CN107840313A - A kind of high concentration SO2Flue gas converts the method and device of extracting sulfuric acid - Google Patents

A kind of high concentration SO2Flue gas converts the method and device of extracting sulfuric acid Download PDF

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Publication number
CN107840313A
CN107840313A CN201711211987.1A CN201711211987A CN107840313A CN 107840313 A CN107840313 A CN 107840313A CN 201711211987 A CN201711211987 A CN 201711211987A CN 107840313 A CN107840313 A CN 107840313A
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China
Prior art keywords
flue gas
sulfuric acid
high concentration
converter
outlet
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CN201711211987.1A
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Chinese (zh)
Inventor
张志清
霍广田
陈有祥
王志亮
霍亚东
何陆洋
徐爱莲
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JIANGSU TIANRUN CHEMICAL EQUIPMENT Co Ltd
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JIANGSU TIANRUN CHEMICAL EQUIPMENT Co Ltd
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Priority to CN201711211987.1A priority Critical patent/CN107840313A/en
Publication of CN107840313A publication Critical patent/CN107840313A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/69Sulfur trioxide; Sulfuric acid
    • C01B17/74Preparation

Abstract

A kind of high concentration SO2Flue gas converts the method and device of extracting sulfuric acid, and the invention belongs to sulfuric acid preparation field, suitable for high concentration SO2Flue gas converts extracting sulfuric acid product, solves high concentration SO2Converted under flue gas one section of reaction heat of extracting sulfuric acid is too high, catalyst because of high temperature deactivation the problem of, the present invention is by dry air and the SO of part high concentration2Flue gas carries out mixed diluting, the SO after dilution2Flue gas concentration controls the SO after 10% ± 0.5%, dilution2Flue gas enters pre-inversion, obtains certain density SO3Flue gas, then SO will be contained3Flue gas mixed with the main flue gas of remainder, converted into main converter, the present invention is by combination drying air by SO2Concentration control is converted to containing certain density SO 10% ± 0.5%, and by pre-inversion3Flue gas, the present invention can control the conversion ratio of each section of conversion well, it is ensured that utilize high concentration SO2Flue gas produces reliable and stable sulfuric acid, while ensures that the catalyst in converter is not damaged by.

Description

A kind of high concentration SO2Flue gas converts the method and device of extracting sulfuric acid
Technical field
The invention belongs to sulfuric acid preparation field, specifically, more particularly to a kind of high concentration SO2Flue gas converts extracting sulfuric acid Method and device.
Background technology
At present, metal sulfide ore rich reserves, especially copper mine, nickel minerals and lead ore in nonferrous metal resources.This A little metal sulfide ores can produce substantial amounts of SO during pyrometallurgical smelting2Gas is general to be given using the method for flue gas Sulphuric acid With recovery.In flue gas process for preparing sulfuric acid, SO2It is converted into SO3Reaction be strongly exothermic reversible reaction, it is necessary at 400~420 DEG C Reaction balance could be approached in the presence of multi-layer catalyst, realizes maximum conversion rate.Under equal flue gas flow, SO2Concentration is higher It is bigger then to react the heat discharged, but is limited to catalyst activity and device intensity, each catalyst layer exit gas temperature Control is required to below 610 DEG C, otherwise catalyst inactivation, reaction can not continue, therefore conventional flue gas process for preparing sulfuric acid enters SO2 volumetric concentrations need to be controlled 10% or so in the flue gas during smelting of conversion.
In the late two decades, a kind of fuel efficiency, energy-saving oxygen-rich smelting technology of can improving is in non-ferrous metal metallurgy Industry obtains more and more extensive application, and incident is SO in flue gas during smelting2Concentration is significantly increased, SO2Concentration is left 20% The right side turns into normality, and high concentration SO2Flue gas convert, because one section of inversion quantity is big, reaction heat is more, one section conversion after flue-gas temperature >= 620 DEG C, catalyst can be made to lose activity.
The content of the invention
Can be by high concentration SO present invention aims at one kind is provided2Flue gas converts the method for extracting sulfuric acid, this method energy Enough utilize SO2Flue gas of the concentration more than 16% produces reliable and stable sulfuric acid, it is ensured that the catalyst in converter is not damaged by.
In order to realize foregoing invention purpose, a kind of high concentration SO of the present invention2The technology that the method for Sulphuric acid uses under flue gas Scheme is:
A kind of high concentration SO2The method of flue gas pre-inversion pre-absorption extracting sulfuric acid, comprises the following steps:
1) SO by volumetric concentration for n2Flue gas is to 420 ± 5 DEG C;
2) SO after heating2Flue gas, it is V to be divided into volume1And V2Two parts, volume V1SO2Flue gas injected slurry volume is V3 Dry air dilution SO2Concentration, the SO after dilution2Flue gas is warming up to 600 ± 5 DEG C
After carry out pre-inversion, be converted into containing SO3Flue gas, conversion ratio be 60% -70%;
3) SO is contained after pre-inversion3Flue gas cool-down to another part volume being V after 420 ± 5 DEG C2SO2Flue gas Mixed, mixed flue gas carries out conversion absorption into converter;The volume is V1SO2Flue gas, volume V2's SO2Flue gas and volume are V3Dry air meet equation below:nV1/(V1+V3)≤0.105 and (nV2+n*0.4V1)/(V1+V2 +V3)≤0.105, n > 16%.The present invention is by setting pre reforming Process, by the SO of part high concentration2Flue gas mixes with dry air Close, by SO after mixing2SO in flue gas2Volumetric concentration is diluted to 10% ± 0.5%, then carries out pre-inversion one through pre-reformer Section has certain density SO3Flue gas, so as to reduce the reaction heat of one section of converter, temperature control is ensured below 610 DEG C, to protect Card catalyst is not destroyed.
Preferably, SO in mixed flue gas in step 3)2Initial conversion about 25%.
Preferably, injected slurry volume is V in step 2)3Dry air temperature be 420 ± 5 DEG C.
Preferably, mixed flue gas is heated to 420 ± 5 DEG C before entering converter in step 3).
Another object of the present invention is to provide a kind of high concentration SO2Flue gas converts the device of extracting sulfuric acid, and the device can Utilize SO2Flue gas of the concentration more than 16% produces reliable and stable sulfuric acid, it is ensured that the catalyst in converter is not damaged by.
In order to realize foregoing invention purpose, a kind of high concentration SO of the present invention2What the device of flue gas conversion extracting sulfuric acid used Technical scheme is:
A kind of high concentration SO2The device of flue gas pre-inversion pre-absorption extracting sulfuric acid, including flue gas pre-drying device, first change Hot device, the second heat exchanger, preheater, air dry-set, pre-converter, converter, flue gas pre-drying device outlet with The import of First Heat Exchanger is connected, and the outlet of First Heat Exchanger is connected with the import of the second heat exchanger, the outlet of the second heat exchanger Being divided to has two branch roads, and tie point is connected with the import of converter, and the second branch road is connected after combining with the first outlet of preheater Pre-converter is connected with, the outlet of pre-converter is connected with the second import of preheater, and the first import and the air of preheater are done The outlet of dry device is connected, and the second outlet of preheater is connected with tie point, the first import of preheater and the of preheater One outlet is connected, and the second import of preheater is connected with the second outlet of preheater.The present invention, will by setting pre-reformer The SO of part high concentration2Flue gas mixes with dry air, by SO2SO in flue gas2Volumetric concentration is diluted to 10% ± 0.5%, then Carrying out one section of pre-inversion through pre-reformer has certain density SO3, so as to reduce by one section of reaction heat, the flue gas after pre-inversion With the SO of high concentration2Also SO is diluted after mixing2Concentration so that SO2Flue gas can realize maximum conversion rate in converter, Temperature control is ensured below 610 DEG C, while ensures that catalyst is not destroyed.Preheater is to coming in from the import of preheater second High temperature mixed flue gas is cooled, and the dry air come in from the import of preheater first is heated, cooling with it is heated Heat circulation is complementary in journey, serves the effect of energy-conservation.
Preferably, the tie point on the second branch road with being equipped with valve.Pass through Valve controlling SO2The flow of flue gas.
Preferably, the converter entrance point is provided with start temp.-elevating electric furnace.By set start temp.-elevating electric furnace can To SO during start2Flue gas is heated.
Preferably, the pre-converter entrance point is provided with temp.-elevating electric furnace.The temp.-elevating electric furnace will enter in pre-converter SO2Flue gas is warmed to 600 ± 5 DEG C.
Preferably, the air dry-set includes drying tower, drying tower be equipped with dry sour circulating slot and with drying The drying acid cooler that sour circulating slot matches.Air dry-set is and SO2The air of flue gas mixing is dried.
Compared with prior art, the beneficial effects of the invention are as follows:
The present invention is by setting pre-reformer, by the SO of part high concentration2Flue gas mixes with dry air, will after mixing SO2SO in flue gas2Volumetric concentration is diluted to 10% ± 0.5%, then has finite concentration through one section of pre-inversion of pre-reformer progress SO3Flue gas, so as to reduce the reaction heat of one section of converter, the SO of flue gas and high concentration after pre-inversion2Also diluted after mixing SO2Concentration so that SO2Flue gas can realize maximum conversion rate in converter, ensure temperature control below 610 DEG C, simultaneously Ensure that catalyst is not destroyed.
Brief description of the drawings
Fig. 1 is the structural representation of the present apparatus
In figure:1. flue gas pre-drying device;2. First Heat Exchanger;3. the second heat exchanger;4. temp.-elevating electric furnace of starting shooting;5. conversion Device;6. preheater;7. temp.-elevating electric furnace;8. pre-converter;9. air dry-set;31. tie point;32. the second branch road;61. Preheater second outlet;62. preheater first outlet;63. the import of preheater second;64. the import of preheater first;91. dry Tower;92. dry acid cooler;93. dry sour circulating slot;311. valve.
Embodiment
With reference to the accompanying drawings and detailed description, the present invention is furture elucidated, it should be understood that these embodiments are only used for Illustrate the present invention rather than limitation the scope of the present invention, after the present invention has been read, those skilled in the art are to the present invention The modifications of the various equivalent form of values fall within the application appended claims limited range.
A kind of high concentration SO2The method that flue gas converts extracting sulfuric acid, comprises the following steps:
1) SO by volumetric concentration for n2Flue gas is to 420 DEG C;
2) SO after heating2Flue gas, it is V to be divided into volume1And V2Two parts, volume V1SO2Flue gas injected slurry volume is V3 Dry air dilution SO2Concentration, the temperature control of dry air is at 420 ± 5 DEG C, the SO after dilution2Flue gas is warming up to Pre-inversion is carried out after 600 ± 5 DEG C, is converted into containing SO3Flue gas, conversion ratio be 60% -70%;
3) SO is contained after pre-inversion3Flue gas cool-down to another part volume being V after 420 ± 5 DEG C2SO2Flue gas Mixed, mixed flue gas carries out conversion absorption into converter, controlled before being converted into converter its temperature 420 ± 5℃;The volume is V1SO2Flue gas, volume V2SO2Flue gas and volume are V3Dry air meet equation below: nV1/(V1+V3)≤0.105 and (nV2+n*0.4V1)/(V1+V2+V3)≤0.105, n > 16%.
A kind of high concentration SO as shown in Figure 12The device of flue gas pre-inversion pre-absorption extracting sulfuric acid, including the predrying dress of flue gas Put 1, First Heat Exchanger 2, the second heat exchanger 3, preheater 6, air dry-set 9, pre-converter 8, converter 5, the flue gas The outlet of pre-drying device 1 is connected with the import of First Heat Exchanger 2, the outlet of First Heat Exchanger 2 and the import phase of the second heat exchanger 3 Even, the outlet of the second heat exchanger 3, which be divided to, two branch roads, and tie point 31 is connected with the import of converter 5, the second branch road 32 and in advance The first outlet 62 of hot device, which is connected after combining, is connected with pre-converter 8, the outlet of pre-converter 8 and the second import 63 of preheater It is connected, the first import 64 of preheater is connected with the outlet of air dry-set 9, the second outlet 62 and tie point of preheater 31 are connected, and the first import of preheater 64 is connected with preheater first outlet 62, and the second import of preheater 63 goes out with preheater second Mouth 61 is connected, and valve 311 is equipped with the branch road 32 of tie point 31 and second, and the entrance point of converter 5 is provided with start Temp.-elevating electric furnace 4, the entrance point of pre-converter 9 are provided with temp.-elevating electric furnace 7, and the air dry-set 9 includes drying tower 91, dry Tower 91 is equipped with the drying acid cooler 92 dried sour circulating slot 93 and matched with the sour circulating slot of drying.
The device specific work process and operation principle:
1) air enters drying tower 91 after filter dedusting, in drying tower 91 after the sulfuric acid that concentration is 98% is dried Heated into preheater 6, SO is transferred out by flue gas pre-drying device drying process2Volumetric concentration is n SO2Flue gas enters first The heat exchanger 3 of heat exchanger 2 and second is heated to 420 ± 5 DEG C, and volume is V after heating1SO2Flue gas enters through the second branch road 32 to be preheated Device and volume are V3Dry air mixing, mixed SO2SO in flue gas2Volumetric concentration control is 10% ± 0.5%, mixing SO afterwards2Flue gas is heated to 600 ± 5 DEG C through temp.-elevating electric furnace 7 and enters pre-converter 8, and its conversion ratio is 60% -70%;
2) SO is contained after the conversion of pre-converter 83Flue gas reenter after preheater 6 from preheater second outlet 61 Output is V with another part volume in the tie point 31 of the second heat exchanger 32SO2Flue gas mixes, SO in mixed flue gas2 Concentration is diluted to less than 10% ± 0.5%, is then converted into converter 5.
Embodiment 1:
100 tons of SO2Volumetric concentration is 20% SO2Flue gas, through this method and present apparatus Sulphuric acid
V1, V2 and V3 value such as following table herein:
V1 V2 V3
50 50 50
Volume is V1SO2Flue gas SO after preheater first outlet mixes with the dry air that volume is V32Concentration is 10% conversion ratio in pre-converter is 65%, SO in mixed flue gas after conversion2With SO3Concentration such as following table:
SO2 SO3
3.5% 6.5%
Flue gas and volume after pre-inversion are V2SO2Flue gas SO after tie point mixing2With SO3Concentration it is as follows Table:
SO2 SO3
9% 4.3%
Each layer conversion ratio is as follows after mixed flue gas enters converter:
One turn Two turns Three turns Four turns
65% 87.7% 95.7% 98.5%
Embodiment 2:
100 tons of SO2Volumetric concentration is 16% SO2Flue gas, through this method and present apparatus Sulphuric acid
V1, V2 and V3 value such as following table herein:
V1 V2 V3
50 50 30
Volume is V1SO2Flue gas and volume are V3Dry air preheater first outlet mixing after SO2Concentration is 10% conversion ratio in pre-converter is 65%, SO in mixed flue gas after conversion2With SO3Concentration such as following table:
SO2 SO3
3.5% 6.5%
Flue gas and volume after pre-inversion are V2SO2Flue gas SO after tie point mixing2With SO3Concentration it is as follows Table:
Each layer conversion ratio is as follows after mixed flue gas enters converter:
One turn Two turns Three turns Four turns
65% 87.7% 95.7% 98.5%
Embodiment 3:
100 tons of SO2Volumetric concentration is 30% SO2Flue gas, through this method and present apparatus Sulphuric acid
V1, V2 and V3 value such as following table herein:
V1 V2 V3
50 50 100
Volume is V1SO2Flue gas SO after preheater first outlet mixes with the dry air that volume is V32Concentration is 10% conversion ratio in pre-converter is 65%, SO in mixed flue gas after conversion2With SO3Concentration such as following table:
SO2 SO3
3.5% 6.5%
Flue gas and volume after pre-inversion are V2SO2Flue gas SO after tie point mixing2With SO3Concentration it is as follows Table:
SO2 SO3
10.1% 4.8%
Each layer conversion ratio is as follows after mixed flue gas enters converter:
One turn Two turns Three turns Four turns
65% 87.7% 95.7% 98.5%

Claims (9)

  1. A kind of 1. high concentration SO2The method that flue gas converts extracting sulfuric acid, it is characterised in that comprise the following steps:
    1) SO by volumetric concentration for n2Flue gas is to 420 ± 5 DEG C;
    2) SO after heating2Flue gas, it is V to be divided into volume1And V2Two parts, volume V1SO2Flue gas injected slurry volume is V3It is dry Dry Dilution air SO2Concentration, the SO after dilution2Flue gas carries out pre-inversion after being warming up to 600 ± 5 DEG C, be converted into containing SO3Flue gas, conversion ratio be 60% -70%;
    3) SO is contained after pre-inversion3Flue gas cool-down to another part volume being V after 420 ± 5 DEG C2SO2Flue gas is carried out Mixing, mixed flue gas carry out conversion absorption into converter;
    The volume is V1SO2Flue gas, volume V2SO2Flue gas and volume are V3Dry air meet equation below: nV1/(V1+V3)≤0.105 and (nV2+n*0.4V1)/(V1+V2+V3)≤0.105, n > 16%.
  2. 2. high concentration SO according to claim 12The method that flue gas converts extracting sulfuric acid, it is characterised in that:Mixed in step 3) SO in flue gas after conjunction2Initial conversion about 25%.
  3. 3. high concentration SO according to claim 12The method that flue gas converts extracting sulfuric acid, it is characterised in that:Noted in step 2) It is V to enter volume3Dry air temperature be 420 ± 5 DEG C.
  4. 4. high concentration SO according to claim 12The method that flue gas converts extracting sulfuric acid, it is characterised in that:Mixed in step 3) Flue gas after conjunction is heated to 420 ± 5 DEG C before entering converter.
  5. 5. high concentration SO according to claim 1 or 22The device of the method for flue gas conversion extracting sulfuric acid, it is characterised in that: Including flue gas pre-drying device, First Heat Exchanger, the second heat exchanger, preheater, air dry-set, pre-converter, converter, The flue gas pre-drying device outlet is connected with the import of First Heat Exchanger, the outlet of First Heat Exchanger and entering for the second heat exchanger Mouth is connected, and the outlet of the second heat exchanger, which is divided to, two branch roads, and tie point is connected with the import of converter, the second branch road and preheating Pre-converter is connected with after the connected combining of the first outlet of device, the outlet of pre-converter is connected with the second import of preheater, in advance The hot import of device first is connected with the outlet of air dry-set, and the second outlet of preheater is connected with tie point, preheater First import is connected with the first outlet of preheater, and the second import of preheater is connected with the second outlet of preheater.
  6. 6. high concentration SO according to claim 32The device of the method for flue gas conversion extracting sulfuric acid, it is characterised in that:It is described Tie point on the second branch road with being equipped with valve.
  7. 7. concentration SO according to claim 32The device of the method for flue gas conversion extracting sulfuric acid, it is characterised in that:Described turn Change device entrance point and be provided with start temp.-elevating electric furnace.
  8. 8. high concentration SO according to claim 32The device of the method for flue gas conversion extracting sulfuric acid, it is characterised in that:It is described Pre-converter entrance point is provided with temp.-elevating electric furnace.
  9. 9. high concentration SO according to claim 32The device of the method for flue gas conversion extracting sulfuric acid, it is characterised in that:It is described Air dry-set includes drying tower, and drying tower is equipped with the drying dried sour circulating slot and matched with the sour circulating slot of drying Acid cooler.
CN201711211987.1A 2017-11-28 2017-11-28 A kind of high concentration SO2Flue gas converts the method and device of extracting sulfuric acid Pending CN107840313A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1268484A (en) * 2000-04-06 2000-10-04 应燮堂 Improvement of high-concentration sulfur dioxide three-conversion three-absorption acid-making process
US20080253957A1 (en) * 2004-03-12 2008-10-16 Karl-Heinz Daum Process and Plant for Producing Sulfuric Acid
CN102079511A (en) * 2011-01-05 2011-06-01 金隆铜业有限公司 Acid making system suitable for high-concentration sulfur dioxide-containing flue gas
CN103072956A (en) * 2012-12-31 2013-05-01 中国瑞林工程技术有限公司 Flue gas processing method and system
CN103303877A (en) * 2013-07-03 2013-09-18 中国瑞林工程技术有限公司 Comprehensive multi-gas source low-concentration SO2 fume recycling acid-making technological process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1268484A (en) * 2000-04-06 2000-10-04 应燮堂 Improvement of high-concentration sulfur dioxide three-conversion three-absorption acid-making process
US20080253957A1 (en) * 2004-03-12 2008-10-16 Karl-Heinz Daum Process and Plant for Producing Sulfuric Acid
CN102079511A (en) * 2011-01-05 2011-06-01 金隆铜业有限公司 Acid making system suitable for high-concentration sulfur dioxide-containing flue gas
CN103072956A (en) * 2012-12-31 2013-05-01 中国瑞林工程技术有限公司 Flue gas processing method and system
CN103303877A (en) * 2013-07-03 2013-09-18 中国瑞林工程技术有限公司 Comprehensive multi-gas source low-concentration SO2 fume recycling acid-making technological process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘少武等: "《硫酸工作手册》", 30 April 2001 *

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