CN113501492A - Long-period transformation process for adjusting water-gas ratio by two-step method for oxo synthesis - Google Patents
Long-period transformation process for adjusting water-gas ratio by two-step method for oxo synthesis Download PDFInfo
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- CN113501492A CN113501492A CN202110762127.7A CN202110762127A CN113501492A CN 113501492 A CN113501492 A CN 113501492A CN 202110762127 A CN202110762127 A CN 202110762127A CN 113501492 A CN113501492 A CN 113501492A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- 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 long-period shift process for adjusting water-gas ratio by a two-step method for oxo synthesis, which has wide application range, is suitable for oxo synthesis in coal chemical industry, comprises the matched carbon monoxide shift technical processes of methanol synthesis, synthetic oil, synthetic natural gas and the like, and has the advantages of short process flow, less equipment quantity, simple control and low investment and operation cost; the invention adopts the 1# shift converter adopting the sectional reaction technology, and can effectively adjust the water-gas ratio of the system by adjusting the amount of gas phase entering the low-pressure steam generator under the condition of equivalent catalyst loading; the problem that the 1# shift converter is possibly over-temperature caused by different load changes can be effectively solved by adjusting the gas amount of the 1# shift converter bypass; meanwhile, the hydrogen-carbon ratio can be flexibly and effectively adjusted by controlling the bypass at the outlet of the 1# converter, and the operation difficulty is reduced; for the working condition that the temperature needs to be raised at the end stage of the catalyst, the conversion depth can also be improved by passing the synthesis gas through the section B and the section A of the 1# conversion furnace in sequence.
Description
Technical Field
The invention relates to a long-period shift process for adjusting water-gas ratio by a two-step method for oxo synthesis.
Background
The carbon monoxide shift device has a very important position in a synthesis gas production device, and the raw synthesis gas from an upstream gasification device is totally or partially reacted to generate hydrogen under the action of a catalyst according to the requirement of a downstream product on the hydrogen-carbon ratio. Different product requirements have a greater impact on the set up of the conversion process flow. For plants producing hydrogen, synthetic ammonia, it is generally necessary to convert as completely as possible the carbon monoxide into hydrogen; for plants producing oxo-synthesis gas, such as methanol, ethylene glycol, synthetic oil, natural gas, etc., the shift reaction depth is shallow and the ratio of carbon monoxide to hydrogen in the synthesis gas needs to be adjusted according to product requirements. The novel continuous pressurized coal gasification technology is mainly divided into coal water slurry gasification technology (such as GE, multi-nozzle, multi-element slurry and the like) and pulverized coal gasification technology (shell, oriental furnace, space furnace, GSP and the like). The concentration of the crude synthesis gas produced by the gasification of the pulverized coal is usually 10-20% higher than that of the coal water slurry, and particularly, the crude synthesis gas produced by the gasification of the chilling type pulverized coal has high carbon monoxide concentration and high water-gas ratio of 0.7-1.0, and the conversion reaction driving force is large, so that the overtemperature of the first conversion furnace is easily caused, and certain difficulty is brought to the process setting of the conversion reaction.
The adiabatic shift process for producing oxo-gas by chilling type powdered coal gasification is usually as follows:
(1) high water-gas ratio conversion process. The steam is added into the inlet of the conversion device in a large amount at one time, so that the steam-gas ratio is increased to be more than 1.6 or even higher. The process has the advantages that the overtemperature of the first shift converter can be avoided, and the operation is safe and stable. However, as the amount of steam input increases, a great waste of energy is caused, and the added steam is separated in a condensate manner in the downstream low-grade heat recovery stage, so that the equipment investment and the operation cost are increased. The service life of the shift catalyst is short, usually 1-2 years, the catalyst has high requirements on the content of coal sulfur, and if the content of hydrogen sulfide in the crude synthesis gas is low, the catalyst is easy to cause reverse vulcanization.
(2) A low water-gas ratio shift process. The low-pressure steam generator is arranged before the first shift converter, so that part of water brought by the crude synthesis gas can be separated, the water-gas ratio is reduced to about 0.25, the shift reaction driving force of the first shift converter is greatly reduced under the condition of no change of load, the purpose of controlling shift overtemperature is achieved, and high-grade steam can be produced as a byproduct. However, because the content of carbon monoxide in the raw synthesis gas entering the first shift converter is still very high (60% -65%), when the operation of the gasification device is unstable or the operation of the pre-low-pressure steam generator is unstable, the water-gas ratio is not reduced, and the methanation reaction of the first shift converter is likely to occur under the working condition of low water-gas ratio, so that the temperature is over-high.
(3) And (4) controlling the catalyst dynamics. The method is characterized in that the temperature of a bed layer is controlled within a controllable range by reducing the catalyst loading of a first shift converter without adding steam and by a method of far reaching reaction balance, boiler water is gradually added for subsequent shift reactions according to the requirement of reaction depth, and steam is basically not required to be added. However, the method also has certain limitations, and due to the dual functions of high carbon monoxide content and high water-gas ratio, the reaction driving force is large, the equilibrium temperature distance is large, and the dosage of the catalyst must be accurately calculated. If the catalyst loading exceeds the range, the reaction depth is increased, and the overtemperature is caused; for the stage with lower start-up load, the raw synthesis gas amount is usually only half of the normal amount or even lower, and for the same catalyst loading, the over-temperature is easily caused. However, since the catalyst loading of the first shift converter is constant, it is difficult to have a control means when the excess temperature occurs.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a long-period shift process for adjusting the water-gas ratio by a two-step method for carbonyl synthesis, which can cope with different water-gas ratios, different hydrogen-carbon ratios and crude synthesis gas loads, and the process can effectively adjust the water-gas ratio of a system, flexibly adjust the hydrogen-carbon ratio, avoid the over-temperature problem and improve the shift depth.
The technical scheme adopted by the invention for solving the technical problems is as follows: a two-step water-to-gas ratio modulated long cycle shift process for oxo synthesis, comprising the steps of:
the method comprises the following steps that firstly, crude synthesis gas from the upstream is subjected to primary liquid separation through a No. 1 gas-liquid separator and then is divided into two parts, one part is sprayed with appropriate amount of mist high-pressure boiler water through a mixer to enable the crude synthesis gas to form a supersaturated state, then the gas enters a low-pressure steam generator to produce low-pressure saturated steam as a byproduct, meanwhile, the temperature of the crude synthesis gas is reduced to separate out condensate, impurities in the gas are settled along with the condensate, and the condensate and the other part of the crude synthesis gas enter a No. 2 gas-liquid separator from the upper part and the lower part respectively to separate out the condensate;
in order to adjust the requirement of the water-gas ratio, the 2# gas-liquid separator is arranged into a two-layer structure, the upper layer gas-phase outlet has a low water-gas ratio, the lower layer gas-phase outlet has a high water-gas ratio, the lower layer gas-phase is heated to a temperature higher than the catalyst activation temperature point through a crude synthesis gas heater, and the raw gas at the outlet of the crude synthesis gas heater passes through a detoxification tank to remove impurities and components which easily cause catalyst poisoning according to the content of the impurities in the raw gas;
in the early stage of catalyst reaction, part of the purified crude synthesis gas enters a section A of a two-section type 1# shift converter, wherein the section A of the 1# shift converter is dynamically controlled, the loading amount of the catalyst is less, the shift reaction is far from reaching balance, and the temperature of shift gas at the outlet of a reactor is controlled to be 300-450 ℃; meanwhile, in order to meet the requirement of long-period operation, the 1# shift converter is provided with a section B as a spare for a section A of the 1# shift converter, the shifted gas from the outlet of the 1# shift converter is cooled by a medium-high pressure steam superheater, a crude synthesis gas heater and a 1# medium-high pressure steam generator, one part of the shifted gas is mixed with the unconverted gas and then is subjected to deep shift conversion by the 2# shift converter, the other part of the shifted gas is mixed with the gas phase at the reaction outlet of the 2# shift converter, and the mixed gas is subjected to heat recovery by the 2# medium-high pressure steam generator and then enters a downstream low-temperature waste heat recovery device for treatment.
Preferably, the 2# conversion furnace is provided with two sections, wherein the upper section is a detoxification section, and the lower section is a reaction section.
Preferably, a synthesis gas bypass 1 for controlling the synthesis gas amount sent to the 1# shift converter is arranged at the outlet of the 2# gas-liquid separator, a control valve for adjusting the flow rate of the non-shift gas is arranged on the bypass line, and the flow rate of the bypass non-shift gas is adjusted through the control valve according to the preset proportion of the shift gas and the non-shift gas so as to meet the final requirement of a synthesis gas product; meanwhile, the possible overtemperature problem of the 1# conversion furnace can be effectively controlled; in addition, in No. 1, the outlet of the high-pressure steam generator is provided with a bypass 2 for further adjusting the hydrogen-carbon ratio so as to further meet the requirements of downstream products.
Preferably, in the later stage of the catalyst reaction, the inlet valve of the section A of the 1# shift converter is closed, so that the synthesis gas preferentially passes through the section B of the 1# shift converter, and after a series of heat recovery, the synthesis gas returns to the section A of the 1# shift converter through the bypass 3 to continue the reaction, so as to further improve and ensure the reaction depth and be beneficial to the later-stage operation of the device.
Preferably, the volume content of carbon monoxide dry basis in the raw synthesis gas from upstream is 30-90%, the volume ratio of water to absolute dry gas is 0.1-1.6, and the pressure range is 1.0-9.0 MPaG.
Preferably, the byproduct saturated steam pressure of the low-pressure steam generator ranges from 0.1 MPaG to 2.5 MPaG; the byproduct saturated steam pressure range of the medium-high pressure steam generator is 2.5-8.0 MPaG.
Preferably, the raw synthesis gas heater is a combination of one or more heat exchangers connected in series or in parallel, and the outlet temperature of the raw synthesis gas is 150-350 ℃; the heat transfer heat exchanger and the waste heat exchanger are formed by combining one or more heat exchangers in series or in parallel, and one side of the waste heat exchanger is provided with cold fluid including but not limited to boiler water, saturated steam and the like; the hot fluid on the other side of the waste heat exchanger is transformed gas, and the outlet temperature is 50-400 ℃; in order to ensure that ash in the synthesis gas can be washed clean, a high-pressure boiler water spray is arranged at the outlet of the No. 1 gas-liquid separator; the 2# gas-liquid separator is divided into an upper section and a lower section, tower internals including but not limited to a tower tray and the like are arranged in the gas-liquid separator, a partition plate is arranged to establish liquid seal, the liquid phase at the upper section can be conveyed to the lower section, and meanwhile, the gas phase at the lower section is extracted from a side line; the waste heat recovery device is formed by combining equipment such as a gas-liquid separator, a heat exchanger, a washing tower and the like, and is used for recycling, cooling, washing and purifying the waste heat of the transformed gas so as to meet the feeding requirement of a downstream acid gas removal device.
Preferably, the No. 1 shift converter is a two-stage semi-isothermal shift converter, which has a vertically extending cylindrical furnace body, the top of the furnace body is provided with a crude synthesis gas inlet, the bottom of the furnace body is provided with a shift gas outlet, a partition board capable of dividing the inner cavity of the furnace body into an upper section and a lower section which are relatively independent is arranged in the furnace body, the inner layer of the upper section is a semi-isothermal zone, the outer layer is an adiabatic zone I, and the lower section is an adiabatic zone II.
The 1# conversion furnace of the present invention comprises:
the inner upper cylinder is arranged in the upper section of the furnace body and is provided with an inner cavity for filling a heat insulation shift reaction catalyst, an air inlet annular space is formed between the outer peripheral wall of the inner upper cylinder and the inner peripheral wall of the furnace body, and a plurality of first air inlets which are arranged at intervals are formed in the outer peripheral wall of the inner upper cylinder;
the central tube is arranged at the central part of the inner upper tube body, the upper end of the central tube is closed, the lower end of the central tube is provided with a lower port communicated with the lower part of the partition plate, and the peripheral wall of the central tube is provided with a plurality of air vents for allowing the gas in the inner upper tube body to enter the central tube;
the boiler water inlet cavity is arranged in the lower section of the boiler body and is close to the partition plate;
the steam collecting cavity is arranged in the upper section of the furnace body, is positioned above the inner upper cylinder body and is used for collecting steam generated by heating boiler water;
the boiler water tubes are arranged on the upper cylinder body, the lower end of each boiler water tube is connected with the boiler water inlet cavity, the upper end of each boiler water tube is connected with the steam collecting cavity, and each boiler water tube is arranged on the periphery of the central tube in a surrounding manner close to the central tube, so that a semi-isothermal area is formed in an area where the boiler water tubes are arranged in the inner upper cylinder body, and an adiabatic area I is formed in an area where the boiler water tubes are not arranged on the periphery of the semi-isothermal area;
the steam pocket is arranged above the furnace body, is communicated with the boiler water inlet cavity through a boiler water descending pipe and is communicated with the steam collecting cavity through a steam ascending pipe, and the steam pocket, the boiler water descending pipe, the boiler water inlet cavity, the boiler water array pipe, the steam collecting cavity and the steam ascending pipe jointly form a controllable saturated steam generating system; and
the inner lower cylinder is arranged in the lower section of the furnace body, is positioned below the boiler water inlet cavity and is provided with an inner cavity for filling a shift reaction catalyst; a gas mixing area is formed between the upper end of the inner lower cylinder and the partition plate, an opening for inputting the mixed gas into the gas mixing area is formed in the side wall of the furnace body, the inner lower cylinder is provided with a second gas inlet for the gas in the gas mixing area to enter and a gas outlet for outputting the reacted gas, and the gas outlet is communicated with the gas changing outlet.
The 1# conversion furnace can reach the activation temperature by mixing with the conversion gas at the upper section outlet of the conversion furnace without independently heating the gas entering the bypass to the activation temperature by a sectional reaction technology, thereby reducing the complexity of the process and the equipment investment; a semi-isothermal zone is formed in the upper section by combining a controllable steam generation system, the temperature of a conversion gas outlet can be effectively adjusted by controlling the bypass air inflow and the boiler water flow according to the load of crude synthesis gas or the water-steam ratio and the working conditions of the initial stage and the final stage of the conversion catalyst, and the stability of a downstream heat exchange system is ensured; the temperature of the transformed gas outlet can be flexibly controlled by controlling the working condition of the semi-isothermal zone, high-pressure saturated steam is superheated, an external superheater is not required to be arranged or is in thermal combination with other devices, the flow of the existing transformation process is shortened, and the investment and operation difficulty are reduced.
Compared with the prior art, the invention has the advantages that:
the invention has wide application range, can be suitable for the oxo synthesis in the coal chemical industry, comprises the technical processes of carbon monoxide transformation matched with methanol synthesis, synthetic oil, synthetic natural gas and the like, and has the advantages of short process flow, less equipment quantity, simple control and low investment and operation cost;
the invention adopts the 1# shift converter adopting the sectional reaction technology, and can effectively adjust the water-gas ratio of the system by adjusting the amount of gas phase entering the low-pressure steam generator under the condition of equivalent catalyst loading; the problem that the 1# shift converter is possibly over-temperature caused by different load changes can be effectively solved by adjusting the gas amount of the 1# shift converter bypass; meanwhile, the hydrogen-carbon ratio can be flexibly and effectively adjusted by controlling the bypass at the outlet of the 1# converter, and the operation difficulty is reduced; for the working condition that the temperature needs to be raised in the final stage of the catalyst, the conversion depth can be improved by passing the synthesis gas through the section B and the section A of the 1# conversion furnace in sequence;
according to the invention, the low-pressure steam generator is arranged at the raw synthesis gas inlet, so that the ash content impurities brought by the upstream raw synthesis gas can be effectively condensed along with the condensate, the load of the detoxification tank is reduced, and the service life of the detoxification tank is prolonged.
Drawings
FIG. 1 is a flowchart of example 1 of the present invention;
FIG. 2 is a schematic view of the structure of a No. 1 shift converter according to embodiments 1 and 2 of the present invention;
FIG. 3 is a sectional view taken along the line A-A in FIG. 2
Fig. 4 is a flowchart of embodiment 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1:
the long-period shift process for adjusting water-gas ratio by two-step method for oxo synthesis in this embodiment adopts a reaction system as shown in fig. 1, and includes a 1# gas-liquid separator 1, a mixer 2, a low-pressure steam generator 4, a 2# gas-liquid separator 6, a raw synthesis gas heater 7, a detoxification tank 8, a 1# shift converter 9, a medium-high pressure steam superheater 10, a 1# medium-high pressure steam generator 11, a 2# shift converter 12, a 2# medium-high pressure steam generator 13, and a waste heat recovery device 14, and specific connection and matching relationships of the devices conform to those in fig. 1, and will not be described herein.
The two-step water-gas ratio-adjusted long cycle shift process for oxo synthesis of this example comprises the steps of:
the raw synthesis gas from the upstream gasification unit has a temperature of 200 ℃, a pressure of 3.8MPaG, a carbon monoxide dry basis content of 65% and a water-gas ratio of 0.9. Firstly, the mixture enters a No. 1 gas-liquid separator 1 for primary liquid separation, and then is divided into two parts: a 60% crude synthesis gas is sprayed into a small amount of high-pressure boiler water through the mixer 2, enters the low-pressure steam generator 4 to produce a 0.8MPaG low-pressure saturated steam as a byproduct, and enters the upper layer of the No. 2 gas-liquid separator 6; the other 40% of the raw synthesis gas enters the lower layer of the No. 2 gas-liquid separator 6 through a raw synthesis gas bypass control valve. The raw synthesis gas from the lower layer of the No. 2 gas-liquid separator 6 is heated to 210 ℃ by a raw synthesis gas heater 7, and then enters a No. 1 shift converter 9A section after impurity components are removed by a detoxification tank 8; the raw synthesis gas which is discharged from the top of the upper layer of the 2# gas-liquid separator 6 and has the water-gas ratio of 0.9 is merged with part of the synthesis gas at the outlet of the 1# shift converter through a non-shift gas bypass regulating valve and then is sent to the 2# shift converter 12 for further reaction; the bottom of the No. 2 gas-liquid separator 6 is high-pressure process condensate which is finally sent to other devices for further treatment. Wherein, a temperature control loop is arranged on one path of the coarse synthesis gas with the medium-high water ratio in the lower layer and is used for adjusting the gas amount of the bypass control valve of the coarse synthesis gas.
In the early stage of catalyst reaction, dynamic control is adopted in the 9A section of the 1# shift converter, the loading amount of the catalyst is less, the shift reaction is far from reaching the balance, and the temperature of the shift gas at the outlet of the reactor is controlled at 450 ℃; the converted gas from the outlet of the 1# conversion furnace sequentially passes through a medium-high pressure steam superheater 10, a crude synthesis gas heater 7 and a 1# medium-high pressure steam generator 11 to recover heat to a set temperature, one part of the converted gas is mixed with unconverted gas to the set temperature through a bypass 2 and then is subjected to deep conversion through a 2# conversion furnace 12, the other part of the converted gas is mixed with the reaction outlet gas phase of the 2# conversion furnace 12 to the set temperature and then is subjected to heat recovery through a 2# medium-high pressure steam generator 13 to the set temperature, and then the heat recovery enters a downstream low-temperature waste heat recovery device 14 to be treated.
In addition, to meet the requirements of long-cycle operation, the 1# shift converter is provided with a 9B section as a backup for the 9A section of the 1# shift converter. When the catalyst in the 9A section enters the middle-end stage, the reaction depth of the raw synthesis gas is reduced, and the catalyst can be considered to be switched to the 9B section to ensure the reaction to be carried out so as to prolong the operation period of the device. Furthermore, at the end stage, the synthesis gas at the outlet of the 9B section can be considered to be sent into the bed layer of the 9A section again through the bypass 3 after heat recovery to continue the reaction so as to improve the reaction depth.
Since the above process flow depends on the specific structure implementation of the 1# shift converter, the structure of the 1# shift converter is described in detail in this embodiment as follows:
the No. 1 shift converter is a two-section type semi-isothermal shift converter, as shown in FIGS. 2 and 3, it has a vertically extending and cylindrical furnace body 19 ', the top of the furnace body 19 ' is provided with a raw synthesis gas inlet 4 ', the bottom is provided with a shift gas outlet 28 ', the furnace body 19 ' is provided with a partition board 1c which can divide the inner cavity thereof into an upper section 1a ' and a lower section 1b ', the inner layer of the upper section 1a ' is a semi-isothermal zone 8 ', the outer layer is an adiabatic zone I6 ', the lower section is an adiabatic zone II14 ', and the middle part of the furnace body 19 ' can also be provided with an outlet for outputting gas after the reaction of the upper section 1a '.
Specifically, the furnace body 19 ' is provided with an inner upper cylinder 2a ', a central tube 21 ', a boiler water inlet cavity 26 ', a steam collecting cavity 5 ', a boiler water tube 10 ', an inner lower cylinder 2b ', and a steam pocket 2 ' at the top of the furnace body 19 '.
The inner upper cylinder 2a ' is arranged in the upper section 1a ' of the furnace body 19 ' and is provided with an inner cavity for filling the adiabatic shift reaction catalyst 20 ', an air inlet annular space 9 ' is formed between the outer peripheral wall of the inner upper cylinder 2a ' and the inner peripheral wall of the furnace body 19 ', and a plurality of first air inlets 22 ' arranged at intervals are formed on the outer peripheral wall of the inner upper cylinder 2a '.
The central tube 21 ' is disposed at the central portion of the upper inner cylinder 2a ', the upper end of the central tube is closed, the lower end of the central tube has a lower port communicated with the lower portion of the partition board 1c ', and the peripheral wall of the central tube 21 ' is provided with a plurality of vent holes 211 ' for allowing the gas in the upper inner cylinder 2a ' to enter the central tube 21 '.
The boiler water inlet chamber 26 'is provided in the lower section 1 b' of the furnace body 19 'and is arranged close to the partition plate 1 c'.
The steam collecting cavity 5 'is arranged in the upper section 1 a' of the furnace body 19 'and is positioned above the inner upper cylinder 2 a' and is used for collecting steam generated by heating boiler water.
The boiler water tubes 10 'are provided with a plurality of boiler water tubes 10', the lower ends of the boiler water tubes 10 'are connected with the boiler water inlet cavity 26', the upper ends of the boiler water tubes are connected with the steam collecting cavity 5 ', and the boiler water tubes 10' are arranged around the central tube 21 'close to the central tube 21', so that a semi-isothermal area 8 'is formed in the area of the inner upper cylinder 2 a' where the boiler water tubes 10 'are arranged, and an adiabatic area I6' is formed in the area of the periphery of the semi-isothermal area 8 'where the boiler water tubes 10' are not arranged.
The steam drum 2 ' is arranged above the furnace body 19 ', the top of the steam drum 2 ' is provided with a steam outlet 1 ', the steam drum 2 ' is communicated with a boiler water inlet cavity 26 ' through a boiler water descending pipe 3 ' and is communicated with a steam collecting cavity 5 ' through a steam ascending pipe 15 ', and the steam drum 2 ' and the boiler water descending pipe 3 ', the boiler water inlet cavity 26 ', the boiler water array pipe 10 ', the steam collecting cavity 5 ' and the steam ascending pipe 15 ' jointly form a controllable saturated steam generating system.
The inner lower cylinder 2b ' is arranged in the lower section 1b ' of the furnace body 19 ' and is positioned below the boiler water inlet cavity 26 ', and is provided with an inner cavity for filling shift reaction catalysts, the inner lower cylinder 2b ' forms an adiabatic region II14 ', a gas mixing region 13 ' is formed between the upper end of the inner lower cylinder 2b ' and the partition plate 1c ', the boiler water inlet cavity 26 ' is positioned in the gas mixing region 13 ', the side wall of the furnace body 19 ' is provided with an opening for inputting mixed gas into the gas mixing region 13 ', the inner lower cylinder 2b ' is provided with a second gas inlet 21b ' for inputting gas in the mixing region 13 ' and a gas outlet 22b ' for outputting reacted gas, and the gas outlet 22b ' is communicated with a shift gas outlet 28 '.
Specifically, an air inlet gap 23b 'is formed between the outer peripheral wall of the inner lower cylinder 2 b' and the inner peripheral wall of the furnace body 19 ', a plurality of second air inlets 21 b' are arranged on the peripheral wall of the inner lower cylinder 2b 'at intervals, a plurality of air guide tubes 24 b' which are vertically arranged, closed at the upper end and open at the lower end are arranged at the central part of the inner lower cylinder 2b ', a plurality of air outlets 22 b' are arranged on the peripheral wall of the air guide tubes 24b 'at intervals, and the lower end ports of the air guide tubes 24 b' extend to a conversion air outlet 28 'of the furnace body 19'. The furnace body 19 ' is provided with a baffle plate 25b ' which is positioned at the bottom of the inner lower cylinder body 2b ' and only allows gas to be output vertically downwards through a gas guide pipe 24 b.
A transversely arranged gas distributor 23 ' with a shower structure is arranged in the mixing zone 13 ', which gas distributor 23 ' has a mixture inlet. The structure is beneficial to improving the gas mixing effect, so that the gas mixing is more uniform.
The two boiler water down-comer pipes 3 'are symmetrically arranged at two sides of the boiler water inlet cavity 26', and one boiler water down-comer pipe 3 'is provided with an adjusting valve 16' which can control the flow of fluid. The natural circulation ratio of water and gas in the system is controlled by adjusting the opening of the adjusting valve 16', so that the aims of adjusting the temperature of the conversion gas and the yield of saturated steam in the semi-isothermal reaction zone are fulfilled. The number, the arrangement range and the density of the boiler water tubes in the semi-isothermal zone can be adjusted according to the water-gas ratio of the crude synthesis gas, the load range and the temperature requirement of the transformed gas outlet, so that the heat of partial transformed gas reaction in the semi-isothermal zone is transferred away through the boiler water, and the transformed reaction in the zone is between adiabatic reaction and isothermal reaction.
The inner top wall of the furnace body 19 'forms an inverted bowl-shaped guide surface 191', the raw synthesis gas inlet 4 'is positioned at the central part of the guide surface 191', and the guide surface 191 'forms a guide structure for guiding the raw synthesis gas to the peripheral gas inlet annular gap 9', so that the structure is favorable for improving the circulation effect during gas input.
The furnace body 19 ' is provided with a catalyst loading and unloading hole I25 ' corresponding to the bottom of the inner upper cylinder body 2a ' and a catalyst loading and unloading hole II27 ' corresponding to the bottom of the inner lower cylinder body 2b ' so as to be convenient for replacing the catalyst; the side wall of the furnace body 19 ' corresponding to the mixing area 13 ' is also provided with an inspection manhole 12 ' for facilitating inspection.
The top and the bottom of the inner upper cylinder 2a ' and the inner lower cylinder 2b ' are filled with ceramic balls 11 ' for protecting and supporting the shift catalyst; the tops of the inner upper cylinder 2a ' and the inner lower cylinder 2b ' are also provided with a pressure grating 18 ' covering the top of the porcelain ball 11 ', and the porcelain ball and the catalyst can be replaced by removing the pressure grating 18 '.
When the raw synthesis gas passes through the No. 1 shift converter, the raw gas at the raw synthesis gas inlet 4 'enters the gas inlet annular space 9' through the upper end enclosure of the shift converter, passes through the adiabatic shift reaction catalyst 20 'from the axial direction through the first gas inlet 22', firstly enters the adiabatic region I6 'for adiabatic shift reaction, and then enters the semi-isothermal region 8'; the conversion gas is subjected to semi-isothermal conversion reaction in the semi-isothermal zone 8 ', the temperature is kept unchanged, redundant heat is absorbed by boiler water in a boiler water array pipe 10' of the semi-isothermal zone to generate saturated steam, and the converted gas after reaction is collected through a central pipe 21 'and enters a lower-section mixing zone 13' of the conversion furnace; the raw synthesis gas from the bypass gas inlet is fully mixed with the shift gas at the outlet of the upper section of the shift converter in the mixing zone 13 'under the action of the gas distributor 23', enters the adiabatic zone II14 'of the lower section of the shift converter for adiabatic reaction again, and is led out from the shift gas outlet 28'; in the above process, the operation flow of the controllable saturated steam generation system is as follows: the low-temperature boiler water from the boiler water downcomer 3 ' firstly enters a boiler water inlet cavity 26 ' to be collected, then enters a boiler water tube array 10 ' of a semi-isothermal zone, the low-temperature boiler water is changed into a water-vapor mixture after absorbing heat of reaction of the semi-isothermal zone 8 ', saturated steam rises along the boiler water tube array 10 ' to a steam collecting cavity 5 ' to be subjected to primary liquid separation, then continuously enters a steam pocket 2 ' along a steam riser 15 ', condensed water is separated again, and then the saturated steam is produced from a steam outlet 1 ' and is sent out of the system.
Example 2:
the long-period shift process for adjusting water-gas ratio by two-step method for oxo synthesis in the embodiment adopts a reaction system as shown in fig. 1, and includes a 1# gas-liquid separator 1, a mixer 2, a low-pressure steam generator 4, a 2# gas-liquid separator 6, a raw synthesis gas heater 7, a detoxification tank 8, a 1# shift converter 9A/B, a medium-high pressure steam superheater 10, a 1# medium-high pressure steam generator 11, a boiler water preheater 15, a 2# shift converter 17, a 2# medium-high pressure steam generator 18, and a waste heat recovery device 20, and the specific connection and matching relationship of the devices conform to fig. 4, which is not described herein.
The two-step water-gas ratio-adjusted long cycle shift process for oxo synthesis of this example comprises the steps of:
the raw synthesis gas from the upstream gasification unit has a temperature of 200 ℃, a pressure of 3.8MPaG, a carbon monoxide dry basis content of 65% and a water-gas ratio of 0.9. Firstly, the mixture enters a No. 1 gas-liquid separator 1 for primary liquid separation, and then is divided into two parts: a 40% of crude synthesis gas is sprayed into a small amount of high-pressure boiler water through the mixer 2, enters the low-pressure steam generator 4 to produce a 0.8MPaG low-pressure saturated steam as a byproduct, and enters the upper layer of the No. 2 gas-liquid separator 6; the other 60% of the raw synthesis gas enters the lower layer of the No. 2 gas-liquid separator 6 through a raw synthesis gas bypass control valve. The raw synthesis gas from the lower layer of the No. 2 gas-liquid separator 6 is heated to 210 ℃ by a raw synthesis gas heater 7, and then enters a No. 1 shift converter 9A section after impurity components are removed by a detoxification tank 8; the raw synthesis gas which is discharged from the top of the upper layer of the 2# gas-liquid separator 6 and has the water-gas ratio of 0.9 is merged with part of the synthesis gas at the outlet of the 1# shift converter through a non-shift gas bypass regulating valve and then is sent to the 2# shift converter 17 for further reaction; the bottom of the No. 2 gas-liquid separator 6 is high-pressure process condensate which is finally sent to other devices for further treatment. Wherein, a temperature control loop is arranged on one path of the coarse synthesis gas with the medium-high water ratio in the lower layer and is used for adjusting the gas amount of the bypass control valve of the coarse synthesis gas.
In the early stage of catalyst reaction, dynamic control is adopted in the 9A section of the 1# shift converter, the loading amount of the catalyst is less, the shift reaction is far from reaching the balance, and the temperature of the shift gas at the outlet of the reactor is controlled at 450 ℃; the converted gas from the outlet 9B of the 1# conversion furnace sequentially passes through a medium-high pressure steam superheater 10, a crude synthesis gas heater 7, a 1# medium-high pressure steam generator 11 and a boiler water preheater 15 to recover heat to 180 ℃, one part of the converted gas is mixed with unconverted gas to 220 ℃, then the converted gas is subjected to deep conversion by a 2# conversion furnace 12, and the other part of the converted gas is mixed with the synthesis gas from the reaction outlet of the 2# conversion furnace 17, which recovers heat by a 2# medium-high pressure steam generator 18, to 120 ℃, and then the mixed gas enters a downstream low-temperature waste heat recovery device 14 for treatment.
In addition, to meet the requirements of long-cycle operation, the 1# shift converter is provided with a 9B section as a backup for the 9A section of the 1# shift converter. When the catalyst in the 9A section enters the middle-end stage, the reaction depth of the raw synthesis gas is reduced, and the catalyst can be considered to be switched to the 9B section to ensure the reaction to be carried out so as to prolong the operation period of the device. Furthermore, at the end stage, the synthesis gas at the outlet of the 9B section can be considered to be sent into the bed layer of the 9A section again through the bypass 3 after heat recovery to continue the reaction so as to improve the reaction depth.
Claims (8)
1. A two-step water-to-gas ratio modulated long cycle shift process for oxo synthesis, comprising the steps of:
the method comprises the following steps that firstly, crude synthesis gas from the upstream is subjected to primary liquid separation through a No. 1 gas-liquid separator and then is divided into two parts, one part is sprayed with appropriate amount of mist high-pressure boiler water through a mixer to enable the crude synthesis gas to form a supersaturated state, then the gas enters a low-pressure steam generator to produce low-pressure saturated steam as a byproduct, meanwhile, the temperature of the crude synthesis gas is reduced to separate out condensate, impurities in the gas are settled along with the condensate, and the condensate and the other part of the crude synthesis gas enter a No. 2 gas-liquid separator from the upper part and the lower part respectively to separate out the condensate;
in order to adjust the requirement of the water-gas ratio, the 2# gas-liquid separator is arranged into a two-layer structure, the upper layer gas-phase outlet has a low water-gas ratio, the lower layer gas-phase outlet has a high water-gas ratio, the lower layer gas-phase is heated to a temperature higher than the catalyst activation temperature point through a crude synthesis gas heater, and the raw gas at the outlet of the crude synthesis gas heater passes through a detoxification tank to remove impurities and components which easily cause catalyst poisoning according to the content of the impurities in the raw gas;
in the early stage of catalyst reaction, part of the purified crude synthesis gas enters a section A of a two-section type 1# shift converter, wherein the section A of the 1# shift converter is dynamically controlled, the loading amount of the catalyst is less, the shift reaction is far from reaching balance, and the temperature of shift gas at the outlet of a reactor is controlled to be 300-450 ℃; meanwhile, in order to meet the requirement of long-period operation, the 1# shift converter is provided with a section B as a spare for a section A of the 1# shift converter, the shifted gas from the outlet of the 1# shift converter is cooled by a medium-high pressure steam superheater, a crude synthesis gas heater and a 1# medium-high pressure steam generator, one part of the shifted gas is mixed with the unconverted gas and then is subjected to deep shift conversion by the 2# shift converter, the other part of the shifted gas is mixed with the gas phase at the reaction outlet of the 2# shift converter, and the mixed gas is subjected to heat recovery by the 2# medium-high pressure steam generator and then enters a downstream low-temperature waste heat recovery device for treatment.
2. The two-step water-gas ratio adjusted long cycle shift process for oxo synthesis according to claim 1, wherein: the 2# conversion furnace is provided with two sections, wherein the upper section is a detoxification section, and the lower section is a reaction section.
3. The two-step water-gas ratio adjusted long cycle shift process for oxo synthesis according to claim 1, wherein: a bypass 1 is arranged between the upper layer gas phase outlet of the 2# gas-liquid separator 6 and the outlet of the medium-high pressure steam superheater 10, and a control valve 15 for regulating the flow rate of non-converted gas is arranged on the bypass 1; a synthesis gas bypass 1 for controlling the amount of synthesis gas sent to the 1# shift converter is arranged at the outlet of the 2# gas-liquid separator 6, so that the proportion of shift gas and non-shift gas is adjusted; meanwhile, in # 1, the outlet of the high pressure steam generator 11 is provided with a bypass 2 for further adjusting the hydrogen-carbon ratio.
4. The two-step water-gas ratio adjusted long cycle shift process for oxo synthesis according to claim 1, wherein: and in the later stage of the catalyst reaction, closing an inlet valve of the section A of the 1# shift converter to ensure that the synthesis gas preferentially passes through the section B of the 1# shift converter, and returning the synthesis gas to the section A of the 1# shift converter for continuous reaction through a bypass 3 after a series of heat recovery.
5. The two-step water-gas ratio adjusted long cycle shift process for oxo synthesis according to claim 1, wherein: the volume content of carbon monoxide dry basis in the crude synthesis gas from upstream is 30-90%, the volume ratio of water to absolute dry gas is 0.1-1.6, and the pressure range is 1.0-9.0 MPaG.
6. The two-step water-gas ratio adjusted long cycle shift process for oxo synthesis according to claim 1, wherein: the byproduct saturated steam pressure range of the low-pressure steam generator is 0.1-2.5 MPaG; the byproduct saturated steam pressure range of the medium-high pressure steam generator is 2.5-8.0 MPaG.
7. The two-step water-gas ratio adjusted long cycle shift process for oxo synthesis according to any one of claims 1 to 6, wherein: the No. 1 conversion furnace is a two-section type semi-isothermal conversion furnace, and is provided with a vertically extending cylindrical furnace body, the top of the furnace body is provided with a crude synthesis gas inlet, the bottom of the furnace body is provided with a conversion gas outlet, a partition plate capable of dividing the inner cavity of the furnace body into an upper section and a lower section which are relatively independent is arranged in the furnace body, the inner layer of the upper section is a semi-isothermal zone, the outer layer is an adiabatic zone I, and the lower section is an adiabatic zone II.
8. The two-step water-gas ratio adjusted long cycle shift process for oxo according to claim 7, wherein: the 1# conversion furnace comprises:
the inner upper cylinder is arranged in the upper section of the furnace body and is provided with an inner cavity for filling a heat insulation shift reaction catalyst, an air inlet annular space is formed between the outer peripheral wall of the inner upper cylinder and the inner peripheral wall of the furnace body, and a plurality of first air inlets which are arranged at intervals are formed in the outer peripheral wall of the inner upper cylinder;
the central tube is arranged at the central part of the inner upper tube body, the upper end of the central tube is closed, the lower end of the central tube is provided with a lower port communicated with the lower part of the partition plate, and the peripheral wall of the central tube is provided with a plurality of air vents for allowing the gas in the inner upper tube body to enter the central tube;
the boiler water inlet cavity is arranged in the lower section of the boiler body and is close to the partition plate;
the steam collecting cavity is arranged in the upper section of the furnace body, is positioned above the inner upper cylinder body and is used for collecting steam generated by heating boiler water;
the boiler water tubes are arranged on the upper cylinder body, the lower end of each boiler water tube is connected with the boiler water inlet cavity, the upper end of each boiler water tube is connected with the steam collecting cavity, and each boiler water tube is arranged on the periphery of the central tube in a surrounding manner close to the central tube, so that a semi-isothermal area is formed in an area where the boiler water tubes are arranged in the inner upper cylinder body, and an adiabatic area I is formed in an area where the boiler water tubes are not arranged on the periphery of the semi-isothermal area;
the steam pocket is arranged above the furnace body, is communicated with the boiler water inlet cavity through a boiler water descending pipe and is communicated with the steam collecting cavity through a steam ascending pipe, and the steam pocket, the boiler water descending pipe, the boiler water inlet cavity, the boiler water array pipe, the steam collecting cavity and the steam ascending pipe jointly form a controllable saturated steam generating system; and
the inner lower cylinder is arranged in the lower section of the furnace body, is positioned below the boiler water inlet cavity and is provided with an inner cavity for filling a shift reaction catalyst; a gas mixing area is formed between the upper end of the inner lower cylinder and the partition plate, an opening for inputting the mixed gas into the gas mixing area is formed in the side wall of the furnace body, the inner lower cylinder is provided with a second gas inlet for the gas in the gas mixing area to enter and a gas outlet for outputting the reacted gas, and the gas outlet is communicated with the gas changing outlet.
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| CN102887481A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | Low water-gas ratio pre-conversion constant-temperature CO conversion technology |
| DE102014007001A1 (en) * | 2014-05-13 | 2015-11-19 | CCP Technology GmbH | Process and plant for the production of H2-rich synthesis gas |
| CN110550602A (en) * | 2019-08-08 | 2019-12-10 | 中石化宁波工程有限公司 | controllable semi-isothermal conversion process for high-concentration carbon monoxide for oxo synthesis |
| 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 |
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| CN102887481A (en) * | 2012-10-08 | 2013-01-23 | 中国石油化工集团公司 | Low water-gas ratio pre-conversion constant-temperature CO conversion technology |
| DE102014007001A1 (en) * | 2014-05-13 | 2015-11-19 | CCP Technology GmbH | Process and plant for the production of H2-rich synthesis gas |
| CN110550602A (en) * | 2019-08-08 | 2019-12-10 | 中石化宁波工程有限公司 | controllable semi-isothermal conversion process for high-concentration carbon monoxide for oxo synthesis |
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