CN1446786A - Method and equips for manufacturing dimethyl ether with synthesis gas as raw material by using circulating current bed - Google Patents
Method and equips for manufacturing dimethyl ether with synthesis gas as raw material by using circulating current bed Download PDFInfo
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- CN1446786A CN1446786A CN 03115820 CN03115820A CN1446786A CN 1446786 A CN1446786 A CN 1446786A CN 03115820 CN03115820 CN 03115820 CN 03115820 A CN03115820 A CN 03115820A CN 1446786 A CN1446786 A CN 1446786A
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Abstract
A process for preparing dimethylether from synthetic gas features use of airflow-bed reactor. The catalyst suspended in liquid and the synthetic gas are respectively atomized by nozzles while come in the reactor. The inertial medium is condensed. The synthetic tail gas carrying product is filtered to remove the foam and catalyst and then comes in downstream steps. Its equipment is composed of an airflow-bed reactor consisting of upper airflow bed and lower bubbling bed, and a circulating pump. Its advantage is high output rate.
Description
Technical Field
The invention relates to a method and a device for synthesizing dimethyl ether by taking synthesis gas as a raw material.
Technical Field
Dimethyl ether is an aerosol, a refrigerant and a foaming agent with good performance, and has great potential particularly as clean civil fuel and vehicle fuel. There are various methods for producing dimethyl ether (DME), such as a liquid phase dehydration method of methanol, a vapor phase dehydration method of methanol, and a recently developed one-step synthesis method of dimethyl ether using synthesis gas as a raw material. The one-step method comprises two types of fixed beds and slurry beds (three-phase beds), and the main chemical reactions are as follows:
numerous patents disclose content relating to one-step processes, such as chinese patent publication nos. CN1382676A, CN1132664A, us US6,458,856B1, european patent EP1010683a 1.
The inventor considers that the method for efficiently synthesizing the dimethyl ether by taking the synthesis gas as the raw material solves the following key technologies: the reaction heat is removed quickly, the catalyst is not overheated, and the service life of the catalyst is prolonged; the retardation of the internal diffusion of the catalyst is eliminated, the utilization rate of the inner surface is improved, and the temperature gradient in catalyst particles is eliminated; the retardation of the diffusion of reaction components from the gas phase main body to the catalyst is reduced; the method improves the amount of the catalyst to treat the synthetic gas and improves the space-time yield. The methods and devices widely used at present have the disadvantages of one kind or the other, and the space-time yield is low.
Disclosure of Invention
The invention aims to solve the technical problem of disclosing a method and a device for producing dimethyl ether by using synthesis gas as a raw material through a circulating entrained flow bed, so as to overcome the defect of low space-time yield in the prior art.
The invention is conceived as follows:
aiming at the key technology, the invention takes the following countermeasures: adopting liquid inert medium to evaporate and remove reaction heat, and adopting a powder catalyst which at least passes through 200 meshes to eliminate internal diffusion and intra-particle temperature gradient; the entrained flow bed is adopted to reduce the thickness of a liquid film, further reduce the external diffusion resistance, increase the circulation amount of the catalyst and improve the space-time yield.
The invention adopts a fluidized bed reactor as a main reactor for synthesizing dimethyl ether. The fluidized bed reactor contains three phases: the gas phase is the evaporation component of the synthesis gas and the reaction products thereof, namely dimethyl ether, water vapor and liquid-phase inert medium; the liquid phase is a medium which is inert to the reaction, in particular a high-boiling liquid hydrocarbon, such as n-pentadecane; the solid phase is a catalyst, such as a conventional copper-based composite catalyst. The catalyst suspended in the liquid is pumped to the nozzle, and the synthesis gas enters the nozzle after being preheated, so that atomization and mixing are realized through the nozzle. After the synthesis gas is discharged from the nozzle, the liquid (containing or not containing the catalyst) forms a dispersed phase, and the synthesis gas is a continuous phase and moves from top to bottom to form an entrained flow. The main reaction process is carried out as follows: the synthetic gas diffuses from the gas main body to the inner and outer surfaces of the catalyst through a liquid film (wrapping the outer layer of the catalyst), adsorption and synthesis reaction are carried out on the surface of the catalyst, the product is desorbed from the surface of the catalyst, diffuses to the outer surface along the micropores of the catalyst, and then enters the gas main body through the liquid film. The heat released by the reaction is balanced by the heat absorption of the inert medium, and the gas enters the gas phase main body together. The medium from the three-phase entrained flow enters the bubbling bed through a downcomer, a small amount of synthetic dimethyl ether reaction can be continuously carried out in the bubbling bed, due to the cooling effect of a heat exchanger in the bubbling bed, the inert mediumgas phase is condensed, and finally the synthetic tail gas carrying the product enters a downstream process from an outlet after the foam and the catalyst carried by the synthetic tail gas are filtered by a filter from the upper part of the bubbling bed.
The method of the invention comprises the following steps:
the liquid inert medium containing the catalyst and the synthetic gas respectively pass through corresponding channels of a nozzle arranged at the top of the entrained flow reactor, enter the entrained flow reactor after being atomized, carry out dimethyl ether synthetic reaction and move from top to bottom.
After the atomization is realized through the nozzle, the droplet diameter of the droplets is in a wide distribution, the diameter is about 5-100 mu m, part of the droplets contain the catalyst, part of the droplets do not contain the catalyst, and the droplets containing the catalyst form a sphere with a catalyst core and a liquid film coated outside. Macroscopically, the droplets are the dispersed phase and the syngas is the continuous phase. The synthetic gas passes through the liquid film from the gas phase main body in a diffusion mode, reaches the inner surface of the catalyst in a diffusion mode in catalyst micropores, is subjected to adsorption and chemical reaction, and along with the release of reaction heat, heat enters the liquid film in a conduction mode to vaporize part of the liquid inert medium, and reaction products sequentially complete desorption, internal diffusion and diffusion penetrating through the liquid film to enter the gas phase main body. In the above-mentioned process, the heat of reaction is the heat of vaporization of inert medium and is removed by the entrained-flow bed jacket heat exchanger, so that the entrained-flow bed is in isothermal state, the axial and radial temperatures of the catalyst in-particle, out-particle and bed layers are basically the same, and thetemperature can be selected to match with the inert medium with proper boiling point.
The unreacted synthesis gas, catalyst, liquid and vapor inert medium enter the bubbling bed at the lower part of the reactor, the synthesis reaction is continuously carried out in the bubbling bed, the main function of the bubbling bed is heat exchange, namely, the vapor inert medium is condensed through a heat exchanger arranged in the bubbling bed, the vapor inert medium is subjected to phase change, heat is released, and the heat is taken away by a cooling medium. The cooling medium can be water, gas or heat conducting oil, so the entrained flow and bubbling bed temperatures are the same.
The liquid inert medium enters a circulating pump from a lower cone outlet of the bubbling bed, the inert medium with the solid content of 5-35% (wt) is pressurized and then distributed to a nozzle laid on the entrained flow bed, and the nozzle outlet speed is 1-30 m/s. And distributing the preheated synthesis gas to each branch pipe and then entering the nozzle, wherein the outlet nozzle speed is 50-300 m/s.
The foam and the catalyst carried by the synthetic tail gas carrying the product are filtered by a filter and enter a downstream procedure from an outlet, the catalyst obtained by filtering returns to a liquid phase without loss, and the liquid inert medium is sent to a nozzle at the top again for recycling.
The catalyst is a conventional dimethyl ether synthesis catalyst, such as a common copper-based composite catalyst. There are a number of patent documents reporting this.
The device for realizing the method at least comprises the following steps:
an entrained flow bed reactor, the upper part of which is an entrained flow bed and the lower part of which is a bubbling bed;
and a circulating pump connected to the bottom and top of the fluidized bed reactor via a pipeline.
The fluidized bed reactor comprises a sealed shell provided with a cooling jacket, a multi-channel nozzle and a heat exchanger, wherein the multi-channel nozzle is arranged at the upper part of the shell, the heat exchanger is arranged at the middle part of a bubbling bed, a synthetic tail gas outlet carrying a product is arranged at the upper part of the bubbling bed, and an outlet for an inert medium is arranged at the lower part of the bubbling bed.
The nozzle is a conventional device, but is preferably a two-channel, three-channel, four-channel, five-channel nozzle, such as the nozzles ZL95111750.5, ZL97235458.1, ZL94214422.8 proposed by the inventors.
The most obvious advantages of the invention can be seen from the above disclosed technical solutions: the space-time yield is high, the reaction heat is removed by adopting the evaporation of an inert medium, the temperature of the entrained flow bed is uniform, and the large-scale production is easy to realize.
Drawings
FIG. 1 is a flow chart of dimethyl ether production by an entrained flow bed.
FIG. 2 is a schematic diagram of the reactor configuration.
Fig. 3 is a schematic view along line a-a in fig. 2.
Fig. 4 is a schematic view of direction B-B in fig. 2.
Detailed Description
Referring to fig. 1 and 2, the apparatus of the present invention comprises:
a fluidized bed reactor 1, the upper part of whichis a fluidized bed and the lower part of which is a bubbling bed;
a circulation pump 2.
The three-phase fluidized bed reactor 1 comprises a shell 102 provided with a cooling jacket 101, a multi-channel nozzle 104 and a heat exchanger 107, wherein the multi-channel nozzle 104 is arranged at the upper part of the shell 102, the heat exchanger 107 is arranged at the middle lower part in the shell 102, and the middle part of the shell 102 is provided with a tail gas outlet 105 carrying products.
In the preferred embodiment of the present invention, the nozzle 104 may be disposed on the periphery and the top of the housing 102, or may be disposed on the periphery of the top of the housing 102, or only on the top of the housing 103. The nozzles arranged on the periphery of the shell 102 should be evenly distributed, and the axis of the nozzle 104 arranged on the top of the shell 102 should coincide with the axis of the entrained-flow reactor 1.
As can be seen from fig. 2, the housing 102 is provided with two syngas outlets 105 in the middle and with a filter 106, the two syngas outlets 105 being used alternately.
The bottom of the housing 102 is provided with a liquid inert medium outlet 103.
The circulating pump 2 is connected with the liquid inert medium outlet 103 at the bottom of the fluidized bed reactor 1 and the nozzle 104 at the top through pipelines.
The method for realizing the invention by adopting the device comprises the following steps:
the liquid inert medium containing the catalyst and the synthesis gas respectively pass through corresponding channels of a nozzle 104 arranged at the top of the entrained-flow bed reactor 1, are atomized and then enter the entrained-flow bed reactor 1 to carry out dimethyl ether synthesis reaction, and move from top to bottom. The unreacted synthesis gas, the catalyst and the liquid and vapor inert media enter a bubbling bed at the lower part of the reactor, the vapor inert media are cooled through a heat exchanger arranged in the bubbling bed, the vapor inert media are subjected to phase change, heat is released, and the heat is taken away by the cooling media. The cooling medium can be water, gas or heat conducting oil, so that the temperature of the entrained flow bed and the bubbling bed is the same.
The synthesis tail gas carrying the product is filtered by a filter 106, the foam and the catalyst carried by the synthesis tail gas enter a downstream process from an outlet 105, and the liquid inert medium is sent to a nozzle 104 at the top from a liquid inert medium outlet 103 at the bottom of the shell 102 again through a circulating pump 2 for recycling.
The liquid inert medium is n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane or a mixture thereof, and preferably n-pentadecane, n-hexadecane or a mixture thereof.
The solid content of the liquid inert medium containing the catalyst is 5-35% (wt), the speed of the liquid inert medium out of the nozzle 104 is 1-30 m/s, and the speed of the synthetic gas out of the nozzle 104 is 50-300 m/s.
The catalyst is a conventional dimethyl ether synthesis catalyst, such as a common copper-based composite catalyst, the reaction temperature is 250-302 ℃, and the reaction pressure is 3.0-10.0 Mp
Example 1
The synthesis gas is used as raw material, the production device produces 10 ten thousand tons of dimethyl ether annually, the dimethyl ether is produced in 13.89t per hour, and the gas composition of the gas inlet flow bed is as follows: h2＝48％，CO＝46％，CO2＝2％，CH44% of the totalweight. The synthetic gas pressure of the inlet airflow bed is 5.0Mpa, the temperature is 268 ℃, and the flow rate is 104000Nm3H is used as the reference value. The inert medium is n-pentadecane with a circulation volume of 196m3Suspended 42m in the circulating liquid3A catalyst.
The entrained flow bed adopts 4 nozzles which are uniformly arranged along the periphery of the upper part of the entrained flow bed, the nozzles adopt a three-channel mode, the spraying speed of the synthesis gas is 190m/s, the temperature of the inert medium containing the catalyst entering the entrained flow bed is 268 ℃, and the spraying speed is 8 m/s. The effective diameter of the entrained flow is 2m and the effective height is 7.5 m. About 1% of the n-pentadecane is vaporized. The effective height of the bubbling bed is 10m, saturated water of 1.0Mpa is adopted for cooling, and 30 tons of byproduct steam per hour are produced. The conversion rate of carbon monoxide is 45%, and the selectivity of dimethyl ether is 97%.
Claims (10)
1. A device for producing dimethyl ether by taking synthesis gas as raw material through a circulating entrained flow bed is characterized by comprising: a fluidized bed reactor (1) with an entrained flow bed at the upper part and a bubbling bed at the lower part; a circulation pump (2);
the fluidized bed reactor (1) comprises a shell (102) provided with a cooling jacket (101), a multi-channel nozzle (104) and a heat exchanger (107), wherein the multi-channel nozzle (104) is arranged at the upper part of the shell (102), the heat exchanger (107) is arranged at the middle lower part in the shell (102), a product-carrying tail gas outlet (105) is arranged in the middle of the shell (102), and a circulating pump (2) is communicated with a liquid inert medium outlet (103) at the bottom of the fluidized bed reactor (1) and the nozzle (104) at the top through pipelines.
2. The device according to claim 1, characterized in that the nozzles (104) are applied to the periphery and top of the housing (102).
3. The device of claim 1, wherein the nozzle (104) is disposed at a periphery of a top portion of the housing (102).
4. The device according to claim 1, wherein the nozzle (104) is arranged at the top of the housing (103).
5. An arrangement according to claim 1, characterized in that the housing (102) is provided with two syngas outlets (105) in the middle and with a filter (106).
6. The method for synthesizing dimethyl ether by using the device as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
the liquid inert medium containing the catalyst and the synthetic gas respectively pass through corresponding channels of a nozzle (104) arranged at the top of the fluidized bed reactor (1), the atomized liquid inert medium and the synthetic gas enter the fluidized bed reactor (1) to carry out dimethyl ether synthesis reaction, the atomized liquid inert medium and the atomized synthetic gas move from top to bottom, and the unreacted synthetic gas, the catalyst and the liquid and vapor inert medium enter a bubbling bed at the lower part of the reactor to be cooled.
The synthesis tail gas carrying the product is filtered by a filter (106) to carry foam and catalyst, and enters a downstream process from an outlet (105), and the liquid inert medium is sent to a nozzle (104) at the top from a liquid inert medium outlet (103) at the bottom of the shell (102) through a circulating pump (2) for recycling.
7. The process according to claim 6, wherein the liquid inert medium is n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane or a mixture thereof, preferably n-pentadecane, n-hexadecane or a mixture thereof.
8. The process according to claim 6, wherein the liquid inert medium containing the catalyst contains a solid content of 5 to 35% (wt).
9. The method according to claim 6, characterized in that the velocity of the liquid inert medium exiting the nozzle (104) is 1 to 30m/s and the velocity of the syngas exiting the nozzle 104 is 50 to 300 m/s.
10. The method according to any one of claims 6 to 9, wherein the catalyst is a conventional catalyst for dimethyl ether synthesis, such as a common copper-based composite catalyst, the reaction temperature is 250 to 302 ℃, and the reaction pressure is 3.0 to 10.0 Mp.
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| CN 03115820 CN1247506C (en) | 2003-03-14 | 2003-03-14 | Method and equips for manufacturing dimethyl ether with synthesis gas as raw material by using circulating current bed |
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| CN 03115820 CN1247506C (en) | 2003-03-14 | 2003-03-14 | Method and equips for manufacturing dimethyl ether with synthesis gas as raw material by using circulating current bed |
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| CN1446786A true CN1446786A (en) | 2003-10-08 |
| CN1247506C CN1247506C (en) | 2006-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106268574A (en) * | 2015-06-04 | 2017-01-04 | 北京化工大学 | A kind of method, device and application being realized selective catalysis reaction by regulation and control liquid film |
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| CN100556538C (en) | 2006-12-14 | 2009-11-04 | 太原理工大学 | A kind of slurried catalyst and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106268574A (en) * | 2015-06-04 | 2017-01-04 | 北京化工大学 | A kind of method, device and application being realized selective catalysis reaction by regulation and control liquid film |
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