CN110550601B - Transformation process for high-concentration CO raw material gas - Google Patents
Transformation process for high-concentration CO raw material gas Download PDFInfo
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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Abstract
The invention relates to a conversion process for high-concentration CO raw material gas, which has wide application range and is suitable for a carbon monoxide conversion technical process matched with coal chemical industry, wherein the volume content of a carbon monoxide dry basis is 30-90 percent, and the volume ratio of water to absolute dry gas is 0.1-1.6; the process flow is short, the system resistance is low, the water-vapor mixing heat transfer shift converter synthesizes the two-stage and three-stage conversion in the traditional adiabatic conversion process flow into the first-stage reaction, not only reduces the number of equipment, but also saves an intermediate waste heat exchanger, shortens the process flow and reduces the system resistance; the invention solves the problems of easy over-temperature and difficult temperature control of the transformation reaction of the high-concentration CO raw material gas, the self-produced high-pressure saturated steam can be superheated, an external superheater does not need to be arranged or is in thermal combination with other devices, and the investment and the operation difficulty are reduced.
Description
Technical Field
The invention relates to a transformation process for high-concentration CO raw material gas.
Background
At present, in advanced coal gasification processes at home and abroad, an entrained flow bed process is widely applied industrially, and mainly comprises two main types of coal water slurry gasification and pulverized coal gasification, wherein the pulverized coal gasification is divided into a waste boiler type and a chilling type due to different cooling modes of high-temperature synthesis gas. A representative waste boiler type process includes a Shell pulverized coal gasification process introduced abroad; the chilling type process comprises a GSP (ground coal gasification) process introduced abroad and a pulverized coal gasification process developed autonomously at home, such as an aerospace furnace and an oriental furnace. The dry-based volume content of the CO in the synthesis gas produced by the gasification devices is usually up to more than 60 percent, wherein the water-gas ratio of the chilling type powder gasification synthesis gas is between the traditional high water-gas ratio and the traditional low water-gas ratio and is 0.7-1.0, the high-concentration CO shift reaction is the most severe in the water-gas ratio range, and the temperature can be up to more than 500 ℃, so that the reaction temperature can be controlled by reducing the water-gas ratio, improving the water-gas ratio or adopting other means.
The low water-gas ratio shift process controls the water-gas ratio of the synthesis gas entering a first shift converter to be 0.1 to 0.4 to limit the conversion rate of CO so as to achieve the purpose of controlling the reaction temperature. However, the risk of methanation reaction under the conditions of high temperature and low water-gas ratio is increased suddenly, so that the temperature runaway of the shift converter is easy to occur, the activity of the catalyst is reduced rapidly, the catalyst is replaced frequently, and the long-period stable operation of the device is influenced. For example, the invention discloses a low water/gas ratio sulfur-tolerant shift process for pulverized coal gasification, which is disclosed in the Chinese patent with the application number of CN200710087573.2, and the invention is improved on the basis of the traditional low water-gas ratio process, the water-gas ratio of the synthesis gas entering a first shift furnace is adjusted to 0.15 to 0.20, and the reaction space velocity is improved to 6000 to 9000h -1 The hot spot temperature of the reaction is reduced, and the aim of controlling the temperature is fulfilled; the process has the advantages that the temperature is controllable and the occurrence of methanation side reaction can be inhibited when the process is under normal load, but the risk of methanation reaction occurring at high temperature of the first shift converter also exists under the low-load working condition or the start working condition.
The high water-gas ratio conversion process is to prevent the first conversion furnace from overtemperature, and a large amount of superheated steam is added at the inlet of the conversion furnace at one time to ensure that the water-gas ratio reaches 1.3 to 1.5 or even higher. For a hydrogen production or ammonia synthesis device, carbon monoxide in synthesis gas needs to be completely converted into hydrogen, so the reaction depth is large, and the water-gas ratio is usually required to be more than 1.2 to meet the requirement; however, for the coal-to-carbonyl synthesis gas (including methanol synthesis, synthetic oil, synthetic natural gas and the like), the total water-gas ratio can meet the requirement of adjusting the hydrogen-carbon ratio without reaching 1.2, so that the energy consumption of the device is high by additionally supplementing steam, and the investment is large. In addition, for plants with low sulfur content in the raw material gas, the anti-vulcanization phenomenon occurs due to high temperature and high water-gas ratio, and the sulfur content in the process gas is increased by using high-sulfur coal or adding sulfur, so that normal production can be maintained, and the selection range of the process is limited. For example, in the invention patent CN200610018566.2, which discloses a high-concentration carbon monoxide graded conversion process, steam is added into the synthesis gas, the water-gas ratio is increased to 0.9 to 1.1, the residence time of the synthesis gas in the first converter is controlled to 1~2 seconds, and the purpose of controlling the reaction temperature is achieved; however, the invention supplements more steam, increases energy consumption, and simultaneously, the water-gas ratio entering the first shift converter is not high enough, so that the risk of overtemperature exists.
The low water-gas ratio and the high water-gas ratio are the traditional conversion process matched with the high-concentration CO synthetic gas, and have the problems of long process flow, difficult control of reaction temperature, large engineering investment, large system resistance and the like, so the isothermal conversion technology is developed at the same time. Isothermal transformation is to utilize heat transfer water tube bundles embedded in a catalyst bed layer to convert the reaction heat of the catalyst bed layer and the redundant low-grade heat energy of a system into high-grade steam, and simultaneously reduce the temperature of the catalyst bed layer, improve the reaction driving force and prolong the service life of the catalyst. With the maturity and industrial application of isothermal technology, isothermal shift converters are diversified, such as an axial isothermal reactor and its supporting process proposed in "an isothermal shift reactor with built-in tube bundle" with application number CN201410455211.4, a radial flow by-product steam isothermal shift converter "with application number CN201420618039.5, an isothermal shift system for removing CO in raw gas" with application number CN201520522410.2, and an isothermal adiabatic radial composite reactor with application number CN 201410334970.5.
However, in the existing isothermal conversion process, most of reaction heat of the isothermal conversion furnace is taken away by a water circulation system, the temperature of an outlet of the isothermal conversion furnace is only about 300 ℃, and a superheat source cannot be provided, so that byproduct steam of a steam drum of the isothermal conversion furnace cannot be superheated, and only a heating furnace is arranged independently or is subjected to heat combination with other devices, so that the complexity of the process and the equipment investment are increased. The utility model patent "high concentration carbon monoxide isothermal conversion system" with application number CN201520139308.4 proposes an adiabatic + isothermal conversion process, and the steam produced by the isothermal conversion furnace is saturated steam, and can not be overheated.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a conversion process for high-concentration CO raw material gas, which has the advantages of simple flow, reliable system, small methanation side reaction, small system resistance, good system temperature control, long service life of a catalyst, and low equipment investment and operation cost.
The technical scheme adopted by the invention for solving the technical problems is as follows: a shift conversion process for high concentration CO feed gas is characterized in that: comprises the following steps
Separating entrained moisture from the upstream crude synthesis gas containing high-concentration CO by a gas-liquid separator, and then feeding the crude synthesis gas into a low-pressure steam generator to produce low-pressure steam as a byproduct, and simultaneously reducing the water-gas ratio of the crude synthesis gas;
the outlet crude synthesis gas is subjected to condensate separation by a gas-liquid separator, heated to the activation temperature of the shift catalyst by a crude synthesis gas heater, and filtered to remove dust and toxic substances by a detoxification tank;
the purified feed gas is divided into two paths, one part of the feed gas enters a steam heat transfer shift converter and a high-pressure steam superheater in sequence, high-pressure steam produced by the steam heat transfer shift converter or outside the steam heat transfer shift converter is preheated, and then the high-pressure steam enters a high-pressure steam generator to produce high-pressure saturated steam as a byproduct; the shifted gas at the outlet of the high-pressure steam generator is mixed with the other part of the crude synthesis gas and then is sent to a water-vapor mixing heat transfer shift converter to preheat boiler water and produce a high-pressure steam as a byproduct;
the waste heat exchanger is used for extracting heat from the waste heat in the converted gas and then the converted gas enters a downstream low-grade heat recovery system by combining the whole plant process flow or the public engineering arrangement, or a section of conversion reactor is arranged after the waste heat is recovered according to the requirement of downstream products on the hydrogen-carbon ratio.
In the above scheme, the steam heat-transfer shift converter comprises a vertically arranged cylindrical shell, a first central pipe which vertically extends along a central axis and is used for collecting and guiding the converted gas after reaction to exit the reactor is arranged in the shell, a steam heat-transfer area is arranged on the periphery of the first central pipe, a raw synthesis gas inlet annular gap is formed between the periphery of the steam heat-transfer area and the inner wall of the shell, a conversion gas partition plate which can divide the shell into an upper section and a lower section which are relatively independent from each other is arranged in the shell, a first raw synthesis gas inlet pipe communicated with the upper section is arranged at the top of the shell, and a saturated steam inlet pipe and a superheated steam outlet pipe are connected to the bottom of the shell. Preferably, the shift gas partition plate is arranged at 1/2 of the total height of the catalyst bed layer, and shift catalysts are filled in the upper section and the lower section. Preferably, the shell is provided with a plurality of U-shaped steam heating pipes penetrating through the upper section and the lower section, and the catalyst is filled in gaps of the U-shaped steam heating pipes.
Preferably, the top of the shell is provided with an upper end enclosure, the bottom of the shell is provided with a lower end enclosure, a steam inlet and outlet partition plate capable of dividing a port of the U-shaped steam heating pipe into an inlet and an outlet is arranged in the lower end enclosure, the saturated steam inlet pipe is connected with the inlet of the U-shaped steam heating pipe, the superheated steam outlet pipe is connected with the outlet of the U-shaped steam heating pipe, and the saturated steam flowing in the U-shaped steam heating pipe takes away the heat of the conversion reaction to obtain superheated steam and outputs the superheated steam from the superheated steam outlet pipe. Preferably, the lower part of the upper section is provided with an upper section catalyst discharge pipe; the lower part of the lower section is provided with a lower section catalyst discharge opening; the upper part of the lower section is connected with a second crude synthesis gas feeding pipe and a first control valve positioned on the second crude synthesis gas feeding pipe, the second crude synthesis gas feeding pipe at the downstream of the first control valve is connected with a sealing gas feeding pipe, and the sealing gas feeding pipe is provided with a switch valve.
Preferably, when the raw gas passes through the steam heat transfer shift converter according to the designed full load of the split gas, the switch valve of the sealed gas feeding pipe is closed, the first control valve of the second feeding pipe of the raw synthesis gas is opened, the raw synthesis gas enters the two sections of steam heat transfer areas for reaction through the uniform distribution of the gas feeding annular gap, the reacted shift gas enters the central pipe and finally leaves the shift converter through the shift gas outlet; and when the load is reduced to below 50%, closing the first control valve of the second feeding pipe of the crude synthesis gas, allowing the crude synthesis gas to only pass through the upper-section steam heat transfer area for reaction, opening the switch valve of the sealing gas feeding pipe at the moment, and introducing sealing gas into the lower-section steam heat transfer area. The sealing gas is a continuous high-pressure gas which has no influence on the reaction and the final product.
Preferably, the water-vapor mixing heat-transfer shift converter comprises a vertically arranged cylinder body, a second central pipe which vertically extends along a central axis and is used for collecting and guiding the converted gas after reaction out of the reactor is arranged in the cylinder body, a water heat transfer area, a water-vapor heat transfer area and a converted gas inlet annular gap which can be uniformly distributed in the raw synthesis gas of the shift converter are sequentially arranged outwards along the radial direction on the periphery of the second central pipe, shift catalysts are filled in the water heat transfer area and the water-vapor heat transfer area, a plurality of vertical extending and penetrating tubes are arranged in the cylinder body, and low-temperature boiler water is introduced into the water heat transfer area tubes and used for taking away the reaction heat and simultaneously preheating the boiler water; high-temperature boiler water is introduced into the tube nest of the water vapor heat transfer area to lead out reaction heat in time, and high-grade saturated steam is produced as a byproduct.
Preferably, a first boiler water collection and liquid collection end socket connected with a water heat transfer area array pipe is arranged at the end part of the water heat transfer area, the first boiler water collection and liquid collection end socket at the top of the cylinder body is connected with a steam drum through a high-temperature boiler water lifting main pipe, the first boiler water collection and liquid collection end socket at the bottom of the cylinder body is connected with a low-temperature boiler water supply pipe, and the first boiler water collection and liquid collection end socket, the low-temperature boiler water supply pipe, the high-temperature boiler water lifting main pipe and the steam drum jointly form a steam drum water supply system; the end part of the water vapor heat transfer area is provided with a second boiler water collection liquid sealing head connected with a water vapor heat transfer area tube, the second boiler water collection liquid sealing head at the top of the barrel is connected with the steam drum through a steam ascending tube, the second boiler water collection liquid sealing head at the bottom of the barrel is connected with the steam drum through a high-temperature boiler water descending tube, and the second boiler water collection liquid sealing head, the steam ascending tube, the steam drum and the high-temperature boiler water descending tube jointly form a saturated steam generation system.
Preferably, the high-temperature boiler water ascending main pipe is provided with a branch high-temperature boiler water ascending branch pipe, and the branch pipe is provided with a second control valve capable of providing high-temperature boiler water for the device according to requirements.
In the scheme, the positions of the water heat transfer area and the water vapor heat transfer area can be interchanged so as to adapt to different gasification technologies and transformation process flows, and finally the purposes that the temperature of the water vapor mixing heat transfer transformation furnace is controllable and the reaction depth meets the requirement are achieved. A low-temperature boiler water supply pipe can be connected to the high-temperature boiler water lifting main pipe, and the low-temperature boiler water supply pipe is opened or closed as required to provide boiler water for steam generation for the steam drum. The waste heat exchanger can be connected with a shift converter according to the product requirements so as to improve the carbon monoxide conversion rate and meet the downstream hydrogen-carbon ratio requirement.
The conversion gas enters the conversion furnace from the conversion gas inlet and radially enters the water vapor heat transfer region from the gas inlet annular gap, the conversion gas is reacted to release heat, and the reaction temperature of the catalyst bed layer is basically stable at a low temperature due to the heat transfer effect of the water vapor in the row pipes of the water vapor heat transfer region, so that the reaction temperature of the water vapor heat transfer region is controllable. The shift gas from the water-vapor heat transfer zone enters the water-heat transfer zone to continue shift reaction, and the temperature of the shift reaction is reduced compared with the reaction temperature of the catalyst bed layer in the water-vapor heat transfer zone due to the heat transfer effect of low-temperature boiler water in the tube array of the water-heat transfer zone, and the equilibrium constant of the shift reaction is increased along with the reduction of the temperature, so the depth of the shift reaction is further improved on the premise of ensuring that the reaction is not over-temperature. Boiler water from the outside forms a natural circulation system through a pipeline between the steam drum and the shift converter body, the density difference of the steam and the boiler water is used as a driving force, and when the saturated steam pressure output by the steam drum is certain, the shift reaction can be controlled not to be over-temperature.
The catalyst is discharged from a catalyst discharge pipe positioned at the lower end socket of the reactor.
In each scheme, the dry volume content of carbon monoxide in the crude synthesis gas containing high-concentration CO from upstream is 30-90%, the volume of water/dry gas is 0.1-1.6, and the pressure range is 1.0-9.0 MPaG. The byproduct saturated vapor pressure range of the low-pressure steam generator is 0.1 to 2.5MPaG. The byproduct saturated steam pressure range of the high-pressure steam generator is 2.5-8.0 MPaG. The raw synthesis gas heater is formed by combining one or more heat exchangers in series or in parallel, and the outlet temperature of the raw synthesis gas is 150-350 ℃.
Preferably, the waste heat exchanger is a combination of one or more heat exchangers connected in series or in parallel, and one side of the heat exchanger is provided with a cold fluid, which can include but is not limited to process materials, public engineering media, and the like, such as desalted water, low-pressure saturated steam, raw synthesis gas, boiler feed water, and the like. The hot fluid on the other side of the heat exchanger is transformed gas, and the outlet temperature is 50-400 ℃.
Preferably, the downstream low grade heat recovery is a combined system of one or more devices for cooling the shift gas and separating the condensate, which may include, but is not limited to, a steam generator, a desalted water preheater, a boiler feed water preheater, a gas-liquid separator, a scrubber, and the like.
Further, the sealing gas can be nitrogen, steam or process gas; preferably, the gas from the outlet of the recycle gas compressor of the downstream low-temperature methanol washing device can be selected.
The invention can also reduce or increase the number of the shift gas baffle plates according to the treatment gas quantity and the reaction depth of the shift converter, and the arrangement positions can be different according to the actual requirements.
Compared with the prior art, the invention has the advantages that: the invention has wide application range and is suitable for the carbon monoxide conversion technical process matched with the coal chemical industry, the volume content of the carbon monoxide dry basis is 30 to 90 percent, and the volume ratio of water to absolute dry gas is 0.1 to 1.6; the process flow is short, the system resistance is low, the water-vapor mixing heat transfer shift converter synthesizes the two-stage and three-stage conversion in the traditional adiabatic conversion process flow into the first-stage reaction, not only reduces the number of equipment, but also saves an intermediate waste heat exchanger, shortens the process flow and reduces the system resistance; the invention solves the problems of easy over-temperature and difficult temperature control of the transformation reaction of the high-concentration CO feed gas, the self-produced high-pressure saturated steam can be superheated without arranging an external superheater or being thermally combined with other devices, and the investment and the operation difficulty are reduced.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the invention;
FIG. 2 is a schematic structural diagram of the steam heat-transfer shift converter in FIG. 1;
FIG. 3 is a schematic structural view of the steam-mixing heat-transfer shift converter in FIG. 1;
FIG. 4 is another process flow 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 shift process equipment for high concentration CO feed gas of the present embodiment comprises: the system comprises a 1# gas-liquid separator 1, a low-pressure steam generator 2, a 2# gas-liquid separator 3, a crude synthesis gas heater 4, a detoxification tank 5, a steam heat transfer shift converter 6, a high-pressure steam superheater 7, a high-pressure steam generator 8, a water-steam mixing heat transfer shift converter 9, a waste heat exchanger 10 and a shift reactor 11.
The system comprises a 1# gas-liquid separator 1, a low-pressure steam generator 2, a low-pressure boiler water replenishing inlet, a low-pressure steam generator 2, a raw synthesis gas heater 4, a detoxifying tank 5, a steam heat-transfer conversion furnace 6, a sealed gas replenishing pipeline, a steam heat-transfer conversion furnace 6 and a steam heat-transfer conversion furnace 6, wherein the side part of the 1# gas-liquid separator 1 is provided with a feed inlet for inputting raw synthesis gas, the bottom of the 1# gas-liquid separator 1 is provided with an outlet for outputting materials, the outlet is connected with an inlet of the low-pressure steam generator 2, the low-pressure steam generator 2 is provided with an inlet for replenishing low-pressure boiler water, the outlet of the low-pressure steam generator 2 is connected with an inlet of the side part of the 2# gas-liquid separator 3, the bottom of the 2# gas-liquid separator 3 is provided with an outlet for outputting high-pressure process condensate, the top of the 2# gas-liquid separator 3 is provided with an outlet connected with an inlet of the raw synthesis gas heater 4, the outlet of the raw synthesis gas heater 4 is connected with an inlet of the detoxifying tank 5, the outlet of the bottom of the detoxifying tank 5 is divided into two ways, one way is connected with the inlet of the steam heat-transfer conversion furnace 6, and the sealed gas heat-transfer conversion furnace is provided with the pipeline for replenishing; an input port for inputting high-pressure saturated steam is arranged at the bottom of the steam heat-transfer shift converter 6, one output port at the bottom of the steam heat-transfer shift converter 6 outputs high-pressure superheated steam, the other output port is connected with the input end of the high-pressure steam superheater 7, one output port of the high-pressure steam superheater 7 outputs high-pressure superheated steam, the other output port of the high-pressure steam superheater 7 is connected with the input end of the high-pressure steam generator 8, the output end of the high-pressure steam generator 8 is connected with the top input end of the water-vapor mixed heat-transfer shift converter 9 after being converged with the other path at the bottom of the detoxification tank 5, the bottom output end of the water-vapor mixed heat-transfer converter 9 is sequentially connected with a waste heat exchanger 10 and a shift reactor 11, and the bottom of the shift reactor 11 is provided with an output port;
the top of the water-vapor mixed heat transfer shift converter 9 is provided with an output pipeline which is divided into two paths, one path of the output pipeline is used for producing saturated steam and is connected with an input port at the bottom of the steam heat transfer shift converter 6, and the other path of the high-temperature boiler water is connected with an input end of the high-pressure steam generator 8; a pipeline for outputting byproduct saturated steam is connected between the high-pressure steam superheater 7 and the high-pressure steam generator 8; the bottom of the water-vapor mixing heat transfer shift converter 9 is provided with an input end for inputting water of the low-temperature boiler.
As shown in fig. 2, the steam heat-transfer shift converter 6 of the present embodiment includes a vertically arranged cylindrical shell 61, the shell 61 is provided with a first central pipe 213 extending vertically along a central axis and used for collecting and guiding the reacted shift gas out of the reactor, the periphery of the first central pipe 213 is provided with a steam heat-transfer area 211, a raw syngas intake annular space 212 is formed between the periphery of the steam heat-transfer area 211 and the inner wall of the shell 61, the shell 61 is provided with a shift gas baffle 28 capable of dividing the shell into an upper section 611 and a lower section 612 which are vertically independent, the top of the shell 61 is provided with a raw syngas first feed pipe 23 communicated with the upper section 611, the bottom of the shell 61 is connected with a saturated steam inlet pipe 21 and a superheated steam outlet pipe 22, and the bottom of the shell 61 is further provided with a shift gas outlet 216.
Specifically, the shift gas partition plate 28 is disposed at 1/2 of the total height of the catalyst bed, and the shift catalyst is filled in both the upper section 611 and the lower section 612. The casing 61 is provided with a plurality of U-shaped steam heating pipes 210 penetrating the upper and lower sections 611 and 612, and a catalyst is filled in the gap between the U-shaped steam heating pipes 210. The top of the shell 61 is provided with an upper end enclosure, the bottom of the shell is provided with a lower end enclosure, a steam inlet-outlet clapboard 29 which can divide the port of the U-shaped steam heating pipe 210 into an inlet and an outlet is arranged in the lower end enclosure, the saturated steam inlet pipe 21 is connected with the inlet of the U-shaped steam heating pipe 210, the superheated steam outlet pipe 22 is connected with the outlet of the U-shaped steam heating pipe 210, and the saturated steam flowing in the U-shaped steam heating pipe 210 takes away the heat of the conversion reaction to obtain superheated steam and outputs the superheated steam from the superheated steam outlet pipe 22. The lower part of the upper section 611 is provided with an upper section catalyst discharge pipe 214; the lower portion of the lower section 612 is provided with a lower section catalyst discharge opening 215. A second raw synthesis gas feed pipe 24 and a first control valve 26 provided on the second raw synthesis gas feed pipe 24 are connected to the upper portion of the lower section 612, a seal gas feed pipe 25 is connected to the second raw synthesis gas feed pipe 24 downstream of the first control valve 26, and an on-off valve 27 is provided on the seal gas feed pipe 25.
As shown in fig. 3, the water-vapor mixing heat-transfer shift converter 9 of the present embodiment includes a vertically arranged cylinder 91, a second central tube 317 is disposed in the cylinder 91, the second central tube 317 extends vertically along a central axis and is used for collecting and guiding the converted gas after reaction out of the reactor, a water heat-transfer region 39, a water-vapor heat-transfer region 310 and a converted gas inlet annular gap 311 capable of uniformly distributing the raw synthesis gas into the converter are sequentially disposed outward from the periphery of the second central tube 317 in the radial direction, both the water heat-transfer region 39 and the water-vapor heat-transfer region 310 are filled with a shift catalyst, a plurality of vertically extending and penetrating tubes are disposed in the cylinder 91, low-temperature boiler water is introduced into the water heat-transfer region tubes 312 for taking away reaction heat and preheating boiler water; high-temperature boiler water is introduced into the water vapor heat transfer area array pipe 313 to lead out reaction heat in time, and high-grade saturated steam is produced as a byproduct.
Specifically, a first boiler water collecting end socket 314 connected with a water heat transfer area array pipe 312 is arranged at the end part of the water heat transfer area 39, the first boiler water collecting end socket 314 at the top of the cylinder 91 is connected with the steam drum 32 through a high-temperature boiler water rising main pipe 34, the first boiler water collecting end socket 314 at the bottom of the cylinder is connected with a low-temperature boiler water supply pipe 37, and the first boiler water collecting end socket 314, the low-temperature boiler water supply pipe 37, the high-temperature boiler water rising main pipe 34 and the steam drum 32 jointly form a steam drum water supply system; the end part of the water vapor heat transfer area 310 is provided with a second boiler water collecting end socket 315 connected with a water vapor heat transfer area tube array 313, the second boiler water collecting end socket 315 at the top of the cylinder body is connected with the steam drum 32 through a steam rising tube 38, the second boiler water collecting end socket 315 at the bottom of the cylinder body is connected with the steam drum 32 through a high-temperature boiler water descending tube 36, and the second boiler water collecting end socket 315, the steam rising tube 38, the steam drum 32 and the high-temperature boiler water descending tube 36 jointly form a saturated steam generating system. The high-temperature boiler water rising main pipe 34 is provided with a branch high-temperature boiler water rising branch pipe 35 which is provided with a second control valve 33 capable of providing high-temperature boiler water for the device according to the requirement. The top of the steam drum 32 has a saturated steam outlet 31. The cylinder 91 has a shift gas inlet 316 at the top and a shift gas outlet 319 at the bottom. The catalyst is discharged from a catalyst discharge tube 318 located at the lower head of the reactor.
In this embodiment, the positions of the water heat transfer region 39 and the water vapor heat transfer region 310 may be interchanged to adapt to different gasification technologies and transformation processes, so as to achieve the purposes of controllable temperature and satisfactory reaction depth of the water vapor mixing heat transfer transformation furnace. A low-temperature boiler water supply pipe can be connected to the high-temperature boiler water lifting main pipe, and the low-temperature boiler water supply pipe is opened or closed as required to provide boiler water for steam generation for the steam drum. The waste heat exchanger can be connected with a shift converter according to the product requirements so as to improve the carbon monoxide conversion rate and meet the downstream hydrogen-carbon ratio requirement.
The shift conversion process for high concentration CO feed gas of this example comprises the following steps:
as shown in FIG. 4, the raw synthesis gas from a chilling process pulverized coal gasification device, which has a temperature of 206 ℃, a pressure of 3.84MPaG, a carbon monoxide dry basis content of 70% and a water-gas ratio of 0.93, firstly enters a No. 1 gas-liquid separator 1 to separate water entrained in the raw synthesis gas, then passes through a No. 1 low-pressure steam generator 2 to produce a byproduct of 0.4MPaG saturated steam, the temperature is reduced to 182 ℃, and then the raw synthesis gas enters a No. 2 gas-liquid separator 3 to separate condensate. The raw synthesis gas at the top outlet of the 2# gas-liquid separator 3 enters a raw synthesis gas heater 4 to exchange heat with the shift gas at the outlet of a water-vapor mixing heat transfer shift converter 9 to 200 ℃, and then is subjected to impurity removal by a detoxification tank 5 to be divided into two parts, wherein one part accounts for about 40% of the total gas amount and enters a steam heat transfer shift converter 6, the superheated water-vapor mixing heat transfer converter 9 produces 3.6MPaG saturated steam to 383 ℃, the temperature is reduced to 380 ℃, and the saturated steam sequentially passes through a high-pressure steam superheater 7 and a high-pressure steam generator 8 and then is mixed with another raw synthesis gas. The temperature of the mixed conversion gas is 230 ℃ below zero, the mixed conversion gas directly enters a water-steam mixed heat transfer shift converter 9 for reaction, 3.6MPaG saturated steam is byproduct, low-temperature boiler water is preheated to 220 ℃ from 132 ℃, and the temperature of the conversion gas is reduced to 260 ℃. The shifted gas is preheated by a crude synthesis gas heater 4, then sent to a waste heat exchanger 10 to recover low-grade heat, and finally sent to a downstream device.
When the raw gas passes through the steam heat transfer shift converter according to the designed full load of the split gas amount, the switch valve 27 of the seal gas feeding pipe 25 is closed, the first control valve 26 of the second feeding pipe 24 of the raw synthesis gas is opened, the raw synthesis gas uniformly enters the two sections of steam heat transfer areas 211 through the gas inlet annular gap 212 for reaction, the reacted shift gas enters the central pipe 213, and finally leaves the shift converter through the shift gas outlet 216; when the load is reduced to below 50%, the first control valve 26 of the second feeding pipe 24 of the raw synthesis gas is closed, the raw synthesis gas is only reacted in the upper steam heat-transfer area 211, and the switch valve 27 of the sealing gas feeding pipe 25 is opened to feed the sealing gas to the lower steam heat-transfer area 211.
When the conversion gas enters the water-vapor mixing heat transfer shift converter 9 from the conversion gas inlet 316, the conversion gas radially enters the water-vapor heat transfer region 39 from the gas inlet annular gap 311, the conversion gas is reacted to release heat, and the reaction temperature of the catalyst bed layer is basically stable at a low temperature due to the heat transfer effect of the water vapor in the water-vapor heat transfer region tube 313, so that the reaction temperature of the water-vapor heat transfer region 39 is controlled. The shift gas from the water-vapor heat transfer zone enters the water-vapor heat transfer zone 310 to continue the shift reaction, and the reaction temperature of the catalyst bed layer in the water-vapor heat transfer zone is reduced compared with that of the catalyst bed layer in the water-vapor heat transfer zone 39 due to the heat transfer effect of low-temperature boiler water in the water-vapor heat transfer zone tubes 312, and the equilibrium constant of the shift reaction is increased along with the reduction of the temperature, so the shift reaction depth is further improved on the premise of ensuring that the reaction is not over-temperature. Boiler water from the outside forms a natural circulation system through a pipeline between the steam drum 32 and the shift converter body, the density difference of the steam and the boiler water is used as a driving force, and when the saturated steam pressure output by the steam drum is certain, the shift reaction can be controlled not to be over-temperature.
Claims (9)
1. A shift conversion process for high concentration CO feed gas is characterized in that: comprises the following steps
Separating entrained moisture from the upstream crude synthesis gas containing high-concentration CO by a gas-liquid separator, and then feeding the crude synthesis gas into a low-pressure steam generator to produce low-pressure steam as a byproduct, and simultaneously reducing the water-gas ratio of the crude synthesis gas;
the outlet crude synthesis gas is subjected to condensate separation by a gas-liquid separator, heated to the activation temperature of the shift catalyst by a crude synthesis gas heater, and filtered to remove dust and toxic substances by a detoxification tank;
the purified feed gas is divided into two paths, one part of the purified feed gas enters a steam heat transfer shift converter and a high-pressure steam superheater in sequence, high-pressure steam from the production or outside is preheated, and then the high-pressure steam enters a high-pressure steam generator to produce a high-pressure saturated steam as a byproduct; mixing the shift gas at the outlet of the high-pressure steam generator with the other part of the crude synthesis gas, sending the mixture to a water-steam mixing heat transfer shift converter, preheating boiler water and producing a high-pressure steam as a byproduct;
combining the whole plant process flow or the public engineering setting, utilizing a waste heat exchanger to take heat from the waste heat in the conversion gas, and then feeding the heat into a downstream low-grade heat recovery system, or according to the requirement of downstream products on the hydrogen-carbon ratio, arranging a section of conversion reactor after the waste heat is recovered;
the steam heat-transfer shift converter comprises a cylindrical shell which is vertically arranged, a first central pipe which vertically extends along a central axis and is used for collecting and guiding converted gas after reaction to be discharged out of the reactor is arranged in the shell, a steam heat-transfer area is arranged on the periphery of the first central pipe, a crude synthesis gas inlet annular gap is formed between the periphery of the steam heat-transfer area and the inner wall of the shell, a conversion gas partition plate which can divide the shell into an upper section and a lower section which are relatively independent from each other is arranged in the shell, a first crude synthesis gas inlet pipe communicated with the upper section is arranged at the top of the shell, and a saturated steam inlet pipe and an overheated steam outlet pipe are connected to the bottom of the shell;
the volume content of carbon monoxide dry basis in the crude synthesis gas containing high-concentration CO from the upstream is 30-90%;
the range of the byproduct saturated vapor pressure of the low-pressure steam generator is 0.1 to 2.5MPaG; the byproduct saturated steam pressure range of the high-pressure steam generator is 2.5-8.0 MPaG.
2. The shift conversion process for a high concentration CO feed gas of claim 1, wherein: the conversion gas partition plate is arranged at 1/2 of the total height of the catalyst bed layer, and conversion catalysts are filled in the upper section and the lower section.
3. The shift conversion process for a high concentration CO feed gas according to claim 2, characterized in that: the shell is internally provided with a plurality of U-shaped steam heating pipes which penetrate through the upper section and the lower section, and the catalyst is filled in the gaps of the U-shaped steam heating pipes.
4. The shift conversion process for a high concentration CO feed gas according to claim 3, characterized in that: the top of casing has the upper cover, the bottom has the low head, be provided with in the low head and divide the port of U type steam heating pipe for the steam exit baffle of import and export, the saturated steam inlet pipe is connected with the import of U type steam heating pipe, superheated steam outlet pipe is connected with the export of U type steam heating pipe, the heat of transform reaction is taken away to the saturated steam that circulates in the U type steam heating pipe obtains superheated steam and exports from the superheated steam outlet pipe.
5. The shift conversion process for a high concentration CO feed gas of claim 1, wherein: the lower part of the upper section is provided with an upper section catalyst discharge pipe; the lower part of the lower section is provided with a lower section catalyst discharge opening; the upper part of the lower section is connected with a second crude synthesis gas feeding pipe and a first control valve positioned on the second crude synthesis gas feeding pipe, the second crude synthesis gas feeding pipe at the downstream of the first control valve is connected with a sealing gas feeding pipe, and the sealing gas feeding pipe is provided with a switch valve.
6. The shift conversion process for a high concentration CO feed gas of claim 1, wherein: when the raw gas passes through the steam heat transfer shift converter according to the designed full load of the split gas quantity, the switch valve of the sealed gas feeding pipe is closed, the first control valve of the second feeding pipe of the raw synthesis gas is opened, the raw synthesis gas enters the two sections of steam heat transfer areas for reaction through the uniform distribution of the gas feeding annular space, the converted gas after the reaction enters the central pipe and finally leaves the shift converter through the converted gas outlet; when the load is reduced to below 50 percent, the first control valve of the second feeding pipe of the crude synthesis gas is closed, the crude synthesis gas only passes through the upper section steam heat transfer area for reaction, at the moment, the switch valve of the sealing gas feeding pipe is opened, and sealing gas is introduced into the lower section steam heat transfer area.
7. The shift conversion process for a high concentration CO feed gas according to any one of claims 1 to 6, wherein: the water-vapor mixed heat-transfer shift converter comprises a vertically arranged cylinder body, a second central pipe which extends vertically along a central axis and is used for collecting and guiding reacted shift gas out of a reactor is arranged in the cylinder body, a water heat transfer area, a water-vapor heat transfer area and a shift gas inlet annular gap of crude synthesis gas which can be uniformly distributed in the shift converter are sequentially arranged outwards along the radial direction on the periphery of the second central pipe, shift catalysts are filled in the water heat transfer area and the water-vapor heat transfer area, a plurality of vertical extending and penetrating tubes are arranged in the cylinder body, low-temperature boiler water is introduced into the water heat transfer area tubes and used for taking away reaction heat, and boiler water is preheated; high-temperature boiler water is introduced into the tube nest of the water vapor heat transfer area to lead out reaction heat in time, and high-grade saturated steam is produced as a byproduct.
8. The shift conversion process for a high concentration CO feed gas of claim 7, wherein: the end part of the water heat transfer area is provided with a first boiler water collection liquid sealing head connected with a water heat transfer area array pipe, the first boiler water collection liquid sealing head at the top of the cylinder body is connected with a steam drum through a high-temperature boiler water lifting main pipe, the first boiler water collection liquid sealing head at the bottom of the cylinder body is connected with a low-temperature boiler water supply pipe, and the first boiler water collection liquid sealing head, the low-temperature boiler water supply pipe, the high-temperature boiler water lifting main pipe and the steam drum form a steam drum water supply system together; the end part of the water vapor heat transfer area is provided with a second boiler water collection liquid sealing head connected with a water vapor heat transfer area tube, the second boiler water collection liquid sealing head at the top of the cylinder body is connected with the steam drum through a steam ascending tube, the second boiler water collection liquid sealing head at the bottom of the cylinder body is connected with the steam drum through a high-temperature boiler water descending tube, and the second boiler water collection liquid sealing head, the steam ascending tube, the steam drum and the high-temperature boiler water descending tube jointly form a saturated steam generation system.
9. The shift conversion process for a high concentration CO feed gas of claim 8, wherein: the high-temperature boiler water rising main pipe is provided with a branch high-temperature boiler water rising branch pipe, and a second control valve capable of providing high-temperature boiler water for the device according to requirements is arranged on the branch pipe.
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CN111268645B (en) * | 2020-01-21 | 2022-04-08 | 华烁科技股份有限公司 | CO-containing raw material gas conversion and heat recovery method |
CN111718760B (en) * | 2020-06-23 | 2021-03-02 | 中国华能集团清洁能源技术研究院有限公司 | Sulfur-tolerant methanation system and method for coal-based natural gas |
CN113479843B (en) * | 2021-07-06 | 2023-02-10 | 中石化宁波工程有限公司 | Carbon monoxide segmented heat transfer semi-reaction conversion process with adjustable water-gas ratio for oxo synthesis |
CN113460959B (en) * | 2021-07-06 | 2022-09-06 | 中石化宁波工程有限公司 | High-concentration carbon monoxide full-conversion segmented heat transfer process with bypass control |
CN113460962B (en) * | 2021-07-06 | 2022-10-11 | 中石化宁波工程有限公司 | Long-period transformation process for adjusting water-gas ratio by one-step method for oxo synthesis |
CN114152113A (en) * | 2021-11-03 | 2022-03-08 | 华能核能技术研究院有限公司 | High temperature resistant type heat exchanger |
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