CN1022400C - Combined non-steady state SO2 converter - Google Patents
Combined non-steady state SO2 converter Download PDFInfo
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- CN1022400C CN1022400C CN 91107321 CN91107321A CN1022400C CN 1022400 C CN1022400 C CN 1022400C CN 91107321 CN91107321 CN 91107321 CN 91107321 A CN91107321 A CN 91107321A CN 1022400 C CN1022400 C CN 1022400C
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Abstract
The present invention discloses a combined non-steady SO2 converter, which is composed of a heating zone, a high temperature zone and a desuperheating zone. A system lies in mild conditions to carry out the catalyzed oxidation reaction of sulfur dioxide of a high concentration by the regulation and the control of initial pretemperature distribution. The requirements of high conversion rate (the total conversion rate of SO2 reaches more than 99%) in sulfuric acid industrial production and sufficiently large airflow velocity (the airspeed of reaction gas is from 0.2 to 0.35 m/s) can be met in one converter.
Description
The present invention relates to a kind of under the unsteady state condition catalytic oxidation of sulphur dioxide make the vitriolic convertor.
In traditional sulfuric acid production process, owing to the energy-conservation needs from thermal transition, the sulfurous gas catalytic oxidation process all is to carry out in being furnished with the multilayer heat insulation fixed-bed conversion device of intermediate heat and external heat exchanger.Its technical process complexity, systemic resistance is big, and steel consumption is remarkable, and the control of each layer reacting gas inlet condition requires high.And because serious pipeline and equipment corrosion, annual overhaul cost is also very remarkable.According to estimates, investment cost and process cost over half all are used on the heat exchanger system.In addition, more and more important environment protection needs further to improve the outlet transformation efficiency of sulfurous gas, and the double conversion and double absorption flow process is widely adopted, yet it has but caused heat exchanger area and systemic resistance to be multiplied.Therefore set up very difficulty of large-scale reactor by traditional technology.
In order to overcome the shortcoming of traditional technology, Y.S.Matros etc. (see United States Patent (USP): 4,478,808,1984) proposed a kind of under the unsteady state condition method of catalytic oxidation of sulphur dioxide gas, solved low concentration SO
2Gas (SO
2Volumn concentration between 1-5%) the Balance of nature problem that transforms, such as the SO in the non-ferrous metal metallurgy flue gas
2The autothermal equilibrium problem that transforms.Because this method got rid of the interchanger part, make that investment cost is relative with process cost to be reduced, energy-saving effect is very remarkable.But, the SO in raw materials technology gas
2Content was greater than 5% o'clock, and such as sulphur and pyrite burning gas, this method only when the air speed of reactant gases very low (less than 0.05 meter per second), just can make the temperature in the bed not continue to surpass the top temperature (600 ℃) that catalyzer allows, and SO
2Total conversion rate very low, have only 85-90%.Obvious this situation does not meet the gas washing in SA production industrialization demands.For this reason, A.A Brassavola husband wait (see non-patent literature X Ν Μ. Π POM.No.12,1987) this method has been done improvement, merged the double conversion and double absorption flow process in the traditional technology, be provided with two unsteady state convertors.Wherein, the beds of first unsteady state convertor has been divided into two sections again, and settled an interchanger that plays thermolysis betwixt, to reduce gas temperature from first section bed-drop to 470 ℃ from 620 ℃, continue above 600 ℃ to prevent bed downstream catalyst temperature; The gas that comes out from the heat radiation heat exchange enters second section bed again.In this case, the reactant gases air speed is brought up to 0.23 meter per second, but transformation efficiency can only reach 90-92%.Remove SO from the reactant gases that the first unsteady state convertor comes out through absorbing
3After, enter second unsteady state convertor again.Technology after the improvement can satisfy high conversion and enough requirements of big gas speed in the industrial production, makes the unsteady state method that the preceding border of industrial application arranged in gas washing in SA production., the flow process of this method is more complicated still, and the operation control of intermediate heat sink is difficulty especially, and investment cost is also higher.This shows, shortcoming in the traditional technology is not also overcome fully, and the production intensity of catalyzer is also low than traditional method, the loadings of catalyzer has increased by 25%, sulfuric acid industry (1987 the 5th phase 52-57 pages or leaves), review paper " new development of Soviet Union's unstable state producing acid by oxidation method ", the commerical test device that is proposed can will contain SO
2The unstripped gas of 2-5% according to unsteady state method oxidising process principle, is realized SO
2The operation of the autothermal equilibrium of oxidising process, transformation efficiency can reach 94.2%～96.5%, and the convertor diameter is 7.2 meters, highly is 7.7 meters (see document table 2 column data), and one deck CB is equipped with in inside
Catalyst, quartz wedge is equipped with in the end; Thermopair and measurement SO that 24 continuous monitoring temperature are used also are housed
2The stopple coupon that concentration and pressure drop are used.This convertor also has the epicone lid except that housing.By the outer reversing valve of device conversion air feed direction periodically.This device has successfully solved low sulfur content unstripped gas (SO
2＜5%) unsteady state method catalytic oxidation process.But because this device only is provided with single thick-layer catalyst, the technology that the loadings of its catalyst is more traditional also wants many 25%(to see the listed correlation data of document table 2), (as contain SO for the dense unstripped gas of height
2Amount reaches 5～10%), then can't carry out the unstable state operation, because high dense SO
2Catalyzed oxidation in single thick-layer catalyst layer, the reaction heat of emitting is very fast overheated with catalyst layer, and temperature surpasses 600 ℃, makes catalyzed reaction away from SO
2Catalyzed oxidation suitable temperature of reaction, suppressed the activity of catalyst, make SO
2Transformation efficiency reduce, so above-mentioned convertor is can not satisfy the dense SO of height
2Change into SO
2Industrial production require.
The objective of the invention is to overcome fully the shortcoming of prior art, a kind of SO of being applicable to is provided
2Content is the 5-10%(percentage by volume) high density SO
2The combined non-steady state SO 2 converter of gas reforming.With this convertor is that the sulfuric acid production process of core has not only been got rid of and realized the various interchanger of autothermal equilibrium, and an interchanger of thermolysis in the middle of having cancelled.Its most outstanding superiority is, in same convertor, has satisfied the needed high conversion (SO of sulfuric acid production process simultaneously
2Transformation efficiency greater than 99%) and the industrial requirement of enough big air speed (air speed of reactant gases is the 0.2-0.35 meter per second).In addition, the production intensity of catalyzer has also improved 50-100% than traditional technology, and promptly the 200-220 from traditional technology rises catalyzer/day, ton acid dropping to 100-150 rises catalyzer/day, ton acid.This is the characteristics of thin bed catalytic unit.
The present invention's said " unsteady state " is though be to refer in particular to operational condition to be the cycle variation, and operating process is metastable." why we select " unsteady state " for use, because academia generally believes and this class process should be defined as " unsteady state " process both at home and abroad, for example by institution of higher education's didactic works " Principles of Chemical Engineering " (first volume of people such as Chen Minheng chief editor, Chemical Industry Press) just the periodically variable heat transfer process of this generic operation condition is called the unsteady state heat transfer process in the 235th page, and for example in english literature, corresponding noun is that Unsteady state (is translated into unsteady state usually, see non-patent literature " Cata-lgtic processes under Unsteady-state conditions " Matros.Yu.sh.Elsivier, 1989) explanation to Unstable state is " unstable state " rather than among the Unstable-state(" English-Chinese technology dictionary "), because of adopting " unstable state " to contain the unsettled meaning, and in fact this class process itself is stable, be Stable, just it operates unsteadiness, i.e. Unsteady.
Design of the present invention is such:
In the face of how the sulfur dioxide gas of high density is realized along SO
2The Optimizing operation of the optimum temps curve of reversible exothermic oxidation reaction.In the convertor of design, beds must have a specific temperature distribution for this reason, i.e. the low temperature distribution in middle high two ends.This has not only guaranteed high conversion, and because the restriction of reaction reversibility, the first layer (heating zone) exit end temperature can be not too high.
The convertor of people such as Matros design, the temperature of its entrance end catalyzer is just up to 500 ℃, as fresh high density SO
2When unstripped gas touched catalyzer under this temperature, because away from balance, speed of response is very big, promptly heating strength was very big, and the temperature of solid catalyst swashs acute the rising, above 600 ℃.Worse, this high temperature will move downstream, and continue to rise, and the amplitude of its rising reaches mobile speed with SO
2The increase of inlet concentration and gas space velocity and increasing.This just people's such as Matros method can not be applicable to high density SO
2The reason of gas.In view of the above, the present invention proposes a kind of pre-method that distributes of reaction bed temperature in the convertor of regulating and control, be about to convertor and be divided into heating zone, high-temperature zone and cooling area, the temperature in each district of control makes its optimum temps curve along the reversible exothermic oxidation reaction of sulfurous gas be optimized operation respectively.
At heating zone, control SO by the vanadium catalyst (abbreviation low temperature catalyst) that adopts the initial pre-temperature distribution (temperature progressively rises from top to bottom vertically, promptly progressively rises to 500～520 ℃ by 200～300 ℃) and the low light-off temperature of packing into
2Transformation efficiency between 85～90%, in addition by adopting inert filler subarea and the combined method in low temperature catalyst subarea at heating zone, to reduce catalyst consumption, (in fact low temperature catalyst also is a kind of inert filler) when temperature is lower than its combustion initiation temperature.
The high temperature vanadium catalyst of packing in the high-temperature zone, the SO in air-flow
2When existing 85～90% quilts transformed, the load of high-temperature zone catalyst was less.
Because of the task of high-temperature zone is SO
2Total conversion rate bring up to about 92% from 85～90%, so, oxidizing sulfur dioxide institute liberated heat seldom, when the initial pre-temperature distribution of high-temperature zone is 520～540 ℃, only the top temperature (central point temperature) with the high-temperature zone rises to 540～570 ℃ (top temperature can be controlled in below 600 ℃), as the SO of heating zone
2During transformation efficiency less than 85%, the central point temperature of high-temperature zone can raise immediately, when the central point temperature rises to 600 ℃, must switch airintake direction, so the high-temperature zone is the reference mark of realizing the present invention's operation.
At cooling area: in axial direction, pack into from down to up low-temperature vanadium catalyst and inert filler (reason is the same with heating zone), its initial pre-temperature distribution is: 500～520 ℃ drop to 300～200 ℃, this pre-temperature distribution and the reversible exothermic oxidation reaction optimum temps of sulfurous gas curve match, so as existing 92%SO
2When the air-flow that is transformed enters cooling area, can make SO wherein
2Total conversion rate rise to more than 99%.
On a large amount of experimental data bases, designed a kind of combined non-steady state SO 2 converter.It mainly is made up of three thin bed catalytic section (district).This convertor can produce following effect:
1. the temperature of regulation and control beds distributes in advance, can make system be in the catalytic oxidation that carries out sulfurous gas under the mild conditions, thereby prevent that bed temperature generation hop from causing the phenomenon of catalyst overheating.
2. combined non-steady state SO
2Convertor not only can be realized the autothermal equilibrium in the sulfuric acid industry production, and satisfy sulfuric acid industry simultaneously and produce needed high conversion (SO in a convertor
2The outlet transformation efficiency can reach more than 99%) and enough big gas velocity (the reactant gases air speed is between the 0.2-0.35 meter per second).
3. improved the production intensity of catalyzer, the comparable traditional technology of catalyst levels reduces 35-50%.
4. systemic resistance is reduced greatly, compare with traditional technology, systemic resistance can descend more than 40%, thereby can significantly improve the throughput of separate unit convertor and reduce blower power consumption.
5. the sulfuric acid production process flow process is simplified greatly, and facility investment and process cost can reduce significantly.
The present invention also is achieved in that
The said combined non-steady state SO 2 converter of the present invention system is made up of three zones, promptly formed by heating zone, high-temperature zone and cooling area, and regularly switch air flow line by the non-steady-state operation principle, realize the sulfurous gas catalyzed oxidation under the non-steady-state operation condition.
Wherein, heating zone has the axially initial pre-temperature distribution of one from 200～300 ℃ to 500～520 ℃ bed, interior dress code name is homemade low-temperature vanadium catalyst and the inert filler of S105, thereby heating zone further is divided into intensification inertia district and temperature reaction district two sub regions again.In the inertia district, the heat transfer of solid to gas mainly takes place, i.e. the intensification of reactant gases, its temperature distribution changes comparatively fast in time; In reaction zone, catalyst surface reaction, solid take place simultaneously to gas heat-transfer and three processes of catalyst solid intensification itself, descend in the reaction zone solid catalyst temperature near the inertia district; Rise in reaction zone solid catalyst temperature, but amplitude is little near the high-temperature zone.The combustion initiation temperature of S105 catalyzer (i.e. the temperature of reaction beginning) is 365-375 ℃, and gas is through behind this zone, and transformation efficiency can reach 85～90%.The insulation fix bed role of the first layer in the traditional technology has been played the part of in reaction subarea in the heating zone here, but has higher conversion capability.Another effect that it produced is exactly the load that has alleviated the high-temperature zone.
The homemade vanadium catalyst that code name is S101 is equipped with in the high-temperature zone, and the initial pre-temperature distribution of bed is 520～540 ℃-520 ℃.The combustion initiation temperature of catalyzer is 390-400 ℃, has better high temperature active than S105.After reactant gases enters this district, SO
2Transformation efficiency can further improve 90-92% owing to enter the SO in the reactant gases in this district
2Existing 85～90% are transformed by the temperature reaction district, in this zone, and SO
2The conversion task heavy, and because temperature is higher, reaction is near balance, heating strength is very little.Generally, this regional catalyst temperature has decline more by a small margin earlier, and rising is more by a small margin arranged.What is interesting is that more the temperature changing speed of high-temperature zone is little far beyond heating zone and cooling area; In the whole ventilation semi-period, almost there is not any variation.
Cooling area adopts the filling mode identical with heating zone, have one from 500-520 ℃ to 300～200 ℃ initial pre-temperature distribution, two sub regions are arranged equally, i.e. the hypothermic response subarea and the inert subarea that lowers the temperature.In the hypothermic response subarea, urge agent surface reaction, gas to take place simultaneously to solid heat transfer and three processes of gas temperature decline; In cooling inertia subarea, gas mainly takes place to conduct heat to solid, i.e. gas cooling and solid heat storage, in two sub regions variation in temperature distribution speed respectively with heating zone in the reaction subarea suitable with the inertia subarea.After reactant gases entered this zone, reaction condition was in close proximity to the optimum temps curve of sulfurous gas reversible exothermic reaction, and the equilibrium conversion of the outlet transformation efficiency of whole convertor during near 365-375 ℃ is greater than 99%.
In another ventilation semi-period, the reverse charging of reactant gases, former cooling area has just become heating zone, and former heating zone has become cooling area; High-temperature area remains unchanged.Each regional principle of work as hereinbefore.
For stability of period (referring to the bed temperature distribution and export final transformation efficiency show good period over time), the curtailment of operation of realizing operation as early as possible, initial pre-temperature distribution is very important.It requires the high-temperature zone catalyst bed temperature between 520-540 ℃, and heating zone and cooling area beds present the temperature variation of 200～500 ℃ and 500-200 ℃ respectively.For obtaining this temperature distribution, must be to each zone preheating respectively of convertor.In the convertor of experiment, every 100mm one group of thermopair is installed, they directly link to each other with quick multipoint mode moisture recorder, write down the temperature variation of each point at any time.Not end in each zone all is provided with thief hole, so that analyze SO
2Concentration, the conversion situation of observing each zone.
Carry out the non-steady state SO 2 oxidizing reaction in above-mentioned convertor, after 4-10 operational cycle, bed temperature distributes and SO
2The outlet transformation efficiency is tending towards cycle stability over time.
Each regional temperature changes as described below:
1. heating zone: when the reactant gases temperature that enters convertor was 60 ℃, the temperature of heating zone bed changed vertically, by 60 ℃ to 500-520 ℃.Have a bit in this zone, its temperature is the combustion initiation temperature of catalyzer, promptly 365-375 ℃, be defined as the point of interface in intensification inert subarea and temperature reaction subarea, and it moves to the bed downstream in time.Therefore, the width of two sub regions of indication changes when operation (being the convertor operation) here.The inertia subarea not merely refers to the zone of inert filler filling, and it might comprise a part of catalyzer filling area; The reaction subarea does not all comprise the catalyzer filling area.The filling inert filler can save catalyst.With regard to the structure of convertor itself, inertia subarea and reaction subarea are exactly corresponding inert filler and catalyzer filling area.The reacting gas inlet end of heating zone, temperature descends very fast, and in 1-2 minute, the temperature of inert filler drops to 60 ℃ from 200 ℃.As time goes on the temperature reaction district is constantly dwindling, and therefore, when the temperature reaction district narrows down to one regularly, must switch the airintake direction of convertor with not enough so that 85% Sulphur Dioxide is fallen, and this moment, heating zone became cooling area.Reactant gases is 0.5-1.5 second in this regional residence time.
2. high-temperature zone: the reactant gases that is come out by heating zone enters the high-temperature zone.The bed temperature in this district is the distribution of near sinusoidal, rises to 540-570 ℃ by 500-520 ℃ vertically, drops to 520-500 ℃ again, and is little over time.But when the transformation efficiency of the sulfurous gas of heating zone reduces to 85% when following, the top temperature of high-temperature zone will significantly rise and above 600 ℃, in other words, because heating zone is out of control, will cause the high-temperature zone to transform the increase of load, the catalyst temperature of high-temperature zone is raise.For the top temperature that makes the high-temperature zone remains under the best situation, promptly under 540～570 ℃, must in time switch the airintake direction of reactant gases.So the central point temperature of high-temperature zone is a major control point of the present invention.Reactant gases is 0.5-1.0 second in this regional residence time.
3. cooling area: the reactant gases that comes out from the high-temperature zone enters cooling area, and the temperature distribution of its bed is near linear and descends, by 520-500 ℃ of temperature that drops to exit gas.Similar to heating zone, there is the point of interface in a reaction subarea and inert subarea in cooling area, and its temperature is 365-375 ℃.Generally, the SO in the charging reactant gases
2The concentration height, outlet reactant gases temperature is also high, such as, when gas inlet concentration was 9.52%, Outlet Gas Temperature was about 320 ℃; When inlet concentration was 5.88%, Outlet Gas Temperature was about 210 ℃.The exit end solid temperature is very short from the time that initial 60 ℃ (going up the entrance end temperature of half period) rise to these temperature, in 1-2 minute.Reactant gases is 0.5-1.5 second in this regional residence time.
When the reverse charging of gas, former cooling area becomes heating zone, repeats the heating zone temperature variation of half period; Former heating zone becomes cooling area, repeats the cooling area temperature variation of half period; And the variation of the temperature distribution of high-temperature zone is less.Therefore, in entire operation in the cycle, the bed temperature of this convertor distributes and presents the variation of a kind of " seesaw " formula, and the high-temperature zone fulcrum of this " seesaw " just.
Further set forth content of the present invention below in conjunction with drawings and Examples.
Accompanying drawing is the said combined non-steady state SO 2 converter synoptic diagram of the present invention
Wherein:
1-convertor housing
2a, 2b-inert filler subarea
3a, 3b-convertor be awl lid, epicone lid down
4a, 4b-low temperature catalyst (S105) subarea
5a, 5b, 5c-support sieve plate
6a, 6b-gas give sparger
7a, 7b-are respectively lower end gas feed (or outlet), upper end pneumatic outlet (or import)
8-high-temperature zone catalyst layer (S101) is placed on the supporting sieve plate 5c
Form heating zone (or cooling area) by 2a and two subareas of 4a
4b and 2b form cooling area (or heating zone) in two subareas, and they are placed on supporting sieve plate 5a respectively, on the 5b
V
1, V
2, V
3, V
4-magnetic valve or pneumavalve.
The said converter of the present invention is mainly formed by housing, lower cone lid, epicone lid and all component combinations of catalytic bed, wherein catalytic bed is made up of heating zone, high-temperature region and cooling area three parts, a lower resistance gas pre-distributor is installed respectively at two ends, to improve the uniformity of vapor solid Contact on the converter cross section, prevent the local overload of catalyst and cause overheated.
At heating zone pack into 0.1-0.2 rice thick inert filler and the thick domestic vanadium catalyst of S105 of 0.2-0.4 rice. Because catalyst has preferably low temperature active, the SO of the reacting gas by heating zone2Conversion ratio can reach 85～90%.
Insert the thick domestic S101 vanadium catalyst of 0.1-0.2 rice in the high-temperature region. Owing to the SO in the reacting gas that enters this district2Concentration significantly reduces (85%-90% has been warmed the district and has transformed), and the load of this district's catalyst is significantly reduced, and because temperature is higher, reaction is near balance, and the reaction heat that produces is limited. So at this district's front portion beds littler temperature rise is arranged, subsequently slow decreasing again. By SO in the afterreaction gas of high-temperature region2Total conversion reaches 90～92%.
At cooling area, the same with heating zone, the thick S105 vanadium catalyst of 0.2-0.4 rice and the thick inert filler of 0.1-0.2 rice are housed. In this district, bed temperature descends vertically, drops to 200-300 ℃ from 500 ℃, just in time meets the requirement of the high conversion low reaction temperatures of sulphur dioxide oxidation. Because reaction is near balance, conversion rate at tube exit is near the equilibrium conversion 99.2-99.5% of 365-375 ℃ of catalyst initiation temperature. Therefore, by this converter, can obtain the high conversion more than 99%.
Present embodiment and following each embodiment carry out in above-mentioned combined non-steady state convertor shown in the drawings.This convertor diameter is φ 108 * 4mm, and total height is 1600mm, and the catalyzer total filling amount is 7.8 liters.Inert filler 2a and S105 catalyst area 4a pack height are respectively 150 and 250mm, and 2b is identical with 2a and 4a respectively with 4b.S101 catalyst area 8 highly is 200mm.The height of conical top cover 3a and 3b is 150mm, and inside is equipped with a gas pre-distributor of being made up of two concentric circular cones.The end in each district is equipped with thief hole, totally four.In bed, one group of thermopair is set, links to each other with quick multi-point temp registering instrument respectively, the temperature variation of each point in the real time record bed every 100mm.Convertor can be accomplished good thermal insulation by suitable insulation.Corresponding to three zones (2a and 4b), (8) and (4b and 2b), be respectively equipped with nichrome wire in the outside of convertor housing, can regulate and control needed initial pre-temperature distribution easily.
Initial pre-temperature distribution below present embodiment adopts:
In 2a, the ascending temperature that axially upwards forms 220-354 ℃ along bed distributes.
In 4a, the ascending temperature that axially upwards forms 354-507 ℃ along bed distributes.
In 8, axially upwards form the temperature distribution of 507-524-507 ℃ near sinusoidal curve along bed.
In 4b, axially upwards form 507-347 ℃ decline temperature distribution along bed.
In 2b, axially upwards form 347-185 ℃ decline temperature distribution along bed.
After treating that each regional temperature distribution tends towards stability, be 60 ℃ with temperature, SO
2Content is the 9.52%(percentage by volume), oxygen content is 11.2%, all the other are that the dry reaction gas of nitrogen feeds (this moment magnetic valve V from the lower end
4, V
2Open V
1, V
3Close).Volumetric flow rate is 95 liters/minute, is equivalent to air speed 0.2 meter per second of convertor reaction gases.
By the multi-point temp registering instrument, can see that the each point temperature has following variation in the bed: the bed central point temperature that is positioned at the high-temperature zone slowly rises before this, through about 55 minutes near steadily, rise to 570 ℃ by original 520 ℃; The temperature of inert district 2a descends fast in the heating zone, entrance end be the start-point temperature in inertia district less than the inlet temperature that just drops to reactant gases in 2 minutes, the temperature of lower end is initial among the temperature reaction district 4a descends comparatively fast, just gradual slow gets off later on; The all very fast at first rising of each point temperature among cooling area 2b and the 4b, the convertor exit end, the inertia of promptly lowering the temperature district terminal temperature just rises to 220 ℃ in less than 2 minutes, and ascensional range is slowly got off again subsequently.Heating zone temperature fall off rate is suitable substantially with cooling area specific temperature rise degree.In the time of 55 minutes, the reaction gas outlet temperature is 316 ℃.
Each regional transformation efficiency changing conditions is as follows: heating zone outlet ventilation in the time of 1 minute transformation efficiency be 88.2%, slowly descend subsequently, be 86.7% during by 50 minutes, the high-temperature zone outlet was 91.2% in the time of 1 minute, slowly descend later on, in the time of 50 minutes, be 90.4%; The cooling area outlet, i.e. convertor outlet was 99.1% in the time of one minute.Slowly rising again subsequently, is 99.4% in the time of 50 minutes.
The aeration time of this example is to determine according to the temperature variation of the central point of high-temperature zone.At up-draught after 55 minutes, change and flow to, make reactant gases enter convertor (this moment magnetic valve V from the upper end
1, V
3Open, V
4, V
2Close), bed each point temperature variation is as follows: the central point temperature slowly descended before this, and fall is about 10 ℃.And slowly rise, approximately steadily approaching after 55 minutes, suitable when temperature value and up-draught, also be 570 ℃.Like this, the gas flow direction switching cycle of present embodiment just is defined as 110 minutes.In this ventilation semi-period, 2b and 4b become heating zone, and 2a and 4a become cooling area, and each regional temperature variation is similar to up-draught.In the time of 50 minutes, the outlet transformation efficiency is 99.3%.
When change flowing to again, when gas advanced from the lower end, the central point temperature variation of high-temperature zone was identical during from last endfeed with last half period, has earlier by a small margin to descend, and slowly rises, when getting back to 570 ℃ of initial temperatures, near steady.Through 6 cycles, bed temperature distributes and is tending towards cycle stability.Convertor exports final transformation efficiency between 99.1-99.4%, and temperature is not more than 320 ℃.
The reactant gases of embodiment 2 consists of SO
28.24%, O
211.4%, all the other nitrogen.Volumetric flow rate is 120 liters/minute, is equivalent to air speed 0.25 meter per second
Its initial pre-temperature distribution is as follows:
In 2a, the ascending temperature that axially upwards forms 237-347 ℃ along bed distributes.
In 4a, the ascending temperature that axially upwards forms 347-540 ℃ along bed distributes.
In 8, axially upwards form the temperature distribution of 540-550-538 ℃ near sinusoidal curve along bed.
In 4b, axially upwards form 538-334 ℃ decline temperature distribution along bed.
In 2b, axially upwards form 334-220 ℃ decline temperature distribution along bed.
The each point temperature variation is similar to embodiment 1 in the bed.The central point top temperature is 564 ℃, and the flow-reversal cycle is 90 minutes, and through 8 all after dates, bed temperature distributes and is tending towards cycle stability.Each distinguishes the conversion profile situation: the heating zone transformation efficiency is 89.1-87.2%, and the high-temperature zone is 91.6-90.6%, and cooling area is 99.0-99.4%, and scope has wherein shown that transformation efficiency over time in the ventilation semi-period.The reaction gas outlet temperature is no more than 280 ℃.
The reactant gases of embodiment 3 consists of SO
26.9%, O
211.4%, all the other are nitrogen.Volumetric flow rate is 130 liters/minute, is equivalent to convertor air speed 0.28 meter per second.Its initial pre-temperature distribution is as follows:
In 2a, the ascending temperature that axially upwards forms 315-360 ℃ along bed distributes.
In 4a, the ascending temperature that axially upwards forms 360-557 ℃ along bed distributes.
In 8, axially upwards form 557-575-540 ℃ temperature distribution along bed.
In 4b, axially upwards form 540-360 ℃ decline temperature distribution along bed.
In 2b, axially upwards form 365-296 ℃ decline temperature distribution along bed.
To this embodiment, adopt the staged strategy that goes into operation.Convertor is 5 cycles of operation under the flow-reversal cycle was 20 minutes at first, then moved 10 cycles down at 40 minutes; Be defined as 60 minutes last transformation period.Through 4 all after dates, bed temperature distributes and is tending towards cycle stability again.The temperature variations of bed is similar to embodiment 1 in each cycle, and bed central point top temperature is 555 ℃.Each regional conversion profile situation is as follows: heating zone is 90.4-88.7%, and the high-temperature zone is 91.6-89.4%, and cooling area is 99.0-99.4%, and the reaction gas outlet temperature in the time of 30 minutes is 230-234 ℃ in unidirectional ventilation.
The reactant gases of embodiment 4 consists of SO
25.88%, O
210.7%, all the other are nitrogen, and volumetric flow rate is 150 liters/minute, and the convertor air speed is 0.32 meter per second.The initial pre-temperature distribution of present embodiment is that the bed temperature of the down-draught of embodiment 1 after through 42 stable periods when finishing distributes.The purpose of doing like this is in order to examine or check the influence of reacting gas inlet change in concentration to convertor processing property of the present invention, promptly to examine or check the turndown ratio of this built-up type convertor.Initial pre-temperature distribution is as follows:
In 2a, the ascending temperature that axially upwards forms 320-315 ℃ along bed distributes.
In 4a, the ascending temperature that axially upwards forms 315-520 ℃ along bed distributes.
In 8, axially upwards form 520-570-540 ℃ temperature distribution along bed.
In 4b, axially upwards form 540-184 ℃ decline temperature distribution along bed.
In 2b, axially upwards form 184-60 ℃ decline temperature distribution along bed.
Switching cycle is 70 minutes, and through 4 all after dates, bed temperature distributes and is tending towards cycle stability.The bed top temperature is 540 ℃, and each regional temperature changes similar with embodiment 1.Each regional conversion profile is: heating zone 89.2-87.4%, high-temperature zone 92.0-91.4%, cooling area 99.1-99.4%.The reaction gas outlet temperature in the time of 35 minutes is 212 ℃ in unidirectional ventilation.
Therefore the present invention has realized high density sulfurous gas (SO well
2Percentage by volume be 5～10%) non-steady-state operation under the air-flow, be expected the vitriolic industrial production is brought huge technical progress.
Claims (2)
1, a kind of combined non-steady state SO 2 converter is combined by housing, following awl lid, epicone lid, gas pre-distributor and all parts of catalytic bed.The invention is characterized in: in said convertor housing, be provided with three catalytic bed, they are respectively and place supporting sieve plate 5a to go up the heating zone catalytic bed, place the high-temperature zone catalytic bed on the supporting sieve plate 5c and place the cooling area catalytic bed that supports on the sieve plate 5b, supporting sieve plate 5a, 5b, 5c then are fixed on the housing respectively;
Wherein, place the heating zone catalytic bed series of strata on the supporting sieve plate 5a to be formed by the vanadium catalyst of S105 by inert filler layer 2a and the low temperature catalyst layer 4a-code name on it,
Wherein, place the cooling area catalytic bed series of strata on the supporting sieve plate 5b to be formed by the vanadium catalyst and the inert filler layer 2b on it of low temperature catalyst layer 4b-code name by S105,
Wherein, placing the high-temperature zone catalytic bed on the supporting sieve plate 5c is that a kind of code name is the vanadium catalyst of S101.
2, convertor according to claim 1, the suitable depth that it is characterized in that the catalyst layer of said low-temperature catalyzed bed is 0.2～0.4 meter, the suitable depth of the catalyst layer of said high-temperature catalytic bed is 0.1～0.2 meter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107321 CN1022400C (en) | 1991-02-02 | 1991-02-02 | Combined non-steady state SO2 converter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107321 CN1022400C (en) | 1991-02-02 | 1991-02-02 | Combined non-steady state SO2 converter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1053220A CN1053220A (en) | 1991-07-24 |
| CN1022400C true CN1022400C (en) | 1993-10-13 |
Family
ID=4908672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91107321 Expired - Fee Related CN1022400C (en) | 1991-02-02 | 1991-02-02 | Combined non-steady state SO2 converter |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1022400C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872717B (en) * | 2011-07-11 | 2015-02-18 | 中国石油化工股份有限公司 | Catalytic oxidation method of desulfurizing liquid |
| CN111056539A (en) * | 2020-02-19 | 2020-04-24 | 中国日用化学研究院有限公司 | Device and method for preparing gaseous sulfur trioxide in laboratory |
-
1991
- 1991-02-02 CN CN 91107321 patent/CN1022400C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053220A (en) | 1991-07-24 |
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