CN110790223B - Transformation hydrogen production method matched with coal water slurry gasification device and isothermal transformation furnace - Google Patents
Transformation hydrogen production method matched with coal water slurry gasification device and isothermal transformation furnace Download PDFInfo
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Abstract
The invention relates to a conversion hydrogen production method and an isothermal conversion furnace matched with a coal water slurry gasification device, wherein crude gas from the coal water slurry gasification device is divided into two streams after heat recovery, condensate separation, heat exchange and detoxification; the first stream of purified gas enters an adiabatic shift converter for adiabatic shift, the obtained adiabatic shift gas is mixed with the second stream of purified gas after heat is recovered, the mixture enters a first reaction cavity of an isothermal shift converter for medium temperature shift reaction, and medium pressure saturated steam is a byproduct; then the mixture enters a second reaction cavity of the isothermal shift converter to carry out low-temperature shift reaction, and low-pressure saturated steam is produced as a byproduct; the dry basis content of CO in the conversion gas discharged from the isothermal conversion furnace is 0.2-0.4 v%, the dry basis content of hydrogen is 45-65 v%, and the conversion gas is sent to the downstream as crude hydrogen after heat is recovered.
Description
Technical Field
The invention relates to a chemical process and chemical equipment, in particular to a conversion hydrogen production method and an isothermal conversion furnace matched with a coal water slurry gasification device.
Background
China is a country with abundant coal resources and relatively short petroleum resources, and since the 21 st century, the coal chemical industry of China enters a rapid development stage. Coal gasification is an important method for chemical processing of coal and is a key to realizing clean utilization of coal. The gasification technology using coal water slurry as raw material includes multi-nozzle opposed coal water slurry gasification technology, GE coal water slurry gasification technology and the like. The carbon monoxide content of the crude gas produced by the gasification technology is about 38 percent to 50 percent (V percent, dry basis), and the molar ratio of water to dry gas is about 1.1 to 1.7.
The CO conversion process is an indispensable loop in the modern coal chemical technology and plays a role in starting and stopping. The purpose of the CO shift is to adjust the H2 and CO concentrations in the syngas to meet the needs of downstream hydrogen users.
At present, the process flow design of the CO transformation hydrogen production process matched with coal water slurry gasification in China mostly adopts a mode of multi-stage adiabatic reaction and indirect heat energy recovery, and the process has a series of problems of easy over-temperature, long process flow, more equipment, large investment, high energy consumption, large system pressure drop, short service life of a catalyst and the like.
The isothermal transformation process developed in recent years is matched with a CO transformation hydrogen production process flow of water-coal-slurry gasification, and an isothermal + adiabatic transformation process or a double isothermal transformation process is mostly adopted, but the process can only produce saturated steam, cannot overheat the steam, and has low steam quality.
For example, as disclosed in the Chinese patent application with application number 201020291829.9, in the 'CO conversion device system matched with a coal water slurry gasification device', the process flow is set to be multi-stage adiabatic conversion reaction and indirect heat energy recovery, and the process has the advantages of long flow, more equipment and large investment.
In the 'water shift heat conversion process for energy-saving deep conversion of by-product high-grade steam', as disclosed in the Chinese invention patent application with the application number of 201210185731.9, the process flow of the embodiment 1 and the embodiment 2 of the patent is set as follows: the double isothermal shift converter series process and the isothermal and adiabatic shift process can only produce saturated steam.
Disclosure of Invention
The invention aims to solve the technical problem of providing a conversion hydrogen production method matched with a coal water slurry gasification device aiming at the current situation of the prior art, which can effectively avoid the overtemperature of an adiabatic conversion furnace and produce medium-pressure superheated steam and low-pressure superheated steam as by-products.
The invention aims to solve another technical problem of providing an isothermal shift furnace used in a shift hydrogen production method matched with a coal water slurry device aiming at the current situation of the prior art, wherein the isothermal shift furnace can simultaneously carry out medium-temperature shift reaction and low-temperature shift reaction.
The technical scheme adopted by the invention for solving the technical problems is as follows: a transformation hydrogen production method matched with a coal water slurry gasification device is characterized by comprising the following steps:
separating out condensate from crude gas from a coal water slurry gasification device, and then feeding the condensate into a detoxification tank to remove impurities to obtain purified gas divided into two streams;
the first stream of purified gas enters an adiabatic shift converter for shift reaction, and the adiabatic shift gas out of the adiabatic shift converter sequentially enters a medium-pressure steam superheater, a crude gas preheater and a low-pressure steam superheater for heat recovery, and is used for respectively superheating medium-pressure saturated steam, preheating the crude gas and superheating low-pressure saturated steam;
then mixing the second stream of purified gas with the mixed gas to form mixed gas, and feeding the mixed gas into an isothermal shift converter;
the second purified gas conveying pipeline is provided with a flow control valve for adjusting the proportion of the two purified gases;
the mixed gas firstly enters a first reaction cavity of the isothermal shift converter to carry out medium temperature shift reaction, and primary isothermal shift gas is generated; boiler water in the first steam drum enters a first heat exchange pipe in the first reaction cavity to take reaction heat away, and medium-pressure saturated steam is a byproduct;
the primary isothermal shift gas enters a second reaction cavity of the isothermal shift converter to carry out low-temperature shift reaction to generate secondary isothermal shift gas; boiler water in the second steam drum enters a second heat exchange pipe in the second reaction cavity to take reaction heat away, and low-pressure saturated steam is a byproduct;
the mixed gas generates CO conversion reaction in the isothermal conversion furnace to generate hydrogen, the dry basis content of CO in the mixed gas is reduced from 20v% -30 v% to 0.2-0.4 v%, and crude hydrogen with the dry basis content of 45v% -65 v% and the temperature of 200-260 ℃, namely secondary isothermal conversion gas, is obtained at the outlet of the isothermal conversion furnace;
the secondary isothermal shift gas discharged from the isothermal shift converter sequentially enters a medium-pressure boiler water preheater for preheating medium-pressure boiler water and a low-pressure boiler water preheater for preheating low-pressure boiler water, the preheated medium-pressure boiler water is sent to a first steam drum, and two preheated low-pressure boiler water streams are respectively sent to a second steam drum and a low-pressure steam generator; the secondary isothermal shift gas after heat recovery is sent to the downstream as crude hydrogen;
the medium-pressure saturated steam returns to the first steam drum for liquid separation and then exchanges heat with the heat-insulation conversion gas discharged from the heat-insulation conversion furnace to obtain medium-pressure superheated steam and sends the medium-pressure superheated steam out of the battery limit region;
and the low-pressure saturated steam returns to the second steam pocket for liquid separation and then exchanges heat with the heat insulation conversion gas discharged from the outlet of the crude gas preheater to obtain low-pressure superheated steam which is sent out of the battery limit.
Preferably, the water-gas ratio of the crude gas from the water-coal-slurry gasification device is 1.1-1.7, the temperature is 220-250 ℃, and the pressure is 3.5-8.0 MPa (G).
Preferably, the raw gas discharged from the feed separator enters a raw gas preheater to be preheated to 240-280 ℃ and then enters a detoxification tank to remove impurities, and then purified gas is divided into two parts; the first strand of purified gas accounts for 10-50 v% of the total amount of purified gas; the second stream of purge gas comprises 50 to 90v% of the total amount of purge gas. The flow distribution of the two purge gases is controlled by a flow control valve.
Preferably, the temperature of the conversion gas of the adiabatic shift converter is 380-450 ℃, the conversion gas enters a medium-pressure steam superheater, medium-pressure saturated steam with the pressure of 3.0-6.0 MPa (G) is superheated to 350-420 ℃, and the temperature of the conversion gas is reduced to 320-400 ℃. Then the mixture enters a crude gas preheater to exchange heat with the crude gas, the temperature is reduced to 230-290 ℃ and the mixture is mixed with the second purified gas to form mixed gas.
Preferably, the medium-pressure saturated steam (G) which is the byproduct of the isothermal shift converter and is 3.0-6.0 MPa enters a medium-pressure steam superheater to be superheated to 350-420 ℃;
sending the byproduct low-pressure saturated steam of 0.4-1.0 MPa (G) to a low-pressure steam superheater to superheat to 190-240 ℃;
the temperature of secondary isothermal transformation ventilation at the outlet of the isothermal transformation furnace is 200-260 ℃, the dry basis content of CO is reduced to 0.2-0.4%, the secondary isothermal transformation ventilation enters a medium-pressure boiler water preheater to heat medium-pressure boiler feed water, a low-pressure boiler water preheater to heat low-pressure boiler feed water, the temperature is reduced to 170-240 ℃, and the low-pressure boiler feed water is sent to a downstream device; preheating the water of the medium-pressure boiler to 200-235 ℃, and sending the water into a first steam drum; the low-pressure boiler water is preheated to 130-170 ℃ and sent into a second steam drum.
The isothermal shift converter matched with the shift hydrogen production method of the water-coal-slurry gasification device is characterized by comprising a furnace body, a catalyst frame arranged in the furnace body and a plurality of heat exchange tubes arranged in the catalyst frame;
a synthesis gas collecting pipeline is further arranged in the catalyst frame, and a reaction cavity is formed by a cavity between the catalyst frame and the synthesis gas collecting pipeline; a gap between the catalyst frame and the furnace body forms a feed gas channel;
each heat exchange tube is spirally wound in the catalyst bed layer by taking the synthesis gas collecting tube as a mandrel; each heat exchange tube is spirally wound to form a plurality of heat exchange tube layers, and a gap for filling a catalyst is formed between every two adjacent heat exchange tube layers; the adjacent heat exchange tube layers have opposite spiral directions;
the heat exchange tubes are divided into two groups and comprise a first group of heat exchange tubes connected with a first refrigerant source and a second group of heat exchange tubes connected with a second refrigerant source, the first group of heat exchange tubes are arranged close to the catalyst frame, and the second group of heat exchange tubes are arranged close to the synthesis gas collecting pipelines.
Preferably, the first refrigerant source is a first steam drum, and the second refrigerant source is a second steam drum; more preferably, the first steam drum produces medium-pressure saturated steam, and the second steam drum produces low-pressure saturated steam;
an inlet of each first heat exchange tube in the first group of heat exchange tubes is connected with a cooling water outlet of a first steam drum, and an outlet of each first heat exchange tube is connected with a steam inlet of the first steam drum;
and the inlet of each second heat exchange tube in the second group of heat exchange tubes is connected with the cooling water outlet of the second steam drum, and the outlet of each second heat exchange tube is connected with the steam inlet of the second steam drum.
As a further improvement of the above schemes, the catalyst frame comprises an inner cylinder and an outer cylinder, the inner cylinder is sleeved in the outer cylinder and has a gap with the outer cylinder, and the gap between the outer cylinder and the side wall of the furnace body forms a feed gas channel; the synthesis gas collecting pipeline is arranged in the inner barrel;
the cross sections of the synthesis gas collecting pipeline, the inner cylinder, the outer cylinder and the furnace body are concentric circles;
the reaction cavity is divided into a first reaction cavity between the outer cylinder and the inner cylinder and a second reaction cavity between the inner cylinder and the synthesis gas collecting pipeline by the inner cylinder;
the first group of heat exchange tubes are arranged in the first reaction cavity, and at least part of the second group of heat exchange tubes are arranged in the second reaction cavity.
The second group of heat exchange tubes are divided into two parts, the first part is arranged in the second reaction cavity, and the second part is arranged in the first reaction cavity, is positioned at the inner side of the first group of heat exchange tubes and is close to the inner cylinder;
the second part is spirally arranged by taking the inner barrel as a mandrel.
In each scheme, the reaction cavity can be filled with the same catalyst, such as a wide-temperature catalyst; preferably, the first reaction cavity is filled with a first catalyst, and the second reaction cavity is filled with a second catalyst; the first catalyst and the second catalyst are different catalysts.
As a further improvement of the above schemes, the heat exchange area of the first group of heat exchange tubes accounts for 0.4-0.6 of the total heat exchange area;
the heat exchange area of the first group of heat exchange tubes is the sum of the external surface areas of the first heat exchange tubes; the heat exchange area of the second group of heat exchange tubes is the sum of the external surface areas of the second heat exchange tubes;
the total heat exchange area is the sum of the heat exchange area of the first group of heat exchange tubes and the heat exchange area of the second group of heat exchange tubes.
Further, the heat exchange area of the second part of the second group of heat exchange tubes in the first reaction cavity accounts for 0.06-0.2 of the total heat exchange area.
Further, a pressure control system for controlling the low-temperature shift reaction depth in the second reaction cavity can be arranged on the second steam drum. The low-variation reaction depth is controlled by adjusting the steam pressure generated by the second steam drum, and the dry basis concentration of CO in the variation gas at the outlet is ensured to be 0.2-0.4 v%.
The pressure control system is conventional.
Compared with the prior art, the invention has the advantages that:
1) Through the arrangement of the heat-insulation shift converter, the high-temperature shift gas at the outlet of the heat-insulation shift converter is used for overheating the medium-pressure steam and preheating the raw gas, so that the problems of overheating the medium-pressure steam and preheating the raw gas are solved.
2) The adiabatic shift converter adopts high water-gas ratio, meets the requirement of subsequent shift reaction depth, and can effectively avoid the overtemperature of the adiabatic shift converter under the working condition of high-concentration CO.
3) And medium-pressure superheated steam and low-pressure superheated steam are simultaneously by-produced.
4) In a preferable scheme, the isothermal shift furnace is characterized in that low-temperature CO shift reaction and medium-temperature CO shift reaction are integrated in one reaction furnace, raw material gas firstly passes through a catalyst outer frame to carry out medium-temperature shift reaction, shift reaction heat is transferred through medium-pressure boiler water to generate medium-pressure saturated steam as a byproduct, reaction gas after medium-temperature shift reaction is cooled through low-pressure boiler water and then enters a catalyst inner frame to carry out low-temperature shift reaction, the dry basis content of CO is reduced to be less than 0.4%, and low-temperature shift reaction heat is transferred through low-pressure boiler water to generate low-pressure saturated steam as a byproduct. The system has short flow, less equipment, low investment and small system pressure drop.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the invention;
FIG. 2 is a longitudinal sectional view of an isothermal shift converter in an embodiment of the present invention;
FIG. 3 is a schematic view of the connection between the isothermal shift converter and two steam drums according to an embodiment of the present invention;
FIG. 4 is an enlarged view taken along section A of FIG. 2;
FIG. 5 is a fixing structure of the heat exchange tube layer in the embodiment of the invention.
Detailed Description
The invention is described in further detail below with reference to the following examples of the drawings.
As shown in fig. 2 to 5, the isothermal shift furnace includes:
the furnace body 1 'is of a conventional structure and comprises an upper seal head 11', a lower seal head 12 'and a cylinder body 13' connected between the upper seal head 11 'and the lower seal head 12'. A manhole 14' is arranged on the upper sealing head 11', a manhole cover is covered on the manhole 14', and the feed gas inlet 35 is arranged on the manhole cover.
The catalyst frame is used for filling a catalyst and is arranged in the cylinder body 13', and a reaction cavity is formed by a cavity between the catalyst frame and the synthesis gas collecting pipeline. The catalyst frame in this embodiment includes an inner cylinder 21 and an outer cylinder 22.
The mounting structure of the catalyst frame may be any one of those in the prior art as required. In this embodiment, the upper and lower ends of the catalyst frame are not closed, the upper and lower ends of the catalyst bed layer in the catalyst frame are filled with refractory balls, the outer cylinder is fixed by the cylinder, and the inner cylinder is supported by the heat exchange tubes at both sides and the first and second tube boxes 51 and 61 at the lower side.
The inner cylinder 21 is sleeved in the outer cylinder 22, a gap is formed between the inner cylinder and the outer cylinder 22, and a feed gas channel 2a is formed by the gap between the outer cylinder and the side wall of the furnace body; the synthesis gas collection pipeline 3' is sleeved in the inner cylinder 21.
The reaction chamber is divided by the inner cylinder into a first reaction chamber 2b between the outer cylinder and the inner cylinder and a second reaction chamber 2c between the inner cylinder and the synthesis gas collection pipe.
The side walls of the inner cylinder 21 and the outer cylinder 22 are both provided with through holes (not shown in the figure), the through holes not only serve as flow channels for raw material gas and synthesis gas, but also play a role of a gas distributor, so that the raw material gas uniformly enters the first reaction cavity, and the primary synthesis gas uniformly enters the second reaction cavity.
In this embodiment, the cross-sectional structures of the cylinder, the inner cylinder, the outer cylinder, and the syngas collection conduit are the same, and are concentrically arranged concentric circular structures.
In this example, the first reaction chamber and the second reaction chamber were filled with different catalysts of a narrow temperature type. The first reaction chamber is filled with a medium temperature shift catalyst, and the second reaction chamber is filled with a low temperature shift catalyst. Different types of catalysts are filled according to respective reaction characteristics, so that the conversion catalyst reaction activity in a specific temperature range is fully utilized, the reaction rate is high, and the CO conversion rate is high. This mode is the preferred mode.
The first reaction cavity and the second reaction cavity can be filled with the same wide-temperature type catalyst, and the wide-temperature type catalyst needs to simultaneously take the medium-temperature conversion activity and the low-temperature conversion activity into consideration, so that the conversion reaction rate and the CO conversion rate are lower than those of the narrow-temperature type catalyst. Meanwhile, the wide-temperature catalyst gives consideration to medium-temperature and low-temperature catalytic activity at the expense of the service life of the catalyst. The use of the wide temperature type catalyst may eliminate the need for an inner cylinder.
The synthesis gas collecting pipeline 3 'is used for collecting the secondary isothermal transformation gas and sending the secondary isothermal transformation gas out of the furnace body 1' through a synthesis gas conveying pipeline 33, is arranged in the middle of the inner cavity of the catalyst frame and is formed by sequentially and detachably connecting a plurality of sections of cylinders 31, and in the embodiment, the adjacent cylinders 31 are connected through flanges 34; the side wall of each cylinder 31 is provided with a plurality of air inlets (not shown in the figure) for the synthesis gas to enter the synthesis gas collecting pipeline 3' from the catalyst bed layer; a plurality of footsteps 32 are sequentially arranged on the inner side wall of the cylinder 31 at intervals along the axial direction. The end cover is detachably connected to the upper end port of the synthesis gas collecting pipeline 3, and is communicated with the inner cavity of the upper end enclosure and the manhole 14 after being disassembled, so that maintainers can enter the synthesis gas collecting pipeline 3'; the lower port of the synthesis gas collection tube 3' is connected to a synthesis gas delivery conduit 33.
The heat exchange tubes include a first heat exchange tube group composed of a plurality of first heat exchange tubes 41 and a second heat exchange tube group composed of a plurality of second heat exchange tubes 42. For the sake of distinction, in fig. 3, the second heat exchange tubes are represented by solid circles and solid fill patterns, and the first heat exchange tubes are represented by open circles.
Each heat exchange tube is sequentially spirally wound outside the synthesis gas collecting tube 3 'by taking the synthesis gas collecting tube 3' as a mandrel to form a plurality of layers, and the spiral directions of the adjacent heat exchange tube layers are opposite.
Each heat exchange tube layer is fixed on a plurality of support rods 7', each support rod 7' is vertically arranged and arranged at intervals, and adjacent support rods are not on the same radial radiation line. Preferably, each heat exchange tube is secured to a support rod by a hoop 71.
Wherein, each first heat exchange tube 41 is coiled to form a plurality of layers and is arranged in the first reaction cavity close to the outer cylinder. The inlet of each first heat exchange pipe is connected with a first cooling water pipe 52 through a first pipe box 51, and the first cooling water pipe 52 is connected with the cooling water outlet of the first steam drum 12; the outlet of each first heat exchange pipe 41 is connected with a first steam pipeline 54 through a first steam collecting device 53, and the first steam pipeline 54 is connected with the steam inlet of the first steam drum 12. The first reaction cavity removes heat through medium pressure boiler water to obtain a byproduct of medium pressure saturated steam with the pressure of 4.0Mpa (G), and the saturation temperature is about 252 ℃.
Each second heat exchange tube 42 is divided into two parts, the first part is arranged in a winding manner to form a plurality of layers and is arranged in the second reaction cavity, and the second part is arranged in a winding manner to form a plurality of layers and is arranged in the first reaction cavity and is close to the inner barrel 21. In this embodiment, 2 layers, preferably 1 to 5 layers, of the second heat exchange tubes 42 are disposed in the first reaction chamber. The inlet of each second heat exchange pipe 42 is connected with a second cooling water pipe 62 through a second pipe box 61, and the second cooling water pipe 62 is connected with the cooling water outlet of the second steam pocket 13; the outlet of each second heat exchange tube 42 is connected to a second steam conduit 64 via a second steam collection device 63, the second steam conduit 64 being connected to the steam inlet of the second drum. The second reaction cavity removes heat through the water of the low-pressure boiler to produce low-pressure saturated steam with the pressure of 0.45Mpa (G), and the temperature of the saturated steam is about 155 ℃.
The diameters of the first heat exchange tube 41 and the second heat exchange tube 42 can be flexibly adjusted according to the scale of the device and the load change, and the diameters of the heat exchange tubes are the same in the embodiment.
In this embodiment, the heat exchange area of the first group of heat exchange tubes accounts for 0.45 of the total heat exchange area; the heat exchange area of the second part of the second group of heat exchange tubes accounts for 0.1 of the total heat exchange area, and the heat exchange area of the first part of the second group of heat exchange tubes arranged in the second reaction cavity accounts for 0.45 of the total heat exchange area.
The heat exchange area of the first group of heat exchange tubes is the sum of the external surface areas of the first heat exchange tubes in the catalyst bed layer; the heat exchange area of the second group of heat exchange tubes is the sum of the external surface areas of the second heat exchange tubes in the catalyst bed layer; the total heat exchange area is the sum of the heat exchange area of the first group of heat exchange tubes and the heat exchange area of the second group of heat exchange tubes.
The medium-temperature shift reaction is carried out in the first reaction cavity, medium-pressure saturated steam of 4.0Mpa (G) is obtained as a byproduct by water heat removal of a medium-pressure boiler at the temperature of about 252 ℃, and the operation temperature of the reaction is maintained between 240 ℃ and 300 ℃. The second reaction chamber is used for low-temperature shift reaction, and the low-pressure saturated steam with the pressure of 0.45Mpa (G) is obtained as a byproduct by water heat removal of a low-pressure boiler at the temperature of about 155 ℃, and the operation temperature of the reaction is maintained between 200 and 250 ℃. In order to better link the temperature of the conversion gas of the first reaction cavity and the second reaction cavity, the second part of the second group of heat exchange tubes is arranged in the first reaction cavity, and the conversion gas is reduced by 10-40 ℃ through strong heat exchange between the boiler water with lower temperature (low-pressure boiler water at about 155 ℃) and the high-temperature conversion gas, so that the temperature of the conversion gas entering the second reaction cavity is about 230 ℃.
The first and second headers 51 and 61 may have a ring pipe structure, as shown in fig. 1 of the present embodiment; the two tube boxes can also be box structures which are arranged in an up-and-down overlapping mode, and the two tube boxes can also be in a tube plate mode.
The first steam collecting means 53 and the second steam collecting means 63 may be a loop pipe or a tube box.
The first and second steam pipes 54 and 64 are each provided with a first expansion joint 54a and a second expansion joint 64a, respectively, for absorbing thermal stresses.
As shown in figure 1, crude gas 1 with the water-gas ratio of 1.67, 246 ℃ and 6.3MPa (G) from a water-coal-slurry device enters a feeding separator 2 to separate condensate, then enters a crude gas preheater 3 to be preheated to 270 ℃ and then enters a detoxification tank 4, and purified gas after impurities such as dust and the like are removed by the detoxification tank 4 is divided into two streams.
Wherein the first purified gas 5 which accounts for about 30v% of the total purified gas enters an adiabatic shift converter 7 for shift reaction, the adiabatic shift gas temperature which is discharged from the adiabatic shift converter 7 is 394 ℃, the first purified gas enters a medium-pressure steam superheater 8, the medium-pressure saturated steam with 4.0MPa (G) is superheated to 380 ℃, and the temperature of the shift gas is reduced to 360 ℃. Then the raw gas enters a raw gas preheater 3 to exchange heat with the raw gas, the temperature is reduced to 280 ℃, and then the raw gas enters a low-pressure steam superheater 9 to superheat low-pressure steam, and the temperature is reduced to 270 ℃. Mixed with the remaining about 70v% of the second purified gas 6 to form a mixed gas, and then the mixed gas enters the isothermal shift converter 11.
In the embodiment, a flow control valve for adjusting the proportion of two purified gases is arranged on the second purified gas conveying pipeline; the distribution ratio of the two purified gases can be flexibly adjusted.
The mixed gas enters a cavity of an upper end socket of the isothermal shift converter through a raw material gas inlet 35 on the isothermal shift converter 11, descends along a raw material gas channel, uniformly enters a catalyst bed layer of a first reaction cavity through each through hole on an outer cylinder, and is subjected to medium-temperature CO shift reaction to form primary isothermal shift gas, wherein the reaction temperature is 240-300 ℃. Boiler water in the first steam drum 12 enters each first heat exchange pipe 41 from the first cooling water pipeline in a natural circulation mode, reaction heat of the catalyst bed layer in the first reaction cavity is taken away, a generated steam-water mixture returns to the first steam drum through the first steam collecting device and the first steam pipeline for steam-liquid separation, and medium-pressure saturated steam of 4.0Mpa (G) is a byproduct.
In order to better link the initial temperature of the primary isothermal shift gas in the first reaction cavity entering the second reaction cavity, partial heat exchange tubes for cooling are arranged in the first reaction cavity, namely the second part of the second group of heat exchange tubes, and the shift gas is reduced by 10-40 ℃ through strong heat exchange between boiler water with the temperature of about 155 ℃ and the primary isothermal shift gas with high temperature, so that the temperature of the shift gas entering the second reaction cavity is about 230 ℃ to meet the requirement of low-temperature shift reaction. The reaction temperature of the second reaction cavity is 200-240 ℃; the resulting secondary isothermal shift gas enters the syngas collection tube 33 and is sent out of the isothermal shift furnace.
Boiler water in the second steam drum 13 enters a second heat exchange pipe in a second reaction cavity of the isothermal shift converter in a natural circulation mode, low-temperature shift reaction heat is taken away, and low-pressure saturated steam of 0.45MPa (G) is produced as a byproduct.
The 4.0MPa (G) medium-pressure saturated steam returns to the first steam drum 12 for liquid separation, then is sent to the medium-pressure steam superheater 8 for superheating to 380 ℃, and the superheated medium-pressure steam is sent to downstream users. And (3) separating the low-pressure saturated steam of 0.45MPa (G) by a second steam drum 13, sending the low-pressure saturated steam to a low-pressure steam superheater 9 for superheating to 200 ℃, and sending the superheated low-pressure steam to downstream users.
The mixed gas generates CO conversion reaction in the isothermal conversion furnace to generate hydrogen, the CO content in the mixed gas is reduced from 26.5 percent (V percent, dry basis) to 0.4 percent (V percent, dry basis), and crude hydrogen with the hydrogen content of about 54 percent (V percent, dry basis) and the temperature of 250 ℃ is obtained at the outlet of the isothermal conversion furnace, namely secondary isothermal conversion gas.
The crude hydrogen gas with the temperature of 250 ℃ from the isothermal shift converter 11 enters a medium-pressure boiler water preheater 14, the feed water of the medium-pressure boiler with the temperature of 104 ℃ is heated to 230 ℃ and is sent to a medium-pressure steam drum 12, and the temperature of the crude hydrogen gas is reduced to 231 ℃. Then enters a low-pressure boiler water preheater 16, preheats the low-pressure boiler water with the temperature of 104 ℃ to 135 ℃, and then is respectively sent into a low-pressure steam drum 13 and a low-pressure steam generator 2 in two parts. The temperature of the crude hydrogen is reduced to 225 ℃, and the crude hydrogen is further cooled and separated and then sent to a downstream device.
Claims (4)
1. A transformation hydrogen production method matched with a coal water slurry gasification device is characterized by comprising the following steps:
separating out condensate from crude gas from a coal water slurry gasification device, and then feeding the condensate into a detoxification tank to remove impurities, wherein the obtained purified gas is divided into two streams;
the first stream of purified gas enters an adiabatic shift converter for shift reaction, and the adiabatic shift gas out of the adiabatic shift converter sequentially enters a medium-pressure steam superheater, a crude gas preheater and a low-pressure steam superheater for heat recovery, and is used for respectively superheating medium-pressure saturated steam, preheating the crude gas and superheating low-pressure saturated steam;
then mixing the mixed gas with a second stream of purified gas to form mixed gas, and feeding the mixed gas into an isothermal conversion furnace;
the second purified gas conveying pipeline is provided with a flow control valve for adjusting the proportion of the two purified gases;
the mixed gas firstly enters a first reaction cavity of the isothermal shift converter to carry out medium temperature shift reaction, and primary isothermal shift gas is generated; boiler water in the first steam drum enters a first heat exchange pipe in the first reaction cavity to take reaction heat away, and medium-pressure saturated steam is a byproduct;
the primary isothermal shift gas enters a second reaction cavity of the isothermal shift converter to carry out low-temperature shift reaction to generate secondary isothermal shift gas; boiler water in the second steam drum enters a second heat exchange pipe in the second reaction cavity to take reaction heat away, and low-pressure saturated steam is a byproduct;
the mixed gas is subjected to CO conversion reaction in an isothermal conversion furnace to generate hydrogen, the content of CO dry basis in the mixed gas is reduced from 20v% to 30v% to 0.2 v% to 0.4v%, and crude hydrogen, namely secondary isothermal conversion gas, with the content of hydrogen dry basis of 45v% to 65v% and the temperature of 200 ℃ to 260 ℃ is obtained at an outlet of the isothermal conversion furnace;
the secondary isothermal shift gas out of the isothermal shift converter sequentially enters a medium-pressure boiler water preheater for preheating medium-pressure boiler water and a low-pressure boiler water preheater for preheating low-pressure boiler water, the preheated medium-pressure boiler water is sent to a first steam drum, and two strands of preheated low-pressure boiler water are respectively sent to a second steam drum and a low-pressure steam generator; the secondary isothermal shift gas after heat recovery is sent to the downstream as crude hydrogen;
the medium-pressure saturated steam returns to the first steam drum for liquid separation and then exchanges heat with the heat-insulation conversion gas discharged from the heat-insulation conversion furnace to obtain medium-pressure superheated steam which is sent out of a battery limit;
the low-pressure saturated steam returns to the second steam drum for liquid separation and then exchanges heat with the heat-insulating conversion gas discharged from the outlet of the crude gas preheater to obtain low-pressure superheated steam which is sent out of the battery limit region;
the water-gas ratio of the crude gas from the water-coal-slurry gasification device is 1.1 to 1.7, the temperature is 220 to 250 ℃, and the pressure is 3.5 to 8.0 MPa;
the discharged raw gas enters a feed separator to separate condensate, and then enters a raw gas preheater to be preheated to 240-280 ℃ and then enters a detoxification tank to remove impurities, so that purified gas is divided into two parts; the first strand of purified gas accounts for 10 to 50v% of the total amount of the purified gas; the second strand of purified gas accounts for 50 to 90v% of the total amount of the purified gas;
the temperature of the converted gas discharged from the heat insulation shift converter is 380-450 ℃, the converted gas enters a medium-pressure steam superheater, the medium-pressure saturated steam with the pressure of 3.0-6.0 MPa is superheated to 350-420 ℃, and the temperature of the converted gas is reduced to 320-400 ℃; then the mixture enters a crude gas preheater to exchange heat with the crude gas, and the temperature is reduced to 230 to 290 ℃ to be mixed with the second strand of purified gas;
the medium-pressure saturated steam which is a byproduct of the isothermal shift converter and is 3.0-6.0 MPa enters a medium-pressure steam superheater to be superheated to 350-420 ℃;
sending the byproduct low-pressure saturated steam of 0.4-1.0 MPa to a low-pressure steam superheater to be superheated to 190-240 ℃;
the secondary isothermal shift ventilation temperature at the outlet of the isothermal shift furnace is 200-260 ℃, the dry basis content of CO is reduced to 0.2-0.4%, the secondary isothermal shift ventilation temperature sequentially enters a medium-pressure boiler water preheater to heat medium-pressure boiler feed water, a low-pressure boiler water preheater to heat low-pressure boiler feed water, the temperature is reduced to 170-240 ℃, and the low-pressure boiler feed water is sent to a downstream device; preheating the water of the medium-pressure boiler to 200-235 ℃, and feeding the water into a first steam drum; preheating the low-pressure boiler water to 130-170 ℃ and feeding the low-pressure boiler water into a second steam drum;
the isothermal converter comprises a furnace body, a catalyst frame arranged in the furnace body and a plurality of heat exchange tubes arranged in the catalyst frame;
a synthesis gas collecting pipeline is further arranged in the catalyst frame, and a reaction cavity is formed by a cavity between the catalyst frame and the synthesis gas collecting pipeline; a gap between the catalyst frame and the furnace body forms a feed gas channel;
each heat exchange tube is spirally wound in the catalyst bed layer by taking the synthesis gas collecting tube as a mandrel; each heat exchange tube is spirally wound to form a plurality of heat exchange tube layers, and a gap for filling a catalyst is formed between every two adjacent heat exchange tube layers; the spiral directions of the adjacent heat exchange tube layers are opposite;
the heat exchange tubes are divided into two groups, and each group of heat exchange tubes comprises a first group of heat exchange tubes connected with a first refrigerant source and a second group of heat exchange tubes connected with a second refrigerant source, the first group of heat exchange tubes are arranged close to the catalyst frame, and the second group of heat exchange tubes are arranged close to the synthesis gas collecting pipeline;
the first refrigerant source is a first steam drum, and the second refrigerant source is a second steam drum;
an inlet of each first heat exchange tube in the first group of heat exchange tubes is connected with a cooling water outlet of a first steam drum, and an outlet of each first heat exchange tube is connected with a steam inlet of the first steam drum;
an inlet of each second heat exchange tube in the second group of heat exchange tubes is connected with a cooling water outlet of the second steam drum, and an outlet of each second heat exchange tube is connected with a steam inlet of the second steam drum;
the catalyst frame comprises an inner cylinder and an outer cylinder, the inner cylinder is sleeved in the outer cylinder, a gap is formed between the inner cylinder and the outer cylinder, and a feed gas channel is formed by the gap between the outer cylinder and the side wall of the furnace body; the synthesis gas collecting pipeline is arranged in the inner barrel;
the cross sections of the synthesis gas collecting pipeline, the inner cylinder, the outer cylinder and the furnace body are concentric circles;
the reaction cavity is divided into a first reaction cavity between the outer cylinder and the inner cylinder and a second reaction cavity between the inner cylinder and the synthesis gas collecting pipeline by the inner cylinder;
the first group of heat exchange tubes are arranged in the first reaction cavity, and at least part of the second group of heat exchange tubes are arranged in the second reaction cavity;
the second group of heat exchange tubes are divided into two parts, the first part is arranged in the second reaction cavity, and the second part is arranged in the first reaction cavity, is positioned at the inner side of the first group of heat exchange tubes and is close to the inner cylinder;
the second part is spirally arranged by taking the inner barrel as a mandrel.
2. The shift hydrogen production method matched with the coal water slurry gasification device according to claim 1, wherein a first catalyst is filled in the first reaction cavity, and a second catalyst is filled in the second reaction cavity;
the first catalyst and the second catalyst are different catalysts.
3. The transformation hydrogen production method matched with the water-coal-slurry gasification device according to claim 1 or 2, wherein the heat exchange area of the first group of heat exchange tubes accounts for 0.4 to 0.6 of the total heat exchange area;
the heat exchange area of the first group of heat exchange tubes is the sum of the external surface areas of the first heat exchange tubes; the heat exchange area of the second group of heat exchange tubes is the sum of the external surface areas of the second heat exchange tubes;
the total heat exchange area is the sum of the heat exchange area of the first group of heat exchange tubes and the heat exchange area of the second group of heat exchange tubes.
4. The shift hydrogen production method matched with the water-coal-slurry gasification device according to claim 3, wherein the heat exchange area of the second part of the second group of heat exchange tubes in the first reaction cavity accounts for 0.06-0.2 of the total heat exchange area.
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| CN112047299A (en) * | 2020-09-14 | 2020-12-08 | 湖南安淳高新技术有限公司 | CO conversion process and conversion device for coal gas |
| CN113460961B (en) * | 2021-07-06 | 2023-05-05 | 中石化宁波工程有限公司 | Sleeve type controllable semi-isothermal shift converter |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768488A (en) * | 2009-12-07 | 2010-07-07 | 赛鼎工程有限公司 | Technique for producing coal natural gas by utilizing crushed coal slag through gasification |
| CN102888253A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | Low-moisture low-variable serial saturation tower thermal CO transformation technology |
| CN102887480A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | CO shift technique by connecting isothermal shift and thermal insulation shift in series |
| CN203484134U (en) * | 2013-09-10 | 2014-03-19 | 张立军 | Water pipe type reaction device with steam pockets |
| WO2016119224A1 (en) * | 2015-01-30 | 2016-08-04 | 湖南安淳高新技术有限公司 | Isothermal and low temperature shift converter and shift conversion process thereof |
| CN108421506A (en) * | 2018-05-22 | 2018-08-21 | 中石化宁波工程有限公司 | A kind of energy-saving radial reactor suitable for strong exothermal reaction |
| CN109081346A (en) * | 2018-09-30 | 2018-12-25 | 中石化宁波工程有限公司 | A kind of high CO isothermal conversion process of mating methanol-fueled CLC |
-
2019
- 2019-10-24 CN CN201911014650.0A patent/CN110790223B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768488A (en) * | 2009-12-07 | 2010-07-07 | 赛鼎工程有限公司 | Technique for producing coal natural gas by utilizing crushed coal slag through gasification |
| CN102888253A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | Low-moisture low-variable serial saturation tower thermal CO transformation technology |
| CN102887480A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | CO shift technique by connecting isothermal shift and thermal insulation shift in series |
| CN203484134U (en) * | 2013-09-10 | 2014-03-19 | 张立军 | Water pipe type reaction device with steam pockets |
| WO2016119224A1 (en) * | 2015-01-30 | 2016-08-04 | 湖南安淳高新技术有限公司 | Isothermal and low temperature shift converter and shift conversion process thereof |
| CN108421506A (en) * | 2018-05-22 | 2018-08-21 | 中石化宁波工程有限公司 | A kind of energy-saving radial reactor suitable for strong exothermal reaction |
| CN109081346A (en) * | 2018-09-30 | 2018-12-25 | 中石化宁波工程有限公司 | A kind of high CO isothermal conversion process of mating methanol-fueled CLC |
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