CN1105770C - Process for cleaning raw gas in conversion reaction - Google Patents
Process for cleaning raw gas in conversion reaction Download PDFInfo
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- CN1105770C CN1105770C CN00111185A CN00111185A CN1105770C CN 1105770 C CN1105770 C CN 1105770C CN 00111185 A CN00111185 A CN 00111185A CN 00111185 A CN00111185 A CN 00111185A CN 1105770 C CN1105770 C CN 1105770C
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Abstract
The present invention relates to a technological process for purifying raw gas in a carbon monoxide conversion reaction. The raw gas is purified in a purifying reactor arranged on the upstream of a conversion reactor, and the purifying reactor is in a radial reactor structure so that the raw gas to be purified can be radially diffused in the purifying reactor. An axial gas distribution tube (1) and a purifying agent bed basket (2) are arranged in the radial purifying reactor, wherein the purifying agents in the radial purifying reactor are purifying agent granules with the granule diameter of 0.5 to 3.0mm. The technological process has the advantages of high deoxidizing efficiency and low resistance on the purifying bed layer.
Description
The present invention relates to a kind of carbon monodixe conversion system that is used for unstripped gas is carried out the processing method of purifying treatment, specifically, the present invention relates to a kind of purifying treatment method that adopts radial reactor to make purification reactor.
In the vast medium and small nitrogen fertilizer device of China, owing to adopt gas-making process with Chinese characteristics, generally contain 0.2～0.5% oxygen in the semi-water gas that is produced, the content that has even up to 0.8%.Change was gone here and there to hang down and is become or full low temperature shift process during present conversion process adopted mostly, i.e. first section employing Fe-Cr of conversion is that hts catalyst or employing cobalt molybdenum are low change catalyzer.For Fe-Cr is hts catalyst, higher oxygen level can cause the higher temperature rise of conversion bed in the semi-water gas, generally when oxygen level reaches 0.5% in the water-gas, can cause the about 50 ℃ temperature rise of conversion bed, oxygen level reaches at 1% o'clock can bring about 100 ℃ temperature rise.The Fe-Cr series catalysts mostly is greatly plays the sheet moulding, and the fluctuation of bed temperature or overtemperature easily make catalyzer efflorescence caking, cause catalyst activity reduction, and bed resistance increases sharply, and produces and keeps difficulty.For Co-Mo is low change catalyzer, owing to contain potassium in the catalyzer, easily forms K under the effect of oxygen in semi-water gas
2SO
4, cause the catalyzer rapid deactivation, what extreme case just caused whole furnace catalyst in following 7 days scraps.
Generally be to add a dry gas purifier before saturator in the existing technology, make that the oxygen in the semi-water gas was taken off before entering conversion section, perhaps interpolation one deck scavenging agent on Co-Mo is the low change catalyzer bed purifies semi-water gas, takes off oxygen wherein.A kind of technology of semi-water gas being carried out purifying treatment has promptly been described among the CN97105846.6, its used method is that semi-water gas is introduced into cleaner before entering saturator, remove wherein dust and iron carbonyl and partial oxygen and part organosulfur with scavenging agent, thus the rising that slows down the inactivation and the transformation catalyst bed resistance of transformation catalyst.Because the purification reactor of this patent adopts general axial flow reactor structure, falls in order to reduce bed resistance, generally select the bigger scavenging agent of particle for use, as select the scavenging agent of Φ 3～5mm for use, thereby deoxidation effect can not be satisfactory.
For deoxygenation
, its Kp constant is 10
50On the order of magnitude, the major control factor of speed of reaction is internal diffusion control.Reduce the granularity of scavenging agent, can significantly improve the speed of scavenging agent deoxygenation, thereby improve the transformation efficiency of oxygen in the raw material gas purifying process.But if use axial flow reactor, less scavenging agent particle can make bed pressure drop sharply rise, and influences normal production process.
Purpose of the present invention just provides a kind of technological process for purifying that can improve deoxidation efficient, can also reduce the scavenging agent resistance simultaneously.
To achieve these goals, the solution that the present invention adopts is the clean-up stage employing radial bed structure of reactor at changing device, the less scavenging agent of while loaded particles, unstripped gas is radial diffusion when entering into purification reactor scavenging agent bed, both improve the deoxidation efficient of scavenging agent, reduced the resistance drop of scavenging agent bed again.
Specifically, the present invention realizes by following method:
The radial reactor of dress small-particle scavenging agent in unstripped gas enters into from opening for feed, radially the axial gas distribution pipe of reactor enters into scavenging agent and radial diffusion, between shell of reactor and scavenging agent bed basket, flow to discharge port then, enter upstream device again.
Radial reactor used among the present invention mainly comprises: axial gas distribution pipe 1 and scavenging agent bed basket 2.The effect of axial gas distribution pipe 1 is to guide reactant gases along the axial direction due of purification reactor, is with holes on the tube wall, and the shape of aperture, the special restriction of the nothing that distributes are passed through as long as be beneficial to gas.Scavenging agent bed basket 2 is one of key parts of the used purification reactor of the present invention, and it is made up of inside and outside two cylindrical walls, is distributed with the aperture of supplied gas diffusion usefulness on each cylindrical wall, and scavenging agent is placed between two cylindrical walls.In fact the inner cylindrical wall of scavenging agent bed basket 2 can be served as by the tube wall of axial gas distribution pipe 1, and if so, then the aperture on axial gas distribution pipe 1 tube wall will ensure scavenging agent is leaked outside.
Used radial reactor also comprises parts such as shell of reactor 3, opening for feed 5 and discharge port 6 among the present invention.Can also comprise internal partition 4 in some purification reactor structure, its effect is a restriction gas flow direction, the purification reactor structure shown in Figure 2 as the present invention.In actual applications, purification reactor can be combined in the reaction tower, as Fig. 2 of the present invention and shown in Figure 3 with shift-converter.
In the present invention's purification reactor shown in Figure 1, after reactant gases enters radial reactor from opening for feed 5, radially inwardly adorn the scavenging agent bed basket diffusion of scavenging agent through axial distribution pipe 1, gas after the purifying treatment flows to discharge port 6 between shell of reactor 3 and scavenging agent bed basket 2, enter upstream device then.
In order to improve deoxidation efficient, the less scavenging agent of loaded particles in the purification reactor of the present invention, scavenging agent particulate diameter between the φ 3.0mm, is preferably in φ 1.0mm between the φ 2.0mm at φ 0.5mm.The scavenging agent particulate reduces, and not only can improve the removal efficiency of oxygen, and can also reduce scavenging agent atomizing tendency.Although experiment shows that the particle of scavenging agent is more little, its ability that removes oxygen is high more, and on the actual industrial device, the scavenging agent particle is too little, can bring many problems, so in the present invention, the scavenging agent particle generally is not less than 0.5mm in the full scale plant.In fact, the scavenging agent granular size just can reach good deoxidation effect between 1.0～2.0mm.The scavenging agent particle of being adorned in the prior art purification reactor is greater than 3.0mm usually, and deoxidation effect is relatively poor relatively.
In such scheme, unstripped gas can be temperature raising and added steam before entering the radial reactor purifying treatment, and steam can be added into degree of saturation, also can be the semi-water gas of doing; The scavenging agent of being adorned in the radial reactor can be the scavenging agent described in CN97105846.6 or the CN97121017.9, and this scavenging agent can make with pickling process or blending method.When adopting pickling process, steeping fluid can be the solution that contains one or more elements in molybdenum, cobalt, iron, nickel, potassium, chromium, tungsten, the platinum, impregnated carrier can be aluminum oxide, magnesium-aluminium spinel, titanium dioxide and spent catalyst, also can be its mixture.When selecting used catalyst support for use, preferably selecting useless Fe-Cr series transformation catalyst, useless cobalt molybdenum for use is transformation catalyst or useless hydrogenation catalyst.The oven dry of dipping back, roasting can make the used scavenging agent of the present invention.When adopting hybrid system, get oxide compound, sulfide or its salt of one or more elements in molybdenum, cobalt, iron, nickel, potassium, platinum, chromium, tungsten, magnesium, aluminium, the titanium, through kneading, oven dry, roasting, pulverizing, beat steps such as sheet, can make the used scavenging agent of the present invention.In the scavenging agent, the content of molybdenum, cobalt, iron, nickel, potassium, chromium, tungsten, platinum isoreactivity element generally is not less than 10.0% (in oxide compound or sulfide), preferably is not less than 17.0%.The effect of scavenging agent is to make most oxygen by catalyzed conversion, thereby reduces the hot(test)-spot temperature of shift converter; Simultaneously, make whole iron carbonyls that the catalysis thermolysis take place on scavenging agent, guarantee that it can not enter conversion section, stop up transformation catalyst.
Owing to adopt radial reactor, can significantly solve the bed pressure drop problems of too.Calculating shows, for the height radial bed identical with diameter, if axial gas distribution pipe radius is less, and be 1/17 of radial reactor radius, with highly and the radius ratio be that 4 axial flow fixed bed reactor is compared, its pressure falls and can reduce 16 times.Simultaneously, owing to adopt radial reactor to make bed resistance descend greatly, thereby can use short grained scavenging agent, this has just improved the transformation efficiency of oxygen in the unstripped gas.
Further specify the present invention below in conjunction with embodiment and accompanying drawing.
Fig. 1 is the purification conversion process flow process of no saturator.
Fig. 2 has saturator and purify the technical process that conversion is finished in a reaction tower.
Fig. 3 is no saturator and purifies the technical process that conversion is finished in a reaction tower.
Among the figure: 1 is the axial gas distribution pipe, and 2 is scavenging agent bed basket, and 3 is shell of reactor, and 4 is internal partition, and 5 is opening for feed, and 6 is discharge port, and 7 is shift converter, and 8 is interchanger, and 9 is water heater, and 10 is pump, and 11 is saturator, and 12 is hot-water tower.
Embodiment 1
By flow process shown in Figure 1,2.1Mpa half water coal vapour after the oil removing, after steam is added in interchanger 8 temperature raisings, enter radial reactor through radial reactor opening for feed 5, temperature in 180-250 ℃, filling patent application CN97105846.6 or the described scavenging agent of CN97121017.9 in the reactor, purified gas enters heating stove 7, dress QCS-02 low change catalyzer in the stove, intersegmental spray cooling enter hypomere to 180-230 ℃, and reacted gas removes conversion gas change boiler after interchanger 8 coolings.Shift converter outlet carbon monoxide is controlled to be 3-7%.
Embodiment 2
By flow process shown in Figure 2,0.8Mpa semi-water gas after the oil removing is through saturator 11 and add steam after interchanger 8 heats up after radial section opening for feed 5 enters radial reactor, temperature is controlled at 280-350 ℃, the scavenging agent described in 1 is implemented in the filling of radial reactor top, bottom filling Fe-Cr is a hts catalyst, reaction back gas water-cooled swashs to 330-360 ℃, enter B117 hts catalyst bed (this bed also can adopt the radial flow design), enter heat exchanger 8 then and be cooled to 180-230 ℃, enter QCS-02 low change catalyzer bed, enter down operation then after entering hot-water tower 12 coolings after water heater 9 coolings, the outlet carbon monoxide is less than 1.5%.The water of hot-water tower 12 is gone into water heater 9 through pump 10 pressurization is laggard, and the water back part that heats up sprays in the shift converter 7, and a part enters in the saturator 11.
Embodiment 3
By flow process shown in Figure 3, the synthetic gas that the back pressure of residual oil vaporization is 2.3Mpa is after interchanger 8 heats up, enter radial reactor by radial reactor opening for feed 5, gas temperature 170-250 ℃, scavenging agent described in the radial reactor internal upper part filling embodiment 1, bottom filling QCS-02 series low change catalyzer, reactant gases to 180-230 ℃, enters the QCS-02 beds through spray cooling.Reactant gases is cooled to 180-230 ℃ through interchanger 8, enters three sections QCS-02 beds of shift converter, goes to high temperature desulfurizing workshop section then, carbon monoxide control about 1% in the gas.
Implement 4
Analyze the content of oxygen in the semi-water gas with portable oxygen analyser XO-326ALA (Japan produces).In the normal pressure activity rating device of laboratory, the scavenging agent 30ml described in the CN97105846.6 of the variable grain size of packing into successively in the reactor.In the experimentation, the air speed of semi-water gas is controlled at about 8000h-1, temperature of reaction is controlled at about 250 ℃, the purifying treatment time is about hour, and then analyze the residual content of oxygen in the semi-water gas after the purifying treatment with above-mentioned oxygen analyzer, calculate the deoxidation efficient of scavenging agent, its calculation formula is:
Deoxidation efficient=(the later half water coal of oxygen level-purifying treatment in the preceding semi-water gas of purifying treatment
Oxygen level in the gas) oxygen level in the preceding semi-water gas of * 100%/purifying treatment
During the experimental result of gained is listed in the table below:
| The granular size of scavenging agent | The deoxidation efficient of scavenging agent |
| 20～40 orders | 93％ |
| Φ1.0mm | 78％ |
| Φ2.0mm | 75％ |
| Φ3.0mm | 69％ |
| Φ5.0mm | 62％ |
The result can learn from table: the scavenging agent particle is more little, and its deoxidation efficient is high more; But on the full scale plant of reality, the scavenging agent particle is too little, can bring a series of problem.In common axial purification reactor, the general scavenging agent of selecting Φ＞3.0mm, if and adopt radial purification reactor of the present invention, the scavenging agent granular size can be chosen between Φ 0.5～3.0mm, this has not only improved the deoxidation efficient of scavenging agent, and also the axial purification reactor bed than routine is little to purify bed pressure drop.
Claims (4)
1, a kind of processing method of in the carbon monodixe conversion reaction unstripped gas being carried out purifying treatment that is applicable to, purifying treatment is finished in purification reactor, and purification reactor is in the upstream of shift-converter, it is characterized in that purification reactor adopts the radial reactor structure, make the unstripped gas of processing to be clean in purification reactor, radially spread, described radial reactor structure comprises the scavenging agent bed basket (2) of axial gas distribution pipe (1) and built-in purifying agent, this scavenging agent bed basket (2) includes inside and outside two cylindrical walls, be distributed with the aperture of ventilation on each cylindrical wall, load scavenging agent between two cylindrical walls.
2, processing method according to claim 1 is characterized in that being equipped with in the described radial purification reactor small-particle scavenging agent that particle diameter is 0.5～3.0mm.
3, processing method according to claim 2 is characterized in that being equipped with in the described radial purification reactor small-particle scavenging agent that particle diameter is 1.0～2.0mm.
4,, contain the compound of a kind of element in molybdenum, cobalt, iron, nickel, potassium, chromium, tungsten, the platinum in the scavenging agent that it is characterized in that being adorned in the described radial purification reactor at least according to claim 2 or 3 described processing methodes.
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| CN00111185A CN1105770C (en) | 2000-06-12 | 2000-06-12 | Process for cleaning raw gas in conversion reaction |
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| CN00111185A CN1105770C (en) | 2000-06-12 | 2000-06-12 | Process for cleaning raw gas in conversion reaction |
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| CN1328115A CN1328115A (en) | 2001-12-26 |
| CN1105770C true CN1105770C (en) | 2003-04-16 |
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| CN00111185A Expired - Fee Related CN1105770C (en) | 2000-06-12 | 2000-06-12 | Process for cleaning raw gas in conversion reaction |
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| CN103241712B (en) * | 2013-04-09 | 2016-03-16 | 内蒙古乌拉山化肥有限责任公司 | A kind of semi-water gas treatment process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198465A (en) * | 1997-05-07 | 1998-11-11 | 中国石化齐鲁石油化工公司 | Conversion process for dry gas purification and purifying agent thereof |
| CN1217291A (en) * | 1997-11-19 | 1999-05-26 | 中国石化齐鲁石油化工公司 | Transformation process without saturation tower |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198465A (en) * | 1997-05-07 | 1998-11-11 | 中国石化齐鲁石油化工公司 | Conversion process for dry gas purification and purifying agent thereof |
| CN1217291A (en) * | 1997-11-19 | 1999-05-26 | 中国石化齐鲁石油化工公司 | Transformation process without saturation tower |
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| CN1328115A (en) | 2001-12-26 |
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