CN103043625B - A kind of sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid - Google Patents
A kind of sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid Download PDFInfo
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- CN103043625B CN103043625B CN201210586496.6A CN201210586496A CN103043625B CN 103043625 B CN103043625 B CN 103043625B CN 201210586496 A CN201210586496 A CN 201210586496A CN 103043625 B CN103043625 B CN 103043625B
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 198
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000005864 Sulphur Substances 0.000 title claims abstract description 88
- 239000002699 waste material Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 44
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 44
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 44
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract 11
- 239000007789 gas Substances 0.000 claims abstract description 185
- 238000010521 absorption reaction Methods 0.000 claims abstract description 94
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 238000000746 purification Methods 0.000 claims abstract description 19
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 238000004781 supercooling Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 50
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 23
- 239000000428 dust Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- -1 ferrous sulfate monohydrate compound Chemical class 0.000 claims description 8
- 239000003546 flue gas Substances 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000003500 flue dust Substances 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000005201 scrubbing Methods 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 239000012717 electrostatic precipitator Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003595 mist Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 235000010269 sulphur dioxide Nutrition 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- 230000001131 transforming effect Effects 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 239000001117 sulphuric acid Substances 0.000 description 9
- 235000011149 sulphuric acid Nutrition 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- XAQHXGSHRMHVMU-UHFFFAOYSA-N [S].[S] Chemical compound [S].[S] XAQHXGSHRMHVMU-UHFFFAOYSA-N 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 210000000056 organ Anatomy 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 2
- 229910052683 pyrite Inorganic materials 0.000 description 2
- 239000011028 pyrite Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical group [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- SCVOEYLBXCPATR-UHFFFAOYSA-L manganese(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O SCVOEYLBXCPATR-UHFFFAOYSA-L 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of sulphur waste material and mix the method that burning ferrous sulfate waste material is prepared sulfuric acid, the method comprises the steps: a) by dry to sulphur waste material and ferrous sulfate waste material; B) will be dried rear waste material and mix, wherein, in sulphur waste material, in sulphur and ferrous sulfate waste material, the weight ratio of ferrous sulfate monohydrate is 3: 7～7: 3; C) by step, the mixed material in b) adds boiling kiln roasting, sintering temperature is 850-1000 DEG C, pass into air, gas speed is 1.0-2.0 meter per second, the time of staying of mixed material in fluidized bed furnace is 4-16 second, after roasting, in furnace gas, sulfur dioxide volumetric concentration is 9-12%, controls the concentration of sulfur dioxide in furnace gas by controlling oxygen intake; D) by step, the furnace gas that contains sulfur dioxide in c) makes sulfuric acid through supercooling, purification, conversion absorption section. Method of the present invention makes full use of the sulfur waste sulphur of coking industry by-product and the ferrous sulfate waste residue of titanium dioxide industry by-product, has reduced production cost, and can significantly reduce energy consumption.
Description
Technical field
The present invention relates to a kind of preparation method of sulfuric acid, relate in particular to a kind of sulphur waste material and mix that to burn ferrous sulfate uselessMaterial is prepared the method for sulfuric acid.
Background technology
The raw material of producing sulfuric acid in prior art has the sulfur-bearings such as troilite, sulphur, flue gas during smelting and ardealite formerMaterial, wherein, with pyrite-based sulfuric acid production, acid production with sulphur technique mature and reliable the most, metallurgical off-gas acid-making is adopted substantiallyWith the technology and equipment similar to pyrite-based sulfuric acid production. Conventionally acid production with sulphur adopts liquid stream incineration technology, and raw material makesBe commodity sulphur, require impurity content very low, with prevent from bringing in sulphur impurity stop up molten sulfur shower nozzle,Cause the problems such as reforming catalyst is poisoning.
Due to the raising of environmental requirement, in the production processes such as synthetic ammonia, oil refining, coke-stove gas, increase in recent yearsAdded desulfurizer, produced the sulphur of many recovery, the sulfur purity that wherein oil refining apparatus reclaims is very high,And contain more impurity in the sulphur reclaiming in synthetic ammonia, coke oven gas desulfurization process, can not adopt liquid streamIncineration technology is prepared sulfuric acid. Therefore the sulphur reclaiming in urgent need solution synthetic ammonia, coke oven gas desulfurization processProblem of complex utilization.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of sulphur waste material and mixes and burn ferrous sulfate waste material and prepare sulfuric acidMethod, make full use of the sulfur waste sulphur of coking industry by-product and the ferrous sulfate waste residue of titanium dioxide industry by-product,Reclaim useful sulphur resource, reduce production costs, and can significantly reduce energy consumption.
For solving the problems of the technologies described above, the invention provides a kind of sulphur waste material and mix and burn ferrous sulfate waste material and prepare sulphurThe method of acid, the method comprises the steps:
A) by dry to sulphur waste material and ferrous sulfate waste material, make sulphur waste material be dehydrated into the thick sulphur of granular, sulphurAfter the ferrous waste material dehydration of acid, obtain ferrous sulfate monohydrate compound;
B) dried sulphur waste material and ferrous sulfate waste material are mixed, wherein, dried sulphur is uselessIn material, in sulphur and ferrous sulfate waste material, the weight ratio of ferrous sulfate monohydrate is 3: 7～7: 3, be preferably 3: 3～7: 3, more preferably 1: 1;
C) by step, the mixed material in b) adds boiling kiln roasting, and sintering temperature is 850-1000 DEG C,Pass into air, gas speed is 1.0-2.0 meter per second, and the time of staying of mixed material in fluidized bed furnace is 4-16 second,After roasting, in furnace gas, sulfur dioxide volumetric concentration is 9-12%, is preferably 12%, comes by controlling oxygen intakeControl the concentration of sulfur dioxide in furnace gas;
D) furnace gas that step is contained to sulfur dioxide in c) is through supercooling, washing, purifying, conversion absorption section systemObtain sulfuric acid.
Above-mentioned sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid, wherein, and described steps d) in,The furnace gas that contains sulfur dioxide is undertaken cooling by steam generator, furnace gas is cooled to 320 DEG C-360 DEG C and enters and washWash purification section, described steam generator produces the low-pressure saturated steam of 1.2-1.3MPa, and the low pressure of by-product is fullCan be connected with low-pressure steam pipe network with steam, for dry and other technical process of sulphur.
Above-mentioned sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid, wherein, and described steps d) in,Described furnace gas washing, purifying adopts dry method dust and wet cleaning, comprises the following steps:
1) cooled furnace gas is removed flue dust by cyclone dust collectors, by these cyclone dust collectors can remove toFew 90% Fe2O3Flue dust;
2) furnace gas after dedusting enters Venturi tube, sprays into the dilute sulfuric acid of 10-40% weight in described venturi throat,Dilute sulfuric acid obtains good atomization in described Venturi tube, furnace gas and dilute sulfuric acid close contact, make furnace gas humidification,Cool and further dedusting, complete preliminary washing, purifying;
3) furnace gas, after described Venturi tube washing, enters stuffing washing tower, with tower top spray 10-40% weightDilute sulfuric acid counter current contacting, washing, purifying, remove impurity and steam wherein, flue gas cleaning completes, purifyIn rear furnace gas, dust content is lower than 0.5mg/m3, the too high meeting of dust content makes the catalyst in follow-up conversion processPoisoning, have a strong impact on the conversion of sulfur dioxide. In washing, purifying workshop section, further, wash through scrubbing towerThe furnace gas of washing can also enter electrostatic precipitator and remove acid mist.
Above-mentioned sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid, wherein, and described steps d) in,Described conversion absorption section adopts double-absorption method, and the equipment of employing comprises drying tower, the first absorption tower and theTwo absorption towers, be provided with the converter of five beds, correspondingly with each beds be provided with firstHeat exchanger, the second heat exchanger, the 3rd heat exchanger, the 4th heat exchanger and the 5th heat exchanger;
Described double-absorption method comprises the steps:
1) furnace gas from washing, purifying workshop section is supplemented to air, make sulfur dioxide volumetric concentration in furnace gas be8-8.5%, passes into drying tower bottom by furnace gas, and dry absorption of the concentrated sulfuric acid of 94% weight spraying through tower top is dryMoisture content≤0.1g/Nm in furnace gas after dry3；
2) furnace gas is after drying successively through the 3rd heat exchanger, First Heat Exchanger heating, the furnace gas temperature after heatingDegree is 410-430 DEG C, and the first paragraph beds that enters converter transforms, by the titanium dioxide in furnace gasSulphur is converted into sulfur trioxide under the effect of catalyst, and the furnace gas after conversion enters First Heat Exchanger cooling, stoveGas enters converter second segment beds and transforms after cooling, enters afterwards the second heat exchanger cooling,Furnace gas enters the 3rd section of beds of converter and transforms after cooling, enters afterwards the 3rd heat exchanger and fallsTemperature;
3) enter the first absorption tower through the furnace gas of the 3rd heat exchanger cooling, the sulfur trioxide in furnace gas is by tower topThe concentrated sulfuric acid of 98% weight of spray absorbs, and the concentrated sulfuric acid after absorption enters and absorbs tower acid circulating slot;
4) furnace gas after the first absorption tower absorbs enters the 5th, the 4th and the second heat exchanger heating successively,After furnace gas is heated, enter the 4th section of beds of converter and transform for the second time, the furnace gas after conversion entersEnter the 4th heat exchanger cooling, enter afterwards the 5th section of beds of converter and transform, the stove after conversionGas is lowered the temperature through the 5th heat exchanger;
5) enter second absorption tower through the furnace gas of the 5th heat exchanger cooling, the sulfur trioxide in furnace gas is by tower topThe concentrated sulfuric acid of 98% weight of spray absorbs, and the concentrated sulfuric acid after absorption enters step 3) described absorption tower acid followsAnnular groove, mixes with the concentrated sulfuric acid that enters circulating slot in the first absorption tower, adds water to absorbing in tower acid circulating slot,Regulate the concentration of sulfuric acid, squeeze into the first absorption tower and second absorption tower circulated sprinkling through cooling rear section sulfuric acid,For absorbing the sulfur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
The present invention adopts sulphur waste material and ferrous sulfate waste material to prepare sulfuric acid, and wherein, sulphur waste material is from syntheticThe sulfur waste sulphur reclaiming in ammonia, coke oven gas desulfurization process, wherein, the dried thick Sulfur from Sulphur of sulphur waste materialSulphur content is greater than 60% weight, and other Main Ingredients and Appearances are (NH4)2SO4(NH4) SCN, and the tar of trace,Benzene, naphthalene etc., also can adopt the sulfur containing waste material after power plant, aluminium manufacturer's desulfurization; Ferrous sulfate waste material is from titanium whiteThe Waste Sulfuric Acid ferrous iron that powder industry produces, wherein ferrous sulfate heptahydrate content is greater than 85% weight, and epsom salt is3-8% weight, and the Manganese sulfate pentahydrate of trace, 18 water aluminum sulfate, calcium sulphate dihydrate, titanyl sulfate etc.
The reaction equation the present invention relates to is as follows:
S+O2＝SO2，3(NH4)2SO4＝4NH3+N2+3SO2+6H2O
4NH4SCN+9O2＝4NH3+4SO2+2N2+4CO2+2H2O
4FeSO4·H2O+S＝2Fe2O3+5SO2+4H2O
2MgSO4·H2O+S→2MgO+3SO2+2H2O
Inventor finds after experimental study, although the present invention adopts two kinds of industrial wastes to prepare sulphur as raw materialAcid, but adopt sulphur waste material and ferrous sulfate waste material prepare sulfuric acid can't cause sulfuric acid product any unfavorableImpact. From above-mentioned reaction equation, after the present invention's reaction, in furnace gas, mainly contain sulfur dioxide, water, ammoniaGas, nitrogen, carbon dioxide etc., water, nitrogen, carbon dioxide there is no impact to sulfur dioxide acid making system,Ammonia can be removed by washing in the washing, purifying stage, can not produce follow-up sulfur dioxide relieving haperacidity workshop sectionImpact, in furnace bottom slag, the mixture such as di-iron trioxide is that iron fine powder can be for ironmaking, in slag, MgO existsIn ironmaking, can significantly improve the metallurgical performance of pellet, other impurity because of be the few silica of content,Alundum (Al2O3), sulphur etc., can not impact iron fine powder product, and in furnace bottom iron fine powder, iron content can reachMore than 65% weight.
Sulfur burning is exothermic reaction, discharges a large amount of heats, ferrous sulfate be decomposed into the endothermic reaction, needAbsorb heat, inventor, through great many of experiments, has selected sulphur and ferrous sulfate in dry rear sulphur waste materialThe rational proportion of ferrous sulfate monohydrate in waste material. Sulphur addition is too much, and the output of the iron fine powder of generation can subtractFew, the recuperation layer of fluidized bed furnace is reduced, cause fluidized bed furnace can not maintain enough heats and divide for ferrous sulfateSeparate, and then need to additionally expend the normal production that more outside heat can keep fluidized bed furnace; If sulphurSulphur addition is very few, and the heat that sulfur burning produces so can not meet ferrous sulfate and decompose required heat.The proportioning of the determined sulphur of method of the present invention and ferrous sulfate monohydrate, can make sulfur burning emitHeat is made full use of by ferrous sulfate, and this heat that not only makes sulfur burning discharge is farthest utilized,Significantly reduce energy consumption, and increased substantially the incorporation of sulphur waste material in ferrous sulfate decomposable process, makeMore sulphur waste material is utilized, and has reduced production cost.
Sulphur waste material of the present invention is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid, has following beneficial effect:
1, with the sulphur waste material that reclaims in synthetic ammonia, coke oven gas desulfurization process and the sulphur of titanium dioxide industry by-productThe ferrous waste residue of acid is raw material, greatly reduces the production cost of sulfuric acid, and is the comprehensive utilization of two kinds of industrial wastesWith new way is provided;
2, the present invention selected dry after ferrous sulfate monohydrate in sulphur and ferrous sulfate waste material in sulphur waste materialRational proportion, takes full advantage of the heat that sulfur burning discharges, and makes the heat of sulfur burning for ferrous sulfateDecomposition, energy-saving effect is remarkable;
3, the 98% industrial sulphuric acid product making by the method for the present invention Grade A that can be up to state standardsRequirement;
4, method of the present invention can byproduct iron fine powder, and can by-product low-pressure saturated steam;
5, the washing, purifying technique that the dry method dust adopting in the present invention and wet cleaning combine, can be by stoveDust content in gas is down to 0.5mg/m3Below, to prevent catalyst poisoning in follow-up conversion section;
6, double-absorption technique of the present invention is prepared sulfuric acid, has improved the conversion ratio of sulfur dioxide, turnsRate can reach more than 99.8%, and utilizes high-temperature furnace gas and low temperature furnace gas in conversion process to carry out heat exchange,Save the energy;
7, adopt method of the present invention, the rate of recovery of sulphur and iron all can reach more than 99%.
Detailed description of the invention
Embodiment 1
(1) dry
Sulphur foam and ferrous sulfate heptahydrate waste material are dried in drying system, make sulphur foam be dehydrated into powderGranular thick sulphur, obtains ferrous sulfate monohydrate compound after ferrous sulfate heptahydrate dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein dried thick Sulfur from Sulphur sulphur and sulphurIn acid ferrous iron, the weight ratio of ferrous sulfate monohydrate is 3: 7, mixed material is sent into boiling kiln roasting, roasting temperatureDegree is 1000 DEG C, passes into air, and gas speed is 1.8 meter per seconds, and the time of staying of mixed material in fluidized bed furnace is4 seconds, after roasting, in furnace gas, sulfur dioxide volumetric concentration was 11%.
(3) cooling
High-temperature furnace gas is passed into steam generator and carry out coolingly, furnace gas is cooled to 360 DEG C, simultaneously steam generatorThe low-pressure saturated steam that produces 1.2MPa is pressed.
(4) washing, purifying
Cooled furnace gas is passed into cyclone dust collectors and remove flue dust, after dedusting, furnace gas enters Venturi tube, at literary compositionShi Guan throat sprays into 10% weight dilute sulfuric acid, and dilute sulfuric acid obtains good atomization in Venturi tube, furnace gas and dilute sulfuric acidClose contact, makes furnace gas humidification, cools and further dedusting, completes preliminary washing, purifying; Furnace gas warpCross after Venturi tube washing, enter stuffing washing tower, with 10% weight dilute sulfuric acid counter current contacting of tower top spray, washWash purification, remove impurity and steam wherein; Enter electrostatic precipitator except disacidify through the furnace gas of scrubbing tower washingMist, flue gas cleaning completes, and in the rear furnace gas of purification, dust content is lower than 0.5mg/m3。
(5) transform and absorb
Transform absorption section and adopt double-absorption method, the equipment of employing comprises drying tower, the first absorption tower and theTwo absorption towers, be provided with the converter of five beds, first heat exchange corresponding with each bedsDevice, the second heat exchanger, the 3rd heat exchanger, the 4th heat exchanger and the 5th heat exchanger;
The double-absorption technique adopting comprises the steps:
A) furnace gas of auto purification workshop section supplements air in the future, and making sulfur dioxide volumetric concentration in furnace gas is 8.5%,Furnace gas is passed into drying tower bottom, the dry absorption of the concentrated sulfuric acid of 94% weight spraying through tower top, furnace gas after being driedMiddle moisture content≤0.1g/Nm3；
B) it is heated that furnace gas after drying enters the shell side of the 3rd heat exchanger, First Heat Exchanger successively, heatingThe temperature of rear furnace gas reaches 410 DEG C, and the first paragraph beds that enters converter transforms, by furnace gasSulfur dioxide under the effect of catalyst, be converted into sulfur trioxide, after transforming, furnace gas enters First Heat ExchangerTube side cooling, enters converter second segment beds and transforms after cooling, enter afterwards the second heat exchangeThe cooling of organ pipe journey, furnace gas enters the 3rd section of beds of converter and transforms after cooling, enters afterwardsThe 3rd heat exchanger tube pass cooling;
C) after the 3rd heat exchanger, furnace gas temperature is down to 165 DEG C, enters the first absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove;
D) furnace gas after the first absorption tower absorbs enters the 5th heat exchanger, the 4th heat exchanger and second successivelyThe shell side heating of heat exchanger, enters the 4th section of beds of converter after furnace gas is heated and turns for the second timeChange, after transforming, furnace gas enters the 4th heat exchanger tube pass cooling, enters the 5th section of converter after being cooled to 405 DEG C to urgeAgent bed transforms, and after transforming, furnace gas is lowered the temperature through the 5th heat exchanger tube pass;
E), after the 5th heat exchanger, the temperature of furnace gas is down to 160 DEG C and is entered second absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove, mixes with the sulfuric acid that enters circulating slot in the first absorption tower, adds water to absorbing in tower acid circulating slot,Regulate the concentration of sulfuric acid, squeeze into the first absorption tower and second absorption tower circulated sprinkling through cooling rear section sulfuric acid,For absorbing the sulfur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
In furnace gas, the conversion ratio of sulfur dioxide can reach 99.85%.
The sulfuric acid product making is 98% industrial sulphuric acid, and product quality is up to state standards in GB/T534-2002The index of Grade A, the industrial sulphuric acid performance indications that make are in table 1:
Table 1
| Project | Index |
| H2SO4 | ≥98％ |
| Ash content | ≤0.025％ |
| Fe | ≤0.008％ |
| As | ≤0.003％ |
| Transparency | ≥50mm |
| Colourity | ≤2.0ml |
| Hg | ≤0.009％ |
| Pb | ≤0.018％ |
In the present embodiment, the sulphur in industrial sulphur waste material and ferrous sulfate waste material and the rate of recovery of iron all reach 99%Above.
Embodiment 2
(1) dry
Sulphur foam and ferrous sulfate heptahydrate waste material are dried in drying system, make sulphur foam be dehydrated into powderGranular thick sulphur, obtains ferrous sulfate monohydrate compound after ferrous sulfate heptahydrate dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein dried thick Sulfur from Sulphur sulphur and sulphurIn acid ferrous iron, the weight ratio of ferrous sulfate monohydrate is 1: 1, mixed material is sent into boiling kiln roasting, roasting temperatureDegree is 850 DEG C, passes into air, and gas speed is 2 meter per seconds, and the time of staying of mixed material in fluidized bed furnace is 8Second, after roasting, in furnace gas, sulfur dioxide volumetric concentration is 12%.
(3) cooling
High-temperature furnace gas is passed into steam generator and carry out coolingly, furnace gas is cooled to 340 DEG C, simultaneously steam generatorThe low-pressure saturated steam that produces 1.25MPa is pressed.
(4) washing, purifying
Cooled furnace gas is passed into cyclone dust collectors and remove flue dust, after dedusting, furnace gas enters Venturi tube, at literary compositionShi Guan throat sprays into 20% weight dilute sulfuric acid, and dilute sulfuric acid obtains good atomization in Venturi tube, furnace gas and dilute sulfuric acidClose contact, makes furnace gas humidification, cools and further dedusting, completes preliminary washing, purifying; Furnace gas warpCross after Venturi tube washing, enter stuffing washing tower, with 20% weight dilute sulfuric acid counter current contacting of tower top spray, washWash purification, remove impurity and steam wherein; Enter electrostatic precipitator except disacidify through the furnace gas of scrubbing tower washingMist, flue gas cleaning completes, and in the rear furnace gas of purification, dust content is lower than 0.5mg/m3。
(5) transform and absorb
Transform absorption section and adopt double-absorption method, the equipment of employing comprises drying tower, the first absorption tower and theTwo absorption towers, be provided with the converter of five beds, first heat exchange corresponding with each bedsDevice, the second heat exchanger, the 3rd heat exchanger, the 4th heat exchanger and the 5th heat exchanger;
The double-absorption technique adopting comprises the steps:
A) furnace gas of auto purification workshop section supplements air in the future, and making sulfur dioxide volumetric concentration in furnace gas is 8.5%,Furnace gas is passed into drying tower bottom, the dry absorption of the concentrated sulfuric acid of 94% weight spraying through tower top, furnace gas after being driedMiddle moisture content≤0.1g/Nm3；
B) it is heated that furnace gas after drying enters the shell side of the 3rd heat exchanger, First Heat Exchanger successively, heatingThe temperature of rear furnace gas reaches 420 DEG C, and the first paragraph beds that enters converter transforms, by furnace gasSulfur dioxide under the effect of catalyst, be converted into sulfur trioxide, after transforming, furnace gas enters First Heat ExchangerTube side cooling, enters converter second segment beds and transforms after cooling, enter afterwards the second heat exchangeThe cooling of organ pipe journey, furnace gas enters the 3rd section of beds of converter and transforms after cooling, enters afterwardsThe 3rd heat exchanger tube pass cooling;
C) after the 3rd heat exchanger, furnace gas temperature is down to 170 DEG C, enters the first absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove;
D) furnace gas after the first absorption tower absorbs enters the 5th heat exchanger, the 4th heat exchanger and second successivelyThe shell side heating of heat exchanger, enters the 4th section of beds of converter after furnace gas is heated and turns for the second timeChange, after transforming, furnace gas enters the 4th heat exchanger tube pass cooling, enters the 5th section of converter after being cooled to 415 DEG C to urgeAgent bed transforms, and after transforming, furnace gas is lowered the temperature through the 5th heat exchanger tube pass;
E), after the 5th heat exchanger, the temperature of furnace gas is down to 165 DEG C and is entered second absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove, mixes with the sulfuric acid that enters circulating slot in the first absorption tower, adds water to absorbing in tower acid circulating slot,Regulate the concentration of sulfuric acid, squeeze into the first absorption tower and second absorption tower circulated sprinkling through cooling rear section sulfuric acid,For absorbing the sulfur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
In furnace gas, the conversion ratio of sulfur dioxide can reach 99.9%.
The sulfuric acid product making is 98% industrial sulphuric acid, and product quality is up to state standards in GB/T534-2002The index of Grade A, the industrial sulphuric acid performance indications that make are in table 2:
Table 2
| Project | Index |
| H2SO4 | ≥98％ |
| Ash content | ≤0.021％ |
| Fe | ≤0.009％ |
| As | ≤0.003％ |
| Transparency | ≥50mm |
| Colourity | ≤2.0ml |
| Hg | ≤0.008％ |
| Pb | ≤0.018％ |
In the present embodiment, the sulphur in industrial sulphur waste material and ferrous sulfate waste material and the rate of recovery of iron all reach 99%Above.
Embodiment 3
(1) dry
Sulphur foam and ferrous sulfate heptahydrate waste material are dried in drying system, make sulphur foam be dehydrated into powderGranular thick sulphur, obtains ferrous sulfate monohydrate compound after ferrous sulfate heptahydrate dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein dried thick Sulfur from Sulphur sulphur and sulphurIn acid ferrous iron, the weight ratio of ferrous sulfate monohydrate is 7: 3, mixed material is sent into boiling kiln roasting, roasting temperatureDegree is 900 DEG C, passes into air, and gas speed is 1.0 meter per seconds, and the time of staying of mixed material in fluidized bed furnace is16 seconds, after roasting, in furnace gas, sulfur dioxide volumetric concentration was 9%.
(3) cooling
High-temperature furnace gas is passed into steam generator and carry out coolingly, furnace gas is cooled to 320 DEG C, simultaneously steam generatorThe low-pressure saturated steam that produces 1.3MPa is pressed.
(4) washing, purifying
Cooled furnace gas is passed into cyclone dust collectors and remove flue dust, after dedusting, furnace gas enters Venturi tube, at literary compositionShi Guan throat sprays into 40% weight dilute sulfuric acid, and dilute sulfuric acid obtains good atomization in Venturi tube, furnace gas and dilute sulfuric acidClose contact, makes furnace gas humidification, cools and further dedusting, completes preliminary washing, purifying; Furnace gas warpCross after Venturi tube washing, enter stuffing washing tower, with 40% weight dilute sulfuric acid counter current contacting of tower top spray, washWash purification, remove impurity and steam wherein; Enter electrostatic precipitator except disacidify through the furnace gas of scrubbing tower washingMist, flue gas cleaning completes, and in the rear furnace gas of purification, dust content is lower than 0.5mg/m3。
(5) transform and absorb
Transform absorption section and adopt double-absorption method, the equipment of employing comprises drying tower, the first absorption tower and theTwo absorption towers, be provided with the converter of five beds, first heat exchange corresponding with each bedsDevice, the second heat exchanger, the 3rd heat exchanger, the 4th heat exchanger and the 5th heat exchanger;
The double-absorption technique adopting comprises the steps:
A) furnace gas of auto purification workshop section supplements air in the future, and making sulfur dioxide volumetric concentration in furnace gas is 8%, willFurnace gas passes into bottom drying tower, and the concentrated sulfuric acid of 94% weight spraying through tower top is dry to be absorbed, in dry rear furnace gasMoisture content≤0.1g/Nm3；
B) it is heated that furnace gas after drying enters the shell side of the 3rd heat exchanger, First Heat Exchanger successively, heatingThe temperature of rear furnace gas reaches 430 DEG C, and the first paragraph beds that enters converter transforms, by furnace gasSulfur dioxide under the effect of catalyst, be converted into sulfur trioxide, after transforming, furnace gas enters First Heat ExchangerTube side cooling, enters converter second segment beds and transforms after cooling, enter afterwards the second heat exchangeThe cooling of organ pipe journey, furnace gas enters the 3rd section of beds of converter and transforms after cooling, enters afterwardsThe 3rd heat exchanger tube pass cooling;
C) after the 3rd heat exchanger, furnace gas temperature is down to 175 DEG C, enters the first absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove;
D) furnace gas after the first absorption tower absorbs enters the 5th heat exchanger, the 4th heat exchanger and second successivelyThe shell side heating of heat exchanger, enters the 4th section of beds of converter after furnace gas is heated and turns for the second timeChange, after transforming, furnace gas enters the 4th heat exchanger tube pass cooling, enters the 5th section of converter after being cooled to 422 DEG C to urgeAgent bed transforms, and after transforming, furnace gas is lowered the temperature through the 5th heat exchanger tube pass;
E), after the 5th heat exchanger, the temperature of furnace gas is down to 168 DEG C and is entered second absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove, mixes with the sulfuric acid that enters circulating slot in the first absorption tower, adds water to absorbing in tower acid circulating slot,Regulate the concentration of sulfuric acid, squeeze into the first absorption tower and second absorption tower circulated sprinkling through cooling rear section sulfuric acid,For absorbing the sulfur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
In furnace gas, the conversion ratio of sulfur dioxide can reach 99.88%.
The sulfuric acid product making is 98% industrial sulphuric acid, and product quality is up to state standards in GB/T534-2002The index of Grade A, the industrial sulphuric acid performance indications that make are in table 3:
Table 3
| Project | Index |
| H2SO4 | ≥98％ |
| Ash content | ≤0.024％ |
| Fe | ≤0.009％ |
| As | ≤0.004％ |
| Transparency | ≥50mm |
| Colourity | ≤2.0ml |
| Hg | ≤0.009％ |
| Pb | ≤0.019％ |
In the present embodiment, the sulphur in industrial sulphur waste material and ferrous sulfate waste material and the rate of recovery of iron all reach 99%Above.
Embodiment 4
(1) dry
Sulphur foam and ferrous sulfate heptahydrate waste material are dried in drying system, make sulphur foam be dehydrated into powderGranular thick sulphur, obtains ferrous sulfate monohydrate compound after ferrous sulfate heptahydrate dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein dried thick Sulfur from Sulphur sulphur and sulphurIn acid ferrous iron, the weight ratio of ferrous sulfate monohydrate is 5: 3, mixed material is sent into boiling kiln roasting, roasting temperatureDegree is 950 DEG C, passes into air, and gas speed is 1.2 meter per seconds, and the time of staying of mixed material in fluidized bed furnace is10 seconds, after roasting, in furnace gas, sulfur dioxide volumetric concentration was 12%.
(3) cooling
High-temperature furnace gas is passed into steam generator and carry out coolingly, furnace gas is cooled to 340 DEG C, simultaneously steam generatorThe low-pressure saturated steam that produces 1.25MPa is pressed.
(4) washing, purifying
Cooled furnace gas is passed into cyclone dust collectors and remove flue dust, after dedusting, furnace gas enters Venturi tube, at literary compositionShi Guan throat sprays into 25% weight dilute sulfuric acid, and dilute sulfuric acid obtains good atomization in Venturi tube, furnace gas and dilute sulfuric acidClose contact, makes furnace gas humidification, cools and further dedusting, completes preliminary washing, purifying; Furnace gas warpCross after Venturi tube washing, enter stuffing washing tower, with 25% weight dilute sulfuric acid counter current contacting of tower top spray, washWash purification, remove impurity and steam wherein; Enter electrostatic precipitator except disacidify through the furnace gas of scrubbing tower washingMist, flue gas cleaning completes, and in the rear furnace gas of purification, dust content is lower than 0.5mg/m3。
(5) transform and absorb
Transform absorption section and adopt double-absorption method, the equipment of employing comprises drying tower, the first absorption tower and theTwo absorption towers, be provided with the converter of five beds, first heat exchange corresponding with each bedsDevice, the second heat exchanger, the 3rd heat exchanger, the 4th heat exchanger and the 5th heat exchanger;
The double-absorption technique adopting comprises the steps:
A) furnace gas of auto purification workshop section supplements air in the future, and making sulfur dioxide volumetric concentration in furnace gas is 8.5%,Furnace gas is passed into drying tower bottom, the dry absorption of the concentrated sulfuric acid of 94% weight spraying through tower top, furnace gas after being driedMiddle moisture content≤0.1g/Nm3；
B) it is heated that furnace gas after drying enters the shell side of the 3rd heat exchanger, First Heat Exchanger successively, heatingThe temperature of rear furnace gas reaches 420 DEG C, and the first paragraph beds that enters converter transforms, by furnace gasSulfur dioxide under the effect of catalyst, be converted into sulfur trioxide, after transforming, furnace gas enters First Heat ExchangerTube side cooling, enters converter second segment beds and transforms after cooling, enter afterwards the second heat exchangeThe cooling of organ pipe journey, furnace gas enters the 3rd section of beds of converter and transforms after cooling, enters afterwardsThe 3rd heat exchanger tube pass cooling;
C) after the 3rd heat exchanger, furnace gas temperature is down to 170 DEG C, enters the first absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove;
D) furnace gas after the first absorption tower absorbs enters the 5th heat exchanger, the 4th heat exchanger and second successivelyThe shell side heating of heat exchanger, enters the 4th section of beds of converter after furnace gas is heated and turns for the second timeChange, after transforming, furnace gas enters the 4th heat exchanger tube pass cooling, enters the 5th section of converter after being cooled to 415 DEG C to urgeAgent bed transforms, and after transforming, furnace gas is lowered the temperature through the 5th heat exchanger tube pass;
E), after the 5th heat exchanger, the temperature of furnace gas is down to 165 DEG C and is entered second absorption tower, in furnace gasThe concentrated sulfuric acid of 98% weight that sulfur trioxide is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters absorption tower acid and followsAnnular groove, mixes with the sulfuric acid that enters circulating slot in the first absorption tower, adds water to absorbing in tower acid circulating slot,Regulate the concentration of sulfuric acid, squeeze into the first absorption tower and second absorption tower circulated sprinkling through cooling rear section sulfuric acid,For absorbing the sulfur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
In furnace gas, the conversion ratio of sulfur dioxide can reach 99.9%.
The sulfuric acid product making is 98% industrial sulphuric acid, and product quality is up to state standards in GB/T534-2002The index of Grade A, the industrial sulphuric acid performance indications that make are in table 4:
Table 4
| Project | Index |
| H2SO1 | ≥98％ |
| Ash content | ≤0.022％ |
| Fe | ≤0.008％ |
| As | ≤0.004％ |
| Transparency | ≥50mm |
| Colourity | ≤2.0ml |
| Hg | ≤0.009％ |
| Pb | ≤0.018％ |
In the present embodiment, the sulphur in industrial sulphur waste material and ferrous sulfate waste material and the rate of recovery of iron all reach 99%Above.
Comparative example 1
Be contrast experiment with the process conditions in embodiment 1, difference is dry rear thick Sulfur from Sulphur sulphurWith the weight ratio of ferrous sulfate monohydrate in ferrous sulfate waste material be 1: 7, compare boiling roaster with embodiment 1Need to expend fuel approximately 35% more.
Comparative example 2
Be contrast experiment with the process conditions in embodiment 1, difference is dry rear thick Sulfur from Sulphur sulphurWith the weight ratio of ferrous sulfate monohydrate in ferrous sulfate waste material be 2: 7, compare boiling roaster with embodiment 1Need to expend fuel approximately 23% more.
Comparative example 3
Be contrast experiment with the process conditions in embodiment 3, difference is dry rear thick Sulfur from Sulphur sulphurWith the weight ratio of ferrous sulfate monohydrate in ferrous sulfate waste material be 7: 1, compare boiling roaster with embodiment 3Need to expend fuel approximately 26% more.
Comparative example 4
Be contrast experiment with the process conditions in embodiment 3, difference is dry rear thick Sulfur from Sulphur sulphurWith the weight ratio of ferrous sulfate monohydrate in ferrous sulfate waste material be 7: 2, compare boiling roaster with embodiment 3Need to expend fuel approximately 20% more.
Comparative example 5
Be contrast experiment with the process conditions in embodiment 2, it is dry that difference is that purification section only adoptsMethod dedusting, without follow-up wet scrubbing cleaning procedure, after purification section, in furnace gas, dust content is 92mg/m3, converter middle part divided catalyst is poisoning, and Sulphur Dioxide rate is 83%.
Comparative example 6
Be contrast experiment with the process conditions in embodiment 2, difference is not adopt in purification section literary compositionFamily name's pipe tentatively washs, and directly enters scrubbing tower washing, warp at furnace gas after cyclone dust collectors dry method dustCrossing after purification section dust content in furnace gas is 15mg/m3, the conversion ratio of sulfur dioxide is 95%.
Claims (10)
1. sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid, and the method comprises the steps:
A) by dry to sulphur waste material and ferrous sulfate waste material, make sulphur waste material be dehydrated into the thick sulphur of granular, after the dehydration of ferrous sulfate waste material, obtain ferrous sulfate monohydrate compound;
B) dried sulphur waste material and ferrous sulfate waste material are mixed, wherein, in sulphur waste material, in sulphur and ferrous sulfate waste material, the weight ratio of ferrous sulfate monohydrate is 3: 7～7: 3;
C) by step, the mixed material in b) adds boiling kiln roasting, sintering temperature is 850-1000 DEG C, passes into air, and gas speed is 1.0-2.0 meter per second, the time of staying of mixed material in fluidized bed furnace is 4-16 second, and after roasting, in furnace gas, sulfur dioxide volumetric concentration is 9-12%;
D) furnace gas that step is contained to sulfur dioxide in c) makes sulfuric acid through supercooling, washing, purifying, conversion absorption section.
The method of claim 1, wherein described step b) in, in dried sulphur waste material, in sulphur and ferrous sulfate waste material, the weight ratio of ferrous sulfate monohydrate is 3: 3～7: 3.
The method of claim 1, wherein described step c) in after roasting in furnace gas sulfur dioxide volumetric concentration be 12%.
4. the method for claim 1, wherein, described steps d) in, the furnace gas that contains sulfur dioxide is undertaken cooling by steam generator, furnace gas is cooled to 320 DEG C-360 DEG C and enters purification section, and described steam generator produces the low-pressure saturated steam of 1.2-1.3MPa.
5. the method for claim 1, wherein described steps d) in, described furnace gas washing, purifying workshop section comprises the following steps:
1) cooled furnace gas is removed flue dust by cyclone dust collectors;
2) furnace gas after dedusting enters Venturi tube, sprays into the dilute sulfuric acid of 10-40% weight in described venturi throat, completes preliminary washing, purifying;
3) furnace gas, after the washing of described Venturi tube, enters stuffing washing tower, with the dilute sulfuric acid counter current contacting of the 10-40% weight of tower top spray, removes impurity and steam wherein, and flue gas cleaning completes, after purifying in furnace gas dust content lower than 0.5mg/m3。
6. method as claimed in claim 5, wherein, described flue gas cleaning workshop section also comprises step 4), by step 3) in send into electrostatic precipitator through the furnace gas of scrubbing tower washing and remove acid mist.
7. the method as described in claim 1 or 5, wherein, described steps d) in, described conversion absorption section adopts double-absorption method, the equipment adopting comprises drying tower, the first absorption tower and second absorption tower, is provided with the converter of five beds, be provided with First Heat Exchanger, second heat exchanger, three heat exchanger, four heat exchanger and five heat exchanger corresponding to each beds;
Described double-absorption method comprises the steps:
1) furnace gas from washing, purifying workshop section is supplemented to air, making sulfur dioxide volumetric concentration in furnace gas is 8-8.5%, and furnace gas is passed into drying tower bottom, the dry absorption of the concentrated sulfuric acid of 94% weight spraying through tower top;
2) furnace gas is after drying successively through the 3rd heat exchanger, First Heat Exchanger heating, the first paragraph beds that furnace gas after heating enters converter transforms, furnace gas after conversion enters First Heat Exchanger cooling, furnace gas enters converter second segment beds and transforms after cooling, enter afterwards the second heat exchanger cooling, furnace gas enters the 3rd section of beds of converter and transforms after cooling, enters afterwards the 3rd heat exchanger cooling;
3) enter the first absorption tower through the furnace gas of the 3rd heat exchanger cooling, the concentrated sulfuric acid of 98% weight that the sulfur trioxide in furnace gas is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters and absorbs tower acid circulating slot;
4) furnace gas after the first absorption tower absorbs enters the 5th, the 4th and the second heat exchanger heating successively, after furnace gas is heated, entering the 4th section of beds of converter transforms for the second time, furnace gas after conversion enters the 4th heat exchanger cooling, enter afterwards the 5th section of beds of converter and transform, the furnace gas after conversion is lowered the temperature through the 5th heat exchanger;
5) enter second absorption tower through the furnace gas of the 5th heat exchanger cooling, the concentrated sulfuric acid of 98% weight that the sulfur trioxide in furnace gas is sprayed by tower top absorbs, and the concentrated sulfuric acid after absorption enters step 3) described absorption tower acid circulating slot.
8. method as claimed in claim 7, wherein, described step 1) in, moisture content≤0.1g/Nm in furnace gas after drying3。
9. method as claimed in claim 7, wherein, described step 2) in through the 3rd and the First Heat Exchanger heating furnace gas temperature that enters converter the first beds be 410-430 DEG C.
10. the method for claim 1, wherein the sulphur waste material of described step in a) is the sulfur containing waste material after synthetic ammonia, coke-stove gas, power plant, aluminium manufacturer's desulfurization.
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| CN103553143B (en) * | 2013-11-08 | 2015-11-18 | 四川大学 | The vitriol of sulphur reduction decomposition iron prepares the method for coproduction of iron oxide red sulfuric acid |
| CN105293448B (en) * | 2015-10-23 | 2018-01-30 | 湖北祥云(集团)化工股份有限公司 | A kind of method of Recovered sulphur slag and pyrite-based sulfuric acid production |
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