CN103043625A - Method for preparing sulfuric acid by blending combustion of sulfur waste and ferrous sulfate waste - Google Patents
Method for preparing sulfuric acid by blending combustion of sulfur waste and ferrous sulfate waste Download PDFInfo
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- CN103043625A CN103043625A CN2012105864966A CN201210586496A CN103043625A CN 103043625 A CN103043625 A CN 103043625A CN 2012105864966 A CN2012105864966 A CN 2012105864966A CN 201210586496 A CN201210586496 A CN 201210586496A CN 103043625 A CN103043625 A CN 103043625A
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Abstract
The invention discloses a method for preparing sulfuric acid by blending combustion of sulfur waste and ferrous sulfate waste. The method comprises the following steps: a) drying the sulfur waste and the ferrous sulfate waste; b) mixing the dried waste uniformly, wherein the weight ratio of sulfur in the sulfur waste to ferrous sulfate monohydrate in the ferrous sulfate waste is 3:7 to 7:3; c) adding the mixture obtained in the step b) into a fluidized bed combustion boiler for roasting at the temperature of 850-1000 DEG C, blowing air into the fluidized bed combustion boiler at the speed of 1.0-2.0m/s, and keeping the mixture in the fluidized bed combustion boiler for 4-16s, wherein the volume concentration of sulfur dioxide in boiler gas after roasting is 9-12% and is controlled by controlling the oxygen supply amount; and d) cooling, purifying, and convert- absorbing the sulfur dioxide-containing boiler gas obtained in the step c, so as to obtain sulfuric acid. The method disclosed by the invention makes the most of a byproduct (sulfur waste) of the coking industry and a byproduct (ferrous sulfate waste) of the titanium dioxide industry to lower the production cost, and can remarkably lower the 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 the method that burning ferrous sulfate waste material prepares sulfuric acid.
Background technology
The raw material of producing sulfuric acid in the prior art has the sulfur-bearing raw materials such as sulfurous iron ore, sulphur, flue gas during smelting and phosphogypsum, wherein with pyrite-based sulfuric acid production, acid production with sulphur technique mature and reliable the most, metallurgical off-gas acid-making adopts the technology and equipment similar to pyrite-based sulfuric acid production basically.Usually acid production with sulphur adopts liquid stream incineration technology, and what raw material used is the commodity sulphur, requires foreign matter content very low, stops up the molten sulfur shower nozzle to prevent from bringing in the sulphur impurity, causes the problem such as conversion catalyst poisoning.
In recent years because the raising of environmental requirement, in the production processes such as synthetic ammonia, oil refining, coke-oven gas, increased desulfurizer, produced the sulphur of many recovery, wherein the sulfur purity of oil refining apparatus recovery is very high, and contain more impurity in the sulphur that reclaims in the synthetic ammonia, coke oven gas desulfurization process, can not adopt liquid stream incineration technology to prepare sulfuric acid.Therefore be badly in need of solving the problem of complex utilization of the sulphur that reclaims in synthetic ammonia, the coke oven gas desulfurization process.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of sulphur waste material and mixes the method that burning ferrous sulfate waste material prepares sulfuric acid, take full advantage 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 the method that burning ferrous sulfate waste material prepares sulfuric acid, the method comprises the steps:
A) sulphur waste material and ferrous sulfate waste material is dry, make the sulphur waste material be dehydrated into the thick sulphur of granular, obtain the ferrous sulfate monohydrate compound after the dehydration of ferrous sulfate waste material;
B) dried sulphur waste material and ferrous sulfate waste material are mixed, wherein, in the dried sulphur waste material in sulphur and the ferrous sulfate waste material weight ratio of ferrous sulfate monohydrate be 3: 7～7: 3, be preferably 3: 3～7: 3, more preferably 1: 1;
C) with step b) in mixture add the boiling kiln roasting, maturing temperature is 850-1000 ℃, pass into air, gas speed is the 1.0-2.0 meter per second, the residence time of mixture in fluidizing furnace is 4-16 second, after the roasting in the furnace gas sulfurous gas volumetric concentration be 9-12%, be preferably 12%, control the concentration of sulfurous gas in the furnace gas by control oxygen intake;
D) with step c) in contain sulfurous gas furnace gas make sulfuric acid through overcooling, washing, purifying, conversion absorption section.
Above-mentioned sulphur waste material is mixed and is burnt the method that the ferrous sulfate waste material prepares sulfuric acid, wherein, described steps d) in, the furnace gas that contains sulfurous gas cools off by vapour generator, furnace gas is cooled to 320 ℃-360 ℃ and enters washing, purifying workshop section, described vapour generator produces the low-pressure saturated steam of 1.2-1.3MPa, and the low-pressure saturated steam of by-product can be connected with the low-pressure steam pipe network, is used for dry and other technological processs of sulphur.
Above-mentioned sulphur waste material is mixed and is burnt the method that the ferrous sulfate waste material prepares sulfuric acid, wherein, and described steps d) in, described furnace gas washing, purifying adopts dry method dust and wet purification, may further comprise the steps:
1) cooled furnace gas is removed flue dust by tornado dust collector, can remove at least 90% Fe by these tornado dust collector
2O
3Flue dust;
2) furnace gas after the dedusting enters Venturi meter, spray into the dilute sulphuric acid of 10-40% weight in described venturi throat, dilute sulphuric acid is well atomized in described Venturi meter, furnace gas and dilute sulphuric acid close contact, make the furnace gas humidification, cool and further dedusting, finish preliminary washing, purifying;
3) after furnace gas washs through described Venturi meter, enter stuffing washing tower, with dilute sulphuric acid counter current contact, the washing, purifying of cat head spray 10-40% weight, remove wherein impurity and steam, flue gas cleaning is finished, and dust content is lower than 0.5mg/m in the rear furnace gas of purification
3, the too high meeting of dust content makes the poisoning of catalyst in the follow-up conversion process, has a strong impact on the conversion of sulfurous gas.In washing, purifying workshop section, further, the furnace gas of process washing tower washing can also enter electrostatic precipitator and remove acid mist.
Above-mentioned sulphur waste material is mixed and is burnt the method that the ferrous sulfate waste material prepares sulfuric acid, wherein, described steps d) in, described conversion absorption section adopts the double conversion and double absorption method, the equipment that adopts comprises drying tower, the first absorption tower and second absorption tower, is provided with the convertor of five beds, corresponding First Heat Exchanger, the second interchanger, the 3rd interchanger, the 4th interchanger and the 5th interchanger of being provided with each beds;
Described double conversion and double absorption method comprises the steps:
1) will replenish air from the furnace gas of washing, purifying workshop section, make that the sulfurous gas volumetric concentration is 8-8.5% in the furnace gas, furnace gas will be passed into the drying tower bottom, absorb moisture content≤0.1g/Nm in the dried furnace gas through the vitriol oil of 94% weight of cat head spray is dry
3
2) after drying furnace gas is successively through the heating of the 3rd interchanger, First Heat Exchanger, furnace gas temperature after the heating is 410-430 ℃, the first paragraph beds that enters convertor transforms, sulfurous gas in the furnace gas is converted into sulphur trioxide under the effect of catalyzer, furnace gas after the conversion enters the First Heat Exchanger cooling, furnace gas enters convertor second segment beds and transforms after cooling, enter afterwards the cooling of the second interchanger, furnace gas enters the 3rd section beds of convertor and transforms after cooling, enter afterwards the cooling of the 3rd interchanger;
3) furnace gas through the cooling of the 3rd interchanger enters the first absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters and absorbs the tower acid circulation groove;
4) enter successively the heating of the 5th, the 4th and second interchanger through the furnace gas after the absorption of the first absorption tower, enter the 4th section beds of convertor after furnace gas is heated carries out transforming the second time, furnace gas after the conversion enters the cooling of the 4th interchanger, enter afterwards the 5th section beds of convertor and transform, the furnace gas after the conversion is lowered the temperature through the 5th interchanger;
5) furnace gas through the cooling of the 5th interchanger enters second absorption tower, sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, the vitriol oil after the absorption enters step 3) described absorption tower acid circulation groove, mix with the vitriol oil that enters circulation groove in the first absorption tower, add entry to absorbing in the tower acid circulation groove, regulate the concentration of sulfuric acid, sulfuric acid is squeezed into the first absorption tower and second absorption tower circulated sprinkling through the cooling rear section, be used for absorbing the sulphur 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, wherein, the sulphur waste material is from the sulfur waste sulphur that reclaims in synthetic ammonia, the coke oven gas desulfurization process, wherein, the dried thick Sulfur from Sulphur sulphur content of sulphur waste material is greater than 60% weight, and other major ingredient are (NH
4) 2SO
4(NH
4) SCN, and the tar, benzene, naphthalene of trace etc. also can adopt the sulfur containing waste material after power plant, the aluminium manufacturer's desulfurization; The ferrous sulfate waste material is ferrous from the Waste Sulfuric Acid that the titanium dioxide industry produces, and wherein iron vitriol content is greater than 85% weight, and magnesium sulfate heptahydrate is 3-8% weight, and the Manganese sulfate pentahydrate of trace, 18 water Tai-Ace S 150, terra alba, titanyl sulfate etc.
The reaction formula that the present invention relates to is as follows:
S+O
2＝SO
2，3(NH
4)
2SO
4＝4NH
3+N
2+3SO
2+6H
2O
4NH
4SCN+9O
2＝4NH
3+4SO
2+2N
2+4CO
2+2H
2O
4FeSO4·H
2O+S＝2Fe
2O
3+5SO
2+4H
2O
2MgSO4·H
2O+S→2MgO+3SO
2+2H
2O
The contriver finds behind experimental study, although the present invention adopts two kinds of industrial wastes to prepare sulfuric acid as raw material, adopts sulphur waste material and ferrous sulfate waste material to prepare sulfuric acid and can't cause any disadvantageous effect to sulfuric acid product.From above-mentioned reaction formula as can be known, after the present invention's reaction, mainly contain sulfurous gas in the furnace gas, water, ammonia, nitrogen, carbonic acid gas etc., water, nitrogen, carbonic acid gas there is no impact to the sulfurous gas acid making system, ammonia can be removed by washing in the washing, purifying stage, can not exert an influence to follow-up sulfurous gas relieving haperacidity workshop section, the mixture such as ferric oxide is that the iron fine powder can be used for ironmaking in the furnace bottom slag, MgO can significantly improve the metallurgical performance of pellet in the slag in ironmaking, other impurity is because being the few silicon-dioxide of content, aluminium sesquioxide, sulphur etc., can not impact iron fine powder product, iron level can reach more than 65% weight in the furnace bottom iron fine powder.
Sulfur burning is thermopositive reaction, discharges a large amount of heats, ferrous sulfate be decomposed into thermo-negative reaction, need absorbing heat, the contriver is through great many of experiments, selected in the dry rear sulphur waste material rational proportion of ferrous sulfate monohydrate in the sulphur and ferrous sulfate waste material.The sulphur add-on is too much, the output of the iron fine powder that produces can reduce, the recuperation layer of fluidizing furnace is reduced, cause fluidizing furnace can not keep enough heats and be used for the ferrous sulfate decomposition, and then need to additionally expend the normal production that more outside heat can keep fluidizing furnace; If the sulphur add-on is very few, the heat of sulfur burning generation can not satisfy the required heat of ferrous sulfate decomposition so.The proportioning of the determined sulphur of method of the present invention and ferrous sulfate monohydrate, sulfur burning institute liberated heat is taken full advantage of by ferrous sulfate, this heat that sulfur burning is discharged is farthest utilized, significantly reduce energy consumption, and increased substantially the incorporation of sulphur waste material in the ferrous sulfate decomposition course, more sulphur waste material is utilized, reduced production cost.
Sulphur waste material of the present invention is mixed and is burnt the method that the ferrous sulfate waste material prepares sulfuric acid, has following beneficial effect:
1, the sulphur waste material that reclaims in synthetic ammonia, the coke oven gas desulfurization process and the ferrous sulfate waste residue of titanium dioxide industry by-product greatly reduce the production cost of sulfuric acid as raw material, and provide new way for the comprehensive utilization of two kinds of industrial wastes;
2, the present invention has selected in the dry rear sulphur waste material rational proportion of ferrous sulfate monohydrate in the sulphur and ferrous sulfate waste material, takes full advantage of the heat that sulfur burning discharges, and makes the heat of sulfur burning be used for the decomposition of ferrous sulfate, and energy-saving effect is remarkable;
3, can the be up to state standards requirement of acceptable end product of the 98% industrial sulphuric acid product that makes by method of the present invention;
4, method of the present invention can the byproduct iron fine powder, and can the by-product low-pressure saturated steam;
5, the washing, purifying technique that the dry method dust that adopts among the present invention and wet purification combine can be down to 0.5mg/m with the dust content in the furnace gas
3Below, to prevent poisoning of catalyst in the follow-up conversion section;
6, double conversion and double absorption technique of the present invention prepares sulfuric acid, has improved the transformation efficiency of sulfurous gas, and transformation efficiency can reach more than 99.8%, and utilizes high-temperature furnace gas and low temperature furnace gas in the conversion process to carry out heat exchange, save energy;
7, adopt method of the present invention, the rate of recovery of sulphur and iron all can reach more than 99%.
Embodiment
Embodiment 1
(1) drying
Sulphur foam and iron vitriol waste material are carried out drying in dehumidification system, make the sulphur foam be dehydrated into the thick sulphur of granular, obtain the ferrous sulfate monohydrate compound after the iron vitriol dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein the weight ratio of ferrous sulfate monohydrate is 3: 7 in dried thick Sulfur from Sulphur sulphur and the ferrous sulfate, mixture is sent into the boiling kiln roasting, maturing temperature is 1000 ℃, pass into air, gas speed is 1.8 meter per seconds, and the residence time of mixture in fluidizing furnace is 4 seconds, after the roasting in the furnace gas sulfurous gas volumetric concentration be 11%.
(3) cooling
High-temperature furnace gas is passed into vapour generator cool off, furnace gas is cooled to 360 ℃, and vapour generator produces the low-pressure saturated steam pressure of 1.2MPa simultaneously.
(4) washing, purifying
Cooled furnace gas is passed into tornado dust collector remove flue dust, furnace gas enters Venturi meter after the dedusting, spray into 10% weight dilute sulphuric acid in venturi throat, dilute sulphuric acid is well atomized in Venturi meter, furnace gas and dilute sulphuric acid close contact, make the furnace gas humidification, cool and further dedusting, finish preliminary washing, purifying; Furnace gas enters stuffing washing tower after washing through Venturi meter, with 10% weight dilute sulphuric acid counter current contact, the washing, purifying of cat head spray, removes wherein impurity and steam; The furnace gas of process washing tower washing enters electrostatic precipitator and removes acid mist, and flue gas cleaning is finished, and dust content is lower than 0.5mg/m in the rear furnace gas of purification
3
(5) transform absorption
Transform absorption section and adopt the double conversion and double absorption method, the equipment that adopts comprises drying tower, the first absorption tower and second absorption tower, is provided with the convertor of five beds, the First Heat Exchanger corresponding with each beds, the second interchanger, the 3rd interchanger, the 4th interchanger and the 5th interchanger;
The double conversion and double absorption technique that adopts comprises the steps:
A) in the future the furnace gas of self-purification workshop section replenishes air, makes that the sulfurous gas volumetric concentration is 8.5% in the furnace gas, and furnace gas is passed into the drying tower bottom, through dry absorption of the vitriol oil of 94% weight of cat head spray, dry after moisture content≤0.1g/Nm in the furnace gas
3
B) after drying furnace gas enters the 3rd interchanger successively, the shell side of First Heat Exchanger is heated, the temperature of furnace gas reaches 410 ℃ after the heating, the first paragraph beds that enters convertor transforms, sulfurous gas in the furnace gas is converted into sulphur trioxide under the effect of catalyzer, furnace gas enters the tube side cooling of First Heat Exchanger after transforming, entering convertor second segment beds after the cooling transforms, enter afterwards the cooling of the second heat exchanger tube pass, furnace gas enters the 3rd section beds of convertor and transforms after cooling, enter afterwards the cooling of the 3rd heat exchanger tube pass;
C) through behind the 3rd interchanger, furnace gas temperature is down to 165 ℃, enters the first absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters and absorbs the tower acid circulation groove;
D) the shell side heating that enters successively the 5th interchanger, the 4th interchanger and the second interchanger of the furnace gas after absorbing through the first absorption tower, enter the 4th section beds of convertor after furnace gas is heated carries out transforming the second time, furnace gas enters the cooling of the 4th heat exchanger tube pass after transforming, enter the 5th section beds of convertor after being cooled to 405 ℃ and transform, furnace gas is lowered the temperature through the 5th heat exchanger tube pass after transforming;
E) through behind the 5th interchanger, the temperature of furnace gas is down to 160 ℃ and is entered second absorption tower, sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, the vitriol oil after the absorption enters and absorbs the tower acid circulation groove, mix with the sulfuric acid that enters circulation groove in the first absorption tower, add entry to absorbing in the tower acid circulation groove, regulate the concentration of sulfuric acid, sulfuric acid is squeezed into the first absorption tower and second absorption tower circulated sprinkling through the cooling rear section, be used for absorbing the sulphur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
The transformation efficiency of sulfurous gas can reach 99.85% in the furnace gas.
The sulfuric acid product that makes is 98% industrial sulphuric acid, the be up to state standards index of acceptable end product among the GB/T534-2002 of quality product, and the industrial sulphuric acid performance index that make see Table 1:
Table 1
| Project | Index |
| H 2SO 4 | ≥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 the ferrous sulfate waste material and the rate of recovery of iron all reach more than 99%.
Embodiment 2
(1) drying
Sulphur foam and iron vitriol waste material are carried out drying in dehumidification system, make the sulphur foam be dehydrated into the thick sulphur of granular, obtain the ferrous sulfate monohydrate compound after the iron vitriol dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein the weight ratio of ferrous sulfate monohydrate is 1: 1 in dried thick Sulfur from Sulphur sulphur and the ferrous sulfate, mixture is sent into the boiling kiln roasting, maturing temperature is 850 ℃, pass into air, gas speed is 2 meter per seconds, and the residence time of mixture in fluidizing furnace is 8 seconds, after the roasting in the furnace gas sulfurous gas volumetric concentration be 12%.
(3) cooling
High-temperature furnace gas is passed into vapour generator cool off, furnace gas is cooled to 340 ℃, and vapour generator produces the low-pressure saturated steam pressure of 1.25MPa simultaneously.
(4) washing, purifying
Cooled furnace gas is passed into tornado dust collector remove flue dust, furnace gas enters Venturi meter after the dedusting, spray into 20% weight dilute sulphuric acid in venturi throat, dilute sulphuric acid is well atomized in Venturi meter, furnace gas and dilute sulphuric acid close contact, make the furnace gas humidification, cool and further dedusting, finish preliminary washing, purifying; Furnace gas enters stuffing washing tower after washing through Venturi meter, with 20% weight dilute sulphuric acid counter current contact, the washing, purifying of cat head spray, removes wherein impurity and steam; The furnace gas of process washing tower washing enters electrostatic precipitator and removes acid mist, and flue gas cleaning is finished, and dust content is lower than 0.5mg/m in the rear furnace gas of purification
3
(5) transform absorption
Transform absorption section and adopt the double conversion and double absorption method, the equipment that adopts comprises drying tower, the first absorption tower and second absorption tower, is provided with the convertor of five beds, the First Heat Exchanger corresponding with each beds, the second interchanger, the 3rd interchanger, the 4th interchanger and the 5th interchanger;
The double conversion and double absorption technique that adopts comprises the steps:
A) in the future the furnace gas of self-purification workshop section replenishes air, makes that the sulfurous gas volumetric concentration is 8.5% in the furnace gas, and furnace gas is passed into the drying tower bottom, through dry absorption of the vitriol oil of 94% weight of cat head spray, dry after moisture content≤0.1g/Nm in the furnace gas
3
B) after drying furnace gas enters the 3rd interchanger successively, the shell side of First Heat Exchanger is heated, the temperature of furnace gas reaches 420 ℃ after the heating, the first paragraph beds that enters convertor transforms, sulfurous gas in the furnace gas is converted into sulphur trioxide under the effect of catalyzer, furnace gas enters the tube side cooling of First Heat Exchanger after transforming, entering convertor second segment beds after the cooling transforms, enter afterwards the cooling of the second heat exchanger tube pass, furnace gas enters the 3rd section beds of convertor and transforms after cooling, enter afterwards the cooling of the 3rd heat exchanger tube pass;
C) through behind the 3rd interchanger, furnace gas temperature is down to 170 ℃, enters the first absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters and absorbs the tower acid circulation groove;
D) the shell side heating that enters successively the 5th interchanger, the 4th interchanger and the second interchanger of the furnace gas after absorbing through the first absorption tower, enter the 4th section beds of convertor after furnace gas is heated carries out transforming the second time, furnace gas enters the cooling of the 4th heat exchanger tube pass after transforming, enter the 5th section beds of convertor after being cooled to 415 ℃ and transform, furnace gas is lowered the temperature through the 5th heat exchanger tube pass after transforming;
E) through behind the 5th interchanger, the temperature of furnace gas is down to 165 ℃ and is entered second absorption tower, sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, the vitriol oil after the absorption enters and absorbs the tower acid circulation groove, mix with the sulfuric acid that enters circulation groove in the first absorption tower, add entry to absorbing in the tower acid circulation groove, regulate the concentration of sulfuric acid, sulfuric acid is squeezed into the first absorption tower and second absorption tower circulated sprinkling through the cooling rear section, be used for absorbing the sulphur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
The transformation efficiency of sulfurous gas can reach 99.9% in the furnace gas.
The sulfuric acid product that makes is 98% industrial sulphuric acid, the be up to state standards index of acceptable end product among the GB/T534-2002 of quality product, and the industrial sulphuric acid performance index that make see Table 2:
Table 2
| Project | Index |
| H 2SO 4 | ≥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 the ferrous sulfate waste material and the rate of recovery of iron all reach more than 99%.
Embodiment 3
(1) drying
Sulphur foam and iron vitriol waste material are carried out drying in dehumidification system, make the sulphur foam be dehydrated into the thick sulphur of granular, obtain the ferrous sulfate monohydrate compound after the iron vitriol dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein the weight ratio of ferrous sulfate monohydrate is 7: 3 in dried thick Sulfur from Sulphur sulphur and the ferrous sulfate, mixture is sent into the boiling kiln roasting, maturing temperature is 900 ℃, pass into air, gas speed is 1.0 meter per seconds, and the residence time of mixture in fluidizing furnace is 16 seconds, after the roasting in the furnace gas sulfurous gas volumetric concentration be 9%.
(3) cooling
High-temperature furnace gas is passed into vapour generator cool off, furnace gas is cooled to 320 ℃, and vapour generator produces the low-pressure saturated steam pressure of 1.3MPa simultaneously.
(4) washing, purifying
Cooled furnace gas is passed into tornado dust collector remove flue dust, furnace gas enters Venturi meter after the dedusting, spray into 40% weight dilute sulphuric acid in venturi throat, dilute sulphuric acid is well atomized in Venturi meter, furnace gas and dilute sulphuric acid close contact, make the furnace gas humidification, cool and further dedusting, finish preliminary washing, purifying; Furnace gas enters stuffing washing tower after washing through Venturi meter, with 40% weight dilute sulphuric acid counter current contact, the washing, purifying of cat head spray, removes wherein impurity and steam; The furnace gas of process washing tower washing enters electrostatic precipitator and removes acid mist, and flue gas cleaning is finished, and dust content is lower than 0.5mg/m in the rear furnace gas of purification
3
(5) transform absorption
Transform absorption section and adopt the double conversion and double absorption method, the equipment that adopts comprises drying tower, the first absorption tower and second absorption tower, is provided with the convertor of five beds, the First Heat Exchanger corresponding with each beds, the second interchanger, the 3rd interchanger, the 4th interchanger and the 5th interchanger;
The double conversion and double absorption technique that adopts comprises the steps:
A) in the future the furnace gas of self-purification workshop section replenishes air, makes that the sulfurous gas volumetric concentration is 8% in the furnace gas, and furnace gas is passed into the drying tower bottom, through dry absorption of the vitriol oil of 94% weight of cat head spray, dry after moisture content≤0.1g/Nm in the furnace gas
3
B) after drying furnace gas enters the 3rd interchanger successively, the shell side of First Heat Exchanger is heated, the temperature of furnace gas reaches 430 ℃ after the heating, the first paragraph beds that enters convertor transforms, sulfurous gas in the furnace gas is converted into sulphur trioxide under the effect of catalyzer, furnace gas enters the tube side cooling of First Heat Exchanger after transforming, entering convertor second segment beds after the cooling transforms, enter afterwards the cooling of the second heat exchanger tube pass, furnace gas enters the 3rd section beds of convertor and transforms after cooling, enter afterwards the cooling of the 3rd heat exchanger tube pass;
C) through behind the 3rd interchanger, furnace gas temperature is down to 175 ℃, enters the first absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters and absorbs the tower acid circulation groove;
D) the shell side heating that enters successively the 5th interchanger, the 4th interchanger and the second interchanger of the furnace gas after absorbing through the first absorption tower, enter the 4th section beds of convertor after furnace gas is heated carries out transforming the second time, furnace gas enters the cooling of the 4th heat exchanger tube pass after transforming, enter the 5th section beds of convertor after being cooled to 422 ℃ and transform, furnace gas is lowered the temperature through the 5th heat exchanger tube pass after transforming;
E) through behind the 5th interchanger, the temperature of furnace gas is down to 168 ℃ and is entered second absorption tower, sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, the vitriol oil after the absorption enters and absorbs the tower acid circulation groove, mix with the sulfuric acid that enters circulation groove in the first absorption tower, add entry to absorbing in the tower acid circulation groove, regulate the concentration of sulfuric acid, sulfuric acid is squeezed into the first absorption tower and second absorption tower circulated sprinkling through the cooling rear section, be used for absorbing the sulphur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
The transformation efficiency of sulfurous gas can reach 99.88% in the furnace gas.
The sulfuric acid product that makes is 98% industrial sulphuric acid, the be up to state standards index of acceptable end product among the GB/T534-2002 of quality product, and the industrial sulphuric acid performance index that make see Table 3:
Table 3
| Project | Index |
| H 2SO 4 | ≥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 the ferrous sulfate waste material and the rate of recovery of iron all reach more than 99%.
Embodiment 4
(1) drying
Sulphur foam and iron vitriol waste material are carried out drying in dehumidification system, make the sulphur foam be dehydrated into the thick sulphur of granular, obtain the ferrous sulfate monohydrate compound after the iron vitriol dehydration.
(2) roasting
Dried thick sulphur and ferrous sulfate are mixed, wherein the weight ratio of ferrous sulfate monohydrate is 5: 3 in dried thick Sulfur from Sulphur sulphur and the ferrous sulfate, mixture is sent into the boiling kiln roasting, maturing temperature is 950 ℃, pass into air, gas speed is 1.2 meter per seconds, and the residence time of mixture in fluidizing furnace is 10 seconds, after the roasting in the furnace gas sulfurous gas volumetric concentration be 12%.
(3) cooling
High-temperature furnace gas is passed into vapour generator cool off, furnace gas is cooled to 340 ℃, and vapour generator produces the low-pressure saturated steam pressure of 1.25MPa simultaneously.
(4) washing, purifying
Cooled furnace gas is passed into tornado dust collector remove flue dust, furnace gas enters Venturi meter after the dedusting, spray into 25% weight dilute sulphuric acid in venturi throat, dilute sulphuric acid is well atomized in Venturi meter, furnace gas and dilute sulphuric acid close contact, make the furnace gas humidification, cool and further dedusting, finish preliminary washing, purifying; Furnace gas enters stuffing washing tower after washing through Venturi meter, with 25% weight dilute sulphuric acid counter current contact, the washing, purifying of cat head spray, removes wherein impurity and steam; The furnace gas of process washing tower washing enters electrostatic precipitator and removes acid mist, and flue gas cleaning is finished, and dust content is lower than 0.5mg/m in the rear furnace gas of purification
3
(5) transform absorption
Transform absorption section and adopt the double conversion and double absorption method, the equipment that adopts comprises drying tower, the first absorption tower and second absorption tower, is provided with the convertor of five beds, the First Heat Exchanger corresponding with each beds, the second interchanger, the 3rd interchanger, the 4th interchanger and the 5th interchanger;
The double conversion and double absorption technique that adopts comprises the steps:
A) in the future the furnace gas of self-purification workshop section replenishes air, makes that the sulfurous gas volumetric concentration is 8.5% in the furnace gas, and furnace gas is passed into the drying tower bottom, through dry absorption of the vitriol oil of 94% weight of cat head spray, dry after moisture content≤0.1g/Nm in the furnace gas
3
B) after drying furnace gas enters the 3rd interchanger successively, the shell side of First Heat Exchanger is heated, the temperature of furnace gas reaches 420 ℃ after the heating, the first paragraph beds that enters convertor transforms, sulfurous gas in the furnace gas is converted into sulphur trioxide under the effect of catalyzer, furnace gas enters the tube side cooling of First Heat Exchanger after transforming, entering convertor second segment beds after the cooling transforms, enter afterwards the cooling of the second heat exchanger tube pass, furnace gas enters the 3rd section beds of convertor and transforms after cooling, enter afterwards the cooling of the 3rd heat exchanger tube pass;
C) through behind the 3rd interchanger, furnace gas temperature is down to 170 ℃, enters the first absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters and absorbs the tower acid circulation groove;
D) the shell side heating that enters successively the 5th interchanger, the 4th interchanger and the second interchanger of the furnace gas after absorbing through the first absorption tower, enter the 4th section beds of convertor after furnace gas is heated carries out transforming the second time, furnace gas enters the cooling of the 4th heat exchanger tube pass after transforming, enter the 5th section beds of convertor after being cooled to 415 ℃ and transform, furnace gas is lowered the temperature through the 5th heat exchanger tube pass after transforming;
E) through behind the 5th interchanger, the temperature of furnace gas is down to 165 ℃ and is entered second absorption tower, sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, the vitriol oil after the absorption enters and absorbs the tower acid circulation groove, mix with the sulfuric acid that enters circulation groove in the first absorption tower, add entry to absorbing in the tower acid circulation groove, regulate the concentration of sulfuric acid, sulfuric acid is squeezed into the first absorption tower and second absorption tower circulated sprinkling through the cooling rear section, be used for absorbing the sulphur trioxide of furnace gas, unnecessary sulfuric acid is sulfuric acid product.
The transformation efficiency of sulfurous gas can reach 99.9% in the furnace gas.
The sulfuric acid product that makes is 98% industrial sulphuric acid, the be up to state standards index of acceptable end product among the GB/T534-2002 of quality product, and the industrial sulphuric acid performance index that make see Table 4:
Table 4
| Project | Index |
| H 2SO 1 | ≥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 the ferrous sulfate waste material and the rate of recovery of iron all reach more than 99%.
Comparative Examples 1
Be the contrast experiment with the processing condition among the embodiment 1, difference is that the weight ratio of ferrous sulfate monohydrate in dry rear thick Sulfur from Sulphur sulphur and the ferrous sulfate waste material is 1: 7, compares with embodiment 1, and boiling roaster needs expend fuel about 35% more.
Comparative Examples 2
Be the contrast experiment with the processing condition among the embodiment 1, difference is that the weight ratio of ferrous sulfate monohydrate in dry rear thick Sulfur from Sulphur sulphur and the ferrous sulfate waste material is 2: 7, compares with embodiment 1, and boiling roaster needs expend fuel about 23% more.
Comparative Examples 3
Be the contrast experiment with the processing condition among the embodiment 3, difference is that the weight ratio of ferrous sulfate monohydrate in dry rear thick Sulfur from Sulphur sulphur and the ferrous sulfate waste material is 7: 1, compares with embodiment 3, and boiling roaster needs expend fuel about 26% more.
Comparative Examples 4
Be the contrast experiment with the processing condition among the embodiment 3, difference is that the weight ratio of ferrous sulfate monohydrate in dry rear thick Sulfur from Sulphur sulphur and the ferrous sulfate waste material is 7: 2, compares with embodiment 3, and boiling roaster needs expend fuel about 20% more.
Comparative Examples 5
Be the contrast experiment with the processing condition among the embodiment 2, difference is that purification section only adopts dry method dust, without follow-up wet scrubbing cleaning section, is 92mg/m through dust content in the furnace gas behind the purification section
3, convertor middle part divided catalyst is poisoned, and the Sulphur Dioxide rate is 83%.
Comparative Examples 6
Be the contrast experiment with the processing condition among the embodiment 2, difference is not adopt in the purification section Venturi meter tentatively to wash, directly entering the washing tower washing at furnace gas behind the tornado dust collector dry method dust, is 15mg/m through dust content in the furnace gas behind the purification section
3, the transformation efficiency of sulfurous gas is 95%.
Claims (10)
1. a sulphur waste material is mixed and is burnt the method that the ferrous sulfate waste material prepares sulfuric acid, and the method comprises the steps:
A) sulphur waste material and ferrous sulfate waste material is dry, make the sulphur waste material be dehydrated into the thick sulphur of granular, obtain the ferrous sulfate monohydrate compound after the dehydration of ferrous sulfate waste material;
B) dried sulphur waste material and ferrous sulfate waste material are mixed, wherein, in the sulphur waste material in sulphur and the ferrous sulfate waste material weight ratio of ferrous sulfate monohydrate be 3: 7～7: 3;
C) with step b) in mixture add the boiling kiln roasting, maturing temperature is 850-1000 ℃, passes into air, and gas speed is the 1.0-2.0 meter per second, the residence time of mixture in fluidizing furnace is 4-16 second, after the roasting in the furnace gas sulfurous gas volumetric concentration be 9-12%;
D) with step c) in contain sulfurous gas furnace gas make sulfuric acid through overcooling, washing, purifying, conversion absorption section.
2. the method for claim 1, wherein described step b), in the dried sulphur waste material in sulphur and the ferrous sulfate waste material weight ratio of ferrous sulfate monohydrate be 3: 3～7: 3.
3. the method for claim 1, wherein described step c) after the roasting in the furnace gas sulfurous gas volumetric concentration be 12%.
4. the method for claim 1, wherein, described steps d) in, the furnace gas that contains sulfurous gas cools off by vapour generator, furnace gas is cooled to 320 ℃-360 ℃ and enters purification section, and described vapour generator produces the low-pressure saturated steam of 1.2-1.3MPa.
5. the method for claim 1, wherein described steps d), described furnace gas washing, purifying workshop section may further comprise the steps:
1) cooled furnace gas is removed flue dust by tornado dust collector;
2) furnace gas after the dedusting enters Venturi meter, sprays into the dilute sulphuric acid of 10-40% weight in described venturi throat, finishes preliminary washing, purifying;
3) furnace gas through the washing of described Venturi meter after, enter stuffing washing tower, with the dilute sulphuric acid counter current contact of the 10-40% weight of cat head spray, remove wherein impurity and steam, flue gas cleaning is finished, after purifying in the furnace gas dust content be lower than 0.5mg/m
3
6. method as claimed in claim 5, wherein, described flue gas cleaning workshop section also comprises step 4, with step 3) in send into electrostatic precipitator through the furnace gas of washing tower washing and remove acid mist.
7. such as claim 1 or 5 described methods, wherein, described steps d) in, described conversion absorption section adopts the double conversion and double absorption method, the equipment that adopts comprises drying tower, the first absorption tower and second absorption tower, is provided with the convertor of five beds, corresponding First Heat Exchanger, the second interchanger, the 3rd interchanger, the 4th interchanger and the 5th interchanger of being provided with each beds;
Described double conversion and double absorption method comprises the steps:
1) will replenish air from the furnace gas of washing, purifying workshop section, make that the sulfurous gas volumetric concentration is 8-8.5% in the furnace gas, furnace gas will be passed into the drying tower bottom, through dry absorption of the vitriol oil of 94% weight of cat head spray;
2) after drying furnace gas is successively through the heating of the 3rd interchanger, First Heat Exchanger, the first paragraph beds that furnace gas after the heating enters convertor transforms, furnace gas after the conversion enters the First Heat Exchanger cooling, furnace gas enters convertor second segment beds and transforms after cooling, enter afterwards the cooling of the second interchanger, furnace gas enters the 3rd section beds of convertor and transforms after cooling, enter afterwards the cooling of the 3rd interchanger;
3) furnace gas through the cooling of the 3rd interchanger enters the first absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters and absorbs the tower acid circulation groove;
4) enter successively the heating of the 5th, the 4th and second interchanger through the furnace gas after the absorption of the first absorption tower, enter the 4th section beds of convertor after furnace gas is heated carries out transforming the second time, furnace gas after the conversion enters the cooling of the 4th interchanger, enter afterwards the 5th section beds of convertor and transform, the furnace gas after the conversion is lowered the temperature through the 5th interchanger;
5) furnace gas through the cooling of the 5th interchanger enters second absorption tower, and the sulphur trioxide in the furnace gas is absorbed by the vitriol oil of 98% weight that cat head sprays, and the vitriol oil after the absorption enters step 3) described absorption tower acid circulation groove.
8. method as claimed in claim 7, wherein, described step 1) in, moisture content≤0.1g/Nm in the furnace gas after drying
3
9. method as claimed in claim 7, wherein, described step 2) through the 3rd and the First Heat Exchanger heating furnace gas temperature that enters convertor the first beds be 410-430 ℃.
10. the method for claim 1, wherein the sulphur waste material of described step in a) is sulfur containing waste material after synthetic ammonia, coke-oven gas, power plant, the aluminium manufacturer's desulfurization.
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| CN103552992A (en) * | 2013-10-30 | 2014-02-05 | 中石化南京工程有限公司 | System and method for preparing acid by using sulfur-containing wastewater through dry method |
| CN103553143A (en) * | 2013-11-08 | 2014-02-05 | 四川大学 | Method for preparing iron oxide red and sulfuric acid by sulfate capable of decomposing iron by sulfur reduction |
| CN105293448A (en) * | 2015-10-23 | 2016-02-03 | 湖北祥云(集团)化工股份有限公司 | Method for recycling sulfur residues and pyrite to make acid and device thereof |
| CN110844941A (en) * | 2019-12-12 | 2020-02-28 | 攀钢集团重庆钛业有限公司 | Iron oxide red production process |
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| CN101439880A (en) * | 2008-12-19 | 2009-05-27 | 彭铁战 | Production process for coproduction of iron oxide red and concentrated sulfuric acid |
| CN101913573A (en) * | 2010-08-30 | 2010-12-15 | 攀枝花圣地元科技有限责任公司 | Method for producing sulfuric acid and iron oxide red |
| CN102674473A (en) * | 2012-06-01 | 2012-09-19 | 湖南恒光化工有限公司 | Process for preparing ferric oxide red by adopting iron vitriol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101439880A (en) * | 2008-12-19 | 2009-05-27 | 彭铁战 | Production process for coproduction of iron oxide red and concentrated sulfuric acid |
| CN101913573A (en) * | 2010-08-30 | 2010-12-15 | 攀枝花圣地元科技有限责任公司 | Method for producing sulfuric acid and iron oxide red |
| CN102674473A (en) * | 2012-06-01 | 2012-09-19 | 湖南恒光化工有限公司 | Process for preparing ferric oxide red by adopting iron vitriol |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103552992A (en) * | 2013-10-30 | 2014-02-05 | 中石化南京工程有限公司 | System and method for preparing acid by using sulfur-containing wastewater through dry method |
| CN103553143A (en) * | 2013-11-08 | 2014-02-05 | 四川大学 | Method for preparing iron oxide red and sulfuric acid by sulfate capable of decomposing iron by sulfur reduction |
| 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 |
| CN105293448A (en) * | 2015-10-23 | 2016-02-03 | 湖北祥云(集团)化工股份有限公司 | Method for recycling sulfur residues and pyrite to make acid and device thereof |
| CN110844941A (en) * | 2019-12-12 | 2020-02-28 | 攀钢集团重庆钛业有限公司 | Iron oxide red production process |
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