CN100562490C - A kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate - Google Patents
A kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate Download PDFInfo
- Publication number
- CN100562490C CN100562490C CNB2006101638640A CN200610163864A CN100562490C CN 100562490 C CN100562490 C CN 100562490C CN B2006101638640 A CNB2006101638640 A CN B2006101638640A CN 200610163864 A CN200610163864 A CN 200610163864A CN 100562490 C CN100562490 C CN 100562490C
- Authority
- CN
- China
- Prior art keywords
- flue gas
- ferrous
- ferrous sulfate
- sulfuric acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 100
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 77
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 59
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 49
- 239000012141 concentrate Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title 1
- 239000003546 flue gas Substances 0.000 claims abstract description 70
- 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 claims abstract description 69
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002253 acid Substances 0.000 claims abstract description 52
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 51
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 25
- 238000005516 engineering process Methods 0.000 claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000428 dust Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 19
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003595 mist Substances 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000001276 controlling effect Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 239000002265 redox agent Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 30
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 23
- 239000006227 byproduct Substances 0.000 abstract description 16
- 239000005864 Sulphur Substances 0.000 abstract description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004408 titanium dioxide Substances 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 3
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate.It is ferrous that technical scheme of the present invention is that the titanium white by product iron vitriol gets anhydrous slufuric acid through thermal dehydration, this anhydrous slufuric acid is ferrous 700 ℃～1000 ℃ of rotary kiln indirect heating, under reducing atmosphere, divide and solve iron ore concentrate and sulfur dioxide gas, the double conversion and double absorption technology system sulfuric acid of sulfur dioxide gas body and function routine.Anhydrous slufuric acid solves iron ore concentrate and sulfur trioxide gas and a spot of sulfur dioxide gas ferrous the branch under oxidizing atmosphere, flue gas is after purifying, absorb sulphur trioxide with the vitriol oil earlier and generate oleum, one of remaining sulfur dioxide gas body and function routine is changeed one and is inhaled technology system sulfuric acid.Method of the present invention is utilized sulphur and the iron resources in the titanium white by product ferrous sulfate simultaneously, be suitable for large-scale production, products obtained therefrom sulfuric acid can return in the Producing Titanium Dioxide flow process and use, and has realized the resource circulation utilization, has eliminated the environmental pollution of ferrous sulfate.
Description
Technical field:
The present invention relates to a kind of method of producing sulfuric acid and iron ore concentrate, belong to the chemical industry metallurgical technical field with ferrous sulfate.
Background technology:
In recent years, the annual production of China's titanium white powder has reached 800,000 tons, and wherein the overwhelming majority is to adopt Production By Sulfuric Acid Process, and 1 ton of titanium dioxide of the every production of sulfuric acid process can produce 3.5～4.0 tons of iron vitriols, by this estimation, about 3,000,000 tons of the titanium white by product ferrous sulfate in China every year.Ferrous sulfate is soluble in water, stack difficulty, the dissolving back flows into rivers and lakes, causes serious environmental to pollute, in addition, ferrous sulfate is again the resource of sulfur-bearing and iron, causes the wasting of resources after the loss, so, ferrous sulfate utilization in large-scale, high-efficiency, to reducing environmental pollution, it is all significant to improve resource utilization, environmental benefit and remarkable in economical benefits.
The method of the titanium white by product ferrous sulfate utilization of resources mainly contains following several:
1, utilize the titanium white by product ferrous sulfate to produce iron oxide pigment
This method has only been utilized the iron resources in the ferrous sulfate, and higher to equipment requirements, power consumption is bigger, and equipment corrosion is serious, and the variation of material composition and character, processing parameter has a strong impact on quality product.
2, utilize the titanium white by product ferrous sulfate to prepare vitriolate of tartar
This method has only been utilized the sulphur resource in the ferrous sulfate, and other raw material that needs is many, and complex process is difficult to realize the large-scale industrialization application.
3, utilize the titanium white by product ferrous sulfate to prepare bodied ferric sulfate
Because ferrous sulfate is limited as water purification agent raw material consumption, is difficult to consume a large amount of ferrous sulfate of titanium white by product, can not thoroughly solve the problem of environmental pollution of titanium white by product ferrous sulfate.
4, utilize the titanium white by product ferrous sulfate to prepare the food grade iron lactate
Because byproduct ferrous sulfate detrimental impurity content height, the iron lactate that makes is difficult to reach the food grade quality standard, and the sulphur resource in the ferrous sulfate is not utilized effectively, so application seldom.
Ferrous sulfate is added in the sulfurous iron ore, the thermolysis ferrous sulfate that produces during the sulfurous iron ore burning, the sulfurous gas of generation is used to make sulfuric acid.In this method, the burning amount of mixing of ferrous sulfate generally about 20%, can reach 40% to 50% abroad, but the adding of ferrous sulfate make fluidizing furnace Control for Kiln Temperature difficulty strengthen, and the sulfate slag ferrous grade is still low, be difficult to satisfy the requirement of ironmaking, at present domesticly use seldom.
Summary of the invention:
The present invention has overcome deficiency and the shortcoming that existing ferrous sulfate utilizes method and technology, provide a kind of and can utilize iron and sulphur resource in the ferrous sulfate simultaneously, can realize scale operation, all consume the titanium white by product ferrous sulfate, iron ore concentrate that the production market demand is huge and sulfuric acid are thoroughly eliminated the method for ferrous sulfate to the disadvantageous effect of environment.
The present invention includes following steps:
1, iron vitriol drying and dehydrating
Iron vitriol adds in indirect heating rotary kiln or direct heating rotary kiln or the continuous frying pan, the temperature that keeps dry is at 250 ℃～350 ℃, seven crystal water are deviate from, by regulating drying temperature and controlling total moisture 0.1%～2% time of drying, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
2, anhydrous slufuric acid ferrous in redox condition thermal degradation system iron ore concentrate
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add redox agent air or C or CO in the rotary kiln simultaneously, the indirect heating temperature is controlled at 700 ℃～1000 ℃, it is 97%～99.9% that period makes the ferrous sulfate rate of decomposition, the add-on of controlled oxidation reductive agent, make in the gaseous product of ferrous sulfate decomposition, the mass ratio of sulphur trioxide and sulfurous gas is K, the rotary kiln flue gas accelerates to 7～20 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 275 ℃～500 ℃, and through 1～3 electric precipitation, the gained dust contained flue gas is controlled at 0.2～0.01g/m again
3, be used for contact process; Decompose solid product and gather dust merge the iron ore concentrate of sulfur-bearing 0.5%～0.01%.
3, the ferrous decomposition flue gas of anhydrous slufuric acid contact process
Route one: anhydrous slufuric acid ferrous oxidation atmosphere is decomposed flue gas changes two suction technology system sulfuric acid through one
When the redox agent that adds in the rotary kiln was air, the add-on of control air made that the mass ratio K of sulphur trioxide and sulfurous gas is 8～100 in the flue gas.Dust-laden 0.2～0.01g/m
3Ferrous sulfate decompose flue gas when water cooler is cooled to 275 ℃～100 ℃, water vapor and sulphur trioxide formation acid mist, the micronic dust that does not eliminate simultaneously also enters in the acid mist drop, by electric separator acid mist is removed.Flue gas through electric separator is cooled to 100 ℃～30 ℃, and the sulfuric acid with 98%～99.5% absorbs sulphur trioxide in the absorption tower, control vitriolic add-on, and making specific absorption is 95%～99.9%, obtains oleum.Flue gas enters a conventional commentaries on classics one suction technology sulfurous gas is wherein made oleum through after once absorbing.
Route two: the ferrous reducing atmosphere of anhydrous slufuric acid decomposes flue gas through double conversion and double absorption technology system sulfuric acid
When the redox agent that adds in the rotary kiln was C or CO, the add-on of control C or CO made that the mass ratio K of sulphur trioxide and sulfurous gas is 0.1～0.01 in the flue gas, dust-laden 0.2～0.01g/m
3Ferrous sulfate decompose flue gas, produce oleum with the double conversion and double absorption technology of routine.
Chemical equation of the present invention is:
1, iron vitriol drying and dehydrating
FeSO
47H
2O (heating 90 ℃)---FeSO
4H
2O+6H
2O
FeSO
47H
2O (heating 250 ℃～350 ℃)---FeSO
4+ 7H
2O
2, ferrous system iron ore concentrate and the SO of in oxidizing atmosphere, decomposing of anhydrous slufuric acid
3Flue gas
4FeSO
4+ O
2(heating 700 ℃～1000 ℃)---2Fe
2O
3+ 4SO
3
3, ferrous system iron ore concentrate and the SO of in reducing atmosphere, decomposing of anhydrous slufuric acid
2Flue gas
2FeSO
4+ C (heating 700 ℃～1000 ℃)---Fe
2O
3+ 2SO
2+ CO
2FeSO
4+ CO (heating 700 ℃～1000 ℃)---Fe
2O
3+ 2SO
2+ CO
2
Sulphur Dioxide becomes sulphur trioxide:
4, the vitriol oil absorbs sulphur trioxide system sulfuric acid
SO
3+ H
2SO
4(98%～99.5%)---H
2SO
4SO
3(oleum)
H
2SO
4SO
3(oleum)+H
2O---2H
2SO
4
Beneficial effect of the present invention is:
1, sulphur in the ferrous sulfate and iron resources are utilized simultaneously, and the iron ore concentrate iron content that obtains is 60%～69%, and sulfur-bearing is 0.5%～0.01%, and the rate of recovery of iron is 98%～99%, and the sulfuric acid that obtains is oleum, and the rate of recovery of sulphur is 95%～99%;
2, this technology is fit to the large-scale production of son, can all handle the ferrous sulfate of titanium white by product, and products obtained therefrom is very big iron-smelting raw material of market demand and industrial chemicals;
3, sulfate process titanium dioxide production needs a large amount of sulfuric acid as raw material, and this technology can be returned with the sulfuric acid of the ferrous sulfate production of titanium white by product and uses in the Producing Titanium Dioxide flow process, has realized the resource circulation utilization.
4, the high-temperature tail gas of indirect heating can be used to concentrate the lower concentration sulfur waste acid of titanium white by product, the oleum that obtains in the sulfur process can with concentrate the dilute sulphuric acid that obtains and mix and obtain 98% sulfuric acid;
5, the ferrous sulfate of titanium white by product and sulfur waste acid are the two big refuses that sulfate process titanium dioxide is produced, cause serious environmental to be polluted owing to efflux, so sulfate process titanium dioxide production is restricted, technology of the present invention is when realizing the efficient utilization of ferrous sulfate, high-temperature tail gas and oleum concentrate the condition that provides for spent acid again, can solve two big cyclic utilization of waste problem, environmental benefit and remarkable in economical benefits in the sulfate process titanium dioxide simultaneously.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Embodiment:
Embodiment one:
Iron vitriol contains FeSO
47H
2O 97%, MgSO
47H
2O 1.4%, water-insoluble 1.1%, and other is 0.5% years old.
This iron vitriol adds in the indirect heating rotary kiln, the temperature that keeps dry deviates from seven crystal water at 300 ℃, is 1% by regulating drying temperature and controlling total moisture time of drying, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add CO in the rotary kiln simultaneously, the indirect heating temperature is controlled at 950 ℃, it is 99.0% that period makes the ferrous sulfate rate of decomposition, the add-on of control CO, make in the gaseous product of ferrous sulfate decomposition, the mass ratio K of sulphur trioxide and sulfurous gas is 0.05, the rotary kiln flue gas accelerates to 15 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 300 ℃, and through 2 electric precipitations, the gained dust contained flue gas is controlled at 0.1g/m again
3, produce oleum with conventional double conversion and double absorption technology, oleum mix with diluted acid 98% sulfuric acid, decompose solid product with gather dust merge the iron ore concentrate of sulfur-bearing 0.35%.
The key technical indexes:
Iron ore concentrate ferrous grade 69%;
The rate of recovery 99.0% of iron in the iron ore concentrate;
Sulfuric acid concentration 98%;
The rate of recovery 99.0% of sulphur.
Embodiment two:
Iron vitriol contains FeSO
47H
2O 96%, MgSO
47H
2O 1.4%, water-insoluble 1.1%, and other is 1.5% years old.
This iron vitriol adds in the direct heating rotary kiln, the temperature that keeps dry deviates from seven crystal water at 350 ℃, is 1% by regulating drying temperature and controlling total moisture time of drying, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add C in the rotary kiln simultaneously, the indirect heating temperature is controlled at 1000 ℃, it is 99.9% that period makes the ferrous sulfate rate of decomposition, the add-on of control C, make in the gaseous product of ferrous sulfate decomposition, the mass ratio K of sulphur trioxide and sulfurous gas is 0.01, the rotary kiln flue gas accelerates to 20 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 500 ℃, and through 3 electric precipitations, the gained dust contained flue gas is controlled at 0.01g/m again
3, produce oleum with conventional double conversion and double absorption technology, oleum mix with diluted acid 98% sulfuric acid, decompose solid product with gather dust merge the iron ore concentrate of sulfur-bearing 0.01%.
The key technical indexes:
Iron ore concentrate ferrous grade 67%;
The rate of recovery 98.5% of iron in the iron ore concentrate;
Sulfuric acid concentration 98%;
The rate of recovery 99.0% of sulphur.
Embodiment three:
Iron vitriol contains FeSO
47H
2O 94%, MgSO
47H
2O 2.4%, water-insoluble 2.1%, and other is 1.5% years old.
This iron vitriol adds in the continuous frying pan, and the temperature that keeps dry deviates from seven crystal water at 250 ℃, is 2% by regulating drying temperature and controlling total moisture time of drying, and flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add C in the rotary kiln simultaneously, the indirect heating temperature is controlled at 700 ℃, and it is 97% that the period makes the ferrous sulfate rate of decomposition, the add-on of control C, make in the gaseous product of ferrous sulfate decomposition, the mass ratio K of sulphur trioxide and sulfurous gas is 0.1, and the rotary kiln flue gas accelerates to 7 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 275 ℃, and through 1 electric precipitation, the gained dust contained flue gas is controlled at 0.2g/m again
3, produce oleum with conventional double conversion and double absorption technology, oleum mix with diluted acid 98% sulfuric acid, decompose solid product with gather dust merge the iron ore concentrate of sulfur-bearing 0.5%.
The key technical indexes:
Iron ore concentrate ferrous grade 63%;
The rate of recovery 98% of iron in the iron ore concentrate;
Sulfuric acid concentration 98%;
The rate of recovery 95% of sulphur.
Embodiment four:
Iron vitriol contains FeSO
47H
2O 92%, MgSO
47H
2O 4.6%, water-insoluble 1.4%, and other is 2.0% years old.
This iron vitriol adds in the continuous frying pan of indirect heating, the temperature that keeps dry deviates from seven crystal water at 250 ℃, by regulating drying temperature and controlling total moisture 2% time of drying, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add air in the rotary kiln simultaneously, the indirect heating temperature is controlled at 700 ℃, and the period makes ferrous sulfate rate of decomposition 97%, the add-on of control air, make in the gaseous product of ferrous sulfate decomposition, the mass ratio K of sulphur trioxide and sulfurous gas is 8, and the rotary kiln flue gas accelerates to 7 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 275 ℃, and through 1 electric precipitation, the gained dust contained flue gas is controlled at 0.2g/m again
3, be used to make sulfuric acid, decompose solid product and gather dust merge the iron ore concentrate of sulfur-bearing 0.5%.
Dust-laden 0.2g/m
3Ferrous sulfate when decomposing flue gas cool-down to 100 ℃, water vapor and sulphur trioxide formation acid mist, the micronic dust that does not eliminate simultaneously also enters in the acid mist drop, by electric separator acid mist is removed.Flue gas through electric separator is cooled to 30 ℃, and the sulfuric acid with 99.5% absorbs sulphur trioxide in the absorption tower, control vitriolic add-on, and making specific absorption is 99.9%, obtains oleum.Flue gas is through after once absorbing, and entering conventional one changes one and inhale technology sulfurous gas is wherein made oleum, oleum mix with diluted acid 98% sulfuric acid.
The key technical indexes:
Iron ore concentrate ferrous grade 64%;
The rate of recovery 98% of iron in the iron ore concentrate;
Sulfuric acid concentration 98%;
The rate of recovery 96% of sulphur.
Embodiment five:
Iron vitriol contains FeSO
47H
2O 90%, MgSO
47H
2O 5.7%, water-insoluble 1.6%, and other is 2.7% years old.
Iron vitriol adds in the direct heating rotary kiln, the temperature that keeps dry deviates from seven crystal water at 350 ℃, by regulating drying temperature and controlling total moisture 0.1% time of drying, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add air in the rotary kiln simultaneously, the indirect heating temperature is controlled at 1000 ℃, it is 99.9% that period makes the ferrous sulfate rate of decomposition, the add-on of control air, make in the gaseous product of ferrous sulfate decomposition, the mass ratio K of sulphur trioxide and sulfurous gas is 100, the rotary kiln flue gas accelerates to 20 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 500 ℃, and through 3 electric precipitations, the gained dust contained flue gas is controlled at 0.01g/m again
3, be used to make sulfuric acid, decompose solid product and gather dust merge the iron ore concentrate of sulfur-bearing 0.01%.
Dust-laden 0.01g/m
3Ferrous sulfate when decomposing flue gas cool-down to 275 ℃, water vapor and sulphur trioxide formation acid mist, the micronic dust that does not eliminate simultaneously also enters in the acid mist drop, by electric separator acid mist is removed.Flue gas through electric separator is cooled to 100 ℃, and the sulfuric acid with 98% absorbs sulphur trioxide in the absorption tower, control vitriolic add-on, and making specific absorption is 95%, obtains oleum.Flue gas is through after once absorbing, and entering conventional one changes one and inhale technology sulfurous gas is wherein made oleum, oleum mix with diluted acid 98% sulfuric acid.
The key technical indexes:
Iron ore concentrate ferrous grade 61%;
The rate of recovery 98% of iron in the iron ore concentrate;
Sulfuric acid concentration 98%;
The rate of recovery of sulphur 〉=99%.
Embodiment six:
Iron vitriol contains FeSO
47H
2O 89%, MgSO
47H
2O 5.7%, water-insoluble 1.6%, and other is 3.7% years old.
Iron vitriol adds in the indirect heating rotary kiln, the temperature that keeps dry deviates from seven crystal water at 300 ℃, by regulating drying temperature and controlling total moisture 0.5% time of drying, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous.
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add air in the rotary kiln simultaneously, the indirect heating temperature is controlled at 850 ℃, it is 99% that period makes the ferrous sulfate rate of decomposition, the add-on of control air, make in the gaseous product of ferrous sulfate decomposition, the mass ratio K of sulphur trioxide and sulfurous gas is 20, the rotary kiln flue gas accelerates to 10 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 400 ℃, and through 2 electric precipitations, the gained dust contained flue gas is controlled at 0.04g/m again
3, be used to make sulfuric acid, decompose solid product and gather dust merge the iron ore concentrate of sulfur-bearing 0.2%.
Dust-laden 0.04g/m
3Ferrous sulfate when decomposing flue gas cool-down to 200 ℃, water vapor and sulphur trioxide formation acid mist, the micronic dust that does not eliminate simultaneously also enters in the acid mist drop, by electric separator acid mist is removed.Flue gas through electric separator is cooled to 50 ℃, and the sulfuric acid with 98.3% absorbs sulphur trioxide in the absorption tower, control vitriolic add-on, and making specific absorption is 98%, obtains oleum.Flue gas is through after once absorbing, and entering conventional one changes one and inhale technology sulfurous gas is wherein made oleum, oleum mix with diluted acid 98% sulfuric acid.
The key technical indexes:
Iron ore concentrate ferrous grade 60%;
The rate of recovery 98% of iron in the iron ore concentrate;
Sulfuric acid concentration 98%;
The rate of recovery 98% of sulphur.
Claims (1)
1, a kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate the steps include:
(1) iron vitriol drying and dehydrating
Iron vitriol adds in indirect heating rotary kiln or direct heating rotary kiln or the continuous frying pan, the temperature that keeps dry is at 250 ℃～350 ℃, seven crystal water are deviate from, by regulating drying temperature and controlling total moisture time of drying is 0.1%～2%, flue gas is emptying behind dust cleaning, and dirt and dried material are that anhydrous slufuric acid is ferrous;
(2) anhydrous slufuric acid ferrous in redox condition the thermal degradation iron ore concentrate
In the rotary kiln of the ferrous adding indirect heating of anhydrous slufuric acid, add redox agent air or C or CO in the rotary kiln simultaneously, the indirect heating temperature is controlled at 700 ℃～1000 ℃, it is 97%～99.9% that period makes the ferrous sulfate rate of decomposition, the add-on of controlled oxidation reductive agent, make in the gaseous product of ferrous sulfate decomposition, the mass ratio of sulphur trioxide and sulfurous gas is K, the rotary kiln flue gas accelerates to 7～20 meter per seconds through blower fan, the flue gas that is accelerated is by the tornado dust collector dedusting, flue gas is cooled to 275 ℃～500 ℃, and through 1～3 electric precipitation, the gained dust contained flue gas is controlled at 0.2～0.01g/m again
3, be used for contact process; Decompose solid product and gather dust merge the iron ore concentrate of sulfur-bearing 0.5%～0.01%;
(3) the ferrous decomposition flue gas of anhydrous slufuric acid contact process
Route one: anhydrous slufuric acid ferrous oxidation atmosphere is decomposed flue gas changes two suction technology system sulfuric acid through one
When the redox agent that adds in the rotary kiln was air, the add-on of control air made that the mass ratio K of sulphur trioxide and sulfurous gas is 8～100 in the flue gas, dust-laden 0.2～0.01g/m
3Ferrous sulfate decompose flue gas when water cooler is cooled to 275 ℃～100 ℃, water vapor and sulphur trioxide form acid mist, by electric separator acid mist is removed, the flue gas through electric separator is cooled to 100 ℃～30 ℃, sulfuric acid with 98%～99.5% absorbs sulphur trioxide in the absorption tower, control vitriolic add-on, making specific absorption is 95%～99.9%, obtains oleum, flue gas enters a conventional commentaries on classics one suction technology sulfurous gas is wherein made oleum through after once absorbing;
Route two: the ferrous reducing atmosphere of anhydrous slufuric acid decomposes flue gas through double conversion and double absorption technology system sulfuric acid
When the redox agent that adds in the rotary kiln was C or CO, the add-on of control C or CO made that the mass ratio K of sulphur trioxide and sulfurous gas is 0.1～0.01 in the flue gas, dust-laden 0.2～0.01g/m
3Ferrous sulfate decompose flue gas, produce oleum with the double conversion and double absorption technology of routine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101638640A CN100562490C (en) | 2006-12-30 | 2006-12-30 | A kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101638640A CN100562490C (en) | 2006-12-30 | 2006-12-30 | A kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1994868A CN1994868A (en) | 2007-07-11 |
| CN100562490C true CN100562490C (en) | 2009-11-25 |
Family
ID=38250090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101638640A Expired - Fee Related CN100562490C (en) | 2006-12-30 | 2006-12-30 | A kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100562490C (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913573B (en) * | 2010-08-30 | 2012-05-09 | 攀枝花圣地元科技有限责任公司 | Method for producing sulfuric acid and iron oxide red |
| CN102502527B (en) * | 2011-10-18 | 2014-05-21 | 中国石油化工集团公司 | Method for joint production of sulfuric acid and refined iron powder by mixed burning of ferrous sulfate and pyrite |
| CN103193278A (en) * | 2013-04-25 | 2013-07-10 | 白银富提拉化工科技有限公司 | Reductive calcining process of ferrous sulfate as byproduct of titanium dioxide |
| CN103332751B (en) * | 2013-05-22 | 2015-08-26 | 玉门市翔宇环保有限公司 | Ferrous sulfate method of comprehensive utilization |
| CN103318975B (en) * | 2013-07-10 | 2015-04-08 | 四川大学 | Recycling method of waste residue and waste sulfuric acid of titanium dioxide produced by sulfuric acid method |
| CN103864130A (en) * | 2014-03-27 | 2014-06-18 | 李科 | Method for production of gypsum and co-production of powdered iron by use of ferrous sulfate |
| CN108083326A (en) * | 2017-12-18 | 2018-05-29 | 广西雅照钛白有限公司 | The method and apparatus of the energy saving Joint Production titanium dioxide of titanium powder plant, sulfuric acid and iron ore concentrate |
| CN111377415A (en) * | 2020-03-23 | 2020-07-07 | 华东理工大学 | Method for preparing sulfuric acid from ferrous sulfate |
| CN113511634B (en) * | 2021-05-08 | 2023-11-10 | 佛山市景嘉机电设备有限公司 | System and method for preparing sulfuric acid by recycling waste ferric sulfate crude salt in steel industry through pickling |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3860696A (en) * | 1971-04-13 | 1975-01-14 | Patrick J Mcgauley | Production of iron sulfate monohydrate |
| CN1114638A (en) * | 1994-07-08 | 1996-01-10 | 江兴全 | Process for producing ferrous sulfate by using sulfuric acid to leach pyrite cinder |
| CN1519205A (en) * | 2003-01-25 | 2004-08-11 | 中南大学 | Preparation method of ferrous sulfate |
-
2006
- 2006-12-30 CN CNB2006101638640A patent/CN100562490C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3860696A (en) * | 1971-04-13 | 1975-01-14 | Patrick J Mcgauley | Production of iron sulfate monohydrate |
| CN1114638A (en) * | 1994-07-08 | 1996-01-10 | 江兴全 | Process for producing ferrous sulfate by using sulfuric acid to leach pyrite cinder |
| CN1519205A (en) * | 2003-01-25 | 2004-08-11 | 中南大学 | Preparation method of ferrous sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1994868A (en) | 2007-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100562490C (en) | A kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate | |
| CN107213774B (en) | Flue gas desulfurization and resource utilization method based on smelting tailing slag | |
| CN100355485C (en) | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent | |
| CN103303877B (en) | Many sources of the gas low concentration SO 2smoke comprehensive reclaims acid-making process flow process | |
| CN104857835A (en) | Integrated flue gas treatment device and method | |
| US4070441A (en) | Method of removing sulfur dioxide from flue gases | |
| CN106756056B (en) | A kind of method of Copper making white cigarette dirt dearsenification | |
| CN108411104A (en) | A kind of Desulphurization method of resource based on low energy consumption thermal decomposition | |
| CN110743344B (en) | Method for removing low-concentration sulfur dioxide in flue gas and preparing sodium metabisulfite | |
| CN101979130B (en) | Method for removing hydrogen sulfide from industrial gas in recycling way | |
| CN102431976B (en) | Method for recovering sulfur and iron resources through reducing and decomposing titanium white waste slag green vitriol by sulfur | |
| CN105217580A (en) | A kind of electrolytic manganese residues high temperature desulfurizing enriched flue gas prepares the method for sulfuric acid | |
| CN101245409B (en) | Method for producing iron ore concentrate with high arsenic ferro-sulphur ore concentrate | |
| CN110170241A (en) | A method of inhibit sulfur trioxide in heavy non-ferrous metal smelting relieving haperacidity flue gas to generate | |
| US20210331922A1 (en) | Process for preparing sulfur from reduction of sulfate/ nitrate by iron-carbon and recovering desulfurization/ denitration agents | |
| CN103230792B (en) | Produce rubidium vanadium catalyst of sulphuric acid and preparation method thereof | |
| CN103043625B (en) | A kind of sulphur waste material is mixed and is burnt the method that ferrous sulfate waste material is prepared sulfuric acid | |
| CN101176837A (en) | Novel technique for controlling and governing bone coal navajoite torrefaction waste gas | |
| CN1273389C (en) | Method of preparing manganese sulphate using gray manganese ore and dialozite to adsorb sulfur dioxide waste gas | |
| CN203558850U (en) | Sulfur-containing waste liquid dry method acid making system | |
| CN103318975B (en) | Recycling method of waste residue and waste sulfuric acid of titanium dioxide produced by sulfuric acid method | |
| CN102935327B (en) | Method for removing sulfur dioxide in tail gas from industrial kiln and method for comprehensively utilizing tail gas from industrial kiln | |
| CN212523615U (en) | Water-saving and white-removing device for sulfur dioxide in zinc oxide removal flue gas | |
| CN102485325B (en) | Flue gas desulphurization technology with ammonium sulfate-calcium hydroxide slurry method | |
| CN106379926B (en) | A kind of method for preparing nanometer calcium sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091125 Termination date: 20111230 |