CN114671731B - Method for improving yield of low-carbon olefin in MTP (methanol to propylene) reaction - Google Patents
Method for improving yield of low-carbon olefin in MTP (methanol to propylene) reaction Download PDFInfo
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- CN114671731B CN114671731B CN202210357324.5A CN202210357324A CN114671731B CN 114671731 B CN114671731 B CN 114671731B CN 202210357324 A CN202210357324 A CN 202210357324A CN 114671731 B CN114671731 B CN 114671731B
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- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
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Abstract
The invention relates to the technical field of chemical separation, in particular to a method for improving the yield of low-carbon olefin in an MTP reaction, which comprises the following steps: the alkane and alkene in the recycle hydrocarbon stream are separated, and the alkene-rich stream is sent back to the MTP reactor for reaction. By adopting the method, the content of olefin in the circulating hydrocarbon is improved on the premise of ensuring the total circulating amount, the advantage of the multi-carbon olefin in the MTP reaction to assist in low-carbon olefin production is effectively exerted, the output of a target product is effectively improved, the energy consumption of the device is reduced, and the quality improvement and the efficiency improvement are realized; preferably, the side extraction device is provided, so that the energy consumption of C4 olefin cyclic evaporation can be saved, the condensing load of the separation tower can be reduced, and the separation efficiency can be effectively improved.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a method for improving the yield of low-carbon olefin in an MTP reaction.
Background
Coal-based olefins are non-petroleum process routes for methanol synthesis using coal as a feedstock. The coal-based olefin plant of the national energy group Ningxia coal industry group adopts MTP process technology developed by Lurgi company of Germany, and the technology is used for producing low-carbon olefin by a two-step method. One of the outstanding features of this process is the need for recycle hydrocarbons in the same proportion as the feed methanol to be recycled back to the reactor to participate in the olefin synthesis.
One of the prominent characteristics of MTP reaction is that the circulating hydrocarbon with the same proportion as the feed methanol is needed to participate in the reaction, and the circulating hydrocarbon consumes energy in the circulating process, which is a main reason for higher energy consumption of MTP reaction compared with the similar process. In the MTP reaction design, the main olefin component in the circulating hydrocarbon participates in the MTP reaction, the energy consumed by alkane which is represented as an inert component in the circulating process is ineffective, the yield of ethylene is directly influenced by C2 circulating hydrocarbon which participates in the circulation, and the contribution of olefin in C4 circulating hydrocarbon to a target product is maximum, so that the olefin has better reaction activity and excellent conversion rate. In the actual operation process, the improvement of propylene yield is facilitated by adjusting the proportion of each circulating hydrocarbon. The general adjustment principle is to reduce C2 and properly increase the circulating amount of C4 and C5/C6 under the premise of ensuring the total amount of circulating hydrocarbon. These means of adjustment are based only on optimization of the circulation amount, and do not reduce the ineffective circulation of alkane, which tends to increase the energy consumption, thus not playing a positive role in terms of the energy consumption of the device.
In the recent 10 years of MTP operation, process optimization mainly surrounds material separation, reaction regeneration, catalyst upgrading and the like, and process optimization of circulating hydrocarbon is not reported yet. According to the characteristics of MTP reaction, the existing process conditions and the properties of various byproducts are fully utilized, an alkane-alkene separation process is designed, the yield of target products is improved, and the non-energy consumption is effectively reduced.
Disclosure of Invention
The invention provides an alkane-alkene separation device and a method in a coal-based methanol-to-propylene process, which are used for separating alkane from alkene in a circulating hydrocarbon stream in an MTP reaction, so that the content of alkene in the circulating hydrocarbon is improved on the premise of ensuring the total circulating amount, the output of a target product is effectively improved, and the energy consumption of the device can be reduced.
In order to achieve the above object, the present invention provides a method for increasing the yield of low-carbon olefin in an MTP reaction, the method comprising: the alkane and alkene in the recycle hydrocarbon stream are separated, and the alkene-rich stream is sent back to the MTP reactor for reaction.
Preferably, the recycle hydrocarbon stream is a stream comprising C4 hydrocarbon components; further preferably, the mass content of C4 hydrocarbon components in the recycle hydrocarbon stream is 93wt% or more; more preferably, the recycle hydrocarbon stream comprises: c4 alkanes, C4 alkenes, methanol, dimethyl ether, and water.
Preferably, the recycle hydrocarbon stream is a C4 hydrocarbon component, preferably the recycle hydrocarbon stream contains: c4 olefins, C4 olefins, methanol, dimethyl ether, and water.
Preferably, where the recycle hydrocarbon stream is a stream comprising C4 paraffins, C4 olefins, methanol and dimethyl ether, the C4 hydrocarbon components are separated to produce a paraffin rich vapour stream and an olefin rich liquid stream, the process comprising:
condensing the vapor stream enriched in alkanes to obtain a liquid phase component and a gaseous phase component; the liquid phase component is liquefied petroleum gas, and is extracted; the gas phase component is sent back to the MTP reactor;
the olefin-rich liquid stream is sent back to the MTP reactor after gasification.
Preferably, the C4 hydrocarbon component separation conditions include: the theoretical plate number is 75-90, the feeding position is 36-45 plates away from the tower bottom, the reflux ratio is 16-18, the pressure at the tower top is controlled to be 0.7-0.8 MPa, the temperature at the tower top is controlled to be 50-60 ℃, the temperature at the tower bottom is controlled to be 85-105 ℃, and the pressure difference at the tower is controlled to be 50-150 kPa.
Preferably, the separation of the C4 hydrocarbon components is performed in an apparatus comprising a separation column, an evaporator and a superheater:
the separation tower is used for separating C4 hydrocarbon components to obtain tower top vapor rich in alkane and tower bottom liquid rich in alkene; the separation tower also comprises a tower top condenser and a reboiler which are matched with the separation tower;
the condenser is used for controlling the temperature of the top of the separation tower and condensing the vapor at the top of the separation tower to obtain a liquid phase component and a gas phase component; the liquid phase component is liquefied petroleum gas, and the gas phase component returns to the MTP reactor after being sent to the superheater;
the reboiler is used for controlling the bottom temperature of the separation tower;
the evaporator evaporates and gasifies the bottom liquid rich in olefin, and then sends the bottom liquid to the superheater and then returns to the MTP reactor. In the whole circulating reaction system, in order to ensure the completeness of the feed components and improve the separation efficiency of the separation tower, a side steam distillate is not added on the separation tower.
Preferably, a sidedraw is also provided in the separation column for adding sidedraw vapor distillate.
Preferably, the side draw position is located 10-15 trays below the top of the separation column.
According to a preferred embodiment of the invention, the side suction pressure is 0.715-0.725MPa
According to a preferred embodiment of the invention, the flow rate of the side draw is 10% -15%.
Preferably, the side stream vapor distillate is sent to a superheater and returned to the MTP reactor for reaction.
Preferably, the condensed separated vapor phase component, bottoms vapor and sidedraw vapor distillate are fed to the MTP reactor after being mixed in the superheater.
Compared with the prior art, the technical scheme provided by the invention has at least the following advantages:
1. the separation device is used for separating alkane and alkene in the circulating hydrocarbon material flow in the MTP reaction, and the content of alkene in the circulating hydrocarbon is improved on the premise of ensuring the total circulating amount, so that the yield of target products is improved, and the energy consumption of the device is reduced.
2. The invention provides a method and a separation device for C4 alkane and alkene in a process for preparing propylene from methanol, wherein the separation device is used for designing an alkane-alkene separation process for C4 hydrocarbon components produced by taking Liquefied Petroleum Gas (LPG) as a byproduct in an MTP reaction, so that the content of alkene in circulating hydrocarbon is improved on the premise of ensuring the total circulating amount, the advantage of multi-carbon alkene in the MTP reaction for assisting in producing low-carbon alkene is brought into play, the output of a target product is effectively improved, the energy consumption of the device is reduced, and the quality and efficiency are improved; preferably, the side extraction device is provided, so that the energy consumption of C4 olefin cyclic evaporation can be saved, the condensing load of the separation tower can be reduced, and the separation efficiency can be effectively improved.
Drawings
FIG. 1 shows a C4 alkane alkene separation device in a process for preparing propylene from coal-based methanol in accordance with one embodiment of the present invention;
FIG. 2 shows a C4 alkane alkene separation device in a process for preparing propylene from coal-based methanol according to another embodiment of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for improving the yield of low-carbon olefin in MTP reaction, which comprises the following steps: and (3) separating alkane from alkene in the circulating hydrocarbon stream, and sending the alkene-rich stream back to the MTP reactor to participate in the reaction, thereby improving the yield of the target product and reducing the energy consumption.
In the MTP reaction according to the invention, the improvement of propylene yield is facilitated by adjusting the ratio of the recycle hydrocarbon streams, preferably a C4 hydrocarbon component-containing stream; further preferably, the mass content of C4 hydrocarbon components in the recycle hydrocarbon stream is 93wt% or more; more preferably, the recycle hydrocarbon stream comprises: c4 alkanes, C4 alkenes, methanol, dimethyl ether, and water.
According to the invention, in the MTP reaction, the olefin in the C4 recycle hydrocarbon contributes most to the target product (propylene) in each recycle hydrocarbon component, preferably the recycle hydrocarbon stream is a C4 hydrocarbon component, preferably the recycle hydrocarbon stream contains: c4 alkanes, C4 alkenes, methanol, and dimethyl ether.
According to the present invention, in order to better achieve the improvement of the content of C4 olefins in the circulating hydrocarbon while effectively reducing the circulation of the inactive components under the premise of ensuring the total circulating amount, preferably, the C4 hydrocarbon component separation conditions include: the theoretical plate number is 75-90, the feeding position is 36-45 plates away from the tower bottom, the reflux ratio is 16-18, the pressure at the tower top is controlled to be 0.7-0.8 MPa, the temperature at the tower top is controlled to be 50-60 ℃, the temperature at the tower bottom is controlled to be 85-105 ℃, and the pressure difference at the tower is controlled to be 50-150 kPa.
According to the method, alkane-alkene separation is designed for C4 hydrocarbon components produced by taking Liquefied Petroleum Gas (LPG) as a byproduct in an MTP reaction, on the premise of ensuring the total circulating amount, the content of alkene in circulating hydrocarbon is improved, the output of a target product is effectively improved, and the energy consumption of a device is reduced, preferably, when the circulating hydrocarbon stream is the C4 hydrocarbon component, the C4 hydrocarbon components are separated to obtain a vapor stream rich in alkane and a liquid stream rich in alkene, and the method comprises the following steps:
condensing the vapor stream enriched in alkanes to obtain a liquid phase component and a gaseous phase component; the liquid phase component is liquefied petroleum gas, and is extracted; the gas phase component is sent back to the MTP reactor;
the olefin-rich liquid stream is sent back to the MTP reactor after gasification.
According to the present invention, in order to better achieve the aim of increasing the olefin content in the circulating hydrocarbon under the premise of ensuring the total circulating amount, preferably, the separation of the C4 hydrocarbon components is carried out in a device comprising a separation column, an evaporator and a superheater; the separation tower also comprises an overhead condenser and a reboiler matched with the separation tower:
the separation tower is used for separating C4 hydrocarbon components to obtain tower top vapor rich in alkane and tower bottom liquid rich in alkene;
the tower top condenser is used for controlling the temperature of the top of the separation tower and condensing the vapor at the top of the separation tower to obtain a liquid phase component and a gas phase component; the liquid phase component is liquefied petroleum gas, and the gas phase component returns to the MTP reactor after being sent to the superheater;
the reboiler is used for controlling the bottom temperature of the separation tower;
the evaporator evaporates and gasifies the bottom liquid rich in olefin, and then sends the bottom liquid to the superheater and then returns to the MTP reactor.
According to the invention, the separation tower increases the purification rate of isobutane and simultaneously reduces the purification rate of n-butane, so that the C4 circulating hydrocarbon is accumulated in the whole closed cycle process, until the purification rate of n-butane and the generation rate of n-butane in the MTP reactor reach a new balance, the proportion of isobutane to n-butane in the feed of the separation tower is changed, the n-butane in the circulating hydrocarbon needs to be separated, and in order to reduce the separation tower provided with n-butane and reduce the loss of olefin, a side pump is arranged in the separation tower, and is used for increasing side steam distillate and taking a small part of isobutane into circulation; the side extraction is arranged, so that the energy consumption of C4 olefin cyclic evaporation is saved, the condensing load of the separation tower can be reduced, and the separation efficiency is improved.
According to the present invention, in order to enhance the separation efficiency of C4 olefins and paraffins while achieving separation of n-butane, isobutane and olefins, it is preferable that the side draw position is located at 10 to 15 trays below the top of the separation column.
According to the invention, in order to improve the separation efficiency of C4 alkene and alkane and simultaneously realize separation of normal butane, isobutane and alkene, preferably, the side pumping pressure is 0.715-0.725MPa, and the flow is 10% -15% of the total flow.
According to the invention, in order to better realize the aim of improving the content of olefin in the circulating hydrocarbon under the premise of ensuring the total circulating amount, the side steam distillate is preferably sent to a superheater and returned to the MTP reactor to participate in the reaction.
According to the present invention, in order to better achieve the improvement of the olefin content in the circulating hydrocarbon under the premise of ensuring the total circulating amount, it is preferable that the condensed and separated gas phase component, the bottom liquid vapor and the side vapor distillate are fed to the MTP reactor after being mixed in the superheater.
According to the method, the separation device is adopted to design the alkane-alkene separation for the C4 hydrocarbon component produced by taking Liquefied Petroleum Gas (LPG) as a byproduct in the MTP reaction, so that the content of olefin in circulating hydrocarbon is improved on the premise of ensuring the total circulating amount, the output of a target product is effectively improved, and the energy consumption of the device is reduced.
The invention has no special limitation to an MTP reactor, in particular to a reactor for preparing propylene from methanol, which is well known in the field, and the process is designed to participate in the reaction by circulating hydrocarbon in the same proportion as raw material methanol, wherein the reaction is a fixed bed catalytic reaction, and the reaction temperature is 480+/-5 ℃.
FIG. 1 shows a C4 alkane alkene separation device in a process for preparing propylene from coal-based methanol in accordance with one embodiment of the present invention; the operation method comprises the following steps: the liquefied petroleum gas is separated by a separation tower, the temperature of the tower top is controlled by a tower top condenser, the temperature of the tower bottom is controlled by a reboiler, the tower top vapor is used for condensing liquid phase components and gas phase components, the liquid phase components are extracted in the form of LPG, and the gas phase components are sent to a superheater and then sent back to an MTP reactor for reaction; the bottom liquid of the separation tower is sent to an evaporator for gasification and then sent to a superheater; and then returned to the MTP reactor to participate in the reaction.
FIG. 2 shows a C4 alkane alkene separation device in a process for preparing propylene from coal-based methanol according to another embodiment of the present invention. The operation method comprises the following steps: the liquefied petroleum gas is separated by a separation tower, the temperature of the tower top is controlled by a tower top condenser, the temperature of the tower bottom is controlled by a reboiler, the tower top vapor is used for condensing liquid phase components and gas phase components, the liquid phase components are extracted in the form of LPG, and the gas phase components are sent to a superheater and then sent back to an MTP reactor for reaction; the bottom liquid of the separation tower is sent to an evaporator for gasification, then sent to a superheater and sent back to the MTP reactor for reaction; the separation tower is laterally pumped, a side steam distillate is added, and the side steam distillate is sent to a superheater and then is sent back to the MTP reactor to participate in the reaction.
Example 1
According to the embodiment of fig. 1; when the recycle hydrocarbon stream is a stream comprising C4 paraffins, C4 olefins, methanol and dimethyl ether, wherein the mass of C4 olefins and C4 paraffins is 94wt%;
the theoretical plate number of the separation tower is 90, the feeding position is 36, the reflux ratio is 16, the tower top pressure is controlled to be 0.7MPa, the tower top temperature of the separation tower is controlled to be 50 ℃, the tower bottom temperature is controlled to be 95 ℃, and the tower pressure difference is controlled to be 150kPa. Can realize the separation of 76% of alkane, the residual hydrocarbon participates in the circulation, and the ratio of the alkene in the circulation hydrocarbon is obviously improved.
Compared with the original MTP reaction system in which most of C4 hydrocarbons are extracted in the form of LPG, the invention increases the ratio of olefins while improving the total circulating amount by increasing the separation of C4 alkane and the LPG to participate in circulation after separating alkane.
Example 2
According to the embodiment of fig. 2; when the recycle hydrocarbon stream is a stream comprising C4 paraffins, C4 olefins, methanol and dimethyl ether, wherein the mass of C4 olefins and C4 paraffins is 94wt%;
the theoretical plate number of the separation tower is 90, the feeding position is 36, the reflux ratio is 16, the tower top pressure is controlled to be 0.7MPa, the side pumping position is positioned at 15, the side pumping pressure is 0.725MPa, the tower top temperature of the separation tower is controlled to be 50 ℃, the tower bottom temperature is controlled to be 85 ℃, and the tower pressure difference is controlled to be 150kPa. 62% alkane separation can be achieved, increasing the proportion of olefins in the recycle hydrocarbon. By side pumping, a small amount of isobutane participates in circulation, so that the influence on the proportion unbalance of C4 alkane in the MTP reactor and the overall product distribution are avoided.
Compared with the original MTP reaction system in which most of C4 hydrocarbons are extracted in the form of LPG, the invention increases the separation of C4 alkane and alkene, and the LPG participates in circulation after alkane is separated, thereby improving the proportion of alkene while realizing the total circulation; the side extraction is increased, so that the energy consumption of C4 olefin cyclic evaporation can be saved, and the condensing load of the separation tower can be reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (3)
1. A method for improving the yield of low-carbon olefin in MTP reaction is characterized in that,
the process is carried out in an apparatus comprising a separation column, an evaporator and a superheater; the separation tower also comprises a tower top condenser and a reboiler which are matched with the separation tower;
the separation tower is used for separating C4 hydrocarbon components to obtain tower top vapor rich in alkane and tower bottom liquid rich in alkene;
the tower top condenser is used for controlling the temperature of the top of the separation tower and condensing the vapor at the top of the separation tower to obtain a liquid phase component and a gas phase component; the liquid phase component is liquefied petroleum gas, and the gas phase component returns to the MTP reactor after being sent to the superheater;
the reboiler is used for controlling the bottom temperature of the separation tower;
the evaporator is used for evaporating and gasifying the tower bottom liquid rich in olefin, and sending the tower bottom liquid to the superheater and then back to the MTP reactor;
the separation tower is also provided with a side draw for adding side steam distillate; the side suction position is positioned 10-15 tower plates below the top of the separation tower;
the method comprises the following steps: separating paraffins from olefins in a recycle hydrocarbon stream, the recycle hydrocarbon stream comprising: c4 alkane, C4 alkene, methanol, dimethyl ether and water, wherein the mass content of C4 hydrocarbon components is more than or equal to 93wt%;
separating the C4 hydrocarbon component in a separation column to obtain an alkane-rich vapor stream and an alkene-rich liquid stream;
condensing the vapor stream enriched in alkanes to obtain a liquid phase component and a gaseous phase component; the liquid phase component is liquefied petroleum gas, and is extracted; the gas phase component is sent back to the MTP reactor;
the olefin-rich liquid stream is sent back to the MTP reactor after gasification;
the side pumping pressure is 0.715-0.725Mpa;
the side pumping flow is 10% -15%;
the side stream vapor distillate is sent to a superheater and returned to the MTP reactor to participate in the reaction.
2. The method of claim 1, wherein the recycle hydrocarbon stream separation is performed in a separation column, the separation conditions comprising:
the theoretical plate number is 75-90, the feeding position is 36-45 plates away from the tower bottom, the reflux ratio is 16-18, the pressure at the tower top is controlled to be 0.7-0.8 MPa, the temperature at the tower top is controlled to be 50-60 ℃, the temperature at the tower bottom is controlled to be 85-105 ℃, and the pressure difference at the tower is controlled to be 50-150 kPa.
3. The process of claim 1 wherein the condensed separated vapor phase component, bottoms liquid vapor and sidedraw vapor distillate are fed to the MTP reactor after being mixed in a superheater.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109070A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Methanol-to-propylene product separation method |
| CN206886986U (en) * | 2017-06-22 | 2018-01-16 | 神华集团有限责任公司 | System for propylene enhancing in process for preparing propylene from methanol |
| CN110041157A (en) * | 2019-05-10 | 2019-07-23 | 国家能源投资集团有限责任公司 | A method of it improving preparing propylene from methanol yield and extends catalyst life |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109070A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Methanol-to-propylene product separation method |
| CN206886986U (en) * | 2017-06-22 | 2018-01-16 | 神华集团有限责任公司 | System for propylene enhancing in process for preparing propylene from methanol |
| CN110041157A (en) * | 2019-05-10 | 2019-07-23 | 国家能源投资集团有限责任公司 | A method of it improving preparing propylene from methanol yield and extends catalyst life |
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