CN1263864A - Process for synthesizing ammonia by partial transform of CO and low-temp. conversion - Google Patents
Process for synthesizing ammonia by partial transform of CO and low-temp. conversion Download PDFInfo
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- CN1263864A CN1263864A CN 00114383 CN00114383A CN1263864A CN 1263864 A CN1263864 A CN 1263864A CN 00114383 CN00114383 CN 00114383 CN 00114383 A CN00114383 A CN 00114383A CN 1263864 A CN1263864 A CN 1263864A
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Abstract
A process for partial conversion and low-temp transform of CO in the synthetic ammonia plant where coal is used to generate gas features that the Fe-Mo catalyst for partial conversion of CO, anti-poisoning agent and Co-Mo catalyst for low-temp conversion are used and the temp of semi-water gas is controlled to 200-260 deg.C at entering anti-poisoning layer, and 150-250 deg.C at the segments of said Co-Mo catalyst layer, and lower than 300 deg.C at bed layer to prevent high-temp reversal of sulfurizing reaction and make the catalyst activity optimal. Its advantages are long service life of catalyst, low system resistance, saving energy and convenient operation.
Description
The present invention relates to a kind of synthetic ammonia CO and partly transform and join low temperature shifting process, belong to Ammonia Production technology.
China is 0.7～0.8Mpa, 1.2～1.3Mpa, 1.9～2.0Mpa with the medium and small synthesis ammonia plant carbon monodixe conversion pressure of coal generating gas at present, adopting iron-chromium is that medium temperature shift catalyst, cobalt-molybdenum low temperature shift catalyst are applied to middle temperature transformation string low temperature shifting process (string is low promptly), go here and there two low temperature shifting processes (promptly, low, low) and after the middle temperature transformation all with cobalt-molybdenum low temperature shift catalyst technology (promptly hanging down change entirely), wherein with in, low, low and full low temperature shift process energy-saving effect is best.But in using, industrial production also exposes the some shortcomings part, as in, low, low technology, it must adopt iron-chromium is medium temperature shift catalyst, because iron-chromium is the medium temperature shift catalyst bad mechanical strength, easily efflorescence, cause catalyst activity reduction, systemic resistance increases, and has increased consumption of compressor, catalyzer was generally 2～3 years work-ing life, energy consumption is higher, and fluctuation of service brings many disadvantages to industrial production.Though and catalyzer, antitoxin, sorbent material physical strength that full low temperature shift process adopts are good, not efflorescence, but because cobalt-molybdenum low temperature shift catalyst low temperature active is good, speed of response is fast, temperature in is 200～220 ℃, so when semi-water gas entered the cobalt-molybdenum low change catalyzer, bed temperature rose to nearly 400 ℃ very soon, under this high temperature, the reversal of cure reaction of cobalt-molybdenum low change catalyzer must take place, cause catalyst activity reduction, fluctuation of service causes certain influence to industrial production.
The easy pulverizing problem of low temperature shift catalyst and because the bed temperature height in the objective of the invention is to solve, cobalt-molybdenum catalyzer reversal of cure reaction problem cuts down the consumption of energy thereby reach, and improves catalyst activity, prolongs catalyzer work-ing life, the purpose of stabilization process.
Technical scheme of the present invention is achieved in that existing low temperature shift process mainly comprises earlier stage treatment process and the low temperature shift process to semi-water gas; it is characterized in that syngas for synthetic ammonia is before entering the cobalt-molybdenum low temperature shift process; be introduced into part and transform antitoxin protective layer; this layer is made up of antitoxin layer, adsorption layer and part layer of reformer catalyst from top to bottom; be cooled to 150～200 ℃ then and enter multistage low temperature shift process again, the light-off temperature of part conversion catalyst is 220～270 ℃.
Above-mentioned synthetic ammonia CO partly transforms and joins low temperature shifting process, it is characterized in that low temperature shifting process divides two sections or three sections, the temperature that the ammonia unstripped gas enters before one section catalyzer of low change cobalt-molybdenum is 150～200 ℃, entering the preceding temperature of two sections catalyzer of low change cobalt-molybdenum is 180～230 ℃, entering the preceding temperature of three sections catalyzer of low change cobalt-molybdenum is 150～200 ℃, when dividing two sections, entering the low temperature that becomes before one section of the cobalt-molybdenum is 150～200 ℃, enters the low temperature that becomes before two sections of the cobalt-molybdenums and is 160～200 ℃.
Above-mentioned synthetic ammonia CO partly transforms and joins low temperature shifting process, it is characterized in that the earlier stage treatment process of semi-water gas mainly comprises coke filtration, saturator humidifying process, and the volume ratio of handling back water vapor and dry gas is 0.26～0.3.
Above-mentioned technology when adopting two sections low temperature shift processes, is applicable to the pure production technique of connection.
This technical process with existing in, lowly, low compared following advantage with full low process-changing:
1, because being provided with CO, this technology partly transforms antitoxin layer, play and carry out the transformationreation of CO part when removing in the semi-water gas objectionable impurities, make in the semi-water gas CO content reduce to 18～24% and reduced CO concentration in the semi-water gas relatively by 26～32%, thereby when having avoided cobalt-molybdenum low change catalyzer bed, because the high caused fierce transformationreation of CO concentration, make that bed temperature rises too fastly, too high caused reversal of cure reaction takes place.
2, the CO in first shift converter partly transforms the transformationreation of antitoxin layer and one section of cobalt-molybdenum low change catalyzer, all utilize the unstripped gas that comes out from saturator, steam-to-gas ratio 0.26～0.3, just can make the CO interconversion rate reach 65～70%, need not to add in addition steam, add steam or water spray at the low one section outlet that becomes then, energy-saving effect than in, low, low and full low temperature shift process is better.
3, to reduce to 150～200 ℃ of original steam-to-gas ratios low again owing to advance one section temperature of cobalt-molybdenum low change catalyzer; be difficult for taking place the reversal of cure reaction; each section of cobalt-molybdenum low change catalyzer bed temperature all is controlled in 300 ℃; protect cobalt-molybdenum low change catalyzer activity to be in optimum regime, prolonged catalyzer work-ing life.
4, with in, low, low technology compares the catalyzer that is used, antitoxin, the well not efflorescence of sorbent material physical strength, systemic resistance is little.
5, stop the pollution problem of chromium, improved the catalyst loading and unloading labour health condition.
6, improve the organosulfur transformation efficiency, alleviated sulphur to decarbonizing liquid, cuprammonia, the harm of ammonia synthesis catalyst.
7, owing to reduced each section of shift converter bed inlet temperature and bed temperature, reduce the corrosion of thermosteresis and equipment and materials, prolonged service life of equipment.
8, because all operations at a lower temperature of transformation system are easy to operate, drive to start soon, improved effective production time, volume increase, energy-conservation, economize on electricity.
Further specify technical process of the present invention and embodiment: Fig. 1 below in conjunction with accompanying drawing and join three sections low temperature shift process schemas; the 1st, cooling tower; 2 is second water heaters; the 3rd, the coke strainer; the 4th, saturated hot-water tower; the 5th, hot water pump; 6 is first water heaters; 7 is second shift converter (two sections low become); 8 is second temperament water heaters; the 9th, heat exchanger; the 10th, electric heater; 11 is first temperament water heaters; 12 is first shift converter (antitoxin protective layers; one section low becomes); its working process is: semi-water gas is after coke filter separates profit; going into hot water counter current contact humidification formation water vapor/dry gas of sending here with hot water pump in the saturator is 0.26～0.3 than (volume); advance heat exchanger 9 and the conversion gas that partly transforms antitoxin layer from CO and carry out heat exchange temperature raising to 200～260 ℃; advance first shift converter by CO part conversion catalyst; antitoxin; the CO that sorbent material is formed partly transforms and carries out the conversion of CO part when antitoxin layer is removed in the semi-water gas objectionable impurities; temperature of reaction is 200～340 ℃; make in the semi-water gas CO content reduce to 18～24% by 26～32%, this conforms to fully with data that field experiment is measured.Enter heat exchanger 9 tops then and carry out going into first temperament water heater 11 after the heat exchange from the semi-water gas of saturator, heat exchange is cooled to 150～200 ℃ and advances the first shift converter cobalt-molybdenum low change catalyzer and carry out a transformationreation for again, temperature is 150～300 ℃, CO content reduces to 6～12% in the outlet conversion gas, steam-to-gas ratio is reduced to below 0.2, therefore to improve steam-to-gas ratio at first shift converter outlet interpolation steam or water spray, enter heat exchanger 9 bottoms again and carry out heat exchange from the semi-water gas of saturator and be cooled to 180～230 ℃, advancing two sections of the second shift converter cobalt-molybdenum low change catalyzers then, to carry out the transformationreation temperature be 180～280 ℃.CO content is 3～5% in the outlet conversion gas, reclaim heat through second temperament water heater 2 again and be cooled to 160～200 ℃, in going into hot-water tower, primary heater reclaims heat then with the next hot water counter current contact of saturator, go out hot-water tower conversion temperature degree and reduce to 65～70 ℃, advance second water heater again and go into condensing tower and be cooled to 30～35 ℃, send back operation desulfurization and decarburization.
When joining two sections low temperature shift processes and above-mentioned technology basic identical, just in second shift converter 7, establish one section low and become, the temperature of advancing hang down before two sections of the change cobalt-molybdenum catalyzer is 160～200 ℃.
Embodiment one
When two retort volumes are 110ml, part transforms antitoxin layer middle part conversion catalyst (light-off temperature is 220～270 ℃) 60ml in second Reaktionsofen, antitoxin 15ml, sorbent material 6ml, first Reaktionsofen is one section of a cobalt-molybdenum low change catalyzer, cobalt-molybdenum low change catalyzer 60ml, the normal pressure air speed was got 1000 o'clock
-1, steam-to-gas ratio gets 0.26, the useful CS of vulcanization process
2Make vulcanizing agent, 220～450 ℃ of curing temperatures, curing time 5～6 hours.The second Reaktionsofen inlet temperature is 240～260 ℃, hot(test)-spot temperature is that CO content is 282% in 260～280 ℃ of import semi-water gass, CO content is 22.8% in the outlet conversion gas, advancing the first Reaktionsofen temperature then is 160～180 ℃, hot(test)-spot temperature is 180～200 ℃, and CO content is 92% (for two sections of this technology shift converters) in the outlet conversion gas.
Embodiment two
Still above-mentioned experimental installation catalyzer, antitoxin, sorbent material loadings and steam-to-gas ratio are constant, and only changing air speed is 800 o'clock
-1The first retort inlet temperature still is 240～260 ℃, hot(test)-spot temperature still is 260～280 ℃, CO content is 28.4% in the import semi-water gas, CO content is that to advance the second retort temperature then be 160～180 ℃ in 212% (for one section of this technology shift converter) in the outlet conversion gas, hot(test)-spot temperature is 180～200 ℃, and CO content is 6.5% in the outlet conversion gas.
Claims (4)
1, a kind of synthetic ammonia CO partly transforms and joins low temperature shifting process; mainly comprise earlier stage treatment process and low temperature shift process to semi-water gas; it is characterized in that syngas for synthetic ammonia is before entering the cobalt-molybdenum low temperature shift process; be introduced into part and transform antitoxin protective layer; this layer is made up of antitoxin layer, adsorption layer and part layer of reformer catalyst from top to bottom; be cooled to 150～200 ℃ then and enter multistage low temperature shift process again, the light-off temperature of part conversion catalyst is 220～270 ℃.
2, synthetic ammonia CO according to claim 1 partly transforms and joins low temperature shifting process, it is characterized in that low temperature shifting process divides two sections or three sections, in the time of three sections, the temperature that the ammonia unstripped gas enters before one section catalyzer of low change cobalt-molybdenum is 150～200 ℃, entering the preceding temperature of two sections catalyzer of low change cobalt-molybdenum is 180～230 ℃, entering the preceding temperature of three sections catalyzer of cobalt-molybdenum is 150～200 ℃, when dividing two sections, enter that temperature is 150～200 ℃ before one section of the low temperature cobalt-molybdenum, the temperature that enters before two sections of the low temperature cobalt-molybdenums is 160～200 ℃.
3, synthetic ammonia CO according to claim 1 and 2 partly transforms and joins low temperature shifting process, it is characterized in that the earlier stage treatment process of semi-water gas mainly comprises coke filtration, saturator humidifying process, and the volume ratio of handling back water vapor and dry gas is 0.26～0.3.
4, technology according to claim 1 and 2 adopts two sections low temperature shift processes to be applicable to the pure production technique of connection.
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| CN 00114383 CN1263864A (en) | 2000-02-23 | 2000-02-23 | Process for synthesizing ammonia by partial transform of CO and low-temp. conversion |
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| CN 00114383 CN1263864A (en) | 2000-02-23 | 2000-02-23 | Process for synthesizing ammonia by partial transform of CO and low-temp. conversion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157442B (en) * | 2007-04-27 | 2010-07-21 | 中国石化集团宁波工程有限公司 | Waste heat reclaiming process for CO transformation |
| CN101050390B (en) * | 2007-04-27 | 2011-04-27 | 中国石化集团宁波工程有限公司 | CO conversion technique matched to coal gasification |
| 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 |
| CN103881765A (en) * | 2014-03-24 | 2014-06-25 | 中石化宁波工程有限公司 | Split circulating CO transformation process |
| CN110508330A (en) * | 2019-08-26 | 2019-11-29 | 宁夏渝丰化工股份有限公司 | A kind of two sections of low change catalyst heating reduction processes |
-
2000
- 2000-02-23 CN CN 00114383 patent/CN1263864A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157442B (en) * | 2007-04-27 | 2010-07-21 | 中国石化集团宁波工程有限公司 | Waste heat reclaiming process for CO transformation |
| CN101050390B (en) * | 2007-04-27 | 2011-04-27 | 中国石化集团宁波工程有限公司 | CO conversion technique matched to coal gasification |
| 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 |
| CN102701149B (en) * | 2012-06-07 | 2014-05-28 | 王揽月 | Water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion |
| CN103881765A (en) * | 2014-03-24 | 2014-06-25 | 中石化宁波工程有限公司 | Split circulating CO transformation process |
| CN110508330A (en) * | 2019-08-26 | 2019-11-29 | 宁夏渝丰化工股份有限公司 | A kind of two sections of low change catalyst heating reduction processes |
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