CN112456437B - Energy-saving sulfur-tolerant conversion system and process with small system resistance and low comprehensive consumption - Google Patents
Energy-saving sulfur-tolerant conversion system and process with small system resistance and low comprehensive consumption Download PDFInfo
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Abstract
The invention belongs to the technical field of synthetic ammonia production processes, and particularly relates to an energy-saving sulfur-tolerant shift system and process with small system resistance and low comprehensive consumption, wherein the energy-saving sulfur-tolerant shift system comprises a crude gas shift reaction and a shift gas cooling treatment, a medium temperature shift furnace and an adiabatic shift furnace are matched and used in parallel in a shift process flow, and high-grade steam is recovered; a process gas route is optimized among the multi-stage conversion furnaces, and the system resistance is reduced; the energy recovery mode of the system is optimized, the steam grade number is reduced, the steam addition amount is reduced through the whole-process optimization, and the comprehensive consumption is reduced.
Description
Technical Field
The invention belongs to the technical field of synthetic ammonia production processes, and particularly relates to an energy-saving sulfur-tolerant shift system and process with small system resistance and low comprehensive consumption.
Background
The CO transformation is an important process in the production process of synthetic ammonia. The conversion device matched with high water-gas ratio and high CO water gas such as pulverized coal pressure gasification, coal water slurry pressure gasification, natural gas conversion and the like is required to complete the conversion task of CO and also consider the recovery task of heat brought into the conversion system by the previous process, particularly along with the progress of a nitrogen fertilizer production process and the popularization and application of a novel coal gasification technology in recent years, a continuous gasification technology is unprecedentedly developed, the content of CO in conversion gas is continuously improved on the basis of 30 percent of the traditional CO, some of the CO is even 70 to 85 percent, if the concentration of CO is more than 65 percent, the traditional CO conversion reaction is very violent, the conversion difficulty is extremely high, the reaction temperature is difficult to control, and the conversion of high water-gas ratio and high carbon monoxide in domestic operation at present basically adopts a cobalt-molybdenum catalyst wide temperature conversion process. Because the CO concentration is high and the water-gas ratio is high, if the dosage of the catalyst of the first shift converter is increased in the production process, the catalyst of the first shift converter is burnt off carelessly; the catalyst consumption of the first shift converter is reduced, the problem of overtemperature is solved, but the service life of the catalyst is short, the catalyst needs to be replaced once a year, the operation period of the catalyst is short, and the catalyst is not suitable for the requirement of a large-scale device; at present, the conversion of the pressurized gasification water gas is mostly four-stage heat insulation, a first conversion furnace is divided into two stages to be connected in parallel for air inlet, the number of system static equipment is 24, wherein 10 heat exchange equipment are provided, the process route is long, the system resistance reaches more than 0.6MPa, the heat energy recovery comprises saturated steam of 0.5MPa, 1.5MPa and 2.5MPa and hot water of 100 ℃, 180 ℃ and 220 ℃, and the consumption of cooling water per ton of ammonia is as high as 7800Kg. The system has more low-grade heat energy and high operation energy consumption.
Although the CO concentration of the conversion process of the coal water slurry gasification is lower, the adopted conversion technology is still a process flow of three-section or four-section adiabatic reaction, sensible heat and latent heat recovery of each stage of water gas or converted gas needs a single indirect heat exchange device, the conversion processes of the shell and the space furnace powder gasification process have the same problems as the coal water slurry conversion, and are all the defects of long process route, large engineering investment, large system resistance, high low-grade heat energy, high energy consumption and the like.
Disclosure of Invention
The invention aims to provide an energy-saving sulfur-tolerant shift system and process with small system resistance and low comprehensive consumption, wherein a medium-temperature shift furnace and a heat-insulating shift furnace are matched and used in parallel in a shift process flow to recover high-grade steam; a process gas route is optimized among the multi-stage conversion furnaces, and the system resistance is reduced; the energy recovery mode of the system is optimized, and the steam grade number is reduced. The whole process is optimized to reduce the steam addition amount and the comprehensive consumption.
In order to achieve the purpose, the invention adopts the technical scheme that:
an energy-saving sulfur-tolerant shift system with small system resistance and low comprehensive consumption comprises a first gas-liquid separator for separating crude gas from a gasification section, a shift converter feeding heat exchanger connected with the first gas-liquid separator, wherein gas coming out of the shift converter feeding heat exchanger is divided into two paths and respectively enters a first detoxification tank and a second detoxification tank, gas coming out of the first detoxification tank and the second detoxification tank is respectively divided into two paths, one path of gas coming out of the first detoxification tank enters a first shift converter, one path of gas coming out of the second detoxification tank enters a second shift converter, gas coming out of the first shift converter and the second shift converter is converged and then enters a shift converter feeding gas heat exchanger tube pass, the other path of gas coming out of the first detoxification tank and the second tank enters a third shift converter, gas coming out of the third shift converter and gas of the shift converter feeding gas heat exchanger tube pass are converged and enter a first medium-pressure evaporation condenser, the outlet of the first medium-pressure evaporative condenser is connected with the inlet of a fourth shift converter, the gas from the fourth shift converter is contacted with the sprayed boiler water for heat exchange, the unvaporized water is separated by a water spray purifier and is discharged, the separated gas enters a second medium-pressure evaporative condenser and is cooled by a condensate heater and then enters a fifth shift converter, the gas from the fifth shift converter enters a first low-pressure evaporative condenser for cooling and then enters a sixth shift converter, the shifted gas from the sixth shift converter is processed by a cooling system, the third, fourth and fifth shift converters are firstly integrated for process balance, the gas entering the third shift converter is communicated with the inlets of the fourth shift converter and the fifth shift converter, the load distribution of each stage of shift converter can be adjusted according to gas components, and the CO content index of the outlet is controlled, in addition, the direct connection pipeline effectively reduces the system resistance, reduces the comprehensive energy consumption of the system and has good energy-saving effect.
Further, the cooling system comprises a boiler feed water preheater and a second low-pressure evaporative condenser connected with an outlet of the boiler feed water preheater, an outlet of the second low-pressure evaporative condenser is connected with a third low-pressure evaporative condenser, the converted gas from an outlet of the third low-pressure evaporative condenser enters a second gas-liquid separator to separate out steam condensate, and the converted gas enters a condensate preheater to be cooled and then enters a first conversion gas-water cooler tube pass to exchange heat and then enters a second conversion gas-water cooler tube pass and then enters a third gas-liquid separator to separate out condensate in the converter.
Furthermore, the shift converter feeding heat exchanger is provided with a tube pass and a shell pass, and gas coming out of the first gas-liquid separator enters the shell pass of the shift converter feeding heat exchanger and gas coming from the first shift converter in the tube pass for heat exchange.
Furthermore, the first shift converter, the second shift converter, the fourth shift converter, the fifth shift converter and the sixth shift converter are adiabatic shift converters, and the third shift converter is an isothermal shift converter. The whole process is optimized to reduce the steam addition amount and reduce the comprehensive consumption.
A transformation process of an energy-saving sulfur-tolerant transformation system with small system resistance and low comprehensive consumption comprises the following steps:
(1) Crude gas shift reaction: raw gas from a gasification section at 3.718MPa and 211 ℃ enters a first gas-liquid separator through a valve, condensate in the raw gas is separated, the raw gas enters a shell pass of a charging heat exchanger of a shift converter, then the raw gas is divided into two paths and respectively passes through a first detoxification slot and a second detoxification slot to remove impurities in the gas, the gas from the first detoxification slot and the second detoxification slot is divided into two paths, the gas from the first detoxification slot enters a first shift converter, the gas from the second detoxification slot enters a second shift converter, the gas from the first shift converter and the second shift converter is converged and then enters a tube pass of the charging heat exchanger of the shift converter, the raw gas is heated to 260 ℃, the temperature of the raw gas is reduced to 311 ℃ per se, the other path of raw gas from the first detoxification slot and the second detoxification slot enters a third shift converter to be subjected to isothermal conversion, the CO content is maintained at 290 ℃ after 35%, gas from the outlet of the third shift converter and gas of the tube pass of a shift converter feeding gas heat exchanger are converged and enter a first medium-pressure evaporation condenser for heat exchange to obtain saturated steam with the temperature of 240 ℃ and the pressure of 1.5MPa, then the saturated steam enters a fourth shift converter for reaction to reach the temperature of 434 ℃, the CO content is 6.7 percent, the saturated steam is sprayed into boiler water for cooling to 338 ℃, then the saturated steam is sprayed into a water spray purifier for separating unvaporized water, the separated gas is cooled to 274 ℃ through a second medium-pressure evaporation condenser and the steam with the pressure of 2.5MPa, then the temperature is cooled to 220 ℃ through a condensate heater, the gas enters a fifth shift converter for reaction to reach the temperature of 260 ℃ and the CO content is reduced to 1.0 percent, the gas from the fifth shift converter enters a first low-pressure evaporation condenser for cooling, and enters a sixth shift converter through low-pressure steam with the pressure of 0.5MPa, and the shift converter outlet of the shift converter is changed to the CO temperature of 204 ℃ lower than 0.4 percent, thus completing the shift reaction of crude gas;
(2) And (3) changing gas and cooling treatment: cooling the conversion gas from the step (1) to 181 ℃ through a boiler feed water preheater, then passing through a second low-pressure evaporative condenser and a third low-pressure evaporative condenser which are connected in parallel to produce a byproduct of saturated steam with the temperature of 0.3MPa and the temperature of 145 ℃, separating steam condensate from the steam condensate in a second separator, passing the conversion gas into a condensate preheater to cool to 84 ℃, passing the conversion gas into a first conversion gas water cooler tube pass to cool to 40 ℃, passing the conversion gas into a second conversion gas water cooler tube pass to cool to 24 ℃, finally passing through a third gas-liquid separator to separate the condensate in the conversion gas, namely cooling the conversion gas, and sending the conversion gas to a low-temperature methanol washing section.
The invention has the advantages that:
1. according to the invention, the isothermal shift converter and the adiabatic shift converter are matched and used in parallel in the shift process flow, high-grade steam is recovered, the process gas route is optimized among the multistage shift converters, the system resistance is reduced, the system energy recovery mode is optimized, the steam grade number is reduced, the steam supplement amount is reduced through the whole process optimization, and the comprehensive consumption is reduced;
2. the third, fourth and fifth shift converters are integrated for process balance for the first time, the coal gas entering the third shift converter is communicated with inlets of the fourth shift converter and the fifth shift converter, the load distribution of each shift converter can be adjusted according to gas components, the CO content index of an outlet is controlled, in addition, a pipeline is directly connected, the system resistance is effectively reduced, the comprehensive energy consumption of the system is reduced, and the energy-saving effect is good;
3. according to the change of an energy recovery mode, the problems of high steam recovery grade and low grade are solved, and the steam recovery grade of a new process flow is mainly concentrated at 2.5Mpa and 0.3Mpa;
4. the energy-saving conversion process not only can thoroughly eliminate the bottleneck restricting the high-load production operation of the device, but also brings obvious economic benefit and social benefit to the enterprise, and calculates the total heat energy of condensed water of the heating desalted water and deoxygenated water process, consumed cooling water and the like into 23MJ according to the coal consumption by converting the steam price of 0.5MPa, 1.5MPa and 2.5MPa into 80 yuan/t, 120 yuan/t and 150 yuan/t and the steam price of raw coal, the electricity price and the circulating water into 850 yuan/t, 0.45 yuan/kWh and 0.8 yuan/t. Compared with the traditional conversion process, the energy-saving conversion process can save 142 yuan of operating cost per ton of ammonia, and 8520 ten thousand yuan can be saved for a single set of 600kt/a ammonia synthesis device all the year round.
Drawings
FIG. 1 is a schematic view of the present invention.
Detailed Description
As shown in the figure, crude gas from a gasification section at 3.718MPa and 211 ℃ enters a first gas-liquid separator 1 through a valve, condensate in the crude gas is separated, the crude gas enters a shell pass of a shift converter feeding heat exchanger 2, then impurities in the gas are removed through a first detoxification groove 3 and a second detoxification groove 4 in two paths, the gas from the first detoxification groove 3 and the second detoxification groove 4 is divided into two paths, one path of gas from the first detoxification groove 3 enters a first shift converter 5, one path of gas from the second detoxification groove 4 enters a second shift converter 6, the gas from the first shift converter 5 and the second shift converter 6 is converged and then enters a shift converter feeding gas heat exchanger 2 pipe pass, the crude gas is heated to 260 ℃, the temperature of the crude gas is reduced to 311 ℃, the other path of crude gas from the first detoxification groove 3 and the second detoxification groove 4 enters a third converter 7 for isothermal shift conversion, the CO content is maintained at 290 ℃, and the isothermal temperature is maintained at 35%, gas from the outlet of the third shift converter 7 and gas of the tube side of the shift converter feeding gas heat exchanger 2 are converged and enter a first medium-pressure evaporation condenser 8 for heat exchange to obtain saturated steam with the temperature of 240 ℃ and 1.5MPa, then enter a fourth shift converter 9 for reaction to reach the temperature of 434 ℃ and the CO content of 6.7 percent, then are sprayed with boiler water for cooling to 338 ℃, then pass through a water spray purifier 10 for separating unvaporized water, the separated gas is cooled to 274 ℃ through a second medium-pressure evaporation condenser 11 and steam with the pressure of 2.5MPa, then pass through a condensate heater 12 for cooling to 220 ℃, enter a fifth shift converter 13 for reaction to reach the temperature of 260 ℃ and the CO content of 1.0 percent, the gas from the fifth shift converter 13 enters a first low-pressure evaporation condenser 14 for cooling and enters a sixth shift converter 15 through low-pressure steam with the pressure of 0.5MPa until the CO of the shift converter outlet is lower than 0.4 percent and the temperature of 204 ℃, thus completing the shift reaction of crude gas, the conversion gas is cooled to 181 ℃ through a boiler feed water preheater 16, and then passes through a second low-pressure evaporative condenser 17 and a third low-pressure evaporative condenser 18 which are connected in parallel to produce a byproduct of saturated steam with the temperature of 0.3MPa and the temperature of 145 ℃, enters a second gas-liquid separator 19 to separate steam condensate, enters a condensate preheater 20 to cool to 84 ℃, enters a first conversion gas water cooler 21 tube pass to cool to 40 ℃, enters a second conversion gas water cooler 22 tube pass to cool to 24 ℃, and finally passes through a third gas-liquid separator 23 to separate condensate in the conversion gas, namely, the conversion gas is cooled, and then the conversion gas is sent to a low-temperature methanol washing section, wherein the first conversion furnace 5, the second conversion furnace 6, the fourth conversion furnace 9, the fifth conversion furnace 13 and the sixth conversion furnace 15 are adiabatic conversion furnaces, and the third conversion furnace 7 is an isothermal conversion furnace.
Comparative experiment
At present, the conversion of pressurized gasification water gas is mostly four-section heat insulation, a first conversion furnace is divided into two sections to be connected in parallel for air inlet, 24 static devices of a system are provided, wherein 10 heat exchange devices are provided, the process route is long, the system resistance reaches over 0.6MPa, the heat energy recovery comprises saturated steam of 0.5MPa, 1.5MPa and 2.5MPa and hot water of 100 ℃, 180 ℃ and 220 ℃, the consumption of cooling water per ton of ammonia is as high as 7800Kg, the system has more low-grade heat energy, and the operation energy consumption is high. Although the CO concentration of the transformation process of the coal water slurry gasification is lower, the adopted transformation technology is still a process flow of three-stage or four-stage adiabatic reaction; the isothermal shift converter used in the energy-saving shift process technology explores an improved direction for a chemical process reactor with large heat effect, provides a basis for the yield expansion energy-saving modification of similar synthetic ammonia devices and the optimization and improvement of CO shift process of methane shift devices in oil-to-coal and gas-to-coal devices, is not only suitable for new synthetic ammonia devices, but also can be used for modifying the shift devices which are already put into operation and have high energy consumption, and solves the technical equipment problem which puzzles enterprises for a long time. The energy-saving transformation process not only can thoroughly eliminate the bottleneck restricting the high-load production and operation of the device, but also brings obvious economic and social benefits to enterprises.
According to the steam prices of 80 yuan/t, 120 yuan/t and 150 yuan/t of 0.5MPa, 1.5MPa and 2.5MPa and the prices of raw material coal, electricity, circulating water and the like of 850 yuan/t, 0.45 yuan/kWh and 0.8 yuan/t respectively, the operation cost of 142 yuan can be saved for ton ammonia of the energy-saving transformation process compared with the traditional transformation process by calculating the coal consumption of 23MJ for heating desalted water, deoxygenated water process condensed water, consumed cooling water and the like according to the heat energy conversion, and 8520 ten thousand yuan can be saved for a single 600kt/a ammonia synthesis device all the year.
Claims (2)
1. A transformation process of an energy-saving sulfur-tolerant transformation system is characterized in that: the system comprises a first gas-liquid separator for separating crude gas from a gasification section, a shift converter feeding heat exchanger connected with the first gas-liquid separator, a first detoxification tank and a second detoxification tank, wherein gas from the shift converter feeding heat exchanger is divided into two paths and respectively enters the first detoxification tank and the second detoxification tank, gas from the first detoxification tank and the second detoxification tank is divided into two paths, gas from the first detoxification tank enters the first shift converter, gas from the second detoxification tank enters the second shift converter, gas from the first shift converter and the second shift converter is converged and then enters a shift converter feeding gas heat exchanger tube pass, gas from the first detoxification tank and the second detoxification tank enters the third shift converter, gas from the third shift converter outlet and gas from the shift converter feeding gas heat exchanger tube pass are converged and enter the first medium-pressure evaporation condenser, the first medium-pressure evaporation condenser outlet is connected with a fourth shift converter inlet, gas from the fourth shift converter enters the fifth shift converter evaporation condenser after contacting with sprayed boiler water for heat exchange, water is separated by a water spray purifier and discharged, and condensate of the second shift converter is cooled and finally enters the shift converter cooling gas from the fifth shift converter; the cooling system comprises a boiler feed water preheater and a second low-pressure evaporative condenser connected with an outlet of the boiler feed water preheater, wherein an outlet of the second low-pressure evaporative condenser is connected with a third low-pressure evaporative condenser, a converted gas from an outlet of the third low-pressure evaporative condenser enters a second gas-liquid separator to separate steam condensate, the converted gas enters a condensate preheater for cooling, enters a first converted gas water cooler tube pass for heat exchange, enters a second converted gas water cooler tube pass, and then enters a third gas-liquid separator to separate condensate in a converter; the first shift converter, the second shift converter, the fourth shift converter, the fifth shift converter and the sixth shift converter are adiabatic shift converters, and the third shift converter is an isothermal shift converter; the conversion process comprises the following steps:
(1) Crude gas shift reaction: raw gas from a gasification section at 3.718MPa and 211 ℃ enters a first gas-liquid separator through a valve, condensate in the raw gas is separated, the raw gas enters a shell pass of a charging gas-liquid exchanger of a shift converter, then the raw gas is divided into two paths and is respectively subjected to impurity removal in the gas through a first detoxification tank and a second detoxification tank, the gas from the first detoxification tank and the gas from the second detoxification tank are respectively divided into two paths, one path of gas from the first detoxification tank enters a first shift converter, one path of gas from the second detoxification tank enters a second shift converter, the gas from the first shift converter and the second shift converter is converged and then enters a tube pass of the charging gas-liquid exchanger of the shift converter, the raw gas from the first gas-liquid separator is heated to 260 ℃, the raw gas is reduced to 311 ℃ by itself, the other path of raw gas from the first detoxification tank and the second detoxification tank enters a third shift converter for isothermal shift, and is maintained at 290 ℃, the CO content is 35%, the gas from the outlet of the third shift converter and the gas of the tube pass of the shift converter feeding gas heat exchanger are converged and enter a first medium-pressure evaporation condenser for heat exchange to obtain saturated steam with the temperature of 240 ℃ and 1.5MPa, then the saturated steam enters a fourth shift converter for reaction to reach the temperature of 434 ℃, the CO content is 6.7%, then the saturated steam is sprayed into boiler water for cooling to 338 ℃, the water which is not vaporized is separated out through a water spray purifier, the separated gas is cooled to 274 ℃ through a second medium-pressure evaporation condenser, the steam with the pressure of 2.5MPa is cooled to 220 ℃ through a condensate heater, the gas enters a fifth shift converter for reaction to reach the temperature of 260 ℃ and the CO content is reduced to 1.0%, the gas from the fifth shift converter enters a first low-pressure evaporation condenser for cooling and enters a sixth shift converter through low-pressure steam with the pressure of 0.5MPa until the CO content of the shift converter outlet is lower than 0.4%, and the shift reaction of 204 ℃ is completed;
(2) Changing gas and cooling: cooling the shift gas from the step (1) to 181 ℃ through a boiler feed water preheater, then passing through a second low-pressure evaporative condenser and a third low-pressure evaporative condenser which are connected in parallel to produce 145 ℃ saturated steam at the temperature of 0.3MPa, entering a second separator to separate steam condensate, entering a condensate preheater to cool to 84 ℃, entering a first shift gas water cooler tube pass to cool to 40 ℃, entering a second shift gas water cooler tube pass to cool to 24 ℃, finally passing through a third gas-liquid separator to separate condensate in the shift gas, namely cooling the shift gas, and sending the shift gas to a low-temperature methanol washing section.
2. The shift process for the energy efficient sulfur tolerant shift system of claim 1, wherein: the shift converter feeding heat exchanger is provided with a tube pass and a shell pass, and gas coming out of the first gas-liquid separator enters the shell pass of the shift converter feeding heat exchanger and gas coming from the first shift converter in the tube pass for heat exchange.
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| CN1686785A (en) * | 2005-04-14 | 2005-10-26 | 天脊煤化工集团有限公司 | Sulfur-resistant conversion technical method of carbon monoxide for synthesizing ammonia |
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| EP2294009A2 (en) * | 2008-06-26 | 2011-03-16 | Haldor Topsoe A/S | Process for the production of ammonia and steam superheater |
| CN102732329A (en) * | 2012-06-12 | 2012-10-17 | 中国石油化工股份有限公司 | Fine coal gasification product crude synthetic gas CO sulfur-tolerant shift technology |
| CN208327391U (en) * | 2018-04-09 | 2019-01-04 | 河南晋开化工投资控股集团有限责任公司 | A kind of carbon monodixe conversion system |
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2020
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1686785A (en) * | 2005-04-14 | 2005-10-26 | 天脊煤化工集团有限公司 | Sulfur-resistant conversion technical method of carbon monoxide for synthesizing ammonia |
| EP2294009A2 (en) * | 2008-06-26 | 2011-03-16 | Haldor Topsoe A/S | Process for the production of ammonia and steam superheater |
| CN101704513A (en) * | 2009-08-13 | 2010-05-12 | 上海国际化建工程咨询公司 | Shunting-type isothermal sulfur-tolerant conversion process and equipment thereof |
| CN102732329A (en) * | 2012-06-12 | 2012-10-17 | 中国石油化工股份有限公司 | Fine coal gasification product crude synthetic gas CO sulfur-tolerant shift technology |
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