CN104353344A - Method for removing sulfide from steel gas - Google Patents
Method for removing sulfide from steel gas Download PDFInfo
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- CN104353344A CN104353344A CN201410617741.4A CN201410617741A CN104353344A CN 104353344 A CN104353344 A CN 104353344A CN 201410617741 A CN201410617741 A CN 201410617741A CN 104353344 A CN104353344 A CN 104353344A
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Abstract
The invention discloses a method for removing sulfide from steel gas. The method comprises the following steps: 1, partially separating sulfur dioxide from the tail gas in a first washing adsorption tower by ammonia; and 2, transferring the tail gas to a second washing adsorption tower, and emptying qualified smoke which is subjected to washing adsorption; and adding a potassium permanganate solution to the second washing adsorption tower to oxidize sulfur dioxide in the smoke into sulfuric acid and separating, so that unreacted ammonia in the first washing adsorption tower and the generated sulfuric acid form washing liquid to realize gas-liquid separation, wherein a composite adsorbent is arranged at the outlet of the second washing adsorption tower, and particularly comprises 20-60wt% of activated carbon, 20-40wt% of ZSM-5 zeolite and 20-30wt% of ZSM-11 zeolite, and the composite adsorbent is prepared by a mixing method. The method for removing sulfide from steel gas is capable of effectively separating sulfur dioxide, also preventing ammonia from releasing and avoiding generation of ammonium sulfate aerosol, has very high desulfurization degree, and realizes clean gas with low concentration of sulfur dioxide and ammonia.
Description
Technical field
The present invention relates to a kind of method removing iron and steel sulfide in flue gas.
Background technology
CN1067828A discloses one " normal temperature essence removal of organic sulfur and inorganic sulfur new technology ", comprise with modified activated carbon or iron oxide desulfurization at normal temperatures by the method, ordinary-temp hydrolysis organic sulfur catalyst is used again at the temperature of 30-120 DEG C, ordinary-pressure hydrolysis absorbs sulphur, or last again with modified activated carbon or iron oxide desulfurization at normal temperatures.Wherein ferric oxide desulfurizer is commercially available TG-1, SN-1 and ET-1, is not documented composition and the preparation method of these desulfurizing agents in that patent.Desulfurization precision is 0.1ppm, does not mention Sulfur capacity.
CN1068356A discloses one " agent of coal gas of high temperature one-step desulfurization ", and the method comprises elementary desulfurization and the desulfurization of high temperature second step, and second step desulfurization is carried out at 650 DEG C.The desulfurizing agent of elementary desulfurization is the bentonite by scrap iron mud blending 4-15% calcium oxide and 10-40%, and under the high temperature of 800-1000 DEG C, roasting is made, desulfuration efficiency > 90%, and Sulfur capacity is 8%.Do not mention the temperature of first step desulfurization in that patent, do not mention the calcination atmosphere of desulfurizing agent yet.The desulfurizing agent of second step desulfurization is iron oxide and zinc oxide blending 10-40% bentonite, and make 800-1000 DEG C of high-temperature roasting, desulfuration efficiency > 90%, Sulfur capacity is 8%.The composition of iron mud is quite complicated, not identical from its composition of the iron mud in different process yet, and containing many impurity in iron mud, as aluminium, phosphorus, sulphur, manganese, carbon etc., in addition, may iron be contained in useless mud, not describe the composition of scrap iron mud in that patent in detail, certainly also just cannot judge the content of iron in iron mud.But as can be seen from its character express, this ferric oxide desulfurizer can only be used for thick desulfurization.In addition, one " normal temp zinc oxide desulfuriging agent and preparation method " is disclosed in CN1094331A.
The performance of desulfurizing agent depends primarily on its Sulfur capacity, a desulfurization precision, and Sulfur capacity is larger, desulfurization precision is higher, then the performance of desulfurizing agent is better.In CN1067828A, the desulfurization precision of desulfurizing agent is not high enough; In CN1068356A, the Sulfur capacity of desulfurizing agent is large not, and desulfurization precision is also not high enough, thus need two steps could desulfurization to≤1ppm.
CN99100754 discloses the Ca that desulfurizing agent contains specific composite construction
2fe
2o
5active component, Ca
2fe
2o
5the amount of active component is greater than 40% of desulfurizing agent gross weight, with the water activation being less than desulfurizing agent gross weight 20% during use.Inventive desulfurization agent can containing the CaO being less than desulfurizing agent gross weight 40%, Ca (OH)
2, Fe
2o
3and SiO
2.Desulfurizing agent prepares as follows like this: Main Ingredients and Appearance is that the powder of iron oxide and/or iron hydroxide and/or ferric nitrate mixes with the powder of calcium oxide and/or calcium hydroxide and/or calcium bicarbonate and/or calcium carbonate by a., and wherein the mol ratio of iron and calcium is 1: 1 to 1: 5; B. add water compound stirring, shaping, dry; C. roasting 0.5 to 24 hour in the oxidizing atmosphere at 700 DEG C ~ 1100 DEG C temperature; D. evenly spray a small amount of water after cooling and obtain desulfurizing agent finished product.
The method removing sulfur dioxide from flue gas is described in DE 37 33 319 C2.It relates to the three stage countercurrent washer techniques for separating of sulfur dioxide, wherein, after dust filter with the quench scrubber step for being separated hydrochloric acid and hydrofluoric acid by washing device with water, is provided with three stage countercurrent washer devices.The first two sulfur dioxide scrubber processing step operates by adding ammonia, and in third step, adds sulfuric acid to be separated the ammonia discharged.
From DE 197 31 062 C2 known a kind of from flue gas, the particularly method of separating acid gas from the tail gas in power station and the tail gas of trash burner.Describe the secondary countercurrent washer technique for separating of sulfur dioxide.For separating SO 2 is to preset dust filter and chilling/washer step by washing removal hydrochloric acid and hydrofluoric acid.In the washer circulation of the first order, ammonium sulfite/ammonium bisulfite is oxidized to ammonium sulfate by oxygen-containing gas.
EP 0 778 067 B1 discloses the equipment of the flue gas for purifying the acid ingredient with different amount and the method for this equipment of operation.Dust filter with for by washing be separated the chilling/washer step of hydrochloric acid and hydrofluoric acid after, arranged countercurrent washer technique with separating SO 2.
Summary of the invention
The object of the invention is to propose a kind of method removing iron and steel sulfide in flue gas.
For reaching this object, the present invention by the following technical solutions:
The method of removing iron and steel sulfide in flue gas, comprises the following steps: 1) in the first washing adsorption tower, from tail gas, partly isolate sulfur dioxide with ammonia; 2) then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 20-60wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 20-30wt% of 20-40wt%, the preparation method of this compound adsorbent is mixing method.
The method can effectively be avoided again the release of ammonia simultaneously and avoid the generation of the Ammonium Sulfate Aerosol produced by it by separating SO 2, has higher desulfurization degree, realizes the clean gas of extremely low sulfur dioxide and ammonia density.
Detailed description of the invention
Embodiment 1
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 30wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 30wt% of 40wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 2
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 40wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 20wt% of 40wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 3
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 50wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 30wt% of 20wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 4
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 60wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 20wt% of 20wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 5
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 50wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 25wt% of 25wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 6
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 50wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 30wt% of 20wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 7
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 45wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 30wt% of 25wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 8
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 55wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 20wt% of 25wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 9
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 50wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 22wt% of 28wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 10
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 50wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 23wt% of 27wt%, the preparation method of this compound adsorbent is mixing method.
Embodiment 11
The method of removing iron and steel sulfide in flue gas, partly isolates sulfur dioxide with ammonia in the first washing adsorption tower from tail gas; Then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; Liquor potassic permanganate is added the second washing adsorption tower the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 50wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 24wt% of 26wt%, the preparation method of this compound adsorbent is mixing method.
Claims (1)
1. remove the method for iron and steel sulfide in flue gas, comprise the following steps: 1) in the first washing adsorption tower, from tail gas, partly isolate sulfur dioxide with ammonia; 2) then tail gas is conveyed into the second washing adsorption tower, by emptying for flue gas qualified after washing adsorption treatment; It is characterized in that: liquor potassic permanganate is added the second washing adsorption tower and the oxidizing sulfur dioxide in flue gas is sulfuric acid and is separated, the sulfuric acid of unreacted ammonia and generation from the first washing adsorption tower is made to form cleaning solution to realize gas-liquid separation thus, and in the outlet of the second washing adsorption tower, compound adsorbent is set, the active carbon specifically consisting of 20-60wt% of compound adsorbent, the ZSM-11 type zeolite of ZSM-5 and 20-30wt% of 20-40wt%, the preparation method of this compound adsorbent is mixing method.
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| CN201410617741.4A CN104353344B (en) | 2014-11-05 | 2014-11-05 | The method removing iron and steel sulfide in flue gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105268293A (en) * | 2015-08-07 | 2016-01-27 | 无锡桥阳机械制造有限公司 | Combined desulfurization method used for metallurgical industry blast furnace flue gas |
| CN106824064A (en) * | 2017-04-13 | 2017-06-13 | 温震烨 | The method that bivalve layer ZSM 5 molecular sieve adsorptions remove sulfur dioxide in flue gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006096376A2 (en) * | 2005-03-03 | 2006-09-14 | Conocophillips Company | Mercury removal sorbent |
| CN102753518A (en) * | 2010-02-12 | 2012-10-24 | 斯塔米卡邦有限公司 | Removal of ammonia in urea finishing |
| CN103566746A (en) * | 2013-11-26 | 2014-02-12 | 武汉凯迪电力环保有限公司 | External efficient oxidation ammonia desulphurization process and device |
| CN103657367A (en) * | 2013-12-13 | 2014-03-26 | 何金整 | Device and process for changing one-tower calcium desulphurization to double-tower ammonia desulphurization |
-
2014
- 2014-11-05 CN CN201410617741.4A patent/CN104353344B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006096376A2 (en) * | 2005-03-03 | 2006-09-14 | Conocophillips Company | Mercury removal sorbent |
| CN102753518A (en) * | 2010-02-12 | 2012-10-24 | 斯塔米卡邦有限公司 | Removal of ammonia in urea finishing |
| CN103566746A (en) * | 2013-11-26 | 2014-02-12 | 武汉凯迪电力环保有限公司 | External efficient oxidation ammonia desulphurization process and device |
| CN103657367A (en) * | 2013-12-13 | 2014-03-26 | 何金整 | Device and process for changing one-tower calcium desulphurization to double-tower ammonia desulphurization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105268293A (en) * | 2015-08-07 | 2016-01-27 | 无锡桥阳机械制造有限公司 | Combined desulfurization method used for metallurgical industry blast furnace flue gas |
| CN106824064A (en) * | 2017-04-13 | 2017-06-13 | 温震烨 | The method that bivalve layer ZSM 5 molecular sieve adsorptions remove sulfur dioxide in flue gas |
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| CN104353344B (en) | 2016-08-24 |
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