulates, and described multiple heat-transfer mediums sparger that circulates is longitudinally distributed between described upper sieve tray and lower sieve tray.
8. reactor according to claim 5, is characterized in that: in described shell bottom, be provided with one and pass into described dme the gas of dimethyl ether sparger that mouth is connected.
9. a method of utilizing device gasoline processed described in claim 1, is characterized in that: comprise step:
S1, by well heater, the inertia heat-transfer medium of well heater inside is heated, while being heated to certain temperature, start reflux pump the inertia heat-transfer medium in well heater is delivered in reactor, so that the catalyzer in reactor is soaked in described inertia heat-transfer medium;
S2, utilize well heater to carry out circulating-heating to the inertia heat-transfer medium in reactor, inside reactor inertia heat-transfer medium temperature is raise, in the time of excess Temperature, stop heating and pass through water supply pump and heat exchanger cooling, so that inside reactor temperature is controlled at 380 DEG C～410 DEG C;
S3, pass into mouth by the dme of reactor lower part and pass into the high-temperature steam of dme and water, dme high-temperature steam fully contacts with the catalyzer in described reactor, react and generate the product as leading taking hydrocarbons and water, export and derive and form gasolene ingredient after gas-liquid separation by reaction gas described.
10. method according to claim 9, is characterized in that: described inertia heat-transfer medium is inertia thermal oil.
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| CN201310086183.9A CN104059686A (en) | 2013-03-18 | 2013-03-18 | Device, reactor and method for preparing gasoline from dimethyl ether |
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|---|---|---|---|
| CN201310086183.9A CN104059686A (en) | 2013-03-18 | 2013-03-18 | Device, reactor and method for preparing gasoline from dimethyl ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097175A (en) * | 2018-01-31 | 2018-06-01 | 新疆美克化工股份有限公司 | Formaldehyde catalyst contrast experiment's self-balancing consersion unit |
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2013
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097175A (en) * | 2018-01-31 | 2018-06-01 | 新疆美克化工股份有限公司 | Formaldehyde catalyst contrast experiment's self-balancing consersion unit |
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Application publication date: 20140924 |