CN104085855B - The processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device - Google Patents
The processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device Download PDFInfo
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Abstract
The present invention relates to the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device, it is characterized in that it comprises: step one oil water removal and temperature shift reaction, the step 6 refrigerated separation steam condensate such as tar, step 2 heat exchange temperature raising, step 3 detoxification, step 4 device outer reverse humidification, step 5.After the synthetic ammonia that the present invention is applied to fixed bed gas and methyl alcohol product installation, have that detoxification is thorough, catalyst cycle long, shift-converter catalyst does not lump and the not advantage such as overtemperature, substantially increase the production efficiency of carbon monodixe conversion.
Description
Technical field
The invention belongs to Coal Chemical Industry production technical field, particularly relate to the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device.
Technical background
Current be in traditional medium and small nitrogen fertilizer factory of raw material with coal, greatly mainly with atmosphere intermission or continuously fixed bed produce unstripped gas, containing the oxygen of 0.3 ~ 0.5% in unstripped gas, oxygen easily makes conversion catalyst sulphating and rapid deactivation.Although be all provided with purification detoxifying agent in common transform technique before entering to convert catalyst now, the gas entering detoxification cleaner is all the moisture after adding steam.Utilize detoxifying agent deoxidation, from deoxidation (H
2+ O
2→ H
2o) angle of chemical reaction equilibrium, 0.2 ~ 0.3 vapour/gas is there is than being oxygen in impossible effective elimination semi-water gas in semi-water gas, thus aerobic bleeds catalyst layer all the time, cause cumulative sulphating, thus making catalyst inactivation, this is the one of the main reasons of the irreversible rapid deactivation of complete low catalyst.If increase vapour/gas ratio in process of production, then deoxidation effectiveness declines.
All with hot water saturator in conversion process under traditional 0.85MPa pressure, easily there is water phenomenon in tower in this hot water saturator technique, causes catalyst to lump, and causes the detoxifying agent on one section of upper strata to lose efficacy, and causes bed to leak oxygen, makes conversion catalyst inactivation; Owing to there being the existence of steam in semi-water gas, easily produce dew point corrosion, require very high to the material of equipment and pipeline.
Containing the carbon monoxide of more than 30% in semi-water gas, under pressurized high-temperature easily and carbon steel piping react and generate iron carbonyl, in the thin rouge and powder of the dust of middle change stove entrance, complete low change one section of entrance, a part is exactly caused by the resolvent of iron carbonyl in coal gas.These dust easily lump when moisture and block the duct of catalyst, and cause specific surface area to decline, cause the activity decrease of catalyst, the resistance of catalyst layer rises simultaneously.
Current China is on the conversion process of the medium and small nitrogen fertilizer factory of raw material with coal, and in order to save steam consumption, recovery system is had more than needed heat energy, all adopts hot water to be humidified semi-water gas, regulates the steam-to-gas ratio in semi-water gas.Work of water sprinkling for better material moisture in the employing humidifier that the method thousand times of humidification is same: semi-water gas enters humidifier from the bottom of humidifier, carries out mass transfer heat exchange, then leave humidifier from the top of humidifier through packing layer and top-down hot water.Because hot water enters from top, and gas goes out from top, is easy to form entrainment.Being entrained with the vaporific globule in semi-water gas can make e-quipment and pipe produce dew point corrosion, the efflorescence of conversion catalyst also can be made to lump simultaneously, cause specific surface area to decline, cause the activity decrease of catalyst, and the resistance of catalyst layer rises simultaneously, and catalyst life reduces.
Current China is on the conversion process of the medium and small nitrogen fertilizer factory of raw material with coal, be no matter medium temperature transformation process, the low technique of middle string, in low technique or total-low process, shift-converter mostly adopts adiabatic reactor.The application of adiabatic reactor will be subject to the impact of the thermostability of catalyst and the selectional restriction of equipment and materials, therefore now all conversion adiabatic reactors all will arrange multistage conversion catalyst bed to complete transformation task, will arrange reaction heat recovery system and the pipeline be connected, valve etc. outside shift-converter.Because the temperature of the exit gas of shift-converter is higher, so heat-exchange equipment and pipeline are all high temperature service and high-temperature pipe, cause present adiabatic conversion process flow process complicated, operation easier is bigger than normal, and the manufacture of equipment and pipeline and maintenance cost higher.
Summary of the invention
The object of the invention is the processing method that the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device is provided for overcoming the deficiencies in the prior art, after the synthetic ammonia that the present invention is applied to fixed bed gas and methyl alcohol product installation, the advantage such as have that detoxification is thorough, catalyst cycle is long, shift-converter catalyst does not lump and temperature of reaction is controlled, can improve the production efficiency of carbon monodixe conversion greatly.
According to the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device that the present invention proposes, it is characterized in that it comprises following concrete steps:
Step one, oil water removal and tar: the semi-water gas that out-of-bounds operation is come is separated with tar filter by water-and-oil separator, deviates from entrained oil water and coal tar in semi-water gas, complete the rough purification process that semi-water gas is carried out;
Step 2, heat exchange temperature raising: semi-water gas carries out heat exchange intensification with reacted conversion gas in First Heat Exchanger and the second interchanger, makes the gas temperature of semi-water gas reach the required temperature 180 DEG C ~ 200 DEG C controlled of detoxification cleaner;
Step 3, detoxification: semi-water gas enters Detoxicating device, in Detoxicating device detoxification catalyzer effect under, remove poisonous substance oxygen and other Toxic of gas, and release reaction heat Q, its principal reaction equation is:
H
2+O
2→H
2O+Q；
The oxygen entered in the semi-water gas of carbon monoxide isothermal shift-converter is thoroughly removed;
Step 4, the outer reverse humidification of device: the semi-water gas after deoxygenation detoxification is carried out work of water sprinkling for better material moisture, humidification high-efficient atomizing shower nozzle is set in the semi-water gas inlet pipe of humidifier, be humidified to semi-water gas with the steam condensate of cleaning or deoxidation soft water, the direction of shower nozzle injection water is contrary with the direction that semi-water gas body flows, gas after humidification enters humidifier packing layer and vaporizes further, can meet the steam-to-gas ratio of the temperature shift reactions such as carbon monoxide double water-gas and the requirement of temperature;
Step 5, waits temperature shift reaction: the wet semi-water gas after humidification enters shift converter beds and carries out transformationreation, and namely generate carbonic acid gas and hydrogen by carbon monoxide and steam reaction, and release reaction heat Q, its reaction equation is:
CO+H
2O→CO
2+H
2+Q；
Reaction heat Q, by the heat exchange curved tube of isothermal shift-converter, utilizes saturated hot-water to be removed in tower by reaction heat Q, to meet the steam needed for by-product production equipment;
Step 6, refrigerated separation steam condensate: reacted conversion gas is successively by the second interchanger, boiler water-suppling heater and First Heat Exchanger, lower the temperature with semi-water gas and oiler feed heat exchange, then this conversion gas enters soft water heater successively, watercooler is cooled to 35 ~ 40 DEG C, finally enter water separator steam condensate is deviate from, obtain qualified conversion gas and leave transformation system.
The present invention compared with prior art its remarkable advantage is:
One is that the present invention adopts semi-water gas to enter the condition of detoxification cleaner detoxification, and be carry out under the state of dry semi-water gas, namely semi-water gas does not add steam or saturated hot-water before entering detoxification reaction device; Owing to entering the semi-water gas of detoxification reaction device not containing saturated vapor, unsaturated vaporific steam in gas, must not be there is; Such detoxifying agent efflorescence can not form caking because there being water, also can not form dew point corrosion to equipment; Because During Detoxification is without steam, detoxifying agent also more can be thorough to deviating from of oxygen.
Two is temperature and steam-to-gas ratios that the present invention regulates carbon monoxide isothermal shift-converter entrance reaction gas, have employed the outer reverse humidification mode of device, before making semi-water gas enter conditioning tower, it is adopted to steam condensate or the deoxidation soft water humidification of the cleaning of high-efficient atomizing shower nozzle high temperature, water spray injection direction is contrary with semi-water gas body flow direction; Gas after humidification enters humidifier filler and increases vaporization further; Efficiently avoid gas work of water sprinkling for better material moisture in device and easily form the drawback of entrainment, transformation catalyst is not lumpd by the impact of condensation spray water xi pearl, also catalyst layer surface can not be made to form sulphating, ensure that the steam-to-gas ratio of semi-water gas and temperature can meet the requirement of the temperature shift reactions such as carbon monoxide.
Three is that the reaction heat of CO shift reaction process in the isothermal CO shift reaction device that adopts of the present invention has come by moving thermoelectric converter in tower, make the hot(test)-spot temperature of CO shift reaction remain at a given steady state value, make the reaction hot(test)-spot temperature in the Outlet Gas Temperature of reactor and device suitable; The hot(test)-spot temperature of reactor can be determined according to steam taste grade needed for different production equipment, the gas outlet temperature of general isothermal reactor is lower than the temperature out of adiabatic reactor about 100 DEG C, and the reaction conversion ratio of CO shift reaction is greatly improved;
Four is present invention eliminates outside the tower needed for adiabatic reactor to move hot equipment and connecting tube, valve etc., the manufacture difficulty of other auxiliary heat-exchanging equipment of shift conversion step is significantly declined, thus it is high to solve the conversion gas temperature out that adiabatic shift-converter brings, causes and move hot equipment outside tower and pipeline manufacture difficulty is higher, take up an area and invest the difficult problems such as bigger than normal.
Accompanying drawing explanation
Accompanying drawing 1 is the schematic flow sheet of the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device that the present invention proposes.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.
Composition graphs 1, the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device that the present invention proposes, it comprises following concrete steps:
Step one, oil water removal and tar: the semi-water gas that out-of-bounds operation is come is separated with tar filter by water-and-oil separator, deviates from entrained oil water and coal tar in semi-water gas, complete the rough purification process that semi-water gas is carried out;
Step 2, heat exchange temperature raising: semi-water gas carries out heat exchange intensification with reacted conversion gas in First Heat Exchanger and the second interchanger, makes the gas temperature of semi-water gas reach the required temperature 180 DEG C ~ 200 DEG C controlled of detoxification cleaner;
Step 3, detoxification: semi-water gas enters Detoxicating device, in Detoxicating device detoxification catalyzer effect under, remove poisonous substance oxygen and other Toxic of gas, and release reaction heat Q, its principal reaction equation is:
H
2+O
2→H
2O+Q；
The oxygen entered in the semi-water gas of carbon monoxide isothermal shift-converter is thoroughly removed;
Step 4, the outer reverse humidification of device: the semi-water gas after deoxygenation detoxification is carried out work of water sprinkling for better material moisture, humidification high-efficient atomizing shower nozzle is set in the semi-water gas inlet pipe of humidifier, be humidified to semi-water gas with the steam condensate of cleaning or deoxidation soft water, the direction of shower nozzle injection water is contrary with the direction that semi-water gas body flows, gas after humidification enters humidifier packing layer and vaporizes further, can meet the steam-to-gas ratio of the temperature shift reactions such as carbon monoxide double water-gas and the requirement of temperature;
Step 5, waits temperature shift reaction: the wet semi-water gas after humidification enters shift converter beds and carries out transformationreation, and namely generate carbonic acid gas and hydrogen by carbon monoxide and steam reaction, and release reaction heat Q, its reaction equation is:
CO+H
2O→CO
2+H
2+Q；
Reaction heat Q, by the heat exchange curved tube of isothermal shift-converter, utilizes saturated hot-water to be removed in tower by reaction heat Q, to meet the steam needed for by-product production equipment;
Step 6, refrigerated separation steam condensate: reacted conversion gas is successively by the second interchanger, boiler water-suppling heater and First Heat Exchanger, lower the temperature with semi-water gas and oiler feed heat exchange, then this conversion gas enters soft water heater successively, watercooler is cooled to 35 ~ 40 DEG C, finally enter water separator steam condensate is deviate from, obtain qualified conversion gas and leave transformation system.
The further preferred version of the present invention is: the distance that arranges of the high-efficient atomizing shower nozzle that is humidified described in step 4 is the humidifier import mouth of pipe 2 meters of; Carbon monoxide described in step 5 and steam reaction carry out under the temperature of reaction of each conversion zone layer in beds remains on Isothermal Condition, and the heat-removing way of the CO shift reaction heat produced is move heat in tower.
Embodiment 1.Be applied to for the present invention and adopt lump coal or the fixed bed of moulded coal raw material, carbon monoxide conversion device that tolerance processed produces 180000 tons of synthetic ammonia and 0.8MPa per year, the specific embodiment of the present invention is described in further detail.
As shown in Figure 1, it comprises water-and-oil separator, strainer, First Heat Exchanger, the second interchanger, detoxification cleaner, humidifier, isothermal shift converter, boiler water-suppling heater, de-salted water well heater, watercooler and water separator etc. to the device of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device disclosed in embodiment 1.
The processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device disclosed in embodiment 1, its concrete steps are as follows:
Step one, from out-of-bounds the normal temperature of operation, the semi-water gas of 0.8MPa successively enter water-and-oil separator and tar filter, the vaporific profit isolating gas entrainment in water-and-oil separator removes side by side, coal tar absorption in tar filter in gas is deviate from, and completes the rough purification process carried out semi-water gas;
Step 2, semi-water gas after rough purification process successively enters in First Heat Exchanger and the second interchanger, carries out heat exchange intensification with reacted conversion gas, makes the gas temperature of semi-water gas reach temperature 180 DEG C ~ 200 DEG C needed for detoxification cleaner;
Step 3, the semi-water gas after intensification enters semi-water gas and enters Detoxicating device, and under the effect of the detoxification catalyzer in Detoxicating device, remove poisonous substance oxygen and other Toxic of gas, and release reaction heat Q, its principal reaction equation is:
H
2+O
2→H
2O+Q；
The oxygen entered in the semi-water gas of carbon monoxide isothermal shift-converter is thoroughly removed;
Step 4, the semi-water gas of 250 after deoxygenation detoxification DEG C ~ 270 DEG C, 0.79MPa is entered in the pipeline of humidifier, humidification high-efficient atomizing shower nozzle is set at the distance humidifier import mouth of pipe about 2 meters of, be humidified to semi-water gas with the steam condensate of cleaning or deoxidation soft water, the direction of shower nozzle injection water is contrary with the direction that semi-water gas body flows; Gas after humidification enters humidifier filler and increases vaporization further; Steam adding tube is set in humidifier simultaneously, in order to regulate steam-to-gas ratio and the vaporization temperature of semi-water gas, make that the temperature of the wet semi-water gas entering isothermal shift converter remains on 180 DEG C ~ 200 DEG C, the mol ratio of steam/dry gas is 0.35, guaranteeing in the wet semi-water gas of humidifier does not definitely have the vaporific globule;
Step 5, the wet semi-water gas going out humidifier is entered shift converter beds and carries out transformationreation, carbon monoxide and water vapor react and generate carbonic acid gas and hydrogen under the effect of temperature 230 DEG C, pressure 0.8MPa and cobalt-molybdenum series catalyst, and release reaction heat Q, and its reaction equation is:
CO+H
2O→CO
2+H
2+Q；
Reaction heat Q, by the heat exchange curved tube of isothermal shift-converter, utilizes saturated hot-water to be removed by reaction heat Q, and to meet by-product 2.0MPa saturation steam, byproduct steam amount is per hour is 10.25 tons;
Step 6, about 0.77MPa after reaction, the conversion gas of 230 DEG C are successively by the second interchanger, boiler water-suppling heater and First Heat Exchanger, lower the temperature with semi-water gas and oiler feed heat exchange, and keep the conversion gas temperature of the second interchanger to be 180 DEG C, go out that the conversion gas temperature of boiler water-suppling heater is 155 DEG C, to go out the conversion gas temperature of First Heat Exchanger be 80 DEG C, then this conversion gas enters soft water heater successively, watercooler is cooled to 35 ~ 40 DEG C, finally enter water separator steam condensate is deviate from, obtain qualified conversion gas and leave transformation system.
Application Example of the present invention remarkable advantage is compared with prior art in table 1.
Table 1: Application Example of the present invention remarkable advantage table look-up compared with prior art
In the present invention, the technique means of all not specified (NS)s is prior art known in those skilled in the art.
Below be the concrete support of the processing method technological thought to the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device that the present invention proposes by reference to the accompanying drawings with the embodiment described in one embodiment of the invention; protection scope of the present invention can not be limited with this; every technological thought proposed according to the present invention; any equivalent variations that the technical program basis is done or the change of equivalence, all still belong to the scope of technical solution of the present invention protection.
Claims (3)
1. a processing method for the outer reverse humidification isothermal carbon monodixe conversion of dry gas Detoxicating device, is characterized in that it comprises following concrete steps:
Step one, oil water removal and tar: the semi-water gas that out-of-bounds operation is come is separated with tar filter by water-and-oil separator, deviates from entrained oil water and coal tar in semi-water gas, complete the rough purification process that semi-water gas is carried out;
Step 2, heat exchange temperature raising: semi-water gas carries out heat exchange intensification with reacted conversion gas in First Heat Exchanger and the second interchanger, makes the gas temperature of semi-water gas reach the required temperature 180 DEG C ~ 200 DEG C controlled of Detoxicating device;
Step 3, detoxification: semi-water gas enters Detoxicating device, in Detoxicating device detoxification catalyzer effect under, remove poisonous substance oxygen and other Toxic of gas, and release reaction heat Q, its principal reaction equation is:
H
2+O
2→H
2O+Q；
The oxygen entered in the semi-water gas of carbon monoxide isothermal shift-converter is thoroughly removed;
Step 4, the outer reverse humidification of device: the semi-water gas after deoxygenation detoxification is carried out work of water sprinkling for better material moisture, humidification high-efficient atomizing shower nozzle is set in the semi-water gas inlet pipe of humidifier, be humidified to semi-water gas with the steam condensate of cleaning or deoxidation soft water, the direction of shower nozzle injection water is contrary with the direction that semi-water gas body flows, gas after humidification enters humidifier packing layer and vaporizes further, can meet the steam-to-gas ratio of the temperature shift reactions such as carbon monoxide double water-gas and the requirement of temperature;
Step 5, waits temperature shift reaction: the wet semi-water gas after humidification enters shift converter beds and carries out transformationreation, and namely generate carbonic acid gas and hydrogen by carbon monoxide and steam reaction, and release reaction heat Q, its reaction equation is:
CO+H
2O→CO
2+H
2+Q；
Reaction heat Q, by the heat exchange curved tube of isothermal shift-converter, utilizes saturated hot-water to be removed in tower by reaction heat Q, to meet the steam needed for by-product production equipment;
Step 6, refrigerated separation steam condensate: reacted conversion gas is successively by the second interchanger, boiler water-suppling heater and First Heat Exchanger, lower the temperature with semi-water gas and oiler feed heat exchange, then this conversion gas enters soft water heater successively, watercooler is cooled to 35 ~ 40 DEG C, finally enter water separator steam condensate is deviate from, obtain qualified conversion gas and leave transformation system.
2. the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device according to claim 1, the high-efficient atomizing shower nozzle that it is characterized in that being humidified described in step 4 distance is set for the humidifier import mouth of pipe 2 meters of.
3. the processing method of the outer reverse humidification isothermal carbon monodixe conversion of a kind of dry gas Detoxicating device according to claim 1 and 2, it is characterized in that carbon monoxide described in step 5 and steam reaction carry out under the temperature of reaction of each conversion zone layer in beds remains on Isothermal Condition, the heat-removing way of the CO shift reaction heat produced is move heat in tower.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172765A (en) * | 1996-08-06 | 1998-02-11 | 河北宣化化肥厂 | Full low-temp. fransforming technology for middle-scale synthetic ammonia producing and purifying transforming system |
| CN102701149A (en) * | 2012-06-07 | 2012-10-03 | 王揽月 | Water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion |
| CN103241712A (en) * | 2013-04-09 | 2013-08-14 | 内蒙古乌拉山化肥有限责任公司 | Semi-water gas treatment method |
| CN103435006A (en) * | 2013-08-20 | 2013-12-11 | 湖南安淳高新技术有限公司 | High-CO high-conversion-rate isothermal shift reactor |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172765A (en) * | 1996-08-06 | 1998-02-11 | 河北宣化化肥厂 | Full low-temp. fransforming technology for middle-scale synthetic ammonia producing and purifying transforming system |
| CN102701149A (en) * | 2012-06-07 | 2012-10-03 | 王揽月 | Water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion |
| CN103241712A (en) * | 2013-04-09 | 2013-08-14 | 内蒙古乌拉山化肥有限责任公司 | Semi-water gas treatment method |
| CN103435006A (en) * | 2013-08-20 | 2013-12-11 | 湖南安淳高新技术有限公司 | High-CO high-conversion-rate isothermal shift reactor |
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