CN105419882A - Water gas desulfurization method and system thereof - Google Patents
Water gas desulfurization method and system thereof Download PDFInfo
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- CN105419882A CN105419882A CN201610020837.1A CN201610020837A CN105419882A CN 105419882 A CN105419882 A CN 105419882A CN 201610020837 A CN201610020837 A CN 201610020837A CN 105419882 A CN105419882 A CN 105419882A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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- Oil, Petroleum & Natural Gas (AREA)
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- Gas Separation By Absorption (AREA)
- Industrial Gases (AREA)
- Treating Waste Gases (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a water gas desulfurization system. The system comprises an oil remover, a crude desulfurization tower, a first gas heat exchanger, a gas cooler, a gas-liquid separation device, a desulfurization and decarburization tower, a first fine desulfurization tower and a second fine desulfurization tower, wherein an inlet of the crude desulfurization tower is connected with an outlet of the oil remover; a first inlet of the first gas heat exchanger is connected with an outlet of the crude desulfurization tower; an inlet of the gas cooler is connected with a first outlet of the first gas heat exchanger; an inlet of the gas-liquid separation device is connected with an outlet of the gas cooler; an inlet of the desulfurization and decarburization tower is connected with an outlet of the gas-liquid separation device, and an outlet of the desulfurization and decarburization tower is connected with a second inlet of the first gas heat exchanger; an inlet of the first fine desulfurization tower is connected with a second outlet of the gas heat exchanger; an inlet of the second fine desulfurization tower is connected with an outlet of the first fine desulfurization tower; the first fine desulfurization tower and the second fine desulfurization tower are filled with a JTZX type normal temperature activated carbon fine desulfurization agent.
Description
Technical field
The invention belongs to water-gas or semiwater gas desulphurizing technical field, be specifically related to a kind of desulfurization of water gas method and system thereof.
Background technology
At present, the sulfur removal technology mending carbon water-gas for methyl alcohol is a lot, and main method is exactly first hydrogenation, be hydrolyzed organic sulfur conversion is inorganic sulfur, then by zinc oxide, ferric oxide or gac, removes hydrogen sulfide.Wherein hydrogenation has cobalt molybdenum hydrogenation and iron molybdenum hydrogenation, all needs comparatively high temps; Hydrolysis point ordinary-temp hydrolysis and a medium temperature hydrolyzation, medium temperature hydrolyzation needs 150 ~ 200 degree, although ordinary-temp hydrolysis can temperature lower, when entrance organosulfur is greater than 50ppm, the percent hydrolysis of organosulfur is not high.Zinc oxide, ferric oxide, gac remove hydrogen sulfide and run substantially at normal temperatures.The problem that sulfur removal technology existing is like this lowered the temperature after there is first temperature raising, technical process is simultaneously long, and equipment is complicated, and energy consumption is high, and investment is large.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of desulfurization of water gas method and system thereof, and desulfurization of water gas system provided by the invention is carried out at a lower temperature, and technique is simple, and energy consumption is little.
The invention provides a kind of desulfurization of water gas system, comprising:
Oil eliminator;
The thick thionizer that entrance is connected with the outlet of described oil eliminator;
The first gas heat exchanger that first entrance is connected with the outlet of described thick thionizer;
Entrance exports with first of described first gas heat exchanger the gas cooler be connected;
The gas-liquid separator that entrance is connected with the outlet of described gas cooler;
The desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger;
Entrance and second of described gas heat exchanger export the first fine de-sulfur tower be connected;
The second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower;
JTZX type normal temperature refined active carbon desulfurizer is provided with in described first fine de-sulfur tower and described second fine de-sulfur tower.
Preferably, also comprise entrance and export with described second fine de-sulfur tower the 3rd fine de-sulfur tower be connected, in described 3rd fine de-sulfur tower, be provided with JTZX type normal temperature refined active carbon desulfurizer.
Preferably, also comprise the second gas heat exchanger be arranged between described first gas heat exchanger and described gas cooler, first outlet of described first gas heat exchanger is connected with the entrance of described second gas heat exchanger, and the outlet of described second gas heat exchanger is connected with the entrance of described gas cooler.
Preferably, also comprise the cooling recirculation system be connected with described desulfurization and decarburization tower, described cooling recirculation system comprises:
Entrance exports with second of described desulfurization and decarburization tower the NHD water cooler be connected;
The high pressure flash groove that entrance is connected with the outlet of described NHD water cooler;
The low-pressure flashing tank that entrance is connected with the outlet of described high pressure flash groove;
The regenerator column that entrance is connected with the outlet of described low-pressure flashing tank;
The recycle pump that entrance is connected with the outlet of described regenerator column;
The ammonia cooler that entrance is connected with described circulation pump outlet, the outlet of described ammonia cooler is connected with the second entrance of described desulfurization and decarburization tower.
Present invention also offers a kind of desulfurization of water gas method, comprise the following steps:
A), after being processed by oil eliminator, thick thionizer, the first gas heat exchanger, gas cooler, gas-liquid separator and desulfurization and decarburization tower successively by sulphurous water coal gas, reactant gases is obtained;
B) after described reactant gases being passed through the first gas heat exchanger, fine de-sulfur is carried out and the second fine de-sulfur tower carries out fine de-sulfur successively again through the first fine de-sulfur tower, obtain desulfurization water-gas, in described first fine de-sulfur tower and described second fine de-sulfur tower, be filled with JTZX type normal temperature refined active carbon desulfurizer respectively.
Preferably, in described reactant gases, the content of COS is 23 ~ 28mg/m
3, H
2the content of S is 0mg/m
3.
Preferably, after described reactant gases carries out fine de-sulfur by Second distillation column, also carry out fine de-sulfur by the 3rd rectifying tower, obtain desulfurization water-gas, in described 3rd fine de-sulfur tower, be filled with JTZX type normal temperature refined active carbon desulfurizer respectively.
Preferably, the temperature that described first fine de-sulfur tower carries out fine de-sulfur is 30 ~ 60 DEG C, and pressure is 2.1 ~ 2.3MPa;
The temperature that described second fine de-sulfur tower carries out fine de-sulfur is 30 ~ 60 DEG C, and pressure is 2.1 ~ 2.3MPa;
The temperature that described 3rd fine de-sulfur tower carries out fine de-sulfur is 30 ~ 60 DEG C, and pressure is 2.1 ~ 2.3MPa.
Preferably, the content < 0.15mg/m of COS in described desulfurization water-gas
3, H
2the content of S is 0mg/m
3.
Preferably, described sulphurous water coal gas comprises following main component according to percent by volume:
The CO of 14.35% ~ 16.43%
2;
The CO of 41.04% ~ 42.51%;
The H of 39.33% ~ 41.86%
2;
The CH of 0.65% ~ 0.88%
4;
The N of 0.35% ~ 0.68%
2;
The O of 0.21% ~ 0.75%
2;
Also 15.2 ~ 20mg/m is comprised in described sulphurous water coal gas
3h
2s and 86 ~ 110mg/m
3cOS.
Compared with prior art, the invention provides a kind of desulfurization of water gas system, comprising: oil eliminator; The thick thionizer that entrance is connected with the outlet of described oil eliminator; The first gas heat exchanger that first entrance is connected with the outlet of described thick thionizer; Entrance exports with first of described first gas heat exchanger the gas cooler be connected; The gas-liquid separator that entrance is connected with the outlet of described gas cooler; The desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger; Entrance and second of described gas heat exchanger export the first fine de-sulfur tower be connected; The second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower; JTZX type normal temperature refined active carbon desulfurizer is filled with in described first fine de-sulfur tower and described second fine de-sulfur tower.Desulfurization of water gas system gas provided by the invention is after desulfurization and decarburization tower, the fine de-sulfur device being filled with desulfurizing agent is directly entered by gas heat exchanger, equipment in system is without the need to insulation, a step fine de-sulfur operation can be completed under cryogenic, equipment operates steadily, technique is simple, and energy consumption is little.
Result shows, sulphurous water coal gas after desulfurization of water gas system provided by the invention, the content < 0.15mg/m of COS
3, H
2the content of S is 0mg/m
3.
Accompanying drawing explanation
Fig. 1 is the structural representation of desulfurization of water gas system provided by the invention.
Embodiment
The invention provides a kind of desulfurization of water gas system, comprising:
Oil eliminator;
The thick thionizer that entrance is connected with the outlet of described oil eliminator;
The first gas heat exchanger that first entrance is connected with the outlet of described thick thionizer;
Entrance exports with first of described first gas heat exchanger the gas cooler be connected;
The gas-liquid separator that entrance is connected with the outlet of described gas cooler;
The desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger;
Entrance and second of described gas heat exchanger export the first fine de-sulfur tower be connected;
The second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower;
JTZX type normal temperature refined active carbon desulfurizer is filled with in described first fine de-sulfur tower and described second fine de-sulfur tower.
Desulfurization of water gas system provided by the invention comprises oil eliminator, and described oil eliminator for removing water, oil and the dust-like material in water-gas, thus reduces the impact on back segment equipment.
Desulfurization of water gas system provided by the invention also comprises the thick thionizer that entrance is connected with the outlet of described oil eliminator, and described thick thionizer is used for tentatively removing the H in water-gas
2s gas.
Desulfurization of water gas system provided by the invention also comprises the first gas heat exchanger that the first entrance is connected with the outlet of described thick thionizer.Described first gas heat exchanger is used for the heat exchange of gas, thus reduces heating and cooling system, reduces energy consumption.
Desulfurization of water gas system provided by the invention also comprises entrance and exports with first of described first gas heat exchanger the gas cooler be connected, and described gas cooler is used for water-gas to cool, and obtains phlegma, thus realizes the purifying of water-gas further.
Preferably, desulfurization of water gas system provided by the invention also comprises the second gas heat exchanger be arranged between described first gas heat exchanger and described gas cooler, first outlet of described first gas heat exchanger is connected with the entrance of described second gas heat exchanger, and the outlet of described second gas heat exchanger is connected with the entrance of described gas cooler.Water-gas, by after three grades of coolings of the first gas heat exchanger, the second gas heat exchanger and gas cooler, obtains phlegma, realizes the purifying of water-gas further.
Desulfurization of water gas system provided by the invention also comprises the gas-liquid separator that entrance is connected with the outlet of described gas cooler.The phlegma that gas cooler obtains by described gas-liquid separator and gas delivery.
Desulfurization of water gas system provided by the invention also comprises the desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, is provided with NHD solution in described desulfurization and decarburization tower, the NHD solution counter current contact in described water-gas and desulfurization and decarburization tower.H in water-gas
2s and most of COS and CO
2be dissolved in NHD solution, gas from thionizer top out.
In the present invention, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger.
Preferably, described desulfurization and decarburization tower is also connected with cooling recirculation system, concrete, and described cooling recirculation system comprises:
Entrance exports with second of described desulfurization and decarburization tower the NHD water cooler be connected;
The high pressure flash groove that entrance is connected with the outlet of described NHD water cooler;
The low-pressure flashing tank that entrance is connected with the outlet of described high pressure flash groove;
The regenerator column that entrance is connected with the outlet of described low-pressure flashing tank;
The recycle pump that entrance is connected with the outlet of described regenerator column;
The ammonia cooler that entrance is connected with described circulation pump outlet, the outlet of described ammonia cooler is connected with the second entrance of described desulfurization and decarburization tower.
Desulfurization of water gas system provided by the invention also comprises entrance and exports with second of described gas heat exchanger the first fine de-sulfur tower be connected.Described first fine de-sulfur tower can be that a fine de-sulfur tower also can adopt two fine de-sulfur towers to be arranged in parallel, and when described water-gas flow is larger, the fine de-sulfur tower that two can be adopted to be arranged in parallel carries out shunting process.JTZX type normal temperature refined active carbon desulfurizer is filled with in described first fine de-sulfur tower.Organosulfur, through reaction bed, is converted into hydrogen sulfide, is then adsorbed and react to generate elemental sulfur.
Desulfurization of water gas system provided by the invention also comprises the second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower.Described second fine de-sulfur tower can be that a fine de-sulfur tower also can adopt two fine de-sulfur towers to be arranged in parallel, and when described water-gas flow is larger, the fine de-sulfur tower that two can be adopted to be arranged in parallel carries out shunting process.JTZX type normal temperature refined active carbon desulfurizer is filled with in described second fine de-sulfur tower.Described second fine de-sulfur tower is used for removing the S-contained substance such as carbonyl sulfide and thiophene further, finally obtains desulfurization water-gas.
Preferably, desulfurization of water gas system provided by the invention also comprises entrance and exports with described second fine de-sulfur tower the 3rd fine de-sulfur tower be connected, and is filled with JTZX type normal temperature refined active carbon desulfurizer in described 3rd fine de-sulfur tower respectively.The number of described fine de-sulfur tower is relevant with the S-contained substance in the water-gas of pre-desulfurization, in the present invention, preferably includes three fine de-sulfur towers, is namely respectively the first fine de-sulfur tower, the second fine de-sulfur tower and the 3rd fine de-sulfur tower.
In the present invention, in described first fine de-sulfur tower, the loadings of described JTZX type normal temperature refined active carbon desulfurizer is preferably 13 ~ 15m
3/ platform fine de-sulfur tower; In described second fine de-sulfur tower, the loadings of described JTZX type normal temperature refined active carbon desulfurizer is preferably 13 ~ 15m
3/ platform fine de-sulfur tower; In described 3rd fine de-sulfur tower, the loadings of described JTZX type normal temperature refined active carbon desulfurizer is preferably 15 ~ 18m
3/ platform fine de-sulfur tower.
See the structural representation that Fig. 1, Fig. 1 are desulfurization of water gas system provided by the invention.Desulfurization of water gas system provided by the invention, comprises oil eliminator; The thick thionizer that entrance is connected with the outlet of described oil eliminator; The first gas heat exchanger that first entrance is connected with the outlet of described thick thionizer; Entrance exports with first of described first gas heat exchanger the second gas heat exchanger be connected, the gas cooler that entrance is connected with the outlet of described second gas heat exchanger; The gas-liquid separator that entrance is connected with the outlet of described gas cooler; The desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger; Entrance and second of described gas heat exchanger export the first fine de-sulfur tower be connected; The second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower; The 3rd fine de-sulfur tower that entrance is connected with the outlet of described second fine de-sulfur tower, described first fine de-sulfur tower is provided with JTZX type normal temperature refined active carbon desulfurizer, the JTZX type normal temperature refined active carbon desulfurizer that described second fine de-sulfur tower is provided with, described 3rd fine de-sulfur tower is provided with JTZX type normal temperature refined active carbon desulfurizer.
Described desulfurization and decarburization tower is also connected with cooling recirculation system, and described cooling recirculation system comprises: entrance exports with second of described desulfurization and decarburization tower the NHD water cooler be connected; The high pressure flash groove that entrance is connected with the outlet of described NHD water cooler; The low-pressure flashing tank that entrance is connected with the outlet of described high pressure flash groove; The regenerator column that entrance is connected with the outlet of described low-pressure flashing tank; The recycle pump that entrance is connected with the outlet of described regenerator column; The ammonia cooler that entrance is connected with described circulation pump outlet, the outlet of described ammonia cooler is connected with the second entrance of described desulfurization and decarburization tower.
Present invention also offers a kind of desulfurization of water gas method, comprise the following steps:
A), after being processed by oil eliminator, thick thionizer, the first gas heat exchanger, gas cooler, gas-liquid separator and desulfurization and decarburization tower successively by sulphurous water coal gas, reactant gases is obtained;
B) after described reactant gases being passed through the first gas heat exchanger, fine de-sulfur is carried out and the second fine de-sulfur tower carries out fine de-sulfur successively again through the first fine de-sulfur tower, obtain desulfurization water-gas, in described first fine de-sulfur tower and described second fine de-sulfur tower, be filled with JTZX type normal temperature refined active carbon desulfurizer respectively.
In the present invention, particular restriction is not had to the source of described sulphurous water coal gas, can according to well known to a person skilled in the art that the preparation method of water-gas is prepared.In the present invention, described sulphurous water coal gas is preferably prepared as follows:
After water vapour and oxygen mix, react with red-hot coke, obtain water-gas.
Concrete, 2.4 ~ 2.7Mpa pure oxygen from air separation facility is decompressed to 0.7 ~ 0.9Mpa through self-adjusting valve, deliver to the first-level buffer tank of 1.0 ~ 1.6Mpa, 0.1Mpa is decompressed to again through self-adjusting valve, deliver to the self-regulated of level 2 buffering tank and be decompressed to 0.05Mpa, with Gas-making Furnace give up pot heat after superheated vapour and outer tube supplement after steam mixes by the flow proportional set after steam buffer tank, enter Gas-making Furnace;
Enter ash bed, zone of oxidation, reducing zone through fire grate uniformly distributing, with red-hot coke gasification reaction, generate semi-water gas.
The above-mentioned semi-water gas of 450 ~ 550 DEG C is discharged by Gas-making Furnace top, through cyclonic separator dedusting, waste heat boiler heat exchange to 190 ~ 210 DEG C, enter each Gas-making Furnace scrubber tower, scrubbing dust collection, be cooled to 38 ~ 42 DEG C, enter the further dedusting of cooling tower by gas main to lower the temperature, then enter thionizer removing H
2send into gas holder after S and part organosulfur, gas holder water-gas out, after the further dedusting of electrostatic precipitation tower, deliver to water-gas compression section, obtain the sulphurous water coal gas of desulfurization of water gas system to be entered.Described sulphurous water coal gas is after overdraft, and its pressure is 2.1 ~ 2.3MPa, and temperature is 38 ~ 42 DEG C.
Preferably, described sulphurous water coal gas comprises following main component according to percent by volume:
The CO of 14.35% ~ 16.43%
2;
The CO of 41.04% ~ 42.51%;
The H of 39.33% ~ 41.86%
2;
The CH of 0.65% ~ 0.88%
4;
The N of 0.35% ~ 0.68%
2;
The O of 0.21% ~ 0.75%
2;
Also 15.2 ~ 20mg/m is comprised in described sulphurous water coal gas
3h
2s and 86 ~ 110mg/m
3cOS.
More have choosing, described sulphurous water coal gas comprises following main component according to percent by volume:
The CO of 15.0% ~ 16.1%
2;
The CO of 41.50% ~ 42.00%;
The H of 40.00% ~ 41.50%
2;
The CH of 0.70% ~ 0.80%
4;
The N of 0.40% ~ 0.60%
2;
The O of 0.25% ~ 0.70%
2;
Also 15.2 ~ 18mg/m is comprised in described sulphurous water coal gas
3h
2s and 86 ~ 100mg/m
3cOS.
The sulphurous water coal gas that the present invention prepares, first by oil eliminator, to remove water, oil and the dust-like material in water-gas, thus reduces the impact on back segment equipment.
Described sulphurous water coal gas by after oil eliminator, then by thick thionizer, tentatively removes the H in water-gas
2s gas.
After thick thionizer, described sulphurous water coal gas is cooled by the first gas heat exchanger and gas cooler.Preferably, by the sulphurous water coal gas of the first gas heat exchanger before entering gas cooler, also through the second gas heat exchanger.
In the present invention, the sulphurous water coal gas by cooling generates phlegma and the sulphurous water coal gas through preliminary desulfurization.Above-mentioned phlegma and through the sulphurous water coal gas of preliminary desulfurization after gas-liquid separator, enter after desulfurization and decarburization tower processes through the sulphurous water coal gas of preliminary desulfurization, obtain reactant gases.NHD solution is provided with, the NHD solution counter current contact in described water-gas and desulfurization and decarburization tower in described desulfurization and decarburization tower.H in water-gas
2s and most of COS and CO
2be dissolved in NHD solution, gas from thionizer top out.
In described reactant gases, the content of COS is preferably 23 ~ 28mg/m
3, be more preferably 23 ~ 28mg/m
3; Described H
2the content of S is 0mg/m
3.
The temperature of the reactant gases obtained after the process of desulfurization and decarburization tower is preferably 10 ~ 15 DEG C, is more preferably 11 ~ 14 DEG C; Pressure is preferably 2.1 ~ 2.3MPa, is more preferably 2.15 ~ 2.25MPa.
The reactant gases obtained after the process of desulfurization and decarburization tower is back to the first gas heat exchanger, carries out heat exchange with the sulphurous water coal gas by thick thionizer.Described reactant gases carries out after heat exchange through the first gas heat exchanger, and the reactant gases temperature obtained is preferably 30 ~ 60 DEG C, is more preferably 35 ~ 55 DEG C, and pressure is 2.1 ~ 2.3MPa, is more preferably 2.15 ~ 2.25MPa.
Described reactant gases by after the first gas heat exchanger, then carries out fine de-sulfur and the second fine de-sulfur tower carries out fine de-sulfur through the first fine de-sulfur tower successively, obtains desulfurization water-gas.JTZX type normal temperature refined active carbon desulfurizer is filled with respectively in described first fine de-sulfur tower and described second fine de-sulfur tower.In the present invention, in described first fine de-sulfur tower, the loadings of described JTZX type normal temperature refined active carbon desulfurizer is preferably 13 ~ 15m
3/ platform fine de-sulfur tower.The temperature that described first fine de-sulfur tower carries out fine de-sulfur is preferably 30 ~ 60 DEG C, and be more preferably 35 ~ 55 DEG C, pressure is 2.1 ~ 2.3MPa, is more preferably 2.15 ~ 2.25MPa; Air speed is preferably 500 ~ 2000h
-1, be more preferably 700 ~ 1800h
-1.After the first fine de-sulfur tower, the content of the COS in described reactant gases is preferably 9 ~ 12mg/m
3, be more preferably 10 ~ 11mg/m
3; Described H
2the content of S is 0mg/m
3.
Described second fine de-sulfur tower is used for removing the S-contained substance such as carbonyl sulfide and thiophene further, finally obtains desulfurization water-gas.In described second fine de-sulfur tower, the loadings of described JTZX type normal temperature refined active carbon desulfurizer is preferably 13 ~ 15m
3/ platform fine de-sulfur tower.The temperature that described second fine de-sulfur tower carries out fine de-sulfur is preferably 30 ~ 60 DEG C, and be more preferably 35 ~ 55 DEG C, pressure is 2.1 ~ 2.3MPa, is more preferably 2.15 ~ 2.25MPa; Air speed is preferably 500 ~ 2000h
-1, be more preferably 700 ~ 1800h
-1.After the second fine de-sulfur tower, the preferred < 6mg/m of content of the COS in described reactant gases
3, more preferably < 0.15mg/m
3, described H
2the content of S is 0mg/m
3.
The number of described fine de-sulfur tower is relevant with the S-contained substance in the water-gas of pre-desulfurization, in the present invention, preferably also comprises the 3rd fine de-sulfur tower, is filled with JTZX type normal temperature refined active carbon desulfurizer in described 3rd fine de-sulfur tower respectively.In described 3rd fine de-sulfur tower, the loadings of described JTZX type normal temperature refined active carbon desulfurizer is preferably 15 ~ 18m
3/ platform fine de-sulfur tower.The temperature that described 3rd fine de-sulfur tower carries out fine de-sulfur is preferably 30 ~ 60 DEG C, and be more preferably 35 ~ 55 DEG C, pressure is 2.1 ~ 2.3MPa, is more preferably 2.15 ~ 2.25MPa; Air speed is preferably 500 ~ 2000h
-1, be more preferably 700 ~ 1800h
-1.After the 3rd fine de-sulfur tower, the content < 0.15mg/m of described COS
3, H
2the content of S is 0mg/m
3, namely the outlet total sulfur content of the 3rd fine de-sulfur tower is lower than 0.1ppm.
Desulfurization of water gas system gas provided by the invention is after desulfurization and decarburization tower, the fine de-sulfur device being filled with desulfurizing agent is directly entered by gas heat exchanger, equipment in system is without the need to insulation, a step fine de-sulfur operation can be completed under cryogenic, equipment operates steadily, technique is simple, and energy consumption is little.
Result shows, sulphurous water coal gas after desulfurization of water gas system provided by the invention, the content < 0.10mg/m of COS
3, H
2the content of S is 0mg/m
3.
In order to understand the present invention further, be described desulfurization of water gas method provided by the invention and system thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
The desulfurization of water gas system that the present embodiment provides, comprises oil eliminator; The thick thionizer that entrance is connected with the outlet of described oil eliminator; The first gas heat exchanger that first entrance is connected with the outlet of described thick thionizer; Entrance exports with first of described first gas heat exchanger the second gas heat exchanger be connected, the gas cooler that entrance is connected with the outlet of described second gas heat exchanger; The gas-liquid separator that entrance is connected with the outlet of described gas cooler; The desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger; Entrance and second of described gas heat exchanger export the first fine de-sulfur tower be connected, and described first fine de-sulfur tower comprises two fine de-sulfur towers be arranged in parallel; The second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower, described second fine de-sulfur tower comprises two fine de-sulfur towers be arranged in parallel; The 3rd fine de-sulfur tower that entrance is connected with the outlet of described second fine de-sulfur tower, described first fine de-sulfur tower is provided with 15m
3the JTZX type normal temperature refined active carbon desulfurizer of/platform fine de-sulfur tower, described second fine de-sulfur tower is provided with 15m
3the JTZX type normal temperature refined active carbon desulfurizer of/platform fine de-sulfur tower, described 3rd fine de-sulfur tower is provided with 18m
3jTZX type normal temperature refined active carbon desulfurizer.
Described desulfurization and decarburization tower is also connected with cooling recirculation system, and described cooling recirculation system comprises: entrance exports with second of described desulfurization and decarburization tower the NHD water cooler be connected; The high pressure flash groove that entrance is connected with the outlet of described NHD water cooler; The low-pressure flashing tank that entrance is connected with the outlet of described high pressure flash groove; The regenerator column that entrance is connected with the outlet of described low-pressure flashing tank; The recycle pump that entrance is connected with the outlet of described regenerator column; The ammonia cooler that entrance is connected with described circulation pump outlet, the outlet of described ammonia cooler is connected with the second entrance of described desulfurization and decarburization tower.
Embodiment 2
By 1600m
3the oxygen of 0.05Mpa mix with the water vapour of 3500kg after, with the red-hot coke gasification reaction of 4500kg, generate 10000m
3water-gas.Wherein, described Gas-making Furnace temperature 450 ~ 500 DEG C, top hole pressure 5Kpa.
Containing the CO of 15.02% in the water-gas prepared
2; The CO of 43.70%; The H of 35.81%
2; The CH of 0.64%
4; The N of 3.41%
2; The O of 1.41%
2.Sulphur content in water-gas is 20mg/m
3h
2s and 100mg/m
3cOS.
Embodiment 3
The desulfurization of water gas system adopting embodiment 1 to provide carries out desulfurization of water gas, by 8000 ~ 10000m prepared by embodiment 2
3/ h water-gas tentatively deviates from H through oil eliminator and thick thionizer
2s and the water of condensation containing a small amount of oil droplet; Then entering the three grades of coolings of the first gas heat exchanger, the second gas exchanger and gas cooler is that the temperature of water-gas is down to less than 15 DEG C and is entered desulfurization and decarburization tower, and in described desulfurization and decarburization tower, water-gas contacts with low temperature NHD solution is reverse, the H in water-gas
2s and most of COS and CO
2be dissolved in NHD solution, obtain reactant gases.
Described reactant gases carries out fine de-sulfur from entering the first fine de-sulfur tower, the second fine de-sulfur tower and the 3rd fine de-sulfur tower successively after desulfurization and decarburization top of tower out enters the first gas interchanger heat exchange again.
Wherein, reactant gases enters the tolerance that the first fine de-sulfur tower carries out fine de-sulfur is 7000 ~ 9000m
3/ h, organosulfur (COS) content: 23 ~ 28mg/m
3, the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 28 DEG C.After the first fine de-sulfur tower fine de-sulfur, organosulfur (COS) content is 10 ~ 12mg/m
3.
After the first fine de-sulfur tower fine de-sulfur, gas enters the second fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 28 DEG C.After the second fine de-sulfur tower fine de-sulfur, measuring organosulfur (COS) content is 3 ~ 4mg/m
3.
After the second fine de-sulfur tower fine de-sulfur, gas enters the 3rd fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 28 DEG C.After the 3rd fine de-sulfur tower fine de-sulfur, obtain desulfurization water-gas, measuring organosulfur (COS) content is 0mg/m
3, namely total sulfur content is 0mg/m
3.
Embodiment 4
The desulfurization of water gas system adopting embodiment 1 to provide carries out desulfurization of water gas, by 8000 ~ 10000m prepared by embodiment 2
3/ h water-gas tentatively deviates from H through oil eliminator and thick thionizer
2s and the water of condensation containing a small amount of oil droplet; Then entering the three grades of coolings of the first gas heat exchanger, the second gas exchanger and gas cooler is that the temperature of water-gas is down to less than 15 DEG C and is entered desulfurization and decarburization tower, and in described desulfurization and decarburization tower, water-gas contacts with low temperature NHD solution is reverse, the H in water-gas
2s and most of COS and CO
2be dissolved in NHD solution, obtain reactant gases.
Described reactant gases carries out fine de-sulfur from entering the first fine de-sulfur tower, the second fine de-sulfur tower and the 3rd fine de-sulfur tower successively after desulfurization and decarburization top of tower out enters the first gas interchanger heat exchange again.
Wherein, reactant gases enters the tolerance that the first fine de-sulfur tower carries out fine de-sulfur is 7000 ~ 9000m
3/ h, organosulfur (COS) content: 23 ~ 28mg/m
3, the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 40 DEG C.After the first fine de-sulfur tower fine de-sulfur, organosulfur (COS) content is 10 ~ 12mg/m
3.
After the first fine de-sulfur tower fine de-sulfur, gas enters the second fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 40 DEG C.After the second fine de-sulfur tower fine de-sulfur, measuring organosulfur (COS) content is 6 ~ 7mg/m
3.
After the second fine de-sulfur tower fine de-sulfur, gas enters the 3rd fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 40 DEG C.After the 3rd fine de-sulfur tower fine de-sulfur, obtain desulfurization water-gas, measure organosulfur (COS) content and be less than 0.15mg/m
3, namely total sulfur content is less than 0.15mg/m
3.
Embodiment 5
The desulfurization of water gas system adopting embodiment 1 to provide carries out desulfurization of water gas, by 8000 ~ 10000m prepared by embodiment 2
3/ h water-gas tentatively deviates from H through oil eliminator and thick thionizer
2s and the water of condensation containing a small amount of oil droplet; Then entering the three grades of coolings of the first gas heat exchanger, the second gas exchanger and gas cooler is that the temperature of water-gas is down to less than 15 DEG C and is entered desulfurization and decarburization tower, and in described desulfurization and decarburization tower, water-gas contacts with low temperature NHD solution is reverse, the H in water-gas
2s and most of COS and CO
2be dissolved in NHD solution, obtain reactant gases.
Described reactant gases carries out fine de-sulfur from entering the first fine de-sulfur tower, the second fine de-sulfur tower and the 3rd fine de-sulfur tower successively after desulfurization and decarburization top of tower out enters the first gas interchanger heat exchange again.
Wherein, reactant gases enters the tolerance that the first fine de-sulfur tower carries out fine de-sulfur is 10000 ~ 15000m
3/ h, organosulfur (COS) content: 23 ~ 28mg/m
3, the system pressure of fine de-sulfur is 2.2 ~ 2.3Mpa, and temperature is 40 DEG C.After the first fine de-sulfur tower fine de-sulfur, organosulfur (COS) content is 9 ~ 12mg/m3.
After the first fine de-sulfur tower fine de-sulfur, gas enters the second fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 40 DEG C.After the second fine de-sulfur tower fine de-sulfur, measuring organosulfur (COS) content is 5 ~ 6mg/m
3.
After the second fine de-sulfur tower fine de-sulfur, gas enters the 3rd fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 40 DEG C.After the 3rd fine de-sulfur tower fine de-sulfur, obtain desulfurization water-gas, measure organosulfur (COS) content and be less than 0.15mg/m
3, namely total sulfur content is less than 0.15mg/m
3.
Embodiment 6
The desulfurization of water gas system adopting embodiment 1 to provide carries out desulfurization of water gas, by 8000 ~ 10000m prepared by embodiment 2
3/ h water-gas tentatively deviates from H through oil eliminator and thick thionizer
2s and the water of condensation containing a small amount of oil droplet; Then entering the three grades of coolings of the first gas heat exchanger, the second gas exchanger and gas cooler is that the temperature of water-gas is down to less than 15 DEG C and is entered desulfurization and decarburization tower, and in described desulfurization and decarburization tower, water-gas contacts with low temperature NHD solution is reverse, the H in water-gas
2s and most of COS and CO
2be dissolved in NHD solution, obtain reactant gases.
Described reactant gases carries out fine de-sulfur from entering the first fine de-sulfur tower, the second fine de-sulfur tower and the 3rd fine de-sulfur tower successively after desulfurization and decarburization top of tower out enters the first gas interchanger heat exchange again.
Wherein, reactant gases enters the tolerance that the first fine de-sulfur tower carries out fine de-sulfur is 16000 ~ 20000m
3/ h, organosulfur (COS) content: 23 ~ 28mg/m
3, the system pressure of fine de-sulfur is 2.2 ~ 2.3Mpa, and temperature is 50 DEG C.After the first fine de-sulfur tower fine de-sulfur, organosulfur (COS) content is 9 ~ 12mg/m
3.
After the first fine de-sulfur tower fine de-sulfur, gas enters the second fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 50 DEG C.After the second fine de-sulfur tower fine de-sulfur, measuring organosulfur (COS) content is 5 ~ 6mg/m
3.
After the second fine de-sulfur tower fine de-sulfur, gas enters the 3rd fine de-sulfur tower and carries out fine de-sulfur, and the system pressure of fine de-sulfur is 2.0 ~ 2.1Mpa, and temperature is 50 DEG C.After the 3rd fine de-sulfur tower fine de-sulfur, obtain desulfurization water-gas, measure organosulfur (COS) content and be less than 0.15mg/m
3, namely total sulfur content is less than 0.15mg/m
3.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a desulfurization of water gas system, is characterized in that, comprising:
Oil eliminator;
The thick thionizer that entrance is connected with the outlet of described oil eliminator;
The first gas heat exchanger that first entrance is connected with the outlet of described thick thionizer;
Entrance exports with first of described first gas heat exchanger the gas cooler be connected;
The gas-liquid separator that entrance is connected with the outlet of described gas cooler;
The desulfurization and decarburization tower that entrance is connected with the outlet of described gas-liquid separator, the outlet of described desulfurization and decarburization tower is connected with the second entrance of described first gas heat exchanger;
Entrance and second of described gas heat exchanger export the first fine de-sulfur tower be connected;
The second fine de-sulfur tower that entrance is connected with the outlet of described first fine de-sulfur tower;
JTZX type normal temperature refined active carbon desulfurizer is provided with in described first fine de-sulfur tower and described second fine de-sulfur tower.
2. desulfurization of water gas system according to claim 1, is characterized in that, also comprises entrance and exports with described second fine de-sulfur tower the 3rd fine de-sulfur tower be connected, be provided with JTZX type normal temperature refined active carbon desulfurizer in described 3rd fine de-sulfur tower.
3. desulfurization of water gas system according to claim 1, it is characterized in that, also comprise the second gas heat exchanger be arranged between described first gas heat exchanger and described gas cooler, first outlet of described first gas heat exchanger is connected with the entrance of described second gas heat exchanger, and the outlet of described second gas heat exchanger is connected with the entrance of described gas cooler.
4. desulfurization of water gas system according to claim 1, is characterized in that, also comprise the cooling recirculation system be connected with described desulfurization and decarburization tower, described cooling recirculation system comprises:
Entrance exports with second of described desulfurization and decarburization tower the NHD water cooler be connected;
The high pressure flash groove that entrance is connected with the outlet of described NHD water cooler;
The low-pressure flashing tank that entrance is connected with the outlet of described high pressure flash groove;
The regenerator column that entrance is connected with the outlet of described low-pressure flashing tank;
The recycle pump that entrance is connected with the outlet of described regenerator column;
The ammonia cooler that entrance is connected with described circulation pump outlet, the outlet of described ammonia cooler is connected with the second entrance of described desulfurization and decarburization tower.
5. a desulfurization of water gas method, is characterized in that, comprises the following steps:
A), after being processed by oil eliminator, thick thionizer, the first gas heat exchanger, gas cooler, gas-liquid separator and desulfurization and decarburization tower successively by sulphurous water coal gas, reactant gases is obtained;
B) after described reactant gases being passed through the first gas heat exchanger, fine de-sulfur is carried out and the second fine de-sulfur tower carries out fine de-sulfur successively again through the first fine de-sulfur tower, obtain desulfurization water-gas, in described first fine de-sulfur tower and described second fine de-sulfur tower, be filled with JTZX type normal temperature refined active carbon desulfurizer respectively.
6. method according to claim 5, is characterized in that, in described reactant gases, the content of COS is 23 ~ 28mg/m
3, H
2the content of S is 0mg/m
3.
7. method according to claim 5, it is characterized in that, after described reactant gases carries out fine de-sulfur by Second distillation column, also carry out fine de-sulfur by the 3rd rectifying tower, obtain desulfurization water-gas, in described 3rd fine de-sulfur tower, be filled with JTZX type normal temperature refined active carbon desulfurizer respectively.
8. the method according to claim 5 ~ 7 any one claim, is characterized in that, the temperature that described first fine de-sulfur tower carries out fine de-sulfur is 30 ~ 60 DEG C, and pressure is 2.1 ~ 2.3MPa;
The temperature that described second fine de-sulfur tower carries out fine de-sulfur is 30 ~ 60 DEG C, and pressure is 2.1 ~ 2.3MPa;
The temperature that described 3rd fine de-sulfur tower carries out fine de-sulfur is 30 ~ 60 DEG C, and pressure is 2.1 ~ 2.3MPa.
9. the method according to claim 5 ~ 7 any one claim, is characterized in that, the content < 0.15mg/m of COS in described desulfurization water-gas
3, H
2the content of S is 0mg/m
3.
10. method according to claim 5, is characterized in that, described sulphurous water coal gas comprises following main component according to percent by volume:
The CO of 14.35% ~ 16.43%
2;
The CO of 41.04% ~ 42.51%;
The H of 39.33% ~ 41.86%
2;
The CH of 0.65% ~ 0.88%
4;
The N of 0.35% ~ 0.68%
2;
The O of 0.21% ~ 0.75%
2;
Also 15.2 ~ 20mg/m is comprised in described sulphurous water coal gas
3h
2s and 86 ~ 110mg/m
3cOS.
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