CN112142003A - Carbon monoxide conversion process - Google Patents
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a carbon monoxide conversion process. The method comprises the following steps: (1) purifying raw material gas; (2) water is vaporized; (3) mixing gas and steam; (4) carrying out a shift reaction; (5) and (5) gas-liquid separation. The carbon monoxide conversion process adopts a desulfurization and dechlorination purification process matched with the conversion process, so that the source range of the raw material gas is widened; compared with the traditional reaction furnace, the isothermal shift reaction furnace can quickly and effectively remove the heat of the reaction, has good protection effect on a copper-based shift catalyst used in the furnace, widens the use conditions of the catalyst, and is suitable for synthesis gas, coke oven gas, blast furnace gas, self-prepared synthesis gas and laboratory coal gasification product gas with the inlet temperature of 180-280 ℃ and the CO volume content of 1-30 percent as raw material gases, and the conversion rate of the carbon monoxide reaches more than 90 percent.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a carbon monoxide conversion process.
Background
The carbon monoxide shift reaction is a reaction in which carbon monoxide and steam are reacted under certain conditions to produce carbon dioxide and hydrogen.
CO+H2O→CO2+H2
The shift reaction is exothermic and low temperature favors the reaction in the forward direction, so lower temperatures favor the reaction. The shift reaction is generally divided into a low temperature (typically 200-. Many of the current hydrogen production plants typically employ high temperature shift in series with low temperature shift processes to ensure more complete shift of CO.
The temperature of the gas after high-temperature transformation is high (generally above 400 ℃), low-temperature transformation reaction can not be directly carried out, and the gas needs to be cooled by heat transfer equipment such as a waste heat boiler and the like in series connection, and then low-temperature transformation reaction is carried out after the conditions are met. The CO volume content of the outlet of the pure high-temperature shift reaction is higher, generally 3-5 percent or even higher, the production requirement cannot be met at all, low-temperature shift needs to be connected in series, and finally the CO volume content in the outlet gas can be controlled below 0.5 percent or even lower.
Improvements to the high temperature-low temperature shift process have been proposed in the prior art.
Chinese patent CN104150439B discloses a carbon monoxide shift process. The technical scheme includes that raw gas is subjected to gas-liquid separation through a gas-liquid separator, is filtered through a filter, is mixed with medium-pressure steam in a steam mixer, enters a gas preheater after being mixed, exchanges heat with reaction gas discharged from an isothermal reactor to be heated, the heated mixed gas enters the isothermal reactor to be reacted, the reacted reaction gas is sent to the gas preheater to exchange heat with the mixed gas to be cooled, and then enters a low-temperature adiabatic reactor to be further reacted to obtain conversion gas. The invention solves the problems of unstable system temperature control and easy inactivation of the catalyst, but has complex process, higher operation cost and low conversion rate of carbon monoxide.
Chinese patent CN1461730A discloses a carbon monoxide shift process and a reactor. The process comprises the following steps: introducing a feed gas into reactor tubes of a reaction unit, the reactor tubes having a fixed bed of shift catalyst located in a reaction zone; contacting the feed gas with a catalyst under shift reaction conditions effective to react carbon monoxide with steam to produce hydrogen; the cooling medium having a falling film form flowing along the shell side of the reactor tube, cooling the reaction by indirect heat exchange with the cooling medium, and removing the heated cooling medium from the falling film to allow hydrogen produced by the shift reaction to pass through the hydrogen selective film to the permeation zone; hydrogen is withdrawn from the permeation zone and a carbon monoxide depleted feed gas is withdrawn from the reaction zone. The process reactor has a complex structure and difficult control of process conditions.
The existing high-temperature-low-temperature conversion process is improved, the biggest problem is the maintenance and the unsafety of a waste heat boiler, so the significance is not large, the isothermal conversion process flow with lower reaction temperature is the future development direction, the existing technology in the aspect is in the stage of starting, the process flow is long, the structure of a conversion reactor is complex, and the cost is higher.
Chinese patent CN 103641067A discloses a carbon monoxide isothermal conversion process, wherein a carbon monoxide shift converter adopts a tube array isothermal conversion converter, a tube pass is filled with a copper catalyst, a shell pass is a constant temperature water bath with boiler feed water, and a steam drum is arranged at the top of the carbon monoxide shift converter and connected with the shell pass constant temperature water bath. The methane fraction process gas passes through the tube side of the carbon monoxide shift converter, generates carbon monoxide shift reaction under the action of a catalyst and then leaves the carbon monoxide shift converter; the shift reaction heat is transferred to the shell pass through the tube wall of the tube array, the boiler feed water is heated, and low-pressure steam is by-produced. The carbon monoxide concentration at the inlet of the carbon monoxide shift converter is high. The invention solves the problem that the catalyst activity is reduced and even inactivated due to high temperature of a catalyst bed layer.
Chinese patent CN 102971252a discloses a carbon monoxide shift device and method and a hydrogen production device. The shift catalyst layer is divided into at least two front and rear stages, a 1 st catalyst is provided on the upstream side, and a 2 nd catalyst is provided on the downstream side, and a combination of the 1 st catalyst and the 2 nd catalyst is adopted, in which the 1 st catalyst has a characteristic that the higher the carbon dioxide concentration in the supplied reaction gas is, the lower the carbon monoxide conversion rate is when the carbon monoxide concentration and the reaction temperature in the supplied reaction gas are constant, and the degree of decrease in the carbon monoxide conversion rate with respect to the increase in the carbon dioxide concentration in the supplied reaction gas in the 2 nd catalyst is smaller than the degree of decrease in the carbon monoxide conversion rate with respect to the increase in the carbon dioxide concentration in the supplied reaction gas in the 1 st catalyst. This makes it possible to improve the carbon monoxide concentration conversion rate of the carbon monoxide shift converter without increasing the amount of shift catalyst used. The invention solves the problem that the prior art needs to use a large amount of shift catalyst.
At present, a carbon monoxide shift reaction process suitable for various raw materials (such as synthesis gas, coke oven gas, blast furnace gas, self-prepared synthesis gas and laboratory coal gasification product gas are used as raw materials) and various conditions does not exist.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a carbon monoxide conversion process suitable for various raw materials and various conditions aiming at the defects of the prior art. The raw material gas adopted by the process has a wide range, and can be synthesis gas, coke oven gas, blast furnace gas, self-prepared synthesis gas, laboratory coal gasification product gas and the like; the process of the invention can be suitable for the shift reaction with the inlet temperature of 180 ℃ and 280 ℃ and the CO volume content of 1-30% in the raw material gas.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme:
the invention provides a carbon monoxide conversion process, which comprises the following process steps:
(1) raw material gas purification: the raw gas containing carbon monoxide sequentially passes through a desulfurization reactor and a dechlorination reactor, and is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw gas with the concentration of sulfide less than 0.1ppm and the concentration of chloride less than 0.05 ppm;
(2) water vaporization: pumping the deionized water into a vaporizer for vaporization, and generating water vapor after vaporization;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter and mixing the feed gas with the water vapor in the step (2);
(4) and (3) shift reaction: introducing the gas mixed in the step (3) into a shift reactor from the upper end of the shift reactor, and allowing the mixed gas of the raw material gas and the water vapor in the shift reactor to pass through a bed layer filled with a shift catalyst to perform a carbon monoxide isothermal shift reaction under the reaction pressure of 2.5-3.0Mpa to generate carbon dioxide and hydrogen;
(5) gas-liquid separation: and after the shift reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain the product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide reaches more than 90 percent.
Preferably, the pressure in the desulfurization and dechlorination reactor in the step (1) is controlled to be 2.5-3.0Mpa, and the temperature is controlled to be 200-250 ℃.
Preferably, in the step (1), the inside of the desulfurization reactor is respectively filled with a crude desulfurization catalyst A and a fine desulfurization catalyst B from top to bottom, and the volume ratio of the filling amount of the catalysts A: and B is 1.5-2.0: 1. The desulfurization catalyst A is at least one of zinc oxide and activated carbon, and the fine desulfurization catalyst B is at least one of cobalt-molybdenum catalyst and ferric oxide.
Preferably, the deionized water in the step (2) is pumped into a vaporizer with the temperature controlled at 250 ℃ and 300 ℃ by a water pump under pressure.
Preferably, the vaporizer internal pipe in step (2) is spirally distributed.
Further preferably, in the step (2), deionized water is introduced from the lower end of the vaporizer and discharged from the upper end.
Preferably, the raw material gas purified in step (3) is mixed with water vapor in a holding furnace controlled at 180-250 ℃.
Preferably, in the step (4), the shift reactor is an isothermal shift reactor, a fixed bed tubular reactor is arranged in the isothermal shift reactor, the reactor is of an annular structure, a sleeve is arranged in the middle of the isothermal shift reactor, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by the reaction.
Preferably, in the step (4), the inner wall of the shift reactor is provided with an annular electric heating jacket.
Preferably, in step (4), the shift reactor is packed with a self-developed intermediate-temperature copper-based carbon monoxide shift catalyst.
The process of the invention can be suitable for the shift reaction with the inlet temperature of 180 ℃ and 280 ℃ and the CO volume content of 1-30 percent in the raw material gas.
The process of the invention can be applied to raw material gases such as synthesis gas, coke oven gas, blast furnace gas, self-prepared synthesis gas and laboratory coal gasification product gas.
Has the advantages that:
the desulfurization and dechlorination purification process matched with the conversion process widens the source range of the raw material gas; compared with the traditional reaction furnace, the isothermal shift reaction furnace has the advantages that the heat of the reaction can be effectively and quickly removed, the copper-based shift catalyst used in the furnace is well protected, the using conditions of the catalyst are widened, the isothermal shift reaction furnace is suitable for all raw materials gas comprising the inlet temperature of 180 ℃ plus 280 ℃ and the CO volume content of 1-30%, coke oven gas, blast furnace gas, self-prepared synthetic gas and laboratory coal gasification product gas, and the conversion rate of carbon monoxide reaches more than 90%.
Drawings
FIG. 1 is a schematic diagram of a carbon monoxide shift process of the present invention.
Detailed Description
The technical solution of the present invention is described in detail below with reference to specific examples and drawings, but the scope of the present invention is not limited to the examples.
Example 1:
the raw material gas is self-prepared synthesis gas, wherein the volume fraction of hydrogen is 64%, the volume fraction of carbon monoxide is 20%, the volume fraction of carbon dioxide is 10%, and the volume fraction of methane is 12%.
The carbon monoxide conversion process flow diagram is shown in figure 1, and the carbon monoxide conversion process comprises the following steps:
(1) raw material gas purification: the raw material gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled at 3.0Mpa and the temperature controlled at 240 ℃, a crude desulfurization catalyst A is zinc oxide, a fine desulfurization catalyst B is a mixture of a cobalt-molybdenum catalyst and iron oxide, the volume ratio of A to B is 1.5:1, and the raw material gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw material gas with the sulfide concentration of 0.08ppm and the chloride concentration of 0.04 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a gasifier with the temperature controlled at 250 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the water vapor in the step (2) in a heat preservation furnace with the temperature controlled at 220 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with an independently developed medium-temperature copper-based carbon monoxide shift catalyst, and the carbon monoxide isothermal shift reaction is carried out under the conditions of the inlet temperature of 230 ℃ and the reaction pressure of 3.0Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas was sampled, analyzed and the contents of the components in the product were measured, and the conversion of CO in this example was found to be 93.7%.
Example 2
The raw material gas is coke oven gas, wherein the volume fraction of hydrogen is 60%, the volume fraction of carbon monoxide is 10%, the volume fraction of carbon dioxide is 3%, the volume fraction of methane is 18%, and hydrocarbon is 3%.
The carbon monoxide shift process comprises the following steps:
1) raw material gas purification: the raw material gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled to be 2.5Mpa and the temperature controlled to be 200 ℃, a crude desulfurization catalyst A is a mixture of zinc oxide and active carbon, a fine desulfurization catalyst B is a cobalt-molybdenum catalyst, the volume ratio of A to B is 2.0:1, and the raw material gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw material gas with the sulfide concentration of 0.05ppm and the chloride concentration of 0.01 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a vaporizer with the temperature controlled at 300 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the steam in the step (2) in a heat preservation furnace with the temperature controlled at 230 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with a medium-temperature copper-based carbon monoxide shift catalyst, and the isothermal shift reaction of the carbon monoxide is carried out under the conditions of the inlet temperature of 260 ℃ and the reaction pressure of 2.5Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide in the example is 94.2%.
Example 3
The raw material gas is a gasification product gas of Mongolian lignite in a laboratory, wherein the volume fraction of hydrogen is 56%, the volume fraction of carbon monoxide is 15%, the volume fraction of carbon dioxide is 14%, the volume fraction of methane is 5%, and hydrocarbon is 6%.
The carbon monoxide shift process comprises the following steps:
1) raw material gas purification: the raw material gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled at 3.0Mpa and the temperature controlled at 240 ℃, a crude desulfurization catalyst A is a mixture of zinc oxide and active carbon, a fine desulfurization catalyst B is a mixture of cobalt molybdenum catalyst and iron oxide, the volume ratio of A to B is 1.8:1, and the raw material gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw material gas with the sulfide concentration of 0.02ppm and the chloride concentration of 0.01 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a gasifier with the temperature controlled at 280 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the water vapor in the step (2) in a heat preservation furnace with the temperature controlled at 230 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with an independently developed medium-temperature copper-based carbon monoxide shift catalyst, and the carbon monoxide isothermal shift reaction is carried out under the conditions of the inlet temperature of 240 ℃ and the reaction pressure of 3.0Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide in the example is 93.5%.
Example 4
The raw material gas is synthesis gas, wherein the volume fraction of hydrogen is 64%, the volume fraction of carbon monoxide is 5%, the volume fraction of carbon dioxide is 12%, the volume fraction of methane is 8%, and the volume fraction of hydrocarbon is 5%.
The carbon monoxide shift process comprises the following steps:
1) raw material gas purification: the synthesis gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled at 2.8Mpa and the temperature controlled at 220 ℃, a crude desulfurization catalyst A is active carbon, a fine desulfurization catalyst B is a mixture of a cobalt-molybdenum catalyst and iron oxide, the volume ratio of A to B is 1.5:1, and the synthesis gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified feed gas with the sulfide concentration of 0.08ppm and the chloride concentration of 0.03 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a gasifier with the temperature controlled at 300 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the water vapor in the step (2) in a heat preservation furnace with the temperature controlled at 230 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with an independently developed medium-temperature copper-based carbon monoxide shift catalyst, and the carbon monoxide isothermal shift reaction is carried out under the conditions of the inlet temperature of 230 ℃ and the reaction pressure of 3.0Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide in the example is 91.7%.
Example 5
The raw material gas is gas treatment gas of a laboratory Xinjiang eastern Junggar lignite gasification product, wherein the volume fraction of hydrogen is 63%, the volume fraction of carbon monoxide is 1%, the volume fraction of carbon dioxide is 15%, the volume fraction of methane is 10%, and hydrocarbon is 6%.
The carbon monoxide shift process comprises the following steps:
1) raw material gas purification: the raw material gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled at 2.5Mpa and the temperature controlled at 250 ℃, a crude desulfurization catalyst A is zinc oxide, a fine desulfurization catalyst B is a cobalt-molybdenum catalyst, the volume ratio of A to B is 2.0:1, and the raw material gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw material gas with the sulfide concentration of 0.01ppm and the chloride concentration of 0.01 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a gasifier with the temperature controlled at 250 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the water vapor in the step (2) in a heat preservation furnace with the temperature controlled at 250 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with an independently developed intermediate temperature copper-based carbon monoxide shift catalyst, and the carbon monoxide isothermal shift reaction is carried out under the conditions of the inlet temperature of 280 ℃ and the reaction pressure of 3.0Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide in the example is 91.9%.
Example 6
The raw material gas is coke oven gas, wherein the volume fraction of hydrogen is 60%, the volume fraction of carbon monoxide is 10%, the volume fraction of carbon dioxide is 3%, the volume fraction of methane is 18%, and hydrocarbon is 3%.
The carbon monoxide shift process comprises the following steps:
1) raw material gas purification: the raw material gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled at 2.5Mpa and the temperature controlled at 200 ℃, a crude desulfurization catalyst A is a mixture of zinc oxide and active carbon, a fine desulfurization catalyst B is ferric oxide, the volume ratio of A to B is 2.0:1, and the raw material gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw material gas with the sulfide concentration of 0.05ppm and the chloride concentration of 0.01 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a vaporizer with the temperature controlled at 300 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the steam in the step (2) in a heat preservation furnace with the temperature controlled at 230 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with an independently developed medium-temperature copper-based carbon monoxide shift catalyst, and the carbon monoxide isothermal shift reaction is carried out under the conditions of the inlet temperature of 260 ℃ and the reaction pressure of 2.5Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide in the example is 93.2%.
Example 7
The raw material gas is blast furnace gas, wherein the volume fraction of hydrogen is 5%, the volume fraction of carbon monoxide is 30%, the volume fraction of carbon dioxide is 12%, nitrogen is 48%, and hydrocarbon is 0.5%.
The carbon monoxide shift process comprises the following steps:
1) raw material gas purification: the raw material gas sequentially passes through a desulfurization and dechlorination reactor with the pressure controlled at 2.5Mpa and the temperature controlled at 250 ℃, a crude desulfurization catalyst A is zinc oxide, a fine desulfurization catalyst B is ferric oxide, the volume ratio of A to B is 2.0:1, and the raw material gas is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw material gas with the sulfide concentration of 0.05ppm and the chloride concentration of 0.04 ppm;
(2) water vaporization: pressurizing deionized water by a water pump, pumping into a vaporizer with the temperature controlled at 250 ℃ for vaporization, and generating water vapor after vaporization; the internal pipeline of the vaporizer is spirally distributed, deionized water enters from the lower end of the vaporizer, and deionized water is discharged from the upper end of the vaporizer;
(3) gas-steam mixing: accurately metering the purified feed gas in the step (1) by a mass flow meter, and mixing the feed gas with the steam in the step (2) in a heat preservation furnace with the temperature controlled at 180 ℃ at a flow rate of 80 l/h;
(4) and (3) shift reaction: the mixed gas in the step (3) enters a shift reactor from the upper end of the shift reactor, the mixed gas of the raw material gas and the water vapor in the shift reactor passes through a bed layer filled with an independently developed intermediate temperature copper-based carbon monoxide shift catalyst, and the carbon monoxide isothermal shift reaction is carried out under the conditions of the inlet temperature of 180 ℃ and the reaction pressure of 3.0Mpa to generate carbon dioxide and hydrogen; the shift reactor is an isothermal shift reactor, a fixed bed tubular reaction furnace is arranged in the shift reactor, the reaction furnace is of an annular structure, a sleeve is arranged in the middle of the reaction furnace, and cold air enters from the lower end of the sleeve and exits from the upper end of the sleeve to take away heat generated by reaction; the inner wall of the shift reactor is provided with an annular electric heating sleeve;
(5) gas-liquid separation: and after the reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain product gas.
The product gas is sampled, analyzed and detected to detect the content of each component in the product, and the conversion rate of the carbon monoxide in the example is 92.2%.
The process is suitable for synthesis gas with the inlet temperature of 180-280 ℃, the CO volume content of 1-30%, coke oven gas, blast furnace gas, self-prepared synthesis gas and laboratory coal gasification product gas as raw material gases, and the conversion rate of the carbon monoxide reaches more than 90%.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A carbon monoxide shift process, characterized by comprising the process steps of:
(1) raw material gas purification: the raw gas containing carbon monoxide sequentially passes through a desulfurization reactor and a dechlorination reactor, and is cooled by a water cooling system and subjected to gas-liquid separation to obtain purified raw gas with the concentration of sulfide less than 0.1ppm and the concentration of chloride less than 0.05 ppm;
(2) water vaporization: pumping the deionized water into a vaporizer for vaporization, and generating water vapor after vaporization;
(3) gas-steam mixing: mixing the purified feed gas in the step (1) with the water vapor in the step (2);
(4) and (3) shift reaction: introducing the gas mixed in the step (3) into a shift reactor from the upper end of the shift reactor, and allowing the mixed gas of the raw material gas and the water vapor in the shift reactor to pass through a bed layer filled with a shift catalyst to perform a carbon monoxide isothermal shift reaction under the reaction pressure of 2.5-3.0Mpa to generate carbon dioxide and hydrogen;
(5) gas-liquid separation: and after the shift reaction, the gas is discharged from an outlet at the lower end of the shift reactor, is cooled by a water cooling system, and then sequentially passes through primary gas-liquid separation and secondary gas-liquid separation to obtain the product gas.
2. The carbon monoxide shift process as recited in claim 1, wherein the pressure in the desulfurization and dechlorination reactor in step (1) is controlled to be 2.5-3.0MPa and the temperature is controlled to be 200-250 ℃.
3. The carbon monoxide shift process according to claim 1 or 2, wherein in the step (1), a coarse desulfurization catalyst A and a fine desulfurization catalyst B are respectively filled in the desulfurization reactor from top to bottom, and the volume ratio of the filling amounts of the catalysts A: and B is 1.5-2.0: 1.
4. The carbon monoxide shift process as recited in claim 1, wherein the deionized water in step (2) is pumped by a water pump into a vaporizer controlled at a temperature of 250 ℃ and 300 ℃.
5. The carbon monoxide shift process as recited in claim 1 or 4, wherein in step (2), the internal piping of the vaporizer is spirally distributed.
6. The carbon monoxide shift process as recited in claim 5, wherein in step (2), deionized water is introduced into the vaporizer at a lower end and discharged at an upper end.
7. The carbon monoxide shift conversion process as recited in claim 1, wherein the purified feed gas in step (3) is mixed with steam in a holding furnace controlled at 180-250 ℃.
8. The carbon monoxide shift conversion process according to claim 1, wherein in the step (4), the shift reactor is an isothermal shift reactor, a fixed bed tubular reactor is arranged in the isothermal shift reactor, the reactor is of an annular structure, a sleeve is arranged in the middle, and cold air enters from the lower end of the sleeve to the upper end of the sleeve and carries away heat generated by the reaction.
9. A carbon monoxide shift process according to claim 1 or 8, wherein in step (4) the shift reactor is provided with an annular electric heating jacket on its inner wall.
10. A carbon monoxide shift process according to claim 1, wherein in step (4) the shift reactor is packed with a self-developed intermediate temperature copper-based carbon monoxide shift catalyst.
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