CN111377415A - Method for preparing sulfuric acid from ferrous sulfate - Google Patents
Method for preparing sulfuric acid from ferrous sulfate Download PDFInfo
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- CN111377415A CN111377415A CN202010209277.0A CN202010209277A CN111377415A CN 111377415 A CN111377415 A CN 111377415A CN 202010209277 A CN202010209277 A CN 202010209277A CN 111377415 A CN111377415 A CN 111377415A
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- ferrous sulfate
- coal
- sulfuric acid
- sulfur
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 124
- 229910000359 iron(II) sulfate Inorganic materials 0.000 title claims abstract description 121
- 239000011790 ferrous sulphate Substances 0.000 title claims abstract description 112
- 235000003891 ferrous sulphate Nutrition 0.000 title claims abstract description 111
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000003245 coal Substances 0.000 claims abstract description 70
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 69
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 52
- 239000001301 oxygen 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 46
- 239000007789 gas Substances 0.000 claims abstract description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 238000000197 pyrolysis Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000007790 solid phase Substances 0.000 claims description 26
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims description 20
- 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 description 19
- 239000000126 substance Substances 0.000 claims description 13
- 239000006227 byproduct Substances 0.000 claims description 12
- 239000002802 bituminous coal Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 239000003077 lignite Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 19
- 230000023556 desulfurization Effects 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 16
- 235000010215 titanium dioxide Nutrition 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 5
- 239000002893 slag Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 19
- 239000003638 chemical reducing agent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000001354 calcination Methods 0.000 description 13
- 239000012141 concentrate Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- -1 and meanwhile Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002265 redox agent Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/745—Preparation from sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention relates to a method for preparing sulfuric acid by ferrous sulfate, belonging to the technical field of comprehensive utilization of solid waste, and the technical scheme of the invention comprises the following steps: ferrous sulfate and coal are mixed evenly and then sent into a pyrolysis furnace, and furnace gas containing sulfur dioxide and Fe are generated after roasting2O3The furnace gas is catalyzed by a converter to generate sulfur trioxide, the sulfur trioxide is absorbed by concentrated sulfuric acid to generate sulfuric acid, the aerobic atmosphere refers to that the volume fraction of oxygen in the gas introduced into the pyrolysis furnace is 5-20%, and the volume fraction of sulfur dioxide in the furnace gas containing sulfur dioxide is more than or equal to 10%. Compared with the prior art, the process of the invention has no waste, the desulfurization rate of the ferrous sulfate is more than or equal to 93 percent, and the Fe in the slag is2O3The content of the iron is more than or equal to 86 percent, and the iron can be directly used as an iron smelting raw material. The invention realizes resource utilization of the waste ferrous sulfate of the titanium white production, develops potential sulfur resources and can relieve the shortage of sulfur resources in ChinaShape; meanwhile, a circular economic industrial chain of enterprises using the sulfate process titanium dioxide is formed.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a method for preparing sulfuric acid by thermal decomposition of ferrous sulfate.
Background
The ferrous sulfate is industrial waste residue generated by the reaction of ilmenite and sulfuric acid in the production process of titanium dioxide by a sulfuric acid method, at present, titanium dioxide is produced by titanium dioxide production enterprises in China basically by a sulfuric acid method process, the byproduct ferrous sulfate of 2.5-4.0 t can be produced by 1t of titanium dioxide, and the byproduct ferrous sulfate can be used as a water purifying agent, a fertilizer, a feed additive, a building material and the like. The disposal of ferrous sulfate becomes one of the factors restricting the sustainable development of the titanizing industry. Therefore, the development and utilization of ferrous sulfate are worth vigorously developing from the viewpoints of comprehensive utilization of resources and environmental protection.
Ferrous sulfate is an important sulfur-iron resource, and the ferrous sulfate is returned to a sulfuric acid production system to produce sulfuric acid and fine iron powder, so that the method is an ideal resource recycling mode. One domestic treatment process is to mix and burn ferrous sulfate and pyrite or sulfur to prepare acid, but the mixed burning process causes the scale expansion of sulfuric acid, and the production cost and the investment are higher.
Chinese patent CN201410118350.8 discloses a method for producing gypsum and co-producing iron concentrate powder by ferrous sulfate, which comprises adding ferrous sulfate heptahydrate, a byproduct of titanium dioxide, into a rotary kiln, drying to remove water to obtain ferrous sulfate, grinding coal cinder into coal powder, and spraying the coal powder into the rotary kiln; roasting ferrous sulfate and coal powder in a rotary kiln at the heating temperature of 850-1000 ℃ for 24-36 h; after the roasting and sintering, the hot slag in the rotary kiln is cooled by a cooler to obtain iron ore concentrate and gas SO3After passing through a dust removal cooling device and a purification cooling device, the mixture enters an oxidation absorption tower to prepare sulfuric acid; the prepared sulfuric acid is placed in a neutralization tank, and lime is added into the neutralization tank for neutralization to obtain gypsum. In the method, the amount of the pulverized coal sprayed into the rotary kiln is 1/15-1/10 of ferrous sulfate heptahydrate, and the corresponding C/S (molar ratio) is 1.55-2.32. To obtainThe main component of the obtained furnace gas is SO3Sulfur trioxide dissolves in water and reacts with water to form sulfuric acid and release a large amount of heat. The strong corrosiveness of sulfuric acid at high temperatures can cause damage to reactor equipment. In addition, the reaction time in the reaction is as long as 24-36 h, which indicates that the material feeding and slow discharging in the reactor are slow, and the SO in the formed furnace gas3The concentration is low, and the requirement of preparing sulfuric acid cannot be met.
Chinese patent CN200610163864.0 discloses a method for producing sulfuric acid and iron ore concentrate by using ferrous sulfate. The technical scheme includes that anhydrous ferrous sulfate is heated and decomposed in an oxidation-reduction atmosphere to prepare iron ore concentrate, and meanwhile, the redox agent is air, namely, the iron ore concentrate is decomposed under an aerobic condition, so that the mass ratio K of sulfur trioxide to sulfur dioxide in flue gas is 8-100, namely, the product of the iron ore concentrate is mainly sulfur trioxide under the aerobic condition, the sulfur trioxide can react with water to generate sulfuric acid under reaction conditions, and the generated sulfuric acid can react with industrial equipment to corrode the equipment. According to the patent, the oxygen-free state is maintained when C or CO is added as a reducing agent, and the oxygen-free condition has high requirements on process equipment and process conditions.
Disclosure of Invention
Aiming at the technical defects of low utilization rate of ferrous sulfate, large scale of mixed-burning sulfuric acid and the like at the present stage, the invention provides a method for preparing sulfuric acid by using ferrous sulfate.
The technical scheme of the invention is that ferrous sulfate and coal are mixed and fed into a pyrolysis furnace, and are roasted under the aerobic condition to prepare sulfuric acid and iron concentrate powder.
The technical scheme of the invention can simultaneously utilize the iron and sulfur resources in the ferrous sulfate to produce iron ore concentrate and sulfuric acid with huge market demand, and realize large-scale resource utilization of the ferrous sulfate byproduct of titanium dioxide.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for preparing sulfuric acid by ferrous sulfate, which comprises the following steps: ferrous sulfate and coal are mixed evenly and then sent into a pyrolysis furnace, and furnace gas containing sulfur dioxide and Fe are generated after roasting2O3The solid-phase substance of (2),the furnace gas is catalyzed by a converter to generate sulfur trioxide, and the sulfur trioxide is absorbed by concentrated sulfuric acid to generate sulfuric acid containing Fe2O3The solid phase substance is also called as iron concentrate powder and can be directly used as a raw material for ironmaking in an iron-making plant, the aerobic state means that the volume fraction of oxygen in the gas introduced into the pyrolysis furnace is 5-20%, and the volume fraction of sulfur dioxide in the sulfur dioxide-containing furnace gas is more than or equal to 10%.
SO2The gas is gas at the reaction temperature, cannot be combined with water vapor to form sulfuric acid corrosion equipment, and can be completely converted into SO by oxidation after entering a subsequent acid preparation process3Then absorbed, SO in the reaction furnace gas2The concentration needs to be more than or equal to 10 percent because of SO in the subsequent two-conversion and two-absorption process2Two times of conversion and two times of absorption are needed, and if the concentration of furnace gas does not meet the requirement, the subsequent process cannot be carried out.
In one embodiment of the invention, the ferrous sulfate comprises ferrous sulfate heptahydrate, ferrous sulfate tetrahydrate, ferrous sulfate monohydrate, or ferrous sulfate anhydrous. The anhydrous ferrous sulfate is also called anhydrous ferrous sulfate and is a product of ferrous sulfate heptahydrate after crystal water is completely lost. Ferrous sulfate heptahydrate gradually loses the last 1mol of crystal water at a temperature above 300 ℃. Different types of ferrous sulfate can be used as raw materials for the reaction, and the ferrous sulfate is preferably ferrous sulfate monohydrate in consideration of technical and economic factors.
In one embodiment of the invention, the raw material ferrous sulfate is selected from industrial solid by-product ferrous sulfate heptahydrate produced in the production of titanium dioxide by a sulfuric acid method.
If the titanium dioxide byproduct ferrous sulfate heptahydrate is used as a raw material, the titanium dioxide byproduct ferrous sulfate heptahydrate is preferably dehydrated into ferrous sulfate monohydrate at a high temperature, and then the ferrous sulfate monohydrate is uniformly mixed with coal for reaction.
In one embodiment of the present invention, the ferrous sulfate monohydrate has the following main chemical components: the weight percentage of the ferrous sulfate monohydrate is 92-94%, the weight percentage of the impurity titanium is 0.5-1.5%, and the content of free acid is 0.2-1%.
In one embodiment of the invention, the coal is selected from one of lignite, coarse coal, bituminous coal, anthracite or high-sulfur coal, preferably bituminous coal.
In one embodiment of the present invention, further, the bituminous coal is required to have a calorific value of 5000cal or more, a particle size of 250 μm or less, and a moisture content of less than 2%.
In one embodiment of the present invention, the ratio of coal to ferrous sulfate is: the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate increases with increasing oxygen concentration.
In one embodiment of the invention, the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate is between 1.25 and 2 at 5% oxygen concentration; under the concentration of 10% oxygen, the ratio of the mole number of C in the coal to the mole number of S in the ferrous sulfate is 2.5-3.5; the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate is between 4.5 and 5.5 at a concentration of 20% oxygen.
In the thermal decomposition reaction of ferrous sulfate, the dosage of coal has an optimized value, and the dosage of coal is too low, SO that SO in furnace gas can be caused on one hand2The concentration is low; on the other hand, a part of SO is also generated3Corrosion is generated on industrial equipment, and the normal production of the subsequent sulfuric acid process is influenced; too much coal can generate a large amount of CO during reaction, thereby causing potential safety hazard and energy waste.
In one embodiment of the present invention, the temperature of calcination in the pyrolysis furnace is 750 ℃ to 950 ℃, i.e., the reaction of the present invention needs to be carried out at high temperature.
In one embodiment of the invention, when the ferrous sulfate and the coal are uniformly mixed and then fed into the pyrolysis furnace for roasting, the temperature of the pyrolysis furnace is increased to a set temperature in advance.
In one embodiment of the invention, the roasting time of the pyrolysis furnace after the ferrous sulfate and the coal are uniformly mixed is 15s-10min, and the roasting time is about 7-10min according to the used high-temperature reactor; when a fluidized bed reactor (fluidized bed furnace) is adopted, the reaction process is strengthened, and the roasting time is greatly shortened to about 15-30 s.
In the application, the reaction time is short, the ferrous sulfate is rapidly decomposed in a short time, and the sulfur element is rapidly removed, SO that SO2The concentration of (A) is increased, and if the reaction time is prolonged, on one hand, the reaction energy consumption is increased, and meanwhile, the sulfur element in the raw material is reduced, SO2The concentration of (c) is decreased.
In one embodiment of the present invention, Fe is contained2O3In the solid phase of (2), the Fe2O3The mass fraction of the component (A) is more than or equal to 86 percent.
In one embodiment of the present invention, the pyrolysis furnace may be selected from a tubular reactor (rotary kiln) or a fluidized bed reactor (fluidized bed furnace).
In the technical scheme of the invention, the method for generating sulfur trioxide by catalyzing furnace gas through a converter and generating sulfuric acid by absorbing sulfur trioxide by concentrated sulfuric acid is a conventional technical means in the field and can be a two-to-two absorption acid making process.
The acid making process using ferrous sulfate as raw material has high requirements for technological conditions and equipment, because the content of sulfur element in ferrous sulfate is relatively low compared with other raw materials for making sulfuric acid, such as pyrite and sulfur, which results in SO in furnace gas generated by decomposition2The concentration is limited and cannot meet the requirement of subsequent SO2The technological requirements of oxidation and absorption for acid making; the ferrous sulfate has various hydrate forms, and the water vapor generated by dehydration decomposition of the ferrous sulfate at high temperature can be converged into the furnace gas to remove the originally low SO in the furnace gas2The concentration is greatly diluted.
In the invention, whether the concentration of sulfur dioxide in furnace gas generated by the thermal decomposition of ferrous sulfate in the presence of a reducing agent coal can provide qualified raw material gas for a subsequent acid making system and whether decomposed solid-phase substances can provide qualified fine iron powder for an iron-making plant is a key problem for developing the technology for preparing sulfuric acid by the thermal cracking of ferrous sulfate.
The invention uses SO in furnace gas obtained by thermal cracking of ferrous sulfate2The concentration and the desulfurization rate of ferrous sulfate are used as indexes, and sulfur dioxide in furnace gas and iron content in solid phase substances are measured by researching different ferrous sulfate hydrates, oxygen concentration, coal types, carbon-sulfur molar ratio and reaction temperatureThe influence of the amount and the like finally determines a method for producing sulfuric acid by thermal decomposition of ferrous sulfate under preferable redox conditions.
The reaction principle of the invention is illustrated by taking ferrous sulfate monohydrate as an example:
when ferrous sulfate is decomposed alone (no oxygen and no reducing agent):
2FeSO4·H2O→2Fe2O3+SO3+SO2+2H2O
when ferrous sulfate decomposes in an oxidizing atmosphere:
4FeSO4·H2O+O2→2Fe2O3+4SO3+4H2O
when ferrous sulfate is decomposed in a reducing atmosphere (C is used as a reducing agent):
4FeSO4·H2O+C→2Fe2O3+4SO2+CO2+4H2O
if no reducing agent is present, the ferrous sulfate decomposes to produce SO in an oxygen atmosphere3(ii) a SO production in the presence of reductant coal fines2The main function of the coal in this application is to provide reducing conditions, to maintain SO2Not oxidized.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method for preparing the sulfuric acid by adopting the thermal cracking of the ferrous sulfate can avoid the defects of the ferrous sulfate blended pyrite or blended sulfur process in the background art. Under the condition of consuming the same quality of ferrous sulfate, the process method of the invention reduces the scale of acid making by about 3 times compared with the mixed burning process, and is a method for efficiently utilizing the ferrous sulfate as a titanium dioxide byproduct. The method can be used for preparing sulfuric acid and co-producing high-grade cinder by thermally cracking ferrous sulfate, can recover sulfur and iron resources to produce sulfuric acid and high-added-value iron concentrate powder, and accords with the current national industrial policy of energy conservation and emission reduction.
2. The process of the invention generates no waste, and the desulfurization rate of the ferrous sulfate is more than or equal to 93 percent. The method reasonably utilizes ferrous sulfate resources, develops potential sulfur resources, forms a circular economic industrial chain of enterprises of sulfuric acid process titanium dioxide, realizes the comprehensive utilization of ferrous sulfate, and can relieve the current situation of sulfur resource shortage in China.
3. The method adopts coal washing as FeSO through process optimization4·H2Reducing agent of O, SO when the C/S value is 1.5 at an oxygen concentration of 5%2The concentration can reach 10.324 percent, and SO3/SO2As low as 0.036, the desulfurization rate of the ferrous sulfate is 94.721 percent, and the content of Fe element in the calcined solid phase is 0.620; SO at an oxygen concentration of 20% when the C/S value is 4.52The concentration can be as high as 10.957 percent, and SO3/SO2The desulfurization rate of the ferrous sulfate is 93.408 percent as low as 0.023, and the content of Fe element in the calcined solid phase is 0.533, so that qualified raw materials can be provided for preparing sulfuric acid and iron concentrate powder for ironmaking respectively.
4. In the invention, the roasting time of the ferrous sulfate and the coal which are uniformly mixed in the high-temperature decomposing furnace is 15s-10min, the reaction time is short, the working procedure time can be saved, and the energy can be saved.
5. In the invention, coal is used as a heat source and is mainly used as a reducing agent, and the main function of the coal is to ensure that the furnace gas component is SO2Avoidance of SO3Is generated, and SO3The presence of the catalyst can cause corrosion of equipment and difficult process operation.
Drawings
FIG. 1 FeSO in air4·7H2O calcination data plot;
FIG. 1 includes (a), (b), (c), (d);
FIG. 1(a) shows FeSO at different temperatures and different C/S values4·7H2Decomposing O to generate SO in furnace gas2A tendency of variation in the average concentration value of (a);
FIG. 1(b) shows FeSO at different temperatures and different C/S values4·7H2Decomposing O to generate SO in furnace gas3/SO2A trend of change in the ratio;
FIG. 1(C) shows FeSO at different temperatures and different C/S values4·7H2The trend of the decomposition desulfurization rate of O;
FIG. 1(d) shows FeSO at different temperatures and different C/S values4·7H2The content of Fe element in the O decomposed solid phase matter has a tendency to change.
FIG. 2 is a data diagram of the individual calcination of the waste ferrous sulfate of titanium white in the air atmosphere;
FIG. 2 includes (a), (b);
FIG. 2(a) shows FeSO in an air atmosphere at different temperatures4·H2After calcination of O alone, SO2Instantaneous concentration versus time;
FIG. 2(b) shows FeSO4·H2Conversion of O decomposition versus time.
FIG. 3 is a graph of the calcination decomposition data of ferrous sulfate in different oxygen concentrations;
FIG. 3 includes (a), (b), (c), (d);
fig. 3 (a): at different oxygen concentrations, SO2The relationship between the average concentration and the C/S value;
fig. 3 (b): at different oxygen concentrations, SO3/SO2And C/S values;
fig. 3 (c): the relationship between desulfurization rate and C/S value at different oxygen concentrations;
fig. 3 (d): the relationship between the iron content of the obtained solid phase and the C/S value under different oxygen concentrations.
Detailed Description
A method for preparing sulfuric acid from ferrous sulfate comprises the following steps: ferrous sulfate and coal are mixed evenly and then sent into a pyrolysis furnace, and furnace gas containing sulfur dioxide and Fe are generated after roasting2O3The furnace gas is catalyzed by a converter to generate sulfur trioxide, and the sulfur trioxide is absorbed by concentrated sulfuric acid to generate sulfuric acid containing Fe2O3The solid phase substance is also called as iron concentrate powder and can be directly used as a raw material for ironmaking in an iron-making plant, the aerobic state means that the volume fraction of oxygen in the gas introduced into the pyrolysis furnace is 5-20%, and the volume fraction of sulfur dioxide in the sulfur dioxide-containing furnace gas is more than or equal to 10%.
In one embodiment of the present invention, the ferrous sulfate comprises ferrous sulfate heptahydrate, ferrous sulfate tetrahydrate, ferrous sulfate monohydrate, or ferrous sulfate anhydrous. The ferrous sulfate heptahydrate is an industrial solid byproduct ferrous sulfate heptahydrate generated in the production of titanium dioxide by a sulfuric acid method.
In one embodiment of the present invention, the ferrous sulfate monohydrate has the following main chemical components: the weight percentage of the ferrous sulfate monohydrate is 92-94%, the weight percentage of the impurity titanium is 0.5-1.5%, and the content of free acid is 0.2-1%.
In one embodiment of the invention, the coal is selected from one of lignite, bituminous coal or anthracite, preferably bituminous coal.
In one embodiment of the present invention, further, the bituminous coal is required to have a calorific value of 5000cal or more, a particle size of 250 μm or less, and a moisture content of less than 2%.
In one embodiment of the present invention, the ratio of coal to ferrous sulfate is: the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate increases with increasing oxygen concentration.
In one embodiment of the invention, the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate is between 1.25 and 2 at 5% oxygen concentration; under the concentration of 10% oxygen, the ratio of the mole number of C in the coal to the mole number of S in the ferrous sulfate is 2.5-3.5; the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate is between 4.5 and 5.5 at a concentration of 20% oxygen.
In one embodiment of the present invention, the temperature of the calcination in the pyrolysis furnace is 750 ℃ to 950 ℃.
In one embodiment of the present invention, Fe is contained2O3In the solid phase of (2), the Fe2O3The mass fraction of the component (A) is more than or equal to 86 percent.
The invention is described in detail below with reference to the figures and specific embodiments.
The experimental analysis method in the following examples is:
the concentration content of each gas in the tail gas is tested by an automatic smoke tester; if not specifically stated, the solid slag is washed and then the total S is measured by a high-frequency infrared carbon-sulfur instrument; SO (SO)3Detecting by adopting a gravimetric method; the Fe content is detected by a potassium dichromate titration method.
Example 1
FeSO4·7H2Calcination experiment of O mixed with coal in air
Analytically pure ferrous sulfate heptahydrate is adopted as a reaction raw material, coal washing is selected as a ferrous sulfate thermal decomposition reducing agent, and analytically pure FeSO is taken4·7H2O and coal are mixed according to different C/S (molar ratio) and then are fed into an atmosphere tube furnace, and calcination is carried out at different temperatures in an air atmosphere. The C/S values are selected according to the reaction equation of ferrous sulfate and coal and are set to be 0.25, 0.67, 1, 1.5 and 2. The experimental temperatures were 650 deg.C, 700 deg.C, 750 deg.C, 800 deg.C, depending on the thermogravimetric results.
The results are shown in FIG. 1.
FIG. 1(a) shows FeSO at different temperatures and different C/S values4·7H2Decomposing O to generate SO in furnace gas2As shown in FIG. 1(a), the average concentration of (A) is determined by reducing a small amount of coal in an air atmosphere to decompose ferrous sulfate to produce SO2The concentration is very low. But SO is generated after adding reducing agent coal in the ferrous sulfate decomposition process2The concentration is obviously improved, and SO in furnace gas generated by decomposition is increased along with the increase of the reducing agent2The volume fraction of (A) is obviously improved, but the average concentration is below 1%. There are three reasons for this: (1) large amount of O in the air2A part of coal is consumed by the reaction with oxygen in the air, and the reducing agent C is not enough for decomposing and reducing ferrous sulfate; (2) the ferrous sulfate reacts with oxygen in the air to generate a large amount of SO3A gas; (3) FeSO4·7H2O contains 7 crystal waters, so that the mass fraction of S element is low.
FIG. 1(b) shows FeSO at different temperatures and different C/S values4·7H2Decomposing O to generate SO in furnace gas3/SO2A ratio. As can be seen from FIG. 1(b), SO was added in an air atmosphere even after the addition of coal as a reducing agent3The concentration of (A) is still high and with increasing C/S, its SO3The rate of decrease of (b) will slow down and eventually approach zero. But the value of the reducing agent consumed by the method is not the value of coal required by decomposing and reducing ferrous sulfate, but the value of the reducing agent consumed by the method is the value of burning oxygen for supplying heat and reducing ferrous sulfateSum of coal values for iron.
FIG. 1(C) shows FeSO at different temperatures and different C/S values4·7H2Decomposition desulfurization degree of O. As shown in fig. 1(c), the desulfurization rate of ferrous sulfate decreases with the increase of coal, because after the coal is added, the coal contains S element, which introduces a part of S element into the solid phase, and the part of S element may not be sulfate or ferrous sulfate, and is difficult to decompose and remove at the decomposition temperature of 650-800 ℃, so that it remains in the solid phase.
FIG. 1(d) shows FeSO at different temperatures and different C/S values4·7H2And O decomposes the content of Fe element in the solid phase substance. From FIG. 1(d), it is understood that the Fe element content decreases with an increase in the C/S value, and the decrease in the Fe element content is partly due to an increase in the S element in the solid matter and partly due to an increase in the introduction of ash into the coal, resulting in an increase in the impurity content ratio.
Example 2
Separate calcination of industrial ferrous sulfate
Respectively mixing the raw materials of FeSO4·H2Grinding and sieving the powder by a 100-target standard sample sieve; then, the temperature of the atmosphere tube furnace is increased to the specified temperature, and 2.0g of industrial FeSO is weighed4·H2O was placed in an atmospheric tube furnace and calcined in an air atmosphere at different temperatures, which produced SO2The instantaneous concentration versus time is shown in FIG. 2, and FeSO is calculated4·H2Conversion of O and desulfurization. The decomposition temperature of some of the sulfate impurity salts contained in the industrial ferrous sulfate was higher than 800 ℃, so the reaction temperature was selected to be 800 ℃, 850 ℃, 900 ℃, 950 ℃ in the examples.
The results refer to fig. 2. FIG. 2(a) shows FeSO at different temperatures in an air atmosphere4·H2After calcination of O alone, SO2Instantaneous concentration versus time. As can be seen from FIG. 2(a), the SO at temperatures above 800 ℃ increases with increasing temperature2The time when the instantaneous concentration reaches the highest point is advanced, SO2The rate of concentration increase will also increase with increasing temperature, which may also be via FeSO4·H2O decomposition conversion As can be seen in FIG. 2(b), FeSO4·H2After calcining for 10min at different temperatures, the conversion rate of O can reach over 75 percent, and after calcining for 60min, the conversion rate approaches to be stable. SO (SO)2The instantaneous concentration will increase with increasing temperature.
Example 3
Oxygen concentration vs. industrial FeSO4·4H2Influence of decomposition of ferrous O sulfate
Respectively mixing the raw materials of FeSO4·4H2Grinding O and coal, and sieving with a 100-target standard sample sieve; reducing agent coal and industrial FeSO4·4H2Mixing O respectively according to different C/S molar ratios, weighing 2.0g, feeding into an atmosphere tube furnace with the temperature reaching the specified temperature, calcining at different temperatures, controlling different oxygen concentrations until no SO is contained in the gas at the furnace outlet2After gassing, the experiment was stopped.
The results are shown in FIG. 3.
As can be seen from FIG. 3(a), the optimal C/S is different at different oxygen concentrations, and the minimum coal value required for reduction is larger as the oxygen concentration is increased. When the oxygen concentration is between 10 and 20 percent, and before the coal value reaches the optimal C/S, SO2The concentration increases with increasing C/S, and SO is added after the optimum C/S is reached2The concentration tends to be stable, which shows that the increase of the reducing agent to SO after the C/S value reaches the optimal value2The influence of the concentration is not great. When the oxygen concentration is 10%, the optimal C/S is 3.5; when the oxygen concentration is 15%, the optimal C/S is 4.5; the optimum C/S ratio was 5.5 at an oxygen concentration of 20. However, when the oxygen concentration is 5%, part of the coal consumes the oxygen in the furnace, and when the oxygen concentration is lower than 4%, the coal stops burning, and the rest of the coal is used as a reducing agent to react with ferrous sulfate. The experimental environment was similar to nitrogen conditions. When the C/S value is 1.25-2, SO2The concentration increases with the increase of the C/S value, and when the C/S value is 2-3, SO2The concentration decreases with increasing C/S value.
Different oxygen concentrations for FeSO4Decomposition to SO3With SO2The effect of the ratio is shown in FIG. 3(b), with O2Increase in concentrationHigh, SO3Concentration and SO2The higher the C content required for the ratio of the concentrations to approach 0. Shows that under the oxidizing atmosphere, the decomposition of ferrous sulfate can generate a large amount of SO3。
FIG. 3(C) shows the desulfurization rates at different C/S with different oxygen concentrations, wherein the reaction desulfurization rate at 5% oxygen concentration is similar to that at nitrogen, the desulfurization rate of the solid phase material gradually increases at 1.25 to 2C/S, and the desulfurization rate of the solid phase material gradually decreases at 2 to 3C/S. When the oxygen concentration is about 10%, the desulfurization degree increases with the increase of C/S at a C/S value of 2 to 3.5, and after the optimum C/S is reached, the desulfurization degree tends to be stable. When the oxygen concentration is more than 15%, the influence of the C/S value on the desulfurization rate is reduced, and the desulfurization rate tends to be stable. As the oxygen concentration increases, it can be seen that the desulfurization rate is gradually decreasing.
Fig. 3(d) shows the variation of the content of Fe in the solid phase for different C/S values of oxygen concentration, and the ash content of coal is a key factor affecting the content of Fe in the solid phase, and it can be seen from fig. 3(d) that the higher the ash content of coal is, the lower the content of Fe element in the solid phase is, and as the oxygen concentration increases, the higher the required coal content is, the more ash is produced, and the lower the content of Fe element is.
Oxygen concentration vs. industrial FeSO4·H2The specific data on the effect of O decomposition are shown in tables 1 and 2. Wherein the solid phase is the unwashed calcined red slag. FeSO (FeSO) from titanium dioxide waste secondary source4·H2O contains many impurities, which are not decomposed at 800 ℃, most of sulfate impurity salt is dissolved in water, and the Fe content of the decomposed solid phase is above 60% after washing.
TABLE 1
TABLE 2
Example 4
Weighing some industrial production ferrous sulfate heptahydrate (ferrous sulfate thereof)93.38 percent) of the total content of the raw materials are baked into ferrous sulfate monohydrate, 2.3g of the ferrous sulfate monohydrate is uniformly mixed with bituminous coal in a proportion of C/S (molar ratio) to 4.5, and the mixture is sent into a thermal decomposition furnace with the oxygen concentration of 20 percent in the atmosphere for reaction and decomposition, the decomposition temperature is 800 ℃, and the SO in furnace gas is2The volume fraction of the Fe-based catalyst can reach 10.96 percent, and Fe in a solid phase substance2O3The content can reach 93.21%.
Example 5
Weighing industrial ferrous sulfate heptahydrate (with ferrous sulfate content of 91.99%), baking to obtain ferrous sulfate monohydrate, mixing 2.3g ferrous sulfate monohydrate with bituminous coal at C/S (molar ratio) of 1.5, and feeding into thermal decomposition furnace with oxygen concentration of 5% in atmosphere for reaction decomposition at 800 deg.C2The volume fraction of the Fe-based catalyst can reach 10.324 percent, and Fe in a solid phase substance2O3The content can reach 94.51 percent.
Example 6
Weighing industrial ferrous sulfate heptahydrate (with ferrous sulfate content of 91.99%), baking to obtain ferrous sulfate monohydrate, mixing 2.3g ferrous sulfate monohydrate with bituminous coal at C/S (molar ratio) of 2.5, and feeding into thermal decomposition furnace with oxygen concentration of 10% in atmosphere for reaction decomposition at 800 deg.C to obtain SO in furnace gas2The volume fraction of the Fe-based catalyst can reach 11.024 percent, and Fe in a solid phase substance2O3The content can reach 95.91 percent.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A method for preparing sulfuric acid by ferrous sulfate is characterized by comprising the following steps: uniformly mixing ferrous sulfate and coalFeeding into a pyrolysis furnace, roasting in an aerobic state to generate sulfur dioxide-containing furnace gas and Fe-containing furnace gas2O3The solid-phase substance is characterized in that furnace gas is catalyzed by a converter to generate sulfur trioxide, the sulfur trioxide is absorbed by concentrated sulfuric acid to generate sulfuric acid, the aerobic state refers to that the volume fraction of oxygen in the atmosphere introduced into the pyrolysis furnace is 5-20%, and the volume fraction of sulfur dioxide in the furnace gas containing the sulfur dioxide is more than or equal to 10%.
2. The method of claim 1, wherein the ferrous sulfate comprises ferrous sulfate heptahydrate, ferrous sulfate tetrahydrate, ferrous sulfate monohydrate, or ferrous sulfate anhydrous.
3. The method for preparing sulfuric acid from ferrous sulfate according to claim 2, further comprising the following main chemical components: the weight percentage of the ferrous sulfate monohydrate is 92-94%, the weight percentage of the impurity titanium is 0.5-1.5%, and the content of free acid is 0.2-1%.
4. The method for preparing sulfuric acid from ferrous sulfate according to claim 2, wherein the ferrous sulfate is selected from ferrous sulfate heptahydrate, which is an industrial solid byproduct produced in the production of titanium dioxide by a sulfuric acid method;
and preferably, when the titanium dioxide byproduct ferrous sulfate heptahydrate is used as a raw material, the titanium dioxide byproduct ferrous sulfate heptahydrate is dehydrated into ferrous sulfate monohydrate at high temperature, and then the ferrous sulfate monohydrate is uniformly mixed with coal for reaction.
5. The method for preparing sulfuric acid from ferrous sulfate according to claim 1, wherein the coal is selected from one of lignite, coarse coal, bituminous coal, anthracite or high-sulfur coal, preferably bituminous coal.
6. The method for preparing sulfuric acid from ferrous sulfate according to claim 1, wherein the ratio of coal to ferrous sulfate is: the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate increases with increasing oxygen concentration.
7. The method for preparing sulfuric acid from ferrous sulfate according to claim 6, wherein the ratio of the number of moles of C in coal to the number of moles of S in ferrous sulfate is between 1.25 and 2 at 5% oxygen concentration; under the concentration of 10% oxygen, the ratio of the mole number of C in the coal to the mole number of S in the ferrous sulfate is 2.5-3.5; the ratio of the number of moles of C in the coal to the number of moles of S in the ferrous sulfate is between 4.5 and 5.5 at a concentration of 20% oxygen.
8. The method for preparing sulfuric acid from ferrous sulfate as claimed in claim 1, wherein the roasting temperature in the pyrolysis furnace is 750-950 ℃.
9. The method for preparing sulfuric acid from ferrous sulfate as claimed in claim 1, wherein the iron content is Fe2O3In the solid phase of (2), the Fe2O3The mass fraction of the component (A) is more than or equal to 86 percent.
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