A kind of high water-gas ratio saturated hot-water tower share split CO conversion process
Technical field
The present invention relates to the CO conversion process, specifically refer to a kind of high water-gas ratio saturated hot-water tower share split CO conversion process.
Background technology
China has successively introduced the large-scale coal chemical engineering equipment that more than ten covers adopt the shell fine coal gasification process beginning of this century, and this technology commercial operation only limits to use the crude synthesis gas combustion and steam combined cycle generating unit after the purification, does not need to arrange the CO shift conversion step.But this technology is used for just facing when gas making comes device such as supporting synthetic ammonia, hydrogen manufacturing, synthesizing methanol a high concentration CO converter technique difficult problem, and do not have the high concentration CO converter technique can be for reference and introduce, converter unit must be finished engineering design voluntarily by domestic engineering corporation.
In the converter unit engineering design process, each engineering corporation and transformation catalyst patent merchant closely cooperate, under the pot destroying process general thought guiding that traditional conversion is adopted, developed high water-gas ratio high concentration CO converter technique, its flow process characteristics are to add a large amount of middle pressure superheated vapours at pre-shift converter entrance, and water/dry gas mol ratio is reached more than 1.30, and transformationreation is carried out in segmentation then, final conversion gas outlet CO butt volume content generally is not higher than 0.4%, and is provided with pre-shift converter.The purpose that adopts high water-gas ratio conversion is to prevent the shift converter overtemperature, it mainly is to consider earlier the CO content in the raw gas suitably to be reduced that pre-shift converter is set, make in the conversion gas after the pre-change CO content near the CO content in the texaco coal-water slurry gasification outlet raw gas, because the shift process that coal water slurry gasification disposes is mature and reliable.But high water-gas ratio converter technique still exposes following problem in actual motion:
1) middle pressure steam consumption is big: because waste heat boiler is adopted in the waste heat recovery of shell coal gasification, rough coal air water/dry gas mol ratio that gasification process is sent is less than 0.2, will be before pre-the change bring up to 1.30 with rough coal air water/dry gas mol ratio is disposable, needing to add a large amount of middle pressure superheated vapours comes humidification and regulates temperature, therefore the consumption of high water-gas ratio conversion process middle pressure steam is big, the plant energy consumption height.
2) become the easy overtemperature of stove in advance: enter the raw gas of pre-change stove through humidification, this moment, CO concentration and water-gas ratio all were in maximum, therefore reacted also maximum of impellent.Becoming the interior transformationreation degree of depth of stove in addition in advance is to be controlled by the loadings of catalyzer, rather than balancing control, so pre-change catalyzer loadings requirement must be accurate, otherwise meeting remarkably influenced bed hot(test)-spot temperature causes pre-change catalyzer bed overtemperature easily.But pre-change catalyzer loadings need be considered catalyst aging and replacement cycle in actual production, and certain filling surplus is all arranged in the design, uses the initial stage to occur bed overtemperature problem easily at pre-change catalyzer.
3) the pre-change catalyzer life-span is short: raw gas water-gas ratio this moment that enters pre-change stove is in maximum, steam partial pressure is big, the dew-point temperature height, operate and careless slightlyly just cause easily that pre-change catalyzer is soaked to harden, active decay rapidly, system pressure drop enlarges markedly, the frequent replacing of having to, have a strong impact on changing device and stablize long-term operation, increased operation energy consumption and process cost.
4) facility investment height: press waste heat boiler and Low Pressure Waste Heat Boiler in being provided with in the flow process, cause the converter unit investment higher.
Be 200710068401.0 Chinese invention patent disclosed " the CO conversion process that a kind of and coal gasification are supporting " as application number, its pre-shift converter water/dry gas mol ratio is 1.3~1.5.Too high water-gas ratio worsens pre-transformation catalyst operating environment, in actual production pre-transformation catalyst in a short time activity sharply fail and harden, system pressure drop significantly increases, pre-change catalyzer is changed frequent, have a strong impact on the long-period stable operation of device, and the middle pressure superheated vapour consumption of this shift process is seriously bigger than normal, has increased the production cost of enterprise.Press waste heat boiler in being provided with in the conversion process flow process in addition, increased the facility investment of converter unit.
Summary of the invention
Technical problem to be solved by this invention is that the present situation at prior art provides a kind of high water-gas ratio saturated hot-water tower share split CO conversion process, middle pressure superheated vapour consumption in the high water-gas ratio conversion process of high density is big, energy consumption is high to solve, and pre-transformation catalyst work-ing life is short, inactivation is fast, it is frequent to change, problems such as system pressure drop is big, facility investment height.
The present invention solves the problems of the technologies described above the technical scheme that adopts: this high water-gas ratio saturated hot-water tower share split CO conversion process is characterized in that comprising the steps:
The raw gas of being sent here by coal gasification workshop section is at first sent into and is isolated liquid phase in the gas-liquid separator; That comes out from the gas-liquid separator top enters saturator through the raw gas behind the separatory from the bottom of saturator, top from saturator after the process recycled water heat exchange to 205 that comes from the technological cycle water out of hot-water tower bottom ℃~225 ℃ enters saturator, and both carry out heat and mass at counter current contact in saturator; Process recycled water is lowered the temperature gradually and is sent from the saturator bottom, and the technological cycle water inlet from hot-water tower returns hot-water tower then;
Be divided into two strands after going out the raw gas heat exchange of saturator, first strand of raw gas with send into first shift converter after middle pressure superheated vapour and medium pressure boiler water fully mix and carry out transformationreation, obtain one and become gas mixture; The raw gas temperature that control enters first shift converter is that 250 ℃~280 ℃, water/dry gas mol ratio are 1.3~1.5;
One becomes behind gas mixture and second strand of raw gas and the stream and sends into second shift converter after medium pressure boiler water fully mixes and carry out transformationreation, obtains two change gas mixtures; The temperature that control enters second shift converter is that 240 ℃~270 ℃, water/dry gas mol ratio are 0.7~0.9, CO butt volume content is 30%~40%;
The throughput ratio of described first strand of raw gas and second strand of raw gas is 3: 7~5: 5;
Go out two of second shift converter and become and to enter the 3rd shift converter after the gas mixture heat exchange to 230 ℃~250 ℃ and proceed transformationreation, obtain three and become gas mixtures;
Go out three of the 3rd shift converter and become and to enter the 4th shift converter after the gas mixture heat exchange to 210 ℃~220 ℃ and proceed transformationreation, obtain four and become gas mixtures;
The four change gas mixtures that go out the 4th shift converter enter hot-water tower from conversion gas mixture entrance, the middle part of hot-water tower with carry out mass-and heat-transfer from the process recycled water counter current contact of saturator, at the top of hot-water tower and purification process phlegma and mend the medium pressure boiler water counter current contact of going into and carry out mass-and heat-transfer, obtain the conversion gas mixture at the top of hot-water tower, obtain process recycled water in the bottom of hot-water tower;
The mol ratio of process recycled water and purification and condensation liquid and medium pressure boiler water is 7.0~10.0 in the above-mentioned hot-water tower, and the consumption of this process recycled water is 4.0~6.0 with the mol ratio that enters the butt raw gas of gas-liquid separator.
The top of above-mentioned hot-water tower tower body is provided with the conversion mixed gas outlet, the bottom of tower body is provided with the technological cycle water out, the bottom of tower body sidewall is provided with four and becomes the gas mixture entrance, the middle part of tower body sidewall is provided with the technological cycle water inlet, the top of tower body sidewall is provided with purification process phlegma and medium pressure boiler water inlet, and described technological cycle water inlet is connected the spray equipment that is arranged in the described tower body respectively with described purification process phlegma and medium pressure boiler water inlet.
For the intrasystem thermal source of more efficient use, above-mentioned technology can also be optimized as follows:
The raw gas of being sent here by coal gasification workshop section is at first sent into gas-liquid separator separates and is gone out liquid phase;
The raw gas through behind the separatory that comes out from the gas-liquid separator top enters saturator from the saturator bottom, the process recycled water that comes from the hot-water tower bottom is successively through first preheater, second preheater, the 3rd preheater and four heat exchange of the 4th preheater, enter saturator from saturator top after being warming up to 205 ℃~225 ℃, raw gas and process recycled water counter current contact in saturator is carried out heat and mass; The technological cycle water temp reduces gradually, sends from saturator bottom, returns the hot-water tower heating that circulates from the process water entrance after saturated column bottoms pump pressurization;
Raw gas after the humidification temperature raising is sent from the saturator top, enters raw gas interchanger and following two and becomes gas mixture heat exchange temperature raisings; The raw gas that goes out the raw gas interchanger is divided into two strands, wherein first strand of raw gas enters first gas liquid mixer, middle pressure superheated vapour and the medium pressure boiler water humidification by mixing of gas temperature raising next with the battery limit (BL), raw gas temperature after the adjustment is that 250 ℃~280 ℃, water/dry gas mol ratio are 1.3~1.5, raw gas enters first shift converter and carries out transformationreation subsequently, obtains one and becomes gas mixture;
One sends into second gas liquid mixer after becoming gas mixture and second strand of raw gas and stream, and the medium pressure boiler water with the battery limit (BL) fully mixes and carries out sending into the 4th preheater heating process recirculated water after the humidification temperature adjustment; Enter second shift converter after one temperature that becomes gas mixture and second strand of raw gas is reduced to 240 ℃~270 ℃ and proceed transformationreation, obtain two and become gas mixture;
Go out two of second shift converter and become gas mixtures and at first enter the raw gas interchanger described raw gas is heated, enter the 3rd preheater heating process recirculated water then after, send into the 3rd shift converter and continue reaction, obtain three and become gas mixtures; Two temperature that become gas mixture that control enters the 3rd shift converter are 230 ℃~250 ℃;
The three change gas mixtures that go out the 3rd shift converter are at first sent into the second preheater heating process recirculated water, send into the 4th shift converter then and proceed transformationreation, obtain four and become gas mixtures; Three temperature that become gas mixture that control enters the 4th shift converter are 210 ℃~220 ℃;
The four change gas mixtures that go out the 4th shift converter are sent into the first preheater heating process recirculated water earlier, enter hot-water tower from conversion gas mixture entrance then, the middle part of hot-water tower with carry out mass-and heat-transfer from the process recycled water counter current contact of saturator, the top of hot-water tower with from the purification process phlegma of back system and mend the medium pressure boiler water counter current contact of going into and carry out mass-and heat-transfer; The conversion gas mixture that obtains at the top of hot-water tower is sent to downstream unit; The process recycled water of sending from the hot-water tower bottom is sent to the first preheater heat exchange after the pressurization of hot water column bottoms pump.
One, compare with the high water-gas ratio CO conversion process of existing high density, the invention has the advantages that:
1) uses saturator that the raw gas that comes from gasification unit is carried out warming and humidifying, can save a large amount of middle superheated vapours of pressing, reduced the steam consumption of converter unit significantly;
2) cancel pre-change stove, thoroughly solved technical barriers such as overtemperature, catalyst life that pre-change heat size is prone to be short;
3) hot-water tower that uses texture improvement becomes the gas mixtures dehumidification of lowering the temperature to four, has alleviated back system to the recovery load of conversion low level waste heat, has simplified the waste heat recovery flow setting, has saved facility investment;
4) cancel middle pressure waste heat boiler, reduced facility investment.
Description of drawings
Fig. 1 is the process flow diagram of the embodiment of the invention;
Fig. 2 is the structural representation of hot-water tower in the embodiment of the invention.
Embodiment
As shown in Figure 2, the top of hot-water tower tower body is provided with conversion gas outlet 141, the bottom of tower body is provided with technological cycle water out 142, the bottom of tower body sidewall is provided with conversion gas mixture entrance 143, the middle part of tower body sidewall is provided with technological cycle water inlet 144, the top of tower body sidewall is provided with purification process phlegma entrance 145, and described technological cycle water inlet 144 is connected the spray equipment 146 that is arranged in the described tower body respectively with described process condensate entrance 145.
Present embodiment is produced the typical chemical fertilizer plant of 520,000 tons of/year urea of 300,000 tons of/year synthetic ammonia in conjunction with the gas making of shell coal gasification, and the present invention is described in further detail.
As shown in Figure 1, the CO conversion process of present embodiment is as follows:
160 ℃ of the raw gas temperature of the saturated water vapour of being sent here by coal gasification workshop section, pressure 3.7Mpa, with pipeline raw gas is being delivered to the process of conversion section because calorific loss from gasification workshop section, a small amount of water vapor in the raw gas generation phlegma that can be condensed, the coexistence in tubing system of raw gas and lime set can cause corrosion and the vibrations of pipeline and equipment, so raw gas at first needs lime set is wherein separated, therefore present embodiment is sent raw gas into gas-liquid separator 1 earlier, and liquid flows out from the outlet at bottom of gas-liquid separator 1.The raw gas through behind the separatory that comes out from gas-liquid separator 1 top enters saturator 2 lower sidewall, the process recycled water that comes from hot-water tower 14 bottoms is through four heat exchange temperature raisings, temperature increases to 217 ℃ process recycled water and enters from saturator 2 side wall upper part, raw gas and process recycled water counter current contact are carried out heat and mass, the technological cycle water temp is reduced to 162 ℃ gradually, send from saturator 2 bottoms, after 16 pressurizations of saturated column bottoms pump, deliver to hot-water tower 14 heating that circulates, extract 3%~8% of technological cycle water inventory simultaneously out and go to the back system to carry out stripping, prevent that objectionable impurities from accumulating at the technological cycle water system.By humidification temperature raising simultaneously, temperature reaches 201 ℃ to raw gas in saturator 2, and water/dry gas mol ratio reaches 0.88, and the raw gas after the humidification temperature raising is sent from saturator 2 tops.Enter raw gas interchanger 3 and two and become gas mixture heat exchange temperature raising, the raw gas that goes out raw gas interchanger 3 is divided into two strands, the ratio of the volumetric flow rate of two strands of raw gass is 4: 6, wherein first strand 40% raw gas enters first gas liquid mixer 4,400 ℃ of temperature with the battery limit (BL), the medium pressure boiler water humidification by mixing of gas temperature raising that the middle pressure superheated vapour of pressure 4.0Mpa and battery limit (BL) come, raw gas temperature after the adjustment is 255 ℃, water/dry gas mol ratio is 1.40, enter first shift converter 5 and carry out the depth conversion reaction, a change mixture temperature that goes out first shift converter 5 is about 460 ℃, and CO butt volume content is about 7.0%.Use second strand 60% raw gas not participating in reaction, one change gas mixture is carried out Quench be cooled to 355 ℃, water/dry gas mol ratio is 0.77, enter gas liquid mixer 6 then, mix with medium pressure boiler water that the battery limit (BL) comes and to carry out the humidification temperature adjustment, after the adjustment one becomes mixture temperature and is 335 ℃, water/dry gas mol ratio is 0.8, CO butt volume content is 33%, enter the 4th preheater 7 heating process recirculated waters, one becomes mixture temperature is reduced to 260 ℃, enter second shift converter 8 and proceed transformationreation, the two change mixture temperatures that go out second shift converter 8 are about 407 ℃, CO butt volume content is about 5.8%, two change gas mixtures enter 3 pairs of raw gass of raw gas interchanger and heat, two change mixture temperatures drop to 360 ℃ simultaneously, enter the 3rd preheater 9 heating process recirculated waters subsequently, two become mixture temperature is reduced to 245 ℃, enter the 3rd shift converter 10 and continue reaction, the three change mixture temperatures that go out the 3rd shift converter 10 are about 276 ℃, CO butt volume content is about 1.4%, three become gas mixture enters second preheater, 11 heating process recirculated waters, simultaneously three become mixture temperatures and drop to 210 ℃ and enter the 4th shift converter 12 and proceed transformationreation, the four change mixture temperatures that go out the 4th shift converter 12 are about 216 ℃, CO butt volume content is about 0.55%, four become gas mixture enters first preheater, 13 heating process recirculated waters, four change mixture temperatures drop to 185 ℃ and enter hot-water tower 14 lower sidewall simultaneously, carrying out countercurrent mass transfer at the middle part of hot-water tower 14 with process recycled water from saturator 2 conducts heat, carrying out countercurrent mass transfer on the top of hot-water tower 14 with the medium pressure boiler water of going into from purification process phlegma and the benefit of back system conducts heat, the medium pressure boiler water that purification process phlegma and benefit are gone into and back at hot-water tower 14 bottoms general designation process recycled water from the process recycled water mixing of saturator 2, four become mixture temperature is reduced to 163 ℃ gradually, send from hot-water tower 14 tops, go to the downstream to carry out the recovery of waste heat and process condensate.The technological cycle water temp of sending from hot-water tower 14 bottoms rises to 173 ℃, through hot-water tower column bottoms pump 15 pressurization and send saturator 2 after the heat exchange to 217 ℃ step by step.
Comparative Examples
For adopting the gas making of shell coal gasification to produce the typical chemical fertilizer plant of 520,000 tons of/year urea of 300,000 tons of/year synthetic ammonia, enter effective gas (H of conversion section
2+ CO) be approximately 85000Nm
3/ h compares high water-gas ratio CO conversion process and saturated hot-water tower height water-gas ratio CO conversion process significant parameter under this benchmark and sees Table 1.
Table 1