CN102002403B - Low water-air ratio and middle water-air ratio carbon monoxide (CO) conversion process - Google Patents

Low water-air ratio and middle water-air ratio carbon monoxide (CO) conversion process Download PDF

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CN102002403B
CN102002403B CN 201010548457 CN201010548457A CN102002403B CN 102002403 B CN102002403 B CN 102002403B CN 201010548457 CN201010548457 CN 201010548457 CN 201010548457 A CN201010548457 A CN 201010548457A CN 102002403 B CN102002403 B CN 102002403B
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gas
shift converter
water
conversion
temperature
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CN 201010548457
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CN102002403A (en
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许仁春
张骏驰
吴艳波
黄彬峰
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中国石油化工股份有限公司
中石化宁波工程有限公司
中石化宁波技术研究院有限公司
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Abstract

The invention relates to a low water-air ratio and middle water-air ratio carbon monoxide (CO) conversion process. The process comprises the following steps of: (1) feeding raw gas into a pre-converter, wherein the temperature of the raw gas entering the inlet of the pre-converter is between 210 and 250 DEG C and the mole ratio of water to dried gas is 0.21 to 0.23; (2) feeding pre-converted mixed gas into a first converter to perform depth conversion, wherein the temperature of the pre-converted mixed gas entering the inlet of the first converter is between 260 and 290 DEG C and the mole ratio of water to dried gas is 0.8 to 1.0; (3) feeding the mixed gas passing through the first converter into a second converter, wherein the temperature of the mixed gas entering the inlet of the second converter is between 220 and 250 DEG C and the mole ratio of water to dried gas is 0.5 to 0.7; (4) feeding the mixed gas passing through the second converter into a third converter, wherein the temperature of the secondary conversion mixed gas entering the inlet of the third converter is between 205and 235 DEG C; and performing conversion on the mixed gas by using the third converter to obtain the mixed gas with the CO content lower than 0.40 percent. The process is unique and has the characteristics of high CO conversion rate, low energy consumption in the conversion process and the like.

Description

The CO conversion process of water-gas ratio in a kind of low water-gas ratio string
Technical field
The present invention relates to a kind of CO conversion process, specifically refer to the conversion process of water-gas ratio CO in a kind of low water-gas ratio string.
Background technology
Since entering 21 century, due to the impact that be becoming tight by petroleum resources day, the Coal Chemical Industry of China has changed the stage of a fast development over to, start one after another take coal as projects such as raw material production synthetic ammonia, methyl alcohol, and the selection of coal gasifying process is from considering all to have adopted Shell bed pulverized coal gasification technology producing synthesis gas to the aspects such as active principle and working cost the requirement of ature of coal and synthetic gas.Due to the crude synthesis gas CO butt volume content that makes up to more than 60%, and the CO conversion is high thermopositive reaction, how effectively to control the bed temperature of CO transformationreation, avoid the generation of methanation side reaction, extend the work-ing life of transformation catalyst and save middle pressure steam consumption, all becoming the Focal point and difficult point of the shift process exploitation that matches with the Shell coal gasification.
The shift process that matches with the Shell coal gasification at present, more general employing the sulfur resistant conversion process flow process of high water-gas ratio or the sulfur resistant conversion process flow process of low water-gas ratio, before shift conversion step all is arranged on the crude synthesis gas desulfurization.Adopt high water-gas ratio sulfur resistant conversion process flow process, its process features is that the entrance at pre-shift converter has added a large amount of middle pressure superheated vapours, water/dry gas mol ratio is reached more than 1.30, and then transformationreation is carried out in segmentation, and final conversion gas outlet CO butt volume content is not generally higher than 0.4%.Adopt low water-gas ratio sulfur resistant conversion process flow process, its process features is that the entrance at the first shift converter does not add steam, utilize the water vapor that raw gas carries to carry out transformationreation, add appropriate steam or process condensate at each follow-up shift converter entrance, each section shift converter inlet water/dry gas mol ratio all is controlled at below 0.5, and final conversion gas outlet CO butt volume content is generally 0.6%.
And for example application number is 200710068401.0 Chinese invention patent application disclosed the CO conversion process of powered coal gasification " a kind of with ", and 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, catalyst change is frequent, affect the long-period stable operation of device, and the middle pressure superheated vapour of this shift process consumes bigger than normal, has increased the production cost of enterprise.
Application number is that 200710087573.2 Chinese invention patent application disclosed " a kind of coal gasification hangs down water/gas sulfur resistant conversion process " is low water-gas ratio CO sulfur resistant conversion process flow process for another example, and each section shift converter inlet water/dry gas mol ratio all is controlled at below 0.5.Because in conversion gas, vapour content is low, expose the transformationreation impellent little in actual production, the shift converter that needs or reaction hop count are more, the facility investment of conversion increases, and final conversion gas outlet CO butt volume content is generally on the low side higher than 0.6%, CO transformation efficiency, and workshop section needs again to consume extra hydrogen and CO reaction generation methane in methanation, for synthetic ammonia, the effective gas consumption that is equivalent to ton ammonia becomes large.
Summary of the invention
Technical problem to be solved by this invention is that the CO conversion process of water-gas ratio in a kind of low water-gas ratio string is provided for the present situation of prior art, short work-ing life with the pre-transformation catalyst that solves in high hydrosphere transformation technique, inactivation is fast, change the problem frequent, that system pressure drop is large, solved simultaneously in low water-gas ratio conversion process that the reaction impellent is little, shift converter or the problem such as the reaction hop count is many and CO low conversion rate, methanation workshop section hydrogen consumption is more serious.The present invention solves the problems of the technologies described above the technical scheme that adopts: the CO conversion process of water-gas ratio in this low water-gas ratio string is characterized in that comprising the steps:
1. the raw gas that coal gasification workshop section is come is sent into pre-shift converter, and controlling temperature in that raw gas enters pre-shift converter and be 210～250 ℃, water/dry gas mol ratio is 0.21～0.23; Obtain becoming in advance gas mixture after pre-shift converter conversion;
2. will become in advance gas mixture and send into the first shift converter and carry out depth conversion, control that pre-to become temperature in that gas mixture enters the first shift converter be 0.8～1.0 into 260～290 ℃, water/dry gas mol ratio; Obtain one and become gas mixture after the first shift converter conversion;
3. become gas mixture with one and send into the second shift converter, controlling one, to become temperature in that gas mixture enters the second shift converter be 0.5～0.7 into 220～250 ℃, water/dry gas mol ratio; Obtain two and become gas mixture after the second shift converter conversion;
4. become gas mixture with two and send into the 3rd shift converter, the temperature in that control two change gas mixtures enter the 3rd shift converter is 205～235 ℃; Obtain CO butt volume content lower than 0.4% gas mixture after the 3rd shift converter conversion.
In such scheme, the use duration of the temperature in of each shift converter and reactor and the activity of catalyzer are relevant.Transformation catalyst in use can be aging gradually, and activity decreased needs suitably to improve the conversion gas temperature of advancing shift converter and the activity that aqueous vapor is recently kept catalyzer this moment.That is to say, along with the prolongation in reaction times, need to change the temperature in of each shift converter and the water of charging/gas mol ratio in above-mentioned scope.
Preferred as such scheme:
1. at first the next raw gas of coal gasification workshop section is sent into gas-liquid separator separates and go out lime set, send into pre-shift converter through the interchanger temperature raising with in allocating on a small quantity after pressure superheated vapour humidification;
2. from pre-shift converter pre-change gas mixture out with send into the first shift converter after pressure superheated vapour and the temperature adjustment of process condensate humidification by mixing of gas;
3. lower the temperature through the waste heat boiler heat exchange from the first shift converter change gas mixture out, then with after the temperature adjustment of process condensate humidification by mixing of gas send into the second shift converter;
4. send into again the 3rd shift converter from the second shift converter two change gas mixtures out after waste heat boiler heat exchange cooling and proceed transformationreation.
As the further improvement of such scheme, from described the second shift converter two becoming gas mixtures enter described shift converter air intake heater after the waste heat boiler heat exchange out, and send into again described the 3rd shift converter after the described raw gas heat exchange that enters this well heater.
Preferably, to enter the temperature in of described pre-shift converter be that 220～240 ℃, water/dry gas mol ratio are 0.22 to described raw gas; The temperature in that described pre-change gas mixture enters the first shift converter is 0.95 into 270～280 ℃, water/dry gas mol ratio; Described one to become temperature in that gas mixture enters the second shift converter be 0.65 into 220～250 ℃, water/dry gas mol ratio; The temperature in that described two change gas mixtures enter the 3rd shift converter is 215～235 ℃; Obtain CO content lower than 0.40% gas mixture after the 3rd shift converter conversion.
One, compare with existing high water-gas ratio CO conversion process, the invention has the advantages that:
1, in pre-conversion process, the main water vapor that uses raw gas to carry carries out transformationreation, do not add or fill on a small quantity middle pressure superheated vapour, the high-temperature gas of pre-shift converter outlet can be before entering the first shift converter operation phlegma quenching humidifying cooling, reduce the middle pressure steam consumption, reduced energy consumption;
2, can use in follow-up conversion process from the middle pressure superheated vapour of pipe network but not the self-produced middle pressure superheated vapour of conversion section, the pipe network steam parameter is stable, so the converter unit operation is more stable;
3, enter the gas mixture water-gas ratio of pre-shift converter low, the dew-point temperature of gas mixture is low, pre-change catalyzer wet basis operation air speed also reduces, the soaked problem that hardens that can avoid the pre-change catalyzer of high hydrosphere transformation flow process very easily to occur, the longer service life of therefore pre-change catalyzer;
4, all lower than high water-gas ratio technique, running environment is gentleer for the operating temperature of the first shift converter inner catalyst and water-gas ratio, and therefore the catalyzer in the first shift converter increases work-ing life, has also played the effect of economy system working cost.
Two, compare with existing low aqueous vapor CO conversion process, the invention has the advantages that:
1, adopt hydrosphere transformation flow process in low aqueous vapor string, each section transformationreation impellent is moderate, and low water-gas ratio technical process reaction impellent is large, has reduced shift converter or transformationreation hop count;
2, in final conversion gas, the low water-gas ratio technique of CO content is low, can reduce the consumption of hydrogen in follow-up methanation workshop section, has been equivalent to reduce effective gas consumption of ton ammonia.
In low water-gas ratio string provided by the present invention, water-gas ratio CO conversion process is particularly suitable for supporting Shell gasifying powder coal device use.
Description of drawings
Fig. 1 is the process flow diagram of the embodiment of the present invention.
Embodiment
Following accompanying drawing embodiment is in conjunction with adopting the gas making of Shell coal gasification to produce the typical chemical fertilizer plant of 520,000 ton/years of urea of 300,000 ton/years of synthetic ammonia, the present invention being described in further detail.
Embodiment
As shown in Figure 1, the CO conversion process of the present embodiment is as follows:
160 ℃ of the raw gas temperature of the saturated water vapor of 1. being sent here by coal gasification workshop section, pressure 3.7Mpa, with pipeline with raw gas from gasification workshop section delivers to the process of conversion section due to calorific loss, a small amount of water vapour in raw gas generation phlegma that can be condensed, corrosion and vibrations that raw gas and lime set coexist in tubing system and can cause pipeline and equipment, so raw gas needed lime set is wherein separated before entering pre-shift converter, therefore the present embodiment is first sent into raw gas gas-liquid separator 1, liquid flows out from the outlet at bottom of gas-liquid separator 1.From gas-liquid separator 1 top out through the raw gas after separatory through 2 heat exchange of shift converter air intake heater and with fully mix from pressure superheated vapour pipe network a small amount of after send into pre-shift converter 3.The raw gas temperature that enters pre-shift converter 3 is about 220 ℃, and water/dry gas mol ratio is 0.22.Obtain becoming in advance gas mixture after pre-shift converter 3 conversion.The pre-gas mixture that becomes is derived from the outlet at bottom of pre-shift converter 3, and this moment, its temperature was about 375 ℃, and CO butt volume content is about 36.0%.
2. will become in advance gas mixture and carry out depth conversion from sending into the first shift converter 4 after the middle pressure superheated vapour of pipe network and process condensate hybrid cooling humidification, controlling the gas mixture temperature in that enters the first shift converter 4 and be 275 ℃, water/dry gas mol ratio is 0.95; Obtain one and become gas mixture after the first shift converter 4 conversion.This change gas mixture is derived from the outlet at bottom of the first shift converter 4, and this moment, its temperature was about 415 ℃, and CO butt volume content is about 7.5%.
3. the temperature out due to a change gas mixture is higher, therefore needs to carry out the heat exchange cooling before entering the second shift converter 6.The present embodiment becomes gas mixture with one and first sends into middle pressure waste heat boiler 5, sends into simultaneously the medium pressure boiler water in addition of middle pressure waste heat boiler 5.Medium pressure boiler water has absorbed one and has become output middle pressure steam after the heat of gas mixture, and the middle pressure steam that obtains sends the battery limit (BL).In the present embodiment, a change gas mixture its temperature out after the interior heat exchange of middle pressure waste heat boiler 5 is 280 ℃, therefore also needs before entering the second shift converter 6 and process condensate hybrid cooling humidification adjustment water-gas ratio.Controlling one, to become temperature in that gas mixture enters the second shift converter 6 be 0.65 into 230 ℃, water/dry gas mol ratio; Obtain two and become gas mixture after the second shift converter 6 conversion.This two changes gas mixture is derived from the outlet at bottom of the second shift converter 6, and its temperature is about 270 ℃, and CO butt volume content is about 1.3%.
4. become gas mixture with two and send into Low Pressure Waste Heat Boiler 7, send into simultaneously the low pressure boiler water in addition of Low Pressure Waste Heat Boiler 7.Low pressure boiler water and two becomes gas mixture in the interior heat exchange of Low Pressure Waste Heat Boiler 7, the low-pressure steam that generates is sent the battery limit (BL), after heat exchange two becomes mixture temperature and is 240 ℃, sends into shift converter air intake heater 2 and again lowers the temperature, and its heat can be for the raw gas heating that enters shift converter air intake heater 2.After heat exchange two become gas mixture send into the 3rd shift converter 8, controlling the temperature in that enters the 3rd shift converter 8 is 215 ℃, and water/dry gas mol ratio is 0.55; Obtain CO butt volume content lower than 0.4% conversion gas mixture at the outlet at bottom of the 3rd shift converter 8 after the 3rd shift converter conversion.
The content that does not relate in the present embodiment is same as the prior art.
Comparative Examples
For adopting the gas making of Shell coal gasification to produce the typical chemical fertilizer plant of 520,000 ton/years of urea of 300,000 ton/years of synthetic ammonia, enter effective gas (H of conversion section 2+ CO) be approximately 85000Nm 3/ h compares water-gas ratio conversion process significant parameter in high water-gas ratio and low string under this benchmark and sees Table 1.
Table 1
For the exemplary device that adopts the gas making of Shell coal gasification to produce the chemical fertilizer of 520,000 ton/years of urea of 300,000 ton/years of synthetic ammonia, enter effective gas (H of conversion section 2+ CO) be 85000Nm 3/ h compares water-gas ratio conversion process significant parameter in low water-gas ratio and low string under this benchmark and sees Table 2.
Table 2

Claims (4)

1. the CO conversion process of water-gas ratio in one kind low water-gas ratio string, is characterized in that comprising the steps:
1. the raw gas that coal gasification workshop section is come is sent into pre-shift converter, and controlling temperature in that raw gas enters pre-shift converter and be 210～250 ℃, water/dry gas mol ratio is 0.21～0.23; Obtain becoming in advance gas mixture after pre-shift converter conversion;
2. will become in advance gas mixture and send into the first shift converter and carry out depth conversion, control that pre-to become temperature in that gas mixture enters the first shift converter be 0.8～1.0 into 270～280 ℃, water/dry gas mol ratio; Obtain one and become gas mixture after the first shift converter conversion;
3. become gas mixture with one and send into the second shift converter, controlling one, to become temperature in that gas mixture enters the second shift converter be 0.5～0.7 into 220～250 ℃, water/dry gas mol ratio; Obtain two and become gas mixture after the second shift converter conversion;
4. become gas mixture with two and send into the 3rd shift converter, the temperature in that control two change gas mixtures enter the 3rd shift converter is 205～235 ℃; Obtain CO content lower than 0.40% gas mixture after the 3rd shift converter conversion.
2. the CO conversion process of water-gas ratio in low water-gas ratio string according to claim 1, is characterized in that
1. at first the next raw gas of coal gasification workshop section is sent into gas-liquid separator separates and go out lime set, send into pre-shift converter through the interchanger temperature raising with in allocating on a small quantity after pressure superheated vapour humidification;
2. from pre-shift converter pre-change gas mixture out with send into the first shift converter after pressure superheated vapour and the temperature adjustment of process condensate humidification by mixing of gas;
3. lower the temperature through the waste heat boiler heat exchange from the first shift converter change gas mixture out, then with after the temperature adjustment of process condensate humidification by mixing of gas send into the second shift converter;
4. send into again the 3rd shift converter from the second shift converter two change gas mixtures out after waste heat boiler heat exchange cooling and proceed transformationreation.
3. the CO conversion process of water-gas ratio in low water-gas ratio string according to claim 2, it is characterized in that from described the second shift converter two becoming gas mixtures enter described interchanger after the waste heat boiler heat exchange out, and send into again described the 3rd shift converter after the described raw gas heat exchange that enters this interchanger.
4. the CO conversion process of water-gas ratio in the described low water-gas ratio string of arbitrary claim of according to claim 1 to 3 is characterized in that temperature in that described raw gas enters described pre-shift converter is that 220～240 ℃, water/dry gas mol ratio are 0.22; The temperature in that described pre-change gas mixture enters the first shift converter is 0.95 into 270～280 ℃, water/dry gas mol ratio; Described one to become temperature in that gas mixture enters the second shift converter be 0.65 into 220～250 ℃, water/dry gas mol ratio; The temperature in that described two change gas mixtures enter the 3rd shift converter is 215～235 ℃; Obtain CO content lower than 0.40% gas mixture after the 3rd shift converter conversion.
CN 201010548457 2010-11-09 2010-11-09 Low water-air ratio and middle water-air ratio carbon monoxide (CO) conversion process CN102002403B (en)

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