CN1053637C - Process for production of sulfuric acid by using high-concentration sulfur-dioxide gas - Google Patents
Process for production of sulfuric acid by using high-concentration sulfur-dioxide gas Download PDFInfo
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- CN1053637C CN1053637C CN95111082A CN95111082A CN1053637C CN 1053637 C CN1053637 C CN 1053637C CN 95111082 A CN95111082 A CN 95111082A CN 95111082 A CN95111082 A CN 95111082A CN 1053637 C CN1053637 C CN 1053637C
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Abstract
The present invention relates to a method for producing sulfuric acid, smelting smoke gas or sulfur combusting furnace gas of a high concentration is used as raw material, a Chinese traditional vanadium catalyst is used as a catalyst, and three-conversion and three-absorption flow is adopted. A technological system can maintain heat balance, the catalyst can be operated in the temperature range of 420 to 600 DEGC, the final conversion rate can reach 99.9%, and the concentration of sulfur dioxide discharged into the atmosphere is less than 100 ppm. The concentration reaction materials and reaction temperature are in gradient distribution in the tower, the reaction materials are placed on the tower disks, and the concentration of the materials are in the gradient distribution from high to low from top to bottom; compared with the two-conversion and two-absorption flow with the same scale, the investment for sulfur combusting furnace gas is reduced by about 5%, and the investment for smelting furnace gas of oxygen enrichment is reduced by about 16%.
Description
The invention relates to a method for producing sulfuric acid by using high-concentration sulfur dioxide furnace gas obtained by oxygen-enriched smelting or sulfur burning as a raw material and adopting three times of conversion and three times of absorption.
The main chemical reactions of the contact sulfuric acid production are as follows:
at present, the total conversion rate of sulfur dioxide which can be achieved by a twice-conversion and twice-absorption method commonly adopted in domestic production of sulfuric acid is 99.5-99.7%, and the concentration of sulfur dioxide in the discharged tail gas is still 500-800 PPm, so that a tail gas sulfur dioxide absorption working section is still arranged behind a final absorption tower of a device with a large domestic production scale, and the concentration of the sulfur dioxide in the tail gas discharged into the atmosphere is reduced to be less than 150 PPm.
At present, the method for producing sulfuric acid by taking smelting flue gas or sulfur as a raw material still adopts a two-conversion two-absorption process.
In order to reduce the device investment and improve the heat energy utilization rate, the former Soviet Union develops a technology for roasting pyrite by using oxygen-enriched (or pure oxygen) (2 months in 1992, P20-28) and the technology for roasting pyrite by using oxygen-enriched (or pure oxygen); the metallurgical industry develops oxygen-enriched smelting, for example, the oxygen content is increased from 21 percent in the original air to 28 percent, the concentration of sulfur dioxide in copper smelting gas can be increased to 17 percent, and the oxygen content is less than 12 percent; in order to adapt to the condition that the concentration of sulfur dioxide is increased and O2/SO2 is obviously lower than 1, and the final conversion rate is still high, many foreign engineering companies strive to develop a low-temperature catalyst with high activity at 380-390 ℃ on the two-turn and two-absorption process SO as to finally achieve the purpose of high conversion rate. (Sulphur 1998, 229)
The company Kemithecs (Chemovirg) Canada developed a six-stage converter with a cesium catalyst for processing sulfur dioxide furnace gases having a concentration of 18%. Two companies, BASF and Lurgi, germany, also conducted intermediate tests on furnace gases with sulfur dioxide concentrations of 17% using cesium-containing low temperature catalysts. This is achieved byThe development and test work is carried out on the basis of a two-rotation and two-suction production method. In order to achieve a final conversion of 99.9%, this process must achieve 96.84% per conversion for the first and second conversions to be equal2/SO2A furnace gas of<1 is difficult to achieve in the first conversion. If the first conversion is reduced to 94%, the second conversion must be more than 98.34% to reach the final conversion of 99.9%, which inevitably requires high low-temperature activity and makes the catalyst use largeThe degree increases.
Due to the limitation of low-temperature activity and high-temperature resistance of the catalyst, the two-conversion and two-absorption process must add air to dilute sulfur dioxide furnace gas with higher concentration to a concentration of not more than 10% before the sulfur dioxide furnace gas enters the converter, so that each section of catalyst is not overheated, and the conversion rate of 99.7% is finally obtained. Thus, compared with the method for preparing acid by adopting high-concentration sulfur dioxide gas, the method has much higher capital investment and operating cost. As reported in the sulfuric acid industry at stage 1, page 26 of 1995, the economic comparison for the production of sulfuric acid with different sulfur dioxide concentrations is as follows:
scale of sulfuric acid production: 1000t/d
Sulfur dioxide concentration% 1016
Air quantity m3/h 93000 58150
Capital cost (mega mark) 3024
Main blower power consumption kW 19001200
Electricity fee (mega mark) 2.11.31
(electric charge standard 0.13 mark/kW. h)
The invention aims to realize the aim of the final conversion rate of more than 99.9 percent by using high-concentration oxygen-enriched smelting flue gas or sulfur-burning furnace gas as raw materials and using the traditional vanadium catalyst produced at present in China through a sulfuric acid production method of three times of conversion and three times of absorption, so that the concentration of sulfur dioxide discharged into the atmosphere is less than or equal to 100 PPm.
When oxygen-enriched smelting flue gas is used as a raw material, the process flow adopted by the invention is shown in figure 1, and the purified clean oxygen-enriched copper smelting flue gas (1) contains SO216％，O211 percent of the mixture enters a drying tower (2) and is dried until the water content is less than 0.1g/Nm3The gas (3) is boosted by a blower (4), the gas (5) is sent to a third heat exchanger (6), furnace gas (7) which is discharged from the thirdheat exchanger enters two first layer heat exchangers (8) and (9) which are connected in parallel, the furnace gas (8) is preheated to 420 ℃, and the gas (10) enters a first layer catalyst of a converter (11) for conversion reaction. A furnace with 40% conversion rate after passing through the first layer catalyst and the temperature rising to 587 DEG CThe gas (12) enters the first layer heat exchangers (8) and (9) which are connected in parallel, the temperature is reduced to 450 ℃, and the furnace gas (13) enters the second layer catalyst of the converter (11) for reaction. The conversion rate of the catalyst in the second layer reaches 70 percent, and the gas (14) with the temperature rising to 575 ℃ enters a heat exchanger (15) in the second layer and is cooled to 420 ℃ in the heat exchanger. The furnace gas (16) at the outlet enters a third layer of catalyst of the converter (11), the conversion rate reaches 80 percent after passing through the third layer of catalyst, the furnace gas (17) with the temperature of 471 ℃ enters a heat exchanger which is a third layer heat exchanger (6) and consists of two same heat exchangers closely connected in series, and the heat exchange is cooled to 178 ℃. The gas (18) leaving the third heat exchanger is subjected to a first absorption. The sulfur dioxide furnace gas (19) after the first absorption enters a heat exchanger which is composed of two same heat exchangers closely connected in series, namely a fifth heat exchanger (20) for heat exchange, the furnace gas (21) after the heat exchange is preheated to 425 ℃ through a first layer of heat exchanger (9), and the gas (22) enters a fourth layer of catalyst of a converter (11) for second conversion. 75% of sulfur dioxide in the furnace gas is converted in the fourth layer of catalyst, and the temperature is raised to 521 ℃. The furnace gas (23) from the fourth layer catalyst enters a fourth layer heat exchanger (24) for heat exchange, the furnace gas (25) enters a fifth layer catalyst of the converter (11) for conversion after being cooled to 430 ℃, the conversion rate reaches 94 percent after passing through the fifth layer catalyst, the temperature rises to 453 ℃, the furnace gas (26) is cooled to 160 ℃ through a fifth layer heat exchanger (20), and the gas (27) is subjected to secondary absorption.
The sulfur dioxide furnace gas (28) after the second absorption is preheated by a sixth layer heat exchanger (29), the furnace gas (30) at the outlet is preheated by a fourth layer heat exchanger (24), the furnace gas (31) at the outlet is finally preheated to 430 ℃ by a second layer heat exchanger (15), and the furnace gas (32) enters a sixth layer catalyst of the converter (11) for the third conversion. The conversion rate of the furnace gas reaches 96 percent after passing through the sixth layer of catalyst, the temperature rises to 436 ℃, the furnace gas (34) enters a low-pressure waste heat boiler (35) to recycle part of waste heat after the heat exchange of the furnace gas (33) through the sixth layer of heat exchanger (29), the temperature is reduced to 180 ℃, and the furnace gas (36) at the outlet is subjected to the third absorption. The concentration of sulfur dioxide discharged in the tail gas after three times of conversion and three times of absorption is approximately equal to 100 PPm. The invention can also be used for the high-concentration sulfur dioxide furnace gas generated by oxygen-enriched roasting of the pyrite.
When using sulfur burning furnaceWhen gas is used as a raw material, the process flow adopted by the invention is shown in figure 2, the pressure of clean and filtered air (1) is increased by an air blower (2), the air (3) enters a drying tower (4), and the water content of the air discharged from the drying tower is less than 0.1g/Nm3The air (5) enters an air preheater (6), the air (7) discharged from the air preheater and having the temperature of 200 ℃ enters a sulfur incinerator (8) and reacts with refined liquid sulfur (9) in the incinerator to generate SO2Concentration 12%, O29 percent of sulfur dioxide furnace gas (10) with the concentration and the temperature of 1260 ℃, the furnace gas enters a waste heat boiler (11) to recover heat and then is cooled to 420 ℃, and the furnace gas (12) enters a first layer of catalyst of a converter (13) to carry out conversion reaction. The conversion rate of the gas (14) passing through the first layer of catalyst is 53 percent, the temperature is raised to 592 ℃, the gas (14) enters a first heat exchanger (15), the gas (16) with the temperature lowered to 430 ℃ after heat exchange enters a second layer of catalyst of a converter (13), the conversion rate of sulfur dioxide is raised to 80 percent from 53 percent after passing through the second layer of catalyst, the air temperature is raised to 517 ℃, and the gas (17) enters a second heat exchanger (18) for heat exchange. The temperature of the gas (19) out of the heat exchanger is 430 ℃, the gas enters a third layer of catalyst of the converter (13), the conversion rate of sulfur dioxide is increased from 80% to 90% after the gas passes through the third layer of catalyst, and the temperature is increased to 462 ℃; the gas (20) is then passed to a third heat exchanger (21) for heat exchange, and the gas (22) is then passed to an air preheater (6) for cooling to 170 ℃. The gas (23) exiting the air preheater is taken for the first absorption. The gas (24) which absorbs the sulfur trioxide generated by the first conversion enters a third heat exchanger (21) for heat exchange, the gas (25) enters the first heat exchanger (15) for heat exchange, and the gas (26) which is discharged from the first heat exchanger (15) is cooledThe fourth layer catalyst preheated to 425 ℃ enters the converter (13) for second conversion, the conversion rate reaches 92%, and the temperature is 463 ℃. The gas (27) from the fourth layer catalyst passesthrough a fourth heat exchanger (28) and then is cooled to 203 ℃ to carry out second absorption on the gas (29). The gas (30) after the second absorption enters a fourth heat exchanger (28) for heat exchange, the gas (31) enters a second heat exchanger (18) again to be heated to 430 ℃, and the gas (32) enters a fifth layer catalyst of the converter (13) for third conversion. After the third conversion, the conversion rate reaches 95%, the furnace gas (33) with the temperature of 433 ℃ enters a low-pressure heat pipe boiler (34), and the cooled furnace gas (35) is absorbed for the third time. Warp beamAfter three times of conversion and three times of absorption, the concentration of sulfur dioxide in the vented tail gas is less than 100 PPm.
The technological parameters of the oxygen-enriched smelting flue gas and the three-conversion and three-absorption sulfuric acid production method by using the sulfur-burning furnace gas are shown in the table 1 and the table 2.
Table 1 shows the furnace gas temperature at the inlet and outlet of each section (layer) of catalyst of the converter, the furnace gas conversion rate at the inlet and outlet of each section of catalyst and the equilibrium conversion rate of each section. Wherein the inlet temperature of the catalyst furnace gas at each section is controlled.
Table 2 shows the inlet and outlet furnace gas temperature values of the tube pass and the shell pass of each heat exchanger.TABLE 1
TABLE 2
The advantages of the present invention over the prior art are apparent.
Because the sulfur dioxide concentration in the oxygen-enriched smelting flue gas is high, the reaction heat is large, and the sulfur-burning furnace gas is not required to be preheated by utilizing the reaction heat when entering the first conversion, the heat balance can be maintained when the two types of furnace gas are converted for three times and absorbed for three times, the catalyst can be operated within the range of 420-600 ℃, the final conversion rate can reach 99.9 percent, and the concentration of the sulfur dioxide discharged into the atmosphere is less than or equal to 100 PPm. Compared with the two-rotation two-suction process with the same production scale, when the conversion rate of the three-rotation three-suction process reaches 99.9 percent and the final conversion rate of the two-rotation two-suction process reaches 99.5 percent and 99.7 percent respectively, the ratio of the amount of sulfur dioxide discharged into the atmosphere is respectively as follows:
the environmental benefit of adopting the three-to-three-suction process is very obvious because (1-0.999): (1-0.997): (1-0.995) ═ 1: 3: 5. Meanwhile, the high-concentration raw material gas is adopted, and the tail gas absorption working section is reduced, so the capital investment and the power consumption are greatly saved. The economic benefit obtained thereby will be considerable.
Compared with the traditional process of adopting a two-rotation two-absorption and tail gas absorption working section, the process of adopting a three-rotation three-absorption process for the oxygen-enriched smelting gas with the concentration of the sulfur dioxide feed gas increased from 9% to 12% and the concentration of the sulfur dioxide increased from 16% and oxygen less than 12%, has obvious difference of economic benefits. The three-conversion three-suction process has the following advantages when being used for newly building a factory:
(1) sulfur dioxide in the discharged tail gas is less than or equal to 100PPm, and a tail gas absorption working section is not needed;
(2) the concentration of the furnace gas is improved from 9-10% to 12%, so that the size of production equipment is reduced;
(3) the utilization rate of sulfur is improved by 0.5 to 0.3 percent;
(4) the power consumption per ton of acid is reduced.
When the three-to-three absorption flow is used for technical transformation of the existing sulfuric acid device, the method has the following advantages:
(1) the concentration of the discharged tail gas is reduced to be less than or equal to 100 PPm;
(2) the production capacity is increased by 20%;
(3) the sulfur consumption quota is reduced by 0.5 to 0.3 percent.
Through the technical economic analysis of the medium-sized sulfuric acid device, the investment saving condition of the three-rotation three-suction process compared with the two-rotation two-suction process is as follows: the investment can be reduced by 5 percent for sulfur-burning furnace gas and 16 percent for oxygen-enriched smelting gas.
Claims (2)
1. A process for preparing sulfuric acid from high-concentration sulfur dioxide gas by three-conversion and three-absorption includes such steps as three-conversion and three-absorption of high-concentration oxygen-enriched smelting gas, and features that the concentration of sulfur dioxide in raw gas is diluted to 16%.
2. The method as claimed in claim 1, wherein the oxygen-enriched smelting gas is used as the raw material, the furnace gas is heat-exchanged by six layers of heat exchangers and reacts with six layers of catalysts in the converter, and the reaction temperature is controlledat 420-600 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111082A CN1053637C (en) | 1995-06-22 | 1995-06-22 | Process for production of sulfuric acid by using high-concentration sulfur-dioxide gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111082A CN1053637C (en) | 1995-06-22 | 1995-06-22 | Process for production of sulfuric acid by using high-concentration sulfur-dioxide gas |
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| CN1129193A CN1129193A (en) | 1996-08-21 |
| CN1053637C true CN1053637C (en) | 2000-06-21 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10249782A1 (en) | 2002-10-24 | 2004-05-06 | Outokumpu Oyj | Process and plant for the production of sulfuric acid from sulfur dioxide-rich gases |
| CN103011092B (en) * | 2012-12-28 | 2015-03-18 | 中国瑞林工程技术有限公司 | Technique for preparing sulfuric acid from SO2 by non-equilibrium state high-concentration twice conversion |
| CN107055488B (en) * | 2017-04-14 | 2023-04-28 | 双盾环境科技有限公司 | Binary adjustable pre-conversion sulfuric acid preparing device for high-concentration sulfur dioxide flue gas |
| CN107720708A (en) * | 2017-11-21 | 2018-02-23 | 宜昌鄂中化工有限公司 | A kind of acid production with sulphur waste heat is used for the device and method of ardealite comprehensive utilization |
| CN115626610B (en) * | 2022-10-27 | 2024-01-02 | 铜陵有色金属集团控股有限公司 | Method for preparing sulfuric acid by directly converting smelting flue gas with high concentration and low oxygen-sulfur ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4138618A1 (en) * | 1990-12-03 | 1992-06-04 | Torunskie Zaklady Przemyslu Ni | Sulphuric acid prodn. in auto-thermal 3-stage contact process - with min. emission by using hot gas from sulphur combustion for heating gas to third stage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4138618A1 (en) * | 1990-12-03 | 1992-06-04 | Torunskie Zaklady Przemyslu Ni | Sulphuric acid prodn. in auto-thermal 3-stage contact process - with min. emission by using hot gas from sulphur combustion for heating gas to third stage |
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