CN110921617B - Isothermal transformation parallel air-cooled transformation synthesis gas preparation process matched with pulverized coal gasification and isothermal transformation furnace - Google Patents
Isothermal transformation parallel air-cooled transformation synthesis gas preparation process matched with pulverized coal gasification and isothermal transformation furnace 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
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- 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
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- 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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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
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Abstract
The invention relates to a process for preparing synthesis gas by isothermal transformation and parallel gas-cooled transformation matched with pulverized coal gasification and an isothermal transformation furnace, which comprises the following steps: separating condensed liquid from crude gas from a pulverized coal gasification device, exchanging heat and detoxifying the gas to obtain three streams, wherein the first stream of purified gas is non-converted gas, the third stream of purified gas is sent into an isothermal shift converter for shift reaction, boiler water in a steam drum is used as a heat taking medium of the isothermal shift converter, and a byproduct of 3.5-6.0 MPa (G) medium-pressure saturated steam is obtained; the first conversion gas discharged from the isothermal conversion furnace recovers heat to preheat water of the medium-pressure boiler; and the second strand of purified gas enters the air-cooled shift converter for shift reaction, medium-pressure saturated steam is used as a heat taking medium of the air-cooled shift converter, the second shifted gas discharged out of the air-cooled shift converter recovers heat and is mixed with the first shifted gas and the first strand of purified gas to obtain crude synthesis gas, and the crude synthesis gas is sent to the downstream after recovering heat.
Description
Technical Field
The invention relates to a CO conversion process, in particular to a process for preparing synthesis gas by isothermal conversion and parallel air-cooled conversion matched with pulverized coal gasification and an isothermal conversion furnace.
Background
China is a country lack of oil, gas and coal, and the resource characteristics determine that the energy and chemical raw material sources of China are mainly coal. Coal gasification is an important method for chemical processing of coal and is a key for realizing clean utilization of coal. The gasification technology (such as an oriental furnace) which takes pulverized coal as a raw material has the CO content of raw gas produced by the gasification technology as high as 60v% -80 v% (dry basis) and the water-gas mole of 0.5-1.0.
The carbon monoxide conversion process is an indispensable ring in the modern coal chemical technology and plays a role in starting and stopping. The purpose of CO shift is to adjust H in the synthesis gas 2 And CO concentration to provide a syngas that meets the process requirements. The downstream products of coal chemical engineering projects are different, the components of the required synthesis gas are different, and the corresponding shift reaction depth and shift process are also different.
The shift reaction is an exothermic reaction, the traditional shift process mostly adopts a mode of 'multi-section adiabatic reaction + indirect heat energy recovery' to set a flow, and the process has a series of problems of long flow, more equipment, large investment, high energy consumption, large system pressure drop, short service life of a catalyst and the like.
The isothermal shift technology developed in recent years is applied to various coal gasification processes, and is paid more attention to due to the technical advantages of short flow, easy control of shift reaction depth and the like, but the technology also has the following defects: in the prior isothermal transformation process, no matter the isothermal transformation process of the adiabatic transformation series, the isothermal transformation series adiabatic transformation process or the double isothermal transformation furnace series connection process, all the transformation furnaces are connected in series, and transformation gas passes through all the transformation furnaces in full gas quantity, so that the equipment size of the transformation furnaces is large, the manufacturing cost is high, and the manufacturing and transportation are difficult. Secondly, part of isothermal transformation process can only produce saturated steam, can not produce superheated steam, and the steam quality is lower.
(1) For example, as disclosed in the chinese patent application with application number 201811160904.5, "a gas-cooling and water-cooling isothermal transformation process for matching coal water slurry gasification", the process flow is as follows: the gas-cooled transformation parallel isothermal transformation and low-temperature transformation process is used for hydrogen production. In order to change the bed temperature of the water-cooled furnace, the CO conversion technology is provided with a boiler circulating water pump, boiler water in a steam drum is subjected to forced circulation to perform water-cooled furnace, and compared with natural circulation, the energy consumption is high and the investment is large; secondly, two groups of heat exchange tubes are arranged in a water cooling furnace matched with the CO conversion technology for switching, and the structure is complex.
(2) The invention discloses an adiabatic series isothermal transformation process for high-concentration CO feed gas, as disclosed in Chinese invention patent application No. 201410439881.7, the process flow is as follows: although the adiabatic + isothermal shift process and the adiabatic + isothermal + adiabatic shift process solve the problem of overheating of steam, when the process is used for raw gas with high CO concentration, the adiabatic shift furnace has the risk of overtemperature.
(3) For example, the invention discloses a water shift heat conversion process for energy-saving deep conversion of byproduct high-grade steam, which is disclosed in Chinese invention patent application with the application number of 201210185731.9, and the process flow is set as follows: the double isothermal shift converter series connection process, the adiabatic + isothermal shift process and the adiabatic + isothermal + adiabatic shift process are characterized in that all three processes can only produce saturated steam, all shift converters are connected in series, the total amount of shift gas passes through all shift converters, and after the device is large-sized, a series of problems of large equipment size, high manufacturing cost, difficulty in manufacturing and transportation and the like of the shift converters can occur.
Disclosure of Invention
The invention aims to solve the technical problem of providing a process for preparing synthesis gas by isothermal transformation and parallel air-cooled transformation matched with pulverized coal gasification, which can produce medium-pressure superheated steam as a byproduct, effectively reduce the size of each transformation furnace, and has the advantages of low device investment, small system pressure drop and long service life of a catalyst.
The invention aims to solve another technical problem of providing an isothermal conversion furnace which has uniform heat removal, high conversion reaction efficiency and low equipment investment aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a process for preparing synthesis gas by isothermal transformation and parallel gas-cooled transformation matched with pulverized coal gasification is characterized by comprising the following steps:
(1) raw gas from a pulverized coal gasification device with the molar ratio of water to gas of 190-220 ℃, 3.0-4.5 MPa (G) and 0.5-1.0 is separated out of condensate by a raw gas feeding separator, then enters a raw gas heater, is heated to 220-270 ℃, enters a detoxification tank to remove impurities, and then obtains purified gas which is divided into three strands, wherein the first strand of purified gas accounting for 15-35 v% of the total amount is non-conversion gas, the second strand of purified gas accounting for 15-35 v% of the total amount is sent to an air-cooled conversion furnace to carry out conversion reaction, and the remaining third strand of purified gas is sent to an isothermal conversion furnace to carry out conversion reaction;
(2) a heat exchange tube bundle is arranged in the isothermal conversion furnace, boiler water in the steam drum is used as a heat taking medium to enter the isothermal conversion furnace to take away reaction heat, and a byproduct of medium-pressure saturated steam of 3.5-6.0 MPa (G) is produced at the same time; the first converted gas with the temperature of 260-320 ℃ obtained at the outlet of the isothermal conversion furnace enters a medium-pressure boiler water preheater to exchange heat with medium-pressure boiler water, the medium-pressure boiler water with the pressure of 3.5-6.0 MPa (G) is preheated to 230-250 ℃ and then is divided into two parts which are respectively sent to a steam drum and a medium-pressure steam generator, and the temperature of the first converted gas is reduced to 200-220 ℃; returning medium-pressure saturated steam with the pressure of 3.5-6.0 MPa (G) as a byproduct of the isothermal shift converter to the drum for liquid separation, and then sending the steam into the air-cooled shift converter;
(3) a heat exchange tube bundle is arranged in the gas-cooled converter, medium-pressure saturated steam from the isothermal converter and the medium-pressure steam generator is converged and then enters the heat exchange tube bundle in the gas-cooled converter as a heat taking medium, the medium-pressure saturated steam is superheated to 350-420 ℃, and the superheated medium-pressure steam is sent to downstream users; the second conversion gas with the temperature of 370-450 ℃ obtained at the outlet of the air-cooled shift converter is firstly sent into a medium-pressure steam generator to produce 3.5-6.0 MPa (G) medium-pressure saturated steam as a byproduct, the temperature is reduced to 330-400 ℃, then the second conversion gas enters a raw gas heater to exchange heat with raw gas, the temperature is reduced to 220-250 ℃, then the second conversion gas enters a low-pressure steam superheater to overheat the low-pressure saturated steam with the pressure of 0.4-1.0 MPa (G) to 180-250 ℃, the temperature of the second conversion gas is reduced to 200-220 ℃, then the second conversion gas is mixed with the first conversion gas from the medium-pressure boiler water preheater and the first purified gas to obtain raw synthesis gas, and then the raw synthesis gas enters a low-pressure steam generator to produce 0.4-1.0 MPa (G) low-pressure saturated steam as a byproduct, and the temperature of the raw synthesis gas is reduced to 170-200 ℃ and sent to the downstream.
Preferably, a flow meter and a first flow control valve may be provided in the first purified gas delivery line to control the flow of H in the raw synthesis gas by adjusting the flow rate of the first purified gas 2 The molar ratio of the carbon monoxide to the CO is 2.0-3.0, and the hydrogen-carbon ratio (H) of the synthesis gas in a downstream device is satisfied 2 CO), and further cooling and separating the crude synthesis gas, and then sending the cooled and separated crude synthesis gas to a downstream device.
Furthermore, a flowmeter and a second flow control valve can be arranged on the third purified gas pipeline and used for distributing the flow of purified gas of the degassing-cooling conversion furnace and the isothermal conversion furnace.
Preferably, the installation position of the steam drum is higher than the isothermal shift converter, and boiler water in the steam drum enters the isothermal shift converter in a natural circulation mode to reduce energy consumption.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the isothermal shift converter used in the process for preparing the synthesis gas by the isothermal shift parallel gas-cooled shift matched with the pulverized coal gasification 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, wherein a synthesis gas collecting pipeline is also arranged in the catalyst frame, and a cavity between the catalyst frame and the synthesis gas collecting pipeline forms a reaction cavity;
the heat exchange tubes are arranged on a plurality of concentric circumferential lines, the heat exchange tubes are uniformly arranged on the respective circumferential lines, and the arrangement intervals of the heat exchange tubes on the respective circumferential lines are gradually increased from outside to inside;
the inlet of each heat exchange tube is respectively connected with a corresponding cooling water distribution tube, and each cooling water distribution tube is communicated with a cooling water conveying pipeline; the outlet of each heat exchange tube is respectively connected with a steam-water collecting distribution tube corresponding to each heat exchange tube, and each steam-water collecting distribution tube is communicated with a steam conveying pipeline;
further, each cooling water distribution pipe and each steam-water collection distribution pipe are radially arranged on the cross section of the reaction cavity. This structure can utilize the space between the distribution pipe to place a plurality of thermoscope. The number of the temperature detectors can be flexibly configured according to the monitoring requirement of the catalyst bed layer temperature. Can all set up the thermoscope at outer district, middle district, inner district, be used for detecting the temperature distribution condition in three district respectively, faithfully feed back the catalyst bed temperature distribution condition, provide effectual detection means for isothermal conversion furnace steady operation.
The cooling water distribution pipe comprises cooling water distribution short pipes and cooling water distribution long pipes which are arranged at intervals; the steam-water collecting distribution pipe comprises steam-water collecting distribution short pipes and steam-water collecting distribution long pipes which are arranged at intervals.
The steam-water collecting distribution long pipe is aligned with the outer end of the steam-water collecting distribution short pipe, the cooling water distribution long pipe is aligned with the outer end of the cooling water distribution short pipe, and the cooling water distribution pipe is symmetrically arranged with the steam-water collecting distribution pipe up and down.
Each steam-water collecting and distributing pipe is connected with the steam conveying pipeline through an annular steam-water collecting pipe; each cooling water distribution pipe is connected with the cooling water conveying pipeline through an annular cooling water connecting pipe; the steam-water collecting pipe and the cooling water collecting pipe are concentrically arranged with the catalyst frame.
Each heat exchange tube is divided into an outer area close to the catalyst frame, an inner area close to the synthesis gas collecting tube and a middle area between the two areas on the cross section of the reaction cavity according to the arrangement density;
the long vapor-water collecting and distributing pipes are communicated with the corresponding outer zone, the middle zone and the heat exchange pipes in the inner zone; the steam-water collecting distribution short pipes are communicated with the heat exchange pipes in the corresponding outer zone and the middle zone;
the cooling water distribution long pipe is communicated with the corresponding outer zone, the middle zone and each heat exchange pipe in the inner zone; the cooling water distribution short pipe is communicated with the heat exchange pipes in the corresponding outer zone and the middle zone;
the number of the heat exchange tubes arranged in the outer zone accounts for 50-70% of the total number of the heat exchange tubes, the number of the heat exchange tubes arranged in the middle zone accounts for 20-40% of the total number of the heat exchange tubes, and the number of the heat exchange tubes arranged in the inner zone accounts for 8-15% of the total number of the heat exchange tubes.
Compared with the traditional isothermal shift converter, the number of the heat exchange tubes of the middle area and the inner area is obviously reduced, and the number of the heat exchange tubes of the isothermal shift converter with the same scale is reduced by 15-25%, so that the equipment investment is obviously reduced.
The circumferential distance between adjacent heat exchange tubes in the outer zone is 60-90 mm; the circumferential distance between adjacent heat exchange tubes in the middle area is 80-140 mm, and the circumferential distance between adjacent heat exchange tubes in the inner area is 100-160 mm;
in the same radial line direction, the distance between the adjacent heat exchange tubes is gradually increased from outside to inside, and the distances are arranged in an equal difference array with the tolerance of 3-10 mm.
The circumferential distance and the radial distance of the heat exchange tubes can well control the temperature difference of a catalyst bed layer according to the characteristics of CO conversion reaction, and also consider the factors of catalyst loading and unloading, investment, welding manufacture and the like. When the distance between the heat exchange tubes is too large, the heat exchange area is small, the heat removal of the bed layer of the isothermal shift converter is small, the high temperature difference of the catalyst bed layer is caused, and the reaction efficiency is further influenced. When the distance between the heat exchange pipes is too small, the heat exchange area is increased, the low temperature difference of a catalyst bed layer can be ensured, the reaction efficiency is improved, the investment is increased, the loading and unloading of the catalyst are difficult, the welding seams of the heat exchange pipes are too close to each other, the manufacturing is difficult, and the welding seam quality is influenced by the mutual overlapping of the welding seam heat affected zones. In consideration of the characteristics of the CO conversion reaction, the raw gas flows through the outer zone, the middle zone and the inner zone in the isothermal conversion furnace in sequence. 60% -80% of CO in the outer zone completes the shift reaction, a large amount of heat is released in the reaction, and dense heat exchange tubes are required to be arranged for heat removal, so that the circumferential distance and the radial distance between adjacent heat exchange tubes in the zone are small. The number of the heat exchange tubes arranged on the outer zone accounts for 50-70% of the total number of the heat exchange tubes. Along with the reaction, the CO content in the middle area and the inner area is gradually reduced, the reaction heat release is gradually reduced, the heat quantity to be removed is smaller and smaller, the circumferential distance and the radial distance between the heat exchange pipes are gradually increased, the arranged heat exchange pipes are gradually sparse,
compared with the prior art, the invention has the advantages that:
the non-shift gas secondary line is arranged for adjusting the components of the synthesis gas, so that the flexibility of the operation of the device is increased, the flow of the crude gas to each shift converter is reduced, the size of each shift converter is reduced, and the equipment investment of the device is reduced.
The isothermal shift converter and the gas-cooled shift converter are connected in parallel, and the raw gas is divided into two streams which respectively enter two different shift converters. After the crude gas is shunted, the gas quantity entering each shift converter is further reduced, and the equipment size of the isothermal shift converter and the air-cooled shift converter can be further reduced.
The heat transfer tube bundle is arranged in the air-cooled shift converter and used for overheating intermediate-pressure steam which is generated as a byproduct by the isothermal shift converter and the intermediate-pressure steam generator, and meanwhile, reaction heat of the air-cooled shift converter is transferred away, so that the overtemperature of the air-cooled shift converter can be effectively avoided.
The non-transformed gas is led out from the outlet of the detoxification slot, thereby effectively avoiding the dust carried in the non-transformed gas from blocking subsequent equipment and pipelines, reducing the probability of scaling on the surface of the heat exchange tube in the subsequent heat exchanger and improving the heat exchange efficiency. At the same time, one non-shift gas steam generator and one non-shift gas separator can be saved.
The isothermal shift converter provided by the invention has the following advantages:
according to the characteristics of CO conversion reaction, heat exchange tubes are arranged in a mode of being dense outside and sparse inside in a mode of keeping the direction consistent with the gas inlet direction of the raw gas; the high-low temperature area of the catalyst bed layer is matched through the density arrangement of the heat exchange tubes; the high-temperature zone heat exchange tubes are densely arranged, the low-temperature zone heat exchange tubes are sparsely arranged, the requirements of heat exchange tube welding, investment, catalyst loading and unloading, catalyst bed temperature difference and the like are considered, the temperature difference of the catalyst bed on the same plane can be accurately controlled to be 3-5 ℃, and the axial temperature difference is controlled to be 5-15 ℃. The arrangement of the heat exchange tubes of the inner zone, the middle zone and the outer zone of the isothermal shift converter is particularly suitable for the raw material gas with the CO dry-basis concentration higher than 60 percent. The high CO concentration means that the heat release of the initial reaction is large, the arrangement density of the heat exchange pipes is set in a targeted and partitioned manner, the uniform distribution of the bed temperature is facilitated, the local overtemperature is avoided, the service life of the catalyst is prolonged, and the equipment investment is reduced.
The size of the isothermal conversion furnace can be flexibly adjusted according to the scale of the device, and the size of the isothermal conversion furnace can be flexibly adjusted to adapt to the treatment capacity of different scales only by changing the lengths of the cooling water distribution pipe and the steam-water collection distribution pipe, and/or increasing or reducing the number of circumferences of the heat exchange pipes, and/or changing the diameter of the cylinder.
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 used in an embodiment of the present invention;
FIG. 3 isbase:Sub>A cross-sectional view taken along line A-A of FIG. 2;
FIG. 4 is a cross-sectional view taken along line B-B of FIG. 2;
FIG. 5 is a partial enlarged view of portion C of FIG. 4;
fig. 6 and 7 are schematic views of connection structures of two heat exchange tubes and cooling water distribution tubes (steam-water collecting distribution tubes).
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
As shown in fig. 2 to 7, the structure of the isothermal conversion furnace used in the present embodiment is described as follows:
the isothermal converter comprises:
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. The upper end enclosure 11 is provided with a manhole 14, the manhole 14 is covered by a manhole cover, and the feed gas inlet 35 is arranged on the manhole cover.
And the catalyst frame 21 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 21 and the synthesis gas collecting pipeline 3. The mounting structure of the catalyst frame 21 may be any one of those in the prior art as required. In this embodiment, the upper and lower ends of the catalyst frame 21 are not closed, the upper and lower ends of the catalyst bed layer in the catalyst frame 21 are filled with refractory balls, and the catalyst frame is fixed by the cylinder 13.
A gap between the catalyst frame 21 and the side wall of the furnace body forms a feed gas channel 2a; the synthesis gas collecting pipeline 3 is sleeved in the catalyst frame 21. A reaction chamber 2b is formed between the catalyst frame 21 and the synthesis gas collecting pipe 3.
The side walls of the catalyst frame 21 are provided with through holes (not shown in the figure), and the through holes not only serve as flow channels for raw material gas and conversion gas, but also serve as gas distributors, so that the raw material gas uniformly enters the reaction chamber.
In this embodiment, the cross-sectional structures of the cylinder, the catalyst frame, and the syngas collection tube are the same, and are concentrically arranged concentric circular structures.
The synthesis gas collecting pipeline 3 is used for collecting the conversion gas and sending the conversion gas out of the furnace body 1 through a synthesis gas conveying pipeline 33, is arranged in the catalyst frame and is coaxially arranged with the catalyst frame, and is formed by sequentially and detachably connecting a plurality of sections of cylinder bodies 31, the length of each cylinder body 31 is 800-1200 mm, and the adjacent cylinder bodies 31 are connected through flanges 34 in the embodiment; the side wall of each cylinder 31 is provided with a plurality of air inlets (not shown in the figure) for the conversion 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 collecting tube 3 is connected with a synthesis gas conveying pipe 33. The synthesis gas collecting pipeline 3 adopts a detachable structure, is convenient to disassemble and assemble, is beneficial to the inspection and maintenance of the isothermal shift converter internals, and is beneficial to the loading and unloading of the catalyst and the leakage detection, maintenance and replacement of the subsequent heat exchange tubes.
And the steam collecting pipe is used for collecting steam-water mixture, is arranged at the upper part of the catalyst frame and is divided into a steam-water collecting pipe 57 and a steam-water collecting distribution pipe 55. The steam-water collecting pipe 57 is an annular pipe and is arranged concentrically with the cylinder, and the outlet of the annular pipe is communicated with the steam conveying pipe 58. The inlet of the annular pipeline is arranged below and is provided with a plurality of openings communicated with the collecting connecting pipes 56, and the number of the openings is the same as that of the collecting connecting pipes 56. The collecting connecting pipe 56 is used for communicating the steam-water collecting pipe 57 and the steam-water collecting distribution pipe 55.
The steam-water collecting and distributing pipes 55 are provided with a plurality of steam-water collecting and distributing pipes which are uniformly arranged in a radial direction of the cylinder body, and the steam-water collecting and distributing pipes are divided into two groups according to the length, namely a steam-water collecting and distributing short pipe 55a and a steam-water collecting and distributing long pipe 55b. The short steam-water collecting and distributing pipes 55a and the long steam-water collecting and distributing pipes 55b are arranged in a staggered manner in sequence. The two ends of the steam-water collecting distribution pipe are provided with pipe caps, the outlet of the steam-water collecting distribution pipe is arranged above the pipe caps and is communicated with the collecting connecting pipes 56, and the number of the collecting connecting pipes 56 is the same as that of the steam-water collecting distribution pipes. The inlets of the steam-water collecting and distributing pipes are provided with a plurality of inlets which are respectively connected with the outlets of the heat exchange pipes corresponding to the inlets.
The cooling water distribution pipe is used for uniformly distributing boiler water in each heat exchange pipe, is arranged at the lower part of the catalyst frame, has the same structural form as the steam collection distribution pipe, and comprises a cooling water connecting pipe 52 and a cooling water distribution pipe 54. The outlet of the cooling water conveying pipeline 51 is connected with the inlet of a cooling water connecting pipe 52, the outlet of the cooling water connecting pipe 52 is communicated with the inlet of a distribution connecting pipe 53, the outlet of the distribution connecting pipe 53 is communicated with the inlet of a cooling water distribution pipe 54, and the outlet of the cooling water distribution pipe 54 is communicated with the inlets of the heat exchange pipes.
The heat exchange tubes are multiple, one end of each heat exchange tube is connected to the cooling water distribution tube 54, the other end of each heat exchange tube is connected to the steam-water collection distribution tube 55, and the heat exchange tubes are vertically arranged in the catalyst bed layer in a penetrating mode and parallel to the axis of the furnace body 1. The heat exchange tubes are arranged on a plurality of concentric circumferential lines in the reaction cavity, the heat exchange tubes on the same circumferential line are uniformly distributed at intervals in the circumferential direction, and the heat exchange tubes are radially arranged along the radial direction of the catalyst frame. According to different density degrees arranged along the circumferential direction of the heat exchange tube, the heat exchange tube is divided into three areas, namely an outer area, a middle area and an inner area from outside to inside along the radial direction. For ease of distinction, and viewing, the heat exchange tubes of the outer zones in fig. 4-5 are represented by circles with cross-hatching ("×") and are designated outer zone heat exchange tubes 41; the middle heat exchange tube is represented by a solid circle and named as a middle heat exchange tube 42; the inner heat exchange tubes are indicated by hollow circles and are designated inner zone heat exchange tubes 43.
In this embodiment, the arrangement principle of each heat exchange tube is as follows: in the circumferential direction, the circumferential distance y of the outer-zone heat exchange tubes 41 is controlled to be between 60 and 90mm; the circumferential distance y of the middle heat exchange tube 42 is controlled between 80 mm and 140mm, and the circumferential distance y of the inner heat exchange tube 43 is controlled between 100 mm and 160 mm. On the same radial line direction, the interval x of heat exchange tube radial direction is 60~ 130mm, and outside-in grow gradually, and the interval becomes the arithmetic progression and arranges, and adjacent radial interval differs 3~10mm, and this embodiment interval differs 3mm.
The same circumference section of each cooling water distribution pipe and each steam-water collection distribution pipe is connected with a plurality of forms of heat exchange pipes, namely, a plurality of heat exchange pipes can be connected on the same section of the distribution pipe, and the number of the connected heat exchange pipes is related to the outer perimeter of the section of the distribution pipe and the size of the heat exchange pipes. In this embodiment, taking the dimensions of each cooling water distribution pipe and each steam-water collecting distribution pipe as DN200 and the heat exchange pipe phi 25 as an example, 2 typical connection forms are adopted in combination with the density form of the heat exchange pipes of the inner zone, the middle zone and the outer zone and the corresponding relationship between the cooling water distribution pipe and each steam-water collecting distribution pipe. As shown in fig. 6 and 7, the heat exchange tubes of the outer zone are dense, and each cooling water distribution tube and each steam-water collecting distribution tube are connected with 6 heat exchange tubes at the same circumferential section. The middle area and the inner area are connected with 3 heat exchange tubes through the same circumferential section of each cooling water distribution tube and each steam-water collection distribution tube. The connecting mode is simplified, the standardization is easy, the batch industrialized production is prefabricated, the production cost is low, and the quality is high.
The raw gas enters the cavity of the upper end socket of the isothermal shift converter through the raw gas inlet 35, goes down along the raw gas channel 2a, uniformly enters the catalyst bed layer of the reaction cavity through each through hole on the catalyst frame, sequentially passes through the outer zone, the middle zone and the inner zone, and performs CO shift reaction in each zone. CO content of outer zone > CO content of middle zone > CO content of inner zone, i.e. heat of reaction of outer zone > heat of reaction of middle zone > heat of reaction of inner zone. 60% -80% of CO conversion reaction is completed in the outer zone, a large amount of reaction heat is generated and accumulated in the conversion reaction, dense heat exchange tubes are required to be arranged for heat removal, the CO content is gradually reduced in the middle zone and the inner zone along with the reaction, the reaction heat release is gradually reduced, the heat required to be removed is smaller and smaller, and the arranged heat exchange tubes are thinner. In this embodiment, the number of the heat exchange tubes in the outer zone accounts for about 60% of the total number of the heat exchange tubes, the number of the heat exchange tubes in the middle zone accounts for about 30% of the total number of the heat exchange tubes, and the number of the heat exchange tubes in the inner zone accounts for about 10% of the total number of the heat exchange tubes. The density arrangement of the heat exchange tubes is favorable for uniform heat removal, and the temperature difference of the catalyst bed layer on the same plane is controlled to be 3-5 ℃ and the axial temperature difference is controlled to be 5-15 ℃ through the reasonable arrangement of the heat exchange tubes.
In order to monitor the distribution condition of the bed layer temperature, the isothermal conversion furnace is provided with a plurality of temperature detectors 61, sleeve pipes of the temperature detectors are parallel to the axis of the furnace body 1 and vertically penetrate through the catalyst bed layers, and a plurality of temperature measuring points are arranged in each temperature detector and used for monitoring the temperature distribution of different catalyst bed layer heights. Thermometers are one type of prior art. Because the steam-water collecting and distributing pipes are radially arranged along the radial direction of the cylinder, the clearance between the steam-water collecting and distributing short pipe 55a and the steam-water collecting and distributing long pipe 55b facilitates the crossing and placement of the temperature detectors 61, and the clearance is uniformly distributed on the radial section of the cylinder, thereby being beneficial to the uniform distribution of the temperature detectors on the radial section of the cylinder. The number of the thermometers can be flexibly configured according to the monitoring requirement of the temperature of the catalyst bed, eighteen sets of thermometers are arranged in the embodiment, and are distributed in the outer zone, the middle zone and the inner zone and are respectively used for detecting the temperature distribution condition of the three zones.
Each heat exchange tube is arranged in a radial shape, and the catalyst is convenient to unload. During maintenance, tools can be inserted into gaps between adjacent radioactive rays for accumulated catalyst blocks so as to conveniently break the catalyst blocks; meanwhile, the filling of the catalyst is facilitated, when the catalyst is filled, the catalyst is simply poured into the catalyst frame from the upper part, catalyst particles fall along gaps among the heat exchange tubes, and the gaps are unobstructed from top to bottom, so that the catalyst cannot be blocked in the falling process, and the inner cavity of the whole catalyst frame can be uniformly distributed.
The steam delivery pipe 58 is provided with an expansion joint 58a for absorbing thermal stress.
The working principle of the isothermal converter is described as follows:
the raw gas enters the cavity of the upper end socket of the isothermal conversion furnace through the raw gas inlet 35, goes down along the raw gas channel, uniformly enters the catalyst bed layer of the reaction cavity through each through hole on the catalyst frame, and sequentially passes through the outer zone, the middle zone and the inner zone to carry out CO conversion reaction to form conversion gas. Boiler water in a steam drum (not shown in the figure) enters each heat exchange tube through a cooling water conveying pipe, a cooling water connecting pipe, a distribution connecting pipe and a cooling water distribution pipe in a natural circulation mode, reaction heat of a catalyst bed layer in a reaction cavity is taken away, a generated steam-water mixture returns to the steam drum through a steam-water collecting pipe, a collection connecting pipe, a steam-water collecting pipe and a steam conveying pipeline for steam-liquid separation, and saturated steam is obtained as a byproduct. The shifted gas is delivered to the downstream system through the syngas collection header 3 via syngas delivery conduit 33.
The cooling water distribution pipe and the steam-water collecting distribution pipe in the embodiment can adopt standard parts, and in the outer area, each heat exchange pipe is connected with the cooling water distribution pipe and the steam-water collecting distribution pipe in the same type; in the middle area and the inner area, each heat exchange tube is connected with a cooling water distribution tube and a steam-water collecting distribution tube in the same type; the cooling water distribution pipe and the steam-water collection distribution pipe are arranged in an up-and-down symmetrical manner; the integral structure of the equipment and the structure of each heat exchange pipe are simple, and the connecting structure of the radial distribution pipes and the heat exchange pipes can realize the modular design and manufacture of the equipment, effectively shorten the manufacturing period of the equipment and reduce the manufacturing cost of the equipment.
Each heat exchange tube is respectively connected to each radial distribution tube. The distribution pipe is provided with a plurality of circumferential sections in the polar axis direction; the polar axis arrangement form of the distribution pipe is favorable for realizing the arrangement structure of the heat exchange pipe with dense outside and sparse inside, is convenient for realizing standardized modular manufacturing, is favorable for factory batch manufacturing, shortens the manufacturing period of equipment, reduces the manufacturing cost of the equipment, and improves the manufacturing quality of the equipment.
As shown in figure 1, crude gas 1' from a pulverized coal gasification device with the temperature of 200 ℃, the pressure of 3.8MPa (G), the CO content of 72.1 percent (dry basis, mol percent) and the water vapor ratio of 0.77 is separated by a crude gas feeding separator 2' to obtain condensate, then the condensate enters a crude gas heater 3', the crude gas heater is heated to 250 ℃ and then enters a detoxification tank 4, purified gas after impurities such as dust and the like are removed by the detoxification tank 4 is divided into three streams, wherein the first stream of purified gas 6 accounting for 25v percent of the total amount is non-conversion gas, the second stream of purified gas 5 accounting for 25v percent of the total amount is sent to an air-cooled conversion furnace 8 for conversion reaction, and the remaining third stream of purified gas 7 is sent to an isothermal conversion furnace 9 for conversion reaction.
A heat exchange tube bundle is arranged in the isothermal converter 9, the installation position of the steam pocket is higher than that of the isothermal converter, boiler water in the steam pocket 10 enters the isothermal converter 9 in a natural circulation mode to take reaction heat away, and a byproduct of 4.0MPa (G) medium-pressure saturated steam is produced. The first converting gas 11' with 280 ℃ at the outlet of the isothermal converting furnace 9 enters a medium-pressure boiler water preheater 12', the medium-pressure boiler water with 4.5MPa (G) is preheated to 240 ℃ and then is sent to a steam drum 10 and a medium-pressure steam generator 13', and the temperature of the first converting gas is reduced to 205 ℃. The byproduct 4.0MPa (G) middle-pressure saturated steam of the isothermal shift converter 9 is sent into the air-cooled shift converter 8 for overheating after being subjected to liquid separation by a steam drum 10.
A heat exchange tube bundle is arranged in the gas-cooled shift converter 8, medium-pressure saturated steam with the pressure of 4.5MPa (G) which is a byproduct of the isothermal shift converter 10 and the medium-pressure steam generator 13' is converged and then enters the heat exchange tube bundle of the gas-cooled shift converter as a heat taking medium, and the medium-pressure steam which is overheated to 400 ℃ is sent to downstream users. The second conversion gas with 430 ℃ at the outlet of the air cooling shift converter 8 is firstly sent into a medium-pressure steam generator 13 'to produce 4.0MPa (G) medium-pressure saturated steam as a byproduct, the temperature is reduced to 360 ℃, then the second conversion gas enters a raw gas heater 3' to exchange heat with raw gas, the temperature is reduced to 220 ℃, then the second conversion gas enters a low-pressure steam superheater 14 to superheat the 0.45MPa (G) low-pressure saturated steam to 200 ℃, the temperature of the second conversion gas is reduced to 205 ℃, the second conversion gas is mixed with the first conversion gas and the first purified gas 6 from the medium-pressure boiler water preheater 12 'to obtain raw synthesis gas, the raw synthesis gas enters a low-pressure steam generator 15' to produce 0.45MPa (G) low-pressure saturated steam as a byproduct, and the temperature of the raw synthesis gas is reduced to 175 ℃.
The first purified gas 6 conveying pipeline is provided with a flowmeter and a first flow control valve 17', and H in the crude synthesis gas is controlled by adjusting the flow of the first purified gas 6 2 And the molar ratio of the raw synthesis gas to the CO is 2.3, and the raw synthesis gas is further cooled, separated and sent to a downstream device.
And a flowmeter and a second flow control valve 16' are arranged on the third purified gas 7 pipeline and are used for distributing the purified gas flow of the cooling-cooling conversion furnace 8 and the isothermal conversion furnace 9.
Effects of the implementation
Taking a CO isothermal conversion device matched with a project of producing 100 ten thousand tons of methanol from coal in one year as an example, the crude gas entering the CO isothermal conversion device is about 274600Nm 3 The main parameters of the prior art and of the invention are compared on a dry basis in Table 1, at a pressure of 3.8MPa (G), a temperature of 201 ℃ and a CO concentration of 72.1% (V% on a dry basis).
TABLE 1
| Prior Art | Examples | |
| Raw gas (dry basis) | 274600Nm 3 /h | 274600Nm 3 /h |
| Number of devices | A set of | A set of |
| Number of devices | 9 tables | 11 tables |
| Entering isothermal conversion furnace gas volume (dry basis) | 219725Nm 3 /h | 157920Nm 3 /h |
| Specification of isothermal shift converter | Φ4600 | Φ4000 |
| Air cooling shift converter | Is free of | 1 table |
| Medium-pressure steam generator | Is free of | 1 table |
| Medium pressure steam | Saturated medium pressure steam | Superheated medium pressure steam |
It can be seen from table 1 that if a conventional isothermal shift process is adopted in a CO shift device for a project of producing 100 ten thousand tons of coal into methanol annually, the specification of the isothermal shift furnace is phi 4600, the process technology of the present invention is adopted, the specification of the isothermal shift furnace is phi 4000, and secondly, only saturated medium pressure steam can be produced in the prior art, and the process technology of the present invention can produce superheated medium pressure steam. Compared with the single steam superheater (the steam superheater consumes fuel gas and the exhaust gas temperature is about 150 ℃), the process of the invention has the advantages of low investment, high heat recovery rate, low energy consumption and the like.
Secondly, because the isothermal conversion furnace of the invention can flexibly adjust the size of the furnace according to the scale of the device, when the scale of the device is not changed, the product structure is adjusted or the process flow is changed, the isothermal conversion furnace is as follows: when the conversion gas quantity, the conversion reaction depth, the ratio of H2 to CO of the synthesis gas and the like are changed, the processing capacity of the furnace can be flexibly adjusted only by changing the lengths of the cooling water distribution pipe and the steam-water collection distribution pipe and increasing or reducing the circumference number of the heat exchange pipes.
Claims (7)
1. A process for preparing synthesis gas by isothermal transformation and parallel gas-cooled transformation matched with pulverized coal gasification is characterized by comprising the following steps:
raw gas from a pulverized coal gasification device with the temperature of 190-220 ℃, the pressure of 3.0-4.5 MPa and the water-gas molar ratio of 0.5-1.0 is separated out of condensate by a raw gas feed separator, then the condensate enters a raw gas heater, the raw gas is heated to 220-270 ℃ and then enters a detoxification tank to remove impurities, and the obtained purified gas is divided into three strands, wherein the first strand of purified gas accounting for 15-35 v% of the total amount is non-converted gas, the second strand of purified gas accounting for 15-35 v% of the total amount is sent to an air-cooled conversion furnace to carry out conversion reaction, and the remaining third strand of purified gas is sent to an isothermal conversion furnace to carry out conversion reaction;
a heat exchange tube bundle is arranged in the isothermal conversion furnace, boiler water in the steam drum is used as a heat taking medium to enter the isothermal conversion furnace to take reaction heat away, and meanwhile, medium-pressure saturated steam with the pressure of 3.5-6.0 MPa is byproduct; the first converted gas with the temperature of 260-320 ℃ obtained at the outlet of the isothermal conversion furnace enters a medium-pressure boiler water preheater to exchange heat with medium-pressure boiler water, the medium-pressure boiler water with the pressure of 3.5-6.0 MPa is preheated to 230-250 ℃ and then is divided into two parts which are respectively sent to a steam drum and a medium-pressure steam generator, and the temperature of the first converted gas is reduced to 200-220 ℃; returning 3.5-6.0 MPa medium-pressure saturated steam as a byproduct of the isothermal shift converter to the steam drum for liquid separation, and then sending the steam into the air-cooled shift converter;
a heat exchange tube bundle is arranged in the gas-cooled converter, medium-pressure saturated steam from the isothermal converter and the medium-pressure steam generator is converged and then enters the heat exchange tube bundle in the gas-cooled converter as a heat taking medium, the medium-pressure saturated steam is superheated to 350-420 ℃, and the superheated medium-pressure steam is sent to downstream users; the second change gas with the temperature of 370-450 ℃ obtained at the outlet of the gas cooling shift converter is firstly sent into a medium-pressure steam generator to produce a byproduct of 3.5-6.0 MPa medium-pressure saturated steam, the temperature is reduced to 330-400 ℃, then the second change gas enters a raw gas heater to exchange heat with the raw gas, the temperature is reduced to 220-250 ℃, then the second change gas enters a low-pressure steam superheater, the low-pressure saturated steam with the pressure of 0.4-1.0 MPa is superheated to 180-250 ℃, the temperature of the second change gas is reduced to 200-220 ℃, then the second change gas is mixed with the first change gas from the medium-pressure boiler water preheater and the first strand of purified gas to obtain a raw synthesis gas, the raw synthesis gas enters the low-pressure steam generator to produce a byproduct of 0.4-1.0 MPa low-pressure saturated steam, and the temperature of the raw synthesis gas is reduced to 170-200 ℃ and then sent to the downstream;
a flowmeter and a first flow control valve are arranged on the first strand of purified gas conveying pipeline, and the flow of H in the crude synthesis gas is controlled by adjusting the flow of the first strand of purified gas 2 The molar ratio of the carbon dioxide to the CO is 2.0 to 3.0;
the third purified gas pipeline is provided with a flowmeter and a second flow control valve and is used for distributing the purified gas flow of the degassing and cold conversion furnace and the isothermal conversion furnace;
the installation position of the steam drum is higher than the isothermal shift converter, and boiler water in the steam drum enters the isothermal shift converter in a natural circulation mode.
2. The process for preparing the synthesis gas by the isothermal transformation and the parallel gas-cooled transformation matched with the pulverized coal gasification as claimed in claim 1, wherein the process 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 cavity between the catalyst frame and the synthesis gas collecting pipeline forms a reaction cavity;
the heat exchange tubes are arranged on a plurality of concentric circumferential lines, the heat exchange tubes are uniformly arranged on the respective circumferential lines, and the arrangement distance of the heat exchange tubes on the respective circumferential lines is gradually increased from outside to inside;
the inlet of each heat exchange tube is respectively connected with a corresponding cooling water distribution tube, and each cooling water distribution tube is communicated with a cooling water conveying pipeline; outlets of the heat exchange tubes are respectively connected with steam-water collecting and distributing tubes corresponding to the outlets, and the steam-water collecting and distributing tubes are communicated with a steam conveying pipeline;
and the cooling water distribution pipes and the steam-water collection distribution pipes are radially arranged on the cross section of the reaction cavity.
3. The isothermal-shift parallel gas-cooled shift synthesis gas process matched with pulverized coal gasification according to claim 2, wherein the cooling water distribution pipe comprises short cooling water distribution pipes and long cooling water distribution pipes which are arranged at intervals; the steam-water collecting distribution pipe comprises steam-water collecting distribution short pipes and steam-water collecting distribution long pipes which are arranged at intervals.
4. The isothermal shift parallel gas-cooled shift synthesis gas process matched with pulverized coal gasification according to claim 3, wherein the long steam-water collecting and distributing pipe is aligned with the outer end of the short steam-water collecting and distributing pipe, the long cooling water distributing pipe is aligned with the outer end of the short cooling water distributing pipe, and the long cooling water distributing pipe and the short steam-water collecting and distributing pipe are arranged symmetrically up and down.
5. The isothermal shift parallel gas-cooled shift synthesis gas process matched with pulverized coal gasification according to claim 4, wherein each steam-water collection distribution pipe is connected with the steam conveying pipeline through an annular steam-water collection pipe; each cooling water distribution pipe is connected with the cooling water conveying pipeline through an annular cooling water connecting pipe; the steam-water collecting pipe and the cooling water collecting pipe are concentrically arranged with the catalyst frame.
6. The process for preparing the synthesis gas by the isothermal transformation parallel air-cooled transformation matched with the pulverized coal gasification of any one of claims 2 to 5, wherein each heat exchange tube is divided into an outer zone close to the catalyst frame, an inner zone close to the synthesis gas collecting tube and a middle zone positioned between the outer zone and the inner zone on the cross section of the reaction cavity according to the arrangement density;
the long vapor-water collecting and distributing pipes are communicated with the corresponding outer zone, the middle zone and the heat exchange pipes in the inner zone; the steam-water collecting distribution short pipes are communicated with the heat exchange pipes in the corresponding outer zone and the middle zone;
the cooling water distribution long pipe is communicated with the corresponding outer zone, the middle zone and each heat exchange pipe in the inner zone; the cooling water distribution short pipe is communicated with the heat exchange pipes in the corresponding outer zone and the middle zone;
the number of the heat exchange tubes arranged in the outer zone accounts for 50-70% of the total number of the heat exchange tubes, the number of the heat exchange tubes arranged in the middle zone accounts for 20-40% of the total number of the heat exchange tubes, and the number of the heat exchange tubes arranged in the inner zone accounts for 8-15% of the total number of the heat exchange tubes.
7. The process for preparing the synthesis gas by the isothermal transformation parallel air-cooled transformation matched with pulverized coal gasification of claim 6, wherein the circumferential distance between adjacent heat exchange tubes in the outer zone is 60-90mm; the circumferential distance between adjacent heat exchange tubes in the middle area ranges from 80 to 140mm, and the circumferential distance between adjacent heat exchange tubes in the inner area ranges from 100 to 160mm;
in the same radial line direction, the distance between adjacent heat exchange tubes is gradually increased from outside to inside, and the distances are arranged in an arithmetic progression with the tolerance of 3-10mm.
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