CN107162872B - Low-pressure methanol synthesis process - Google Patents
Low-pressure methanol synthesis process Download PDFInfo
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- CN107162872B CN107162872B CN201710296261.6A CN201710296261A CN107162872B CN 107162872 B CN107162872 B CN 107162872B CN 201710296261 A CN201710296261 A CN 201710296261A CN 107162872 B CN107162872 B CN 107162872B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
Abstract
The invention relates to a low-pressure methanol synthesis process, wherein a primary reactor and a secondary reactor in the process both adopt a boiler water supply forced circulation heat transfer technology, the heat transfer is rapid and efficient, the arrangement of a device can be effectively simplified, the engineering investment of a device frame is reduced, and the problems of reduction of circulation multiplying power, unsatisfactory heat taking effect and the like caused by inaccurate calculation of the arrangement height of a steam pocket can be avoided; the circulation rate can be effectively improved through forced circulation, the reaction heat is efficiently and reasonably utilized, and the heat transfer effect is enhanced; the overline is arranged between the outlet of the synthesis gas compressor and the inlet of the secondary reactor, so that the stable operation of the catalyst of the secondary reactor at different stages of the service life is realized, the load of the reactor can be conveniently and powerfully adjusted through the overline, and the yield ratio of medium-pressure steam and low-pressure steam is flexibly adjusted; the fresh synthesis gas access position is arranged behind the synthesis gas temperature regulator, so that the heat exchange area and specification of the synthesis gas temperature regulator can be reduced, and the engineering investment is reduced.
Description
Technical Field
The invention relates to a low-pressure methanol synthesis process.
Background
Methanol is an important C1 chemical basic product and organic chemical raw material, and the synthesis of methanol is a reversible exothermic reaction with reduced volume. Since the successful development of high-temperature high-pressure gas-phase methanol synthesis process by basf corporation in germany in 1923, the methanol synthesis process has undergone the technological development process from high pressure to low pressure of synthesis gas, from high temperature to low temperature of synthesis gas and from adiabatic to isothermal of reactor. In recent years, with the progress of methanol synthesis technology and the continuous improvement of national requirements on energy consumption and environmental protection, the methanol synthesis technology is continuously developing towards large-scale, energy-saving and environmental protection.
The Chinese patent application with the application number of 201510658690.4 discloses an energy-saving type super-large-scale methanol synthesis method and device for producing steam with different grades, and the process has the following technical defects:
(1) The first methanol reactor and the second methanol reactor both adopt a natural circulation technology for removing reaction heat, and the technology has strict requirements on arrangement of a steam drum connected with the reactors, has the problems of low heat exchange efficiency, high investment, no contribution to large-scale reactors and the like;
(2) The lack of an effective reaction load adjustment means between the first reactor and the second reactor has two adverse consequences: firstly, when the catalysts of the first reactor and the second reactor are in different service life states, the load of the two-stage reactor connected in series cannot be effectively adjusted; secondly, the gas production of the medium-pressure steam drum and the low-pressure steam drum cannot be properly adjusted;
(3) The access position of fresh synthetic gas and circulating gas is reasonable inadequately, because fresh synthetic gas is great through the pressure ratio of compressor, and the temperature after the compression is higher, mixes with microthermal circulating gas this moment, causes the temperature of mixed gas to rise, carries out the heat transfer afterwards and can make the logarithmic mean temperature difference diminish, and then has increased heat transfer area, heat exchanger specification and engineering investment.
Therefore, the current methanol synthesis process is to be further improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a low-pressure methanol synthesis process which is rapid and efficient in heat transfer, convenient and powerful in reactor load adjustment and efficient and reasonable in reaction heat utilization aiming at the current situation of the prior art, and the process can greatly simplify the arrangement of devices and effectively reduce engineering investment and energy consumption.
The technical scheme adopted by the invention for solving the technical problems is as follows: a low-pressure methanol synthesis process is characterized by comprising the following steps:
pressurizing fresh synthesis gas by a synthesis gas compressor, mixing the pressurized fresh synthesis gas with the circulating gas preheated by the synthesis gas temperature regulator, preheating the mixture by a gas-gas heat exchanger, feeding the preheated mixture into a first-stage reactor, and carrying out methanol synthesis reaction under the action of a catalyst; cooling high-temperature first-stage reaction gas at the outlet of the first-stage reactor by a gas-gas heat exchanger, allowing the high-temperature first-stage reaction gas to enter a second-stage reactor for methanol synthesis reaction, allowing the high-temperature second-stage reaction gas at the outlet of the second-stage reactor to enter a synthesis gas temperature regulator to be cooled by circulating gas, cooling the high-temperature second-stage reaction gas by an air cooler and a water cooler in sequence, and allowing the high-temperature second-stage reaction gas to enter a separator for gas-liquid separation; the separated gas phase as circulating gas enters a circulating gas compressor to be pressurized and then returns to a synthesis loop, part of the separated circulating gas is discharged as purge gas, and the separated liquid phase crude methanol is output and sent to a downstream process for treatment;
feeding low-pressure boiler water from the outside into a low-pressure steam drum, pressurizing boiler feed water in the low-pressure steam drum through a low-pressure circulating pump, feeding the pressurized boiler feed water into a secondary reactor, removing reaction heat released during methanol synthesis reaction in the secondary reactor, and returning the low-pressure boiler feed water after absorbing heat to the low-pressure steam drum for steam-liquid phase separation to produce low-pressure saturated steam; the low-pressure saturated steam enters a synthesis gas compressor turbine to be used as driving steam;
the method comprises the following steps that (1) medium-pressure boiler water from the outside enters a medium-pressure steam drum, boiler feed water in the medium-pressure steam drum is pressurized by a medium-pressure circulating pump and then enters a first-stage reactor, reaction heat released during methanol synthesis reaction in the first-stage reactor is removed, the medium-pressure boiler feed water absorbing heat returns to the medium-pressure steam drum to perform steam-liquid phase separation, and medium-pressure saturated steam is produced; after the medium-pressure saturated steam is superheated by the hot furnace, part of the medium-pressure saturated steam is sent to a synthesis gas compressor turbine to be used as driving steam, and abundant medium-pressure superheated steam is output for use.
In the above scheme, the fresh synthesis gas is pressurized to 6.0 to 10.0MPaG in the synthesis gas compressor.
Preferably, the fresh synthesis gas is mixed with the recycle gas, preheated to 210-250 ℃ in a gas-gas heat exchanger and then enters the primary reactor.
Preferably, the temperature of the high-temperature first-stage reaction gas at the outlet of the first-stage reactor is 250-280 ℃, and the high-temperature first-stage reaction gas is cooled to 200-220 ℃ after passing through a gas-gas heat exchanger.
Preferably, the high-temperature secondary reaction gas at the outlet of the secondary reactor enters a synthesis gas temperature regulator, is cooled to 100-140 ℃ by circulating gas, is cooled to 60-80 ℃ by an air cooler, and is cooled to 35-45 ℃ by a water cooler.
Preferably, the purge gas to fresh synthesis gas molar ratio is from 3 to 5.
Preferably, the low-pressure drum produces 1.0-2.0 MPaG of low-pressure saturated steam after the steam-liquid phase separation.
Preferably, the vapor-liquid phase separation in the medium-pressure steam drum produces medium-pressure saturated steam of 2.5 to 4.0 MPaG.
Preferably, the medium-pressure saturated steam is superheated to 360-400 ℃ by a hot furnace.
Preferably, a crossover line capable of directly conveying the fresh synthesis gas from the synthesis gas compressor to the secondary reactor is arranged between the synthesis gas compressor and the secondary reactor. The structure is arranged so as to adjust the load distribution of the secondary reactor by adjusting the fresh synthesis gas amount entering the secondary reactor according to the activity degree of the catalyst in the primary reactor; of course, the load of the two-stage reactor can be adjusted according to the balance condition of the steam in the whole plant, so that the yield ratio of the two grades of steam can be adjusted.
Compared with the prior art, the invention has the advantages that:
according to the invention, the primary reactor and the secondary reactor both adopt a boiler water supply forced circulation heat transfer technology, so that heat transfer is fast and efficient, the installation heights and technical requirements of a medium-pressure steam drum and a low-pressure steam drum can be effectively reduced, the device arrangement is greatly simplified, the engineering investment of a device frame is reduced, and the problems of reduction of circulation multiplying power, unsatisfactory heat taking effect and the like caused by inaccurate calculation of the arrangement heights of the steam drums can be avoided; through forced circulation, the circulation rate can be effectively improved, the reaction heat is efficiently and reasonably utilized, and the heat transfer effect is enhanced, so that the specification and size of the reactor can be reduced;
the overline is arranged between the outlet of the synthesis gas compressor and the inlet of the secondary reactor, and the reaction load distribution of the secondary reactor is adjusted in actual operation, so that the stable operation of the catalyst of the secondary reactor at different stages of the service life is realized, and meanwhile, the load of the reactor can be conveniently and powerfully adjusted through the overline in normal operation, and further, the yield ratio of medium-pressure steam and low-pressure steam can be flexibly adjusted;
the fresh synthesis gas access position is arranged behind the synthesis gas temperature regulator, so that the heat exchange area and specification of the synthesis gas temperature regulator can be reduced, and the engineering investment is reduced.
Drawings
Fig. 1 is a schematic structural diagram of an embodiment of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
As shown in fig. 1, the low pressure methanol synthesis process of this example comprises the following steps:
fresh synthesis gas (main component H) from upstream process 2 、CO、CO 2 The molar ratio is as follows: (H) 2 -CO 2 )/(CO+CO 2 ) = 2.05-2.15) pressurizing to 6.0-10.0 MPaG by a synthesis gas compressor 2, mixing with circulating gas preheated by a synthesis gas temperature regulator 8, preheating to 210-250 ℃ by a gas-gas heat exchanger 4, entering two parallel primary reactors 5 and 6, and carrying out methanol synthesis reaction under the action of a copper-based methanol synthesis catalyst; the high-temperature first-stage reaction gas at the outlets of the first-stage reactors 5 and 6 has the temperature of 250-280 ℃, is cooled to 200-220 ℃ by the gas-gas heat exchanger 4, and enters the second-stage reactor 7 to continue the methanol synthesis reaction; the second-stage reaction gas at the outlet of the second-stage reactor 7 exchanges heat with the circulating gas through a synthesis temperature regulator 8, the synthesis temperature regulator 8 adopts a baffling rod type heat exchange structure to improve the heat exchange efficiency,cooling the secondary reaction gas to 100-140 ℃, cooling the secondary reaction gas to 60-80 ℃ through an air cooler 9 in sequence, cooling the secondary reaction gas to 35-45 ℃ through a water cooler 10, finally, introducing the secondary reaction gas into a separator 11 for gas-liquid separation, introducing the separated gas phase serving as circulating gas into a circulating gas compressor 3 for pressurization and returning the gas phase to a synthesis loop, and simultaneously, in order to prevent inert gas accumulation, discharging the separated part of the circulating gas serving as purge gas, and outputting the separated liquid phase crude methanol and sending the liquid phase crude methanol to a downstream process for continuous treatment;
low-pressure boiler water from a battery compartment enters a low-pressure steam drum 15, boiler feed water in the low-pressure steam drum 15 enters a secondary reactor 7 after being pressurized by a low-pressure circulating pump 16, heat emitted in the reaction of the secondary reactor 7 is removed, the low-pressure boiler feed water absorbing the heat returns to the low-pressure steam drum 15 for steam-liquid phase separation, low-pressure saturated steam of 1.0-2.0 MPaG is produced, and the low-pressure saturated steam enters a synthesis gas compressor turbine 1 and is used as drive steam;
feeding water from a medium-pressure boiler in a boundary area into a medium-pressure steam drum 12, pressurizing the feeding water of the boiler in the medium-pressure steam drum 12 through a medium-pressure circulating pump 13, then feeding the pressurized feeding water into first-stage reactors 5 and 6, removing heat released in the reactions of the first-stage reactors 5 and 6, returning the feeding water of the medium-pressure boiler after absorbing the heat to the medium-pressure steam drum 12 for steam-liquid phase separation, producing medium-pressure saturated steam of 2.5-4.0 MPaG, overheating the medium-pressure saturated steam to 360-400 ℃ through a heating furnace 14, partially feeding the medium-pressure saturated steam to a synthetic gas compressor turbine 1 to be used as driving steam, supplementing the insufficient part of the low-pressure steam, and feeding the abundant part of the medium-pressure superheated steam into a corresponding steam pipe network.
In this embodiment, a crossover a capable of directly delivering fresh synthesis gas from the synthesis gas compressor to the secondary reactor is arranged between the synthesis gas compressor 2 and the secondary reactor 7, so as to adjust the load distribution of the secondary reactor by adjusting the amount of fresh synthesis gas entering the secondary reactor according to the activity degree of the catalyst in the primary reactor; of course, the load of the two-stage reactor can be adjusted according to the balance condition of the steam in the whole plant, so that the yield ratio of the two grades of steam can be adjusted.
Compared with the methanol synthesis process in the prior art, the methanol synthesis process has the advantages that the advantages are mainly embodied in the heat transfer mode of the reactor, the reaction load regulation measure and the fresh synthesis gas access, the process of the embodiment adopts a forced circulation heat transfer technology, the requirement on steam drum arrangement is low, the heat exchange efficiency is high, the specification of the reactor is small, and the investment is low; reaction load regulation measures are provided, and the distribution of the load of the two-stage reactor and the output proportion of medium-pressure steam and low-pressure steam can be effectively regulated; the fresh synthesis gas is connected behind the synthesis gas temperature regulator, the synthesis gas temperature regulator has large heat transfer temperature difference, small heat exchange area and low equipment investment.
Claims (9)
1. A low-pressure methanol synthesis process is characterized by comprising the following steps:
pressurizing fresh synthesis gas by a synthesis gas compressor (2), mixing the fresh synthesis gas with the circulating gas preheated by a synthesis gas temperature regulator (8), preheating the fresh synthesis gas by a gas-gas heat exchanger (4), feeding the mixture into first-stage reactors (5 and 6), and carrying out methanol synthesis reaction under the action of a catalyst; high-temperature first-stage reaction gas at the outlets of the first-stage reactors (5 and 6) is cooled by a gas-gas heat exchanger (4) and enters a second-stage reactor (7) for methanol synthesis reaction, and high-temperature second-stage reaction gas at the outlet of the second-stage reactor (7) firstly enters a synthesis gas temperature regulator (8) to be cooled by circulating gas, then sequentially passes through an air cooler (9) and a water cooler (10) for cooling, and finally enters a separator (11) for gas-liquid separation; the separated gas phase as circulating gas enters a circulating gas compressor (3) for pressurization and then returns to a synthesis loop, part of the separated circulating gas is discharged as purge gas, and the separated liquid phase crude methanol is output and sent to a downstream process for treatment;
low-pressure boiler water from the outside is sent into a low-pressure steam drum (15), boiler feed water in the low-pressure steam drum (15) is pressurized by a low-pressure circulating pump (16) and then enters a secondary reactor (7), reaction heat emitted by the secondary reactor (7) during methanol synthesis reaction is removed, the low-pressure boiler feed water absorbing heat returns to the low-pressure steam drum (15) for steam-liquid phase separation, and low-pressure saturated steam is produced; the low-pressure saturated steam enters a synthesis gas compressor turbine (1) to be used as driving steam;
the method comprises the following steps that medium-pressure boiler water from the outside enters a medium-pressure steam drum (12), boiler feed water in the medium-pressure steam drum (12) is pressurized by a medium-pressure circulating pump (13) and then enters first-stage reactors (5 and 6), reaction heat emitted by the first-stage reactors (5 and 6) during methanol synthesis reaction is removed, the medium-pressure boiler feed water after heat absorption returns to the medium-pressure steam drum (12) to perform steam-liquid phase separation, and medium-pressure saturated steam is produced; after the medium-pressure saturated steam is superheated by the hot furnace (14), part of the medium-pressure saturated steam is sent to the synthesis gas compressor turbine (1) to be used as driving steam, and surplus medium-pressure superheated steam is output for use.
2. The low pressure methanol synthesis process of claim 1, wherein: and pressurizing the fresh synthesis gas to 6.0-10.0 MPaG in a synthesis gas compressor (2).
3. The low pressure methanol synthesis process of claim 1, wherein: the fresh synthesis gas and the circulating gas are mixed, preheated to 210-250 ℃ in a gas-gas heat exchanger (4) and then enter a first-stage reactor (5, 6).
4. A low pressure methanol synthesis process according to claim 1, characterized in that: the temperature of high-temperature first-stage reaction gas at the outlets of the first-stage reactors (5, 6) is 250-280 ℃, and the high-temperature first-stage reaction gas is cooled to 200-220 ℃ after passing through a gas-gas heat exchanger (4).
5. The low pressure methanol synthesis process of claim 1, wherein: and high-temperature secondary reaction gas at the outlet of the secondary reactor (7) enters a synthesis gas temperature regulator (8) and is cooled to 100-140 ℃ by circulating gas, then is cooled to 60-80 ℃ by an air cooler (9), and is cooled to 35-45 ℃ by a water cooler (10).
6. The low pressure methanol synthesis process of claim 1, wherein: and the low-pressure saturated steam of 1.0-2.0 MPaG is produced after the steam-liquid phase separation in the low-pressure steam drum (15).
7. The low pressure methanol synthesis process of claim 1, wherein: and the vapor-liquid phase in the medium-pressure steam drum (12) is separated to produce medium-pressure saturated steam of 2.5-4.0 MPaG.
8. A low pressure methanol synthesis process according to claim 7, wherein: the medium-pressure saturated steam is superheated to 360-400 ℃ through a hot furnace (14).
9. The low pressure methanol synthesis process of claim 1, wherein: and a cross wire (a) capable of directly conveying fresh synthesis gas from the synthesis gas compressor to the secondary reactor is arranged between the synthesis gas compressor (2) and the secondary reactor (7).
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| CN109232179B (en) * | 2018-09-30 | 2022-03-22 | 中石化宁波工程有限公司 | Methanol synthesis process |
| CN109384647A (en) * | 2018-10-25 | 2019-02-26 | 中石化南京工程有限公司 | A kind of transformation methanolizing integrated production equipment and method |
| CN110066214A (en) * | 2019-05-27 | 2019-07-30 | 河北金牛旭阳化工有限公司 | A kind of methanol synthesizer and the method using the device synthesizing methanol |
| CN110215886B (en) * | 2019-06-05 | 2021-07-27 | 国家能源投资集团有限责任公司 | Reaction temperature control method for reactor for preparing low-carbon alcohol from synthesis gas |
| CN113548945A (en) * | 2021-07-29 | 2021-10-26 | 中国石油天然气股份有限公司 | Low-temperature activity utilization process of catalyst |
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| CN102850183A (en) * | 2012-09-28 | 2013-01-02 | 神华集团有限责任公司 | Methanol synthesis system and method |
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| CN103232321A (en) * | 2013-04-09 | 2013-08-07 | 中石化宁波工程有限公司 | Large-scale methanol synthesis process |
| CN105399604A (en) * | 2015-10-12 | 2016-03-16 | 上海国际化建工程咨询公司 | Energy-efficient super-large scale methanol-synthesizing method with production of steam of different grades and apparatus thereof |
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Patent Citations (4)
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| CN102850183A (en) * | 2012-09-28 | 2013-01-02 | 神华集团有限责任公司 | Methanol synthesis system and method |
| CN202808648U (en) * | 2012-09-28 | 2013-03-20 | 神华集团有限责任公司 | Methanol synthetic system |
| CN103232321A (en) * | 2013-04-09 | 2013-08-07 | 中石化宁波工程有限公司 | Large-scale methanol synthesis process |
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