CN104045063A - Waste sulfuric acid solution treatment method - Google Patents
Waste sulfuric acid solution treatment method Download PDFInfo
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- CN104045063A CN104045063A CN201310529027.5A CN201310529027A CN104045063A CN 104045063 A CN104045063 A CN 104045063A CN 201310529027 A CN201310529027 A CN 201310529027A CN 104045063 A CN104045063 A CN 104045063A
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Abstract
The invention provides a waste sulfuric acid solution treatment method. The above waste sulfuric acid solution contains sulfuric acid and ferrous sulfate, the concentration of sulfuric acid in the waste sulfuric acid solution is not higher than 20wt%. The method comprises the following steps: removing crystal water in copperas, calcining, allowing exhaust gas obtained after the calcining to have first contact with the waste sulfuric acid solution until the concentration of sulfuric acid in the waste sulfuric acid solution reaches 45-50wt%, carrying out solid-liquid separation on the waste sulfuric acid solution, and allowing the above obtained filtrate to continuously have second contact with the exhaust gas. The method enables the waste sulfuric acid solution to be purified and reused, so the waste raw material can be effectively used, the pressure to the environment can be mitigated, and the method has a great industrial application prospect.
Description
Technical field
The present invention relates to a kind for the treatment of process of waste sulfuric acid solution.
Background technology
Titanium dioxide is a kind of good white pigment, is widely used at present the industries such as paint, coating, papermaking, plastics and welding electrode.
At present, the technique of producing titanium dioxide mainly contains sulfuric acid process and chlorination process, and two kinds of techniques are also deposited, and productivity is all very huge.But these two kinds of production technique all have certain environmental stress.For Production By Sulfuric Acid Process technique, in production process, a large amount of hydrolysis spent acid and the green vitriol (FeSO that contains seven crystal water will be produced
47H
2o).When taking ilmenite concentrate, (main component is as metatitanic acid iron FeTiO
3, wherein the content of titanium dioxide is 45-50 % by weight) and when the raw material, generally produce 1 ton of titanium dioxide by output 3.5-4 ton seven melanterites.
Green vitriol is generally used for prepares pigment, water purification agent etc.Because the annual production of every production line of Titanium White Production By Sulfuric Acid Process is generally all ten thousand tons of 2-4, this is by seven melanterites of more than 10 ten thousand tons of outputs, the application of so a large amount of green vitriols, for the sulfuric acid method titanium pigment producer of countries in the world, is all the problem of a headache.European countries consider that a large amount of green vitriols exist the problem of difficult treatment, therefore turn to chlorination process to produce to avoid.In addition, adopting titanium slag is that raw material carries out Production By Sulfuric Acid Process, also can avoid this problem.
But, on the one hand, the production of domestic titanium dioxide, chlorination process just starts starting, and technique is not mature enough; On the other hand, due to production cost, less employing titanium slag is raw material production titanium dioxide, still need to produce titanium dioxide taking ilmenite concentrate as raw material, and therefore, effective utilization of by-product green vitriol is exactly a problem that needs think better of.
At present, green vitriol can be used as water purification agent, fodder additives, improvement saltings etc., and still, the amount of these purposes consumption green vitriols very little, can not solve the problem of utilizing of a large amount of by-product green vitriols far away.
CN1994868A discloses a kind of method of producing sulfuric acid and iron ore concentrate with ferrous sulfate, and specifically disclose and produce titanium dioxide by-product iron vitriol through heating (Heating temperature is 250-350 DEG C) the anhydrous slufuric acid ferrous iron that dewaters to obtain, this anhydrous slufuric acid ferrous iron is heated to 700-1000 DEG C in the middle of rotary kiln, under reducing atmosphere, decompose and obtain iron ore concentrate and sulfur dioxide gas, conventional double conversion and double absorption technique sulfuric acid processed for sulfur dioxide gas.Adopt the method can make sulphur and iron resources in titanium white by product ferrous sulfate be utilized simultaneously, be suitable for large-scale production.But, when the above-mentioned method with ferrous sulfate production sulfuric acid and iron ore concentrate does not consider that green vitriol is dried, remove crystal water and bother very much.Because the fusing point of iron vitriol is low, be only 64 DEG C, FeSO in drying and dehydrating process at 250-350 DEG C
4very easily be dissolved in the crystal water of self, cause drying plant fouling, sticky wall, effective utilization of drying plant is reduced, cause equipment failure.
In addition, owing to adopting, the waste sulfuric acid solution quantum of output of method for producing gtitanium dioxide with sulphuric acid by-product is too large, and contains a certain amount of ferrous sulfate, makes can not utilize this waste sulfuric acid solution in the field of other use dilute sulphuric acids.At present, conventionally adopt in Wingdale and with the method that generates calcium sulfate, this waste sulfuric acid solution is processed.But the calcium sulfate obtaining does not have utility value and can only store up, this does not only utilize raw material well, but also can cause larger pressure to environment.
Summary of the invention
The object of the invention is to adopt existing method to process the waste sulfuric acid solution that adopts method for producing gtitanium dioxide with sulphuric acid by-product in order to overcome, not only can not effectively utilize raw material, but also can cause the defect of larger pressure to environment, can carry out the method for effectively processing to the waste sulfuric acid solution of employing method for producing gtitanium dioxide with sulphuric acid by-product and provide a kind of.
The invention provides a kind for the treatment of process of waste sulfuric acid solution, described waste sulfuric acid solution contains sulfuric acid and ferrous sulfate, and taking the gross weight of described waste sulfuric acid solution as benchmark, in described waste sulfuric acid solution, the concentration of sulfuric acid is not higher than 20 % by weight, wherein, the method comprises the crystal water in green vitriol is removed to rear calcining, and the waste gas that obtains after calcining is carried out to first with described waste sulfuric acid solution contact, until the concentration of sulfuric acid reaches 45-50 % by weight in described waste sulfuric acid solution, then described waste sulfuric acid solution is carried out to solid-liquid separation, and the continuation of the filtrate that obtains is carried out to second with described waste gas contact.
The present inventor finds after deep research, adopts method of the present invention finally can obtain the sulphuric acid soln of concentration higher (70-99.9 % by weight).Infer its reason, may be due to: if described waste gas is constantly passed in described waste sulfuric acid solution and ferrous sulfate is not wherein separated, in the time that the concentration of sulfuric acid in solution increases to 60 % by weight left and right, the ferrous sulfate in solution will be combined with sulfuric acid and be made the concentration of sulfuric acid cannot continue to improve so; And method provided by the invention has effectively utilized the SO containing in the waste gas of emitting after the green vitriol calcining removing after crystal water
3to improve the concentration of sulfuric acid in described waste sulfuric acid solution, in the process increasing gradually at sulfuric acid concentration, ferrous sulfate wherein is constantly separated out, in the time that the concentration of sulfuric acid in waste sulfuric acid solution reaches 45-50 % by weight, ferrous sulfate is separated out substantially completely, and removed by carrying out solid-liquid separation, after continuing to pass into described gas, the sulfuric acid concentration in solution can be easy to continue to raise.The treatment process of waste sulfuric acid solution provided by the invention has not only effectively utilized useless raw material, but also can alleviate the pressure that environment is caused, and has prospects for commercial application.
In addition, the present inventor stumbles on, in the drying process of green vitriol, add a certain amount of ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron, fouling, the wall sticking phenomenon that can very effectively avoid described green vitriol to occur in drying process, carry out drying process smoothly.Therefore, a preferred embodiment of the invention, when the method that the crystal water in described green vitriol is removed comprises described green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid is ferrous when mixing and being dried to remove crystal water, can also further solve the problem of drying plant fouling, bonding.
According to another kind of preferred implementation of the present invention, when described dry mode is first by the mixture of green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron dry 1-5 hour at 60-80 DEG C, again temperature is risen to 100-150 DEG C of dry 1-5 hour, and then when temperature is risen to 300-350 DEG C of dry 1-5 hour, the fouling, the wall sticking phenomenon that adopt the mode of this temperature programming can more effectively avoid described green vitriol to occur in drying process.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind for the treatment of process of waste sulfuric acid solution, described waste sulfuric acid solution contains sulfuric acid and ferrous sulfate, and taking the gross weight of described waste sulfuric acid solution as benchmark, in described waste sulfuric acid solution, the concentration of sulfuric acid is not higher than 20 % by weight, wherein, the method comprises the crystal water in green vitriol is removed to rear calcining, and the waste gas that obtains after calcining is carried out to first with described waste sulfuric acid solution contact, until the concentration of sulfuric acid reaches 45-50 % by weight in described waste sulfuric acid solution, then described waste sulfuric acid solution is carried out to solid-liquid separation, and the continuation of the filtrate that obtains is carried out to second with described waste gas contact.
In above-mentioned treating processes, be hydrolyzed the rising of ferrous sulfate contained in spent acid along with sulfuric acid concentration, its solubleness significantly reduces, in order not affect absorption, need to, in the time that sulfuric acid concentration is increased to 45-50 % by weight, absorption liquid be carried out to solid-liquid separation, and gained product liquid is continued to use as absorption agent, the ferrous sulfate of separating out can carry out calcination processing, and the vitriol oil obtaining after the second contact can be used as one of two kinds of main raw materials of sulfuric acid method titanium pigment production.
The present invention is not particularly limited the source of described waste sulfuric acid solution and green vitriol, from being easy to get property of raw material and effectively solve the waste sulfuric acid solution of method for producing gtitanium dioxide with sulphuric acid by-product and the angle of the problem that green vitriol brings, described waste sulfuric acid solution and green vitriol are particularly preferably the waste sulfuric acid solution and the green vitriol that adopt method for producing gtitanium dioxide with sulphuric acid by-product.In addition, in the green vitriol due to employing method for producing gtitanium dioxide with sulphuric acid by-product, conventionally contain a certain amount of free-water, therefore, before described green vitriol is removed to crystal water, conventionally need first by free water removal wherein.Remove free-water for example can carry out in centrifugation apparatus.
According to the present invention, for the waste sulfuric acid solution that adopts method for producing gtitanium dioxide with sulphuric acid by-product, taking the gross weight of pending waste sulfuric acid solution as benchmark, in pending waste sulfuric acid solution, the concentration of sulfuric acid can be 17-20 % by weight conventionally, and the concentration of ferrous sulfate can be 2-3 % by weight conventionally.
The present invention is all not particularly limited with the second condition contacting described the first contact, as long as the SO in the waste gas that can be conducive to obtain after calcining
3dissolving in described waste sulfuric acid solution.As a rule, described waste gas contacts at lower temperature with waste sulfuric acid solution and is conducive to the dissolving of waste gas in waste sulfuric acid solution, but maintain lower Contact Temperature and need to consume the energy, therefore, consider in all its bearings, described the first contact is preferably carried out with the second temperature contacting under room temperature (being 20-35 DEG C).In addition, in the waste sulfuric acid solution that the time of described the first contact need to ensure to obtain after the first contact, the concentration of sulfuric acid reaches 45-50 % by weight, the concentration of the sulphuric acid soln that the time of the second contact can obtain is as required selected, for example, in the time need to obtaining the higher sulphuric acid soln of concentration, can extend the time of the second contact; And in the time need to obtaining the lower sulphuric acid soln of concentration, can shorten the time of the second contact.
According to the present invention, can adopt existing the whole bag of tricks that the crystal water in described green vitriol is removed, but in order effectively to avoid the generation of drying plant fouling, wall sticking phenomenon, preferably, the method crystal water in described green vitriol being removed comprises described green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid is ferrous mixes and be dried to remove crystal water.
According to the present invention, although just can avoid well the fouling of drying plant, the generation of wall sticking phenomenon as long as add ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron in described green vitriol, but remove the efficiency of crystal water in order to improve more significantly described green vitriol, taking the described green vitriol of 100 weight parts as benchmark, total consumption of described ferrous sulfate monohydrate and anhydrous slufuric acid ferrous iron is preferably 20-45 weight part, more preferably 30-45 weight part.It should be noted that, in dry process, in the time only adding ferrous sulfate monohydrate, total consumption of described ferrous sulfate monohydrate and anhydrous slufuric acid ferrous iron refers to the consumption of ferrous sulfate monohydrate; In the time only adding anhydrous slufuric acid ferrous, total consumption of described ferrous sulfate monohydrate and anhydrous slufuric acid ferrous iron refers to the consumption of anhydrous slufuric acid ferrous iron; In the time adding ferrous sulfate monohydrate and anhydrous slufuric acid ferrous, total consumption of described ferrous sulfate monohydrate and anhydrous slufuric acid ferrous iron refers to the consumption sum of consumption and the anhydrous slufuric acid ferrous iron of ferrous sulfate monohydrate simultaneously.
The present invention is not particularly limited described dry temperature, and for example, described dry temperature can be 60-350 DEG C.In addition, the present invention is also not particularly limited described dry mode, as long as the crystal water in described green vitriol can be removed, thereby it is ferrous to obtain anhydrous slufuric acid.Preferably, described dry mode is first by the mixture of green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron dry 1-5 hour at 60-80 DEG C, again temperature is risen to 100-150 DEG C of dry 1-5 hour, and then temperature is risen to 300-350 DEG C of dry 1-5 hour, can more effectively avoid like this generation of fouling, wall sticking phenomenon, and improve drying efficiency.
According to the present invention, described ferrous sulfate monohydrate and anhydrous slufuric acid ferrous iron all can be by commercially available.In addition, described ferrous sulfate monohydrate can also be by being slowly dried appropriate green vitriol to obtain at 50-60 DEG C.
According to the present invention, in order to shorten the time that removes crystal water, improve the processing power of drying plant, the described method that removes crystal water in green vitriol is also preferably included in when the mixture of described green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron is dried, pass into flowing air (, introduce from one end of drying plant, and draw from the other end).
Described air can be the air under normal temperature, can be also the warm air after heating, is preferably warm air, can more effectively the crystal water removing be taken away like this, thereby shorten time of drying and improve the processing power of drying plant.Wherein, the temperature of described air can be 20-350 DEG C.
The present invention is not particularly limited the flow of described air, as a rule, the flow of air more greatly is more conducive to be dried, but also can corresponding increase pass into the required energy consumption of air, therefore, combined factors from every side considers, taking the green vitriol of 1kg crystal water to be removed as benchmark, the flow of described air is preferably 0.1-5m
3/ h, more preferably 0.5-3m
3/ h.
According to the present invention, described solid-liquid separation can be existingly variously can realize the method that solid phase separates with liquid phase (being sulphuric acid soln and the ferrous sulfate of separating out), for example suction filtration, press filtration or centrifugation.The present invention is not particularly limited the condition of press filtration, is as the criterion with separating of liquid phase to realize as far as possible fully solid phase, and therefore not to repeat here.
The treatment process of waste sulfuric acid solution provided by the invention also preferably includes the sulphuric acid soln that obtains after processing for dissolving ilmenite concentrate to prepare titanium dioxide, can realize like this recycle of raw material, has more prospects for commercial application.Detailed process can be same as the prior art, will repeat no more at this.
Below will describe the present invention by embodiment.
In following examples and comparative example, pending waste sulfuric acid solution is the waste sulfuric acid solution that adopts method for producing gtitanium dioxide with sulphuric acid by-product, and green vitriol is the green vitriol that adopts method for producing gtitanium dioxide with sulphuric acid by-product.
In following examples, the purity of sulphuric acid soln is by measuring purchased from the high performance liquid chromatograph of Shimadzu company.
Embodiment 1
This embodiment is for illustrating the treatment process of waste sulfuric acid solution provided by the invention.
(1) green vitriol removes crystal water:
Green vitriol is removed in whizzer to free-water, be then placed in Temperature Setting forced air drying 8 hours in the convection oven of 50-60 DEG C, obtain ferrous sulfate monohydrate.
Add rotary kiln (purchased from Beijing Zhuo Chuan Electronic Science and Technology Co., Ltd. wait removing after the green vitriol of crystal water and the ferrous sulfate monohydrate obtaining according to above method of 3 weight parts mix 7 weight parts, model is ZZ99-SHY-I) in, (taking the green vitriol of 1kg crystal water to be removed as benchmark, the flow of air is 1m in rotary kiln, to pass into continuously temperature and be the air of 30 DEG C
3/ h), and at the temperature of 60 DEG C dry 5 hours, then by the temperature of rotary kiln rise to 120 DEG C dry 2 hours, and then by the temperature of rotary kiln rise to 300 DEG C dry 5 hours, obtain anhydrous slufuric acid ferrous iron.Result shows, in rotary kiln, do not occur fouling, wall sticking phenomenon, the production capacity of rotary kiln be 12kg anhydrous slufuric acid ferrous iron/hour.
(2) processing of waste sulfuric acid solution:
The anhydrous slufuric acid ferrous iron that step (1) is obtained is placed in chamber type electric resistance furnace, and be warming up to 880 DEG C of calcinings, then the waste sulfuric acid solution that the waste gas that obtains after calcining is passed into continuously to temperature and be 30 DEG C (contains sulfuric acid and ferrous sulfate, and taking the gross weight of described waste sulfuric acid solution as benchmark, the content of sulfuric acid is 17 % by weight, the content of ferrous sulfate is 2 % by weight) in, until when in described waste sulfuric acid solution, the concentration of sulfuric acid reaches 45 % by weight, described waste sulfuric acid solution is carried out to suction filtration, then the solid product ferrous sulfate obtaining is carried out to calcination processing, and above-mentioned waste gas is continued to pass in the filtrate obtaining, until obtain the sulphuric acid soln that concentration is 80 % by weight, and this sulphuric acid soln is used for to acidolysis ilmenite concentrate.
Embodiment 2
This embodiment is for illustrating the treatment process of waste sulfuric acid solution provided by the invention.
(1) green vitriol removes crystal water:
By adding in rotary kiln wait removing after the green vitriol of crystal water mixes with the anhydrous slufuric acid ferrous iron of 2.5 weight parts (method according to embodiment 1 prepares) of 7 weight parts, (taking the green vitriol of 1kg crystal water to be removed as benchmark, the flow of air is 1m in rotary kiln, to pass into continuously temperature and be the air of 350 DEG C
3/ h), and at the temperature of 80 DEG C dry 2 hours, then by the temperature of rotary kiln rise to 100 DEG C dry 1 hour, and then by the temperature of rotary kiln rise to 350 DEG C dry 1 hour, obtain anhydrous slufuric acid ferrous iron.Result shows, in rotary kiln, do not occur fouling, wall sticking phenomenon, the production capacity of rotary kiln be 14kg anhydrous slufuric acid ferrous iron/hour.
(2) processing of waste sulfuric acid solution:
The anhydrous slufuric acid ferrous iron that step (1) is obtained is placed in chamber type electric resistance furnace, and be warming up to 880 DEG C of calcinings, then the waste sulfuric acid solution that the waste gas that obtains after calcining is passed into continuously to temperature and be 20 DEG C (contains sulfuric acid and ferrous sulfate, and taking the gross weight of described waste sulfuric acid solution as benchmark, the content of sulfuric acid is 20 % by weight, the content of ferrous sulfate is 3 % by weight) in, until when in described waste sulfuric acid solution, the concentration of sulfuric acid reaches 50 % by weight, described waste sulfuric acid solution is carried out to suction filtration, then the solid product ferrous sulfate obtaining is carried out to calcination processing, and above-mentioned waste gas is continued to pass in the filtrate obtaining, until obtain the sulphuric acid soln that concentration is 80 % by weight, and this sulphuric acid soln is used for to acidolysis ilmenite concentrate.
Embodiment 3
This embodiment is for illustrating the treatment process of waste sulfuric acid solution provided by the invention.
(1) green vitriol removes crystal water:
Green vitriol is removed in whizzer to free-water, be then placed in Temperature Setting forced air drying 8 hours in the convection oven of 50-60 DEG C, obtain ferrous sulfate monohydrate.
By adding in rotary kiln wait removing after the green vitriol of crystal water and the ferrous sulfate monohydrate obtaining according to above method of 2.75 weight parts mix of 7 weight parts, (taking the green vitriol of 1kg crystal water to be removed as benchmark, the flow of air is 1m in rotary kiln, to pass into continuously temperature and be the air of 150 DEG C
3/ h), and at the temperature of 70 DEG C dry 2 hours, then by the temperature of rotary kiln rise to 110 DEG C dry 1 hour, and then by the temperature of rotary kiln rise to 320 DEG C dry 1.5 hours, obtain anhydrous slufuric acid ferrous iron.Result shows, in rotary kiln, do not occur fouling, wall sticking phenomenon, the production capacity of rotary kiln be 12kg anhydrous slufuric acid ferrous iron/hour.
(2) processing of waste sulfuric acid solution:
The anhydrous slufuric acid ferrous iron that step (1) is obtained is placed in chamber type electric resistance furnace, and be warming up to 880 DEG C of calcinings, then the waste sulfuric acid solution that the waste gas that obtains after calcining is passed into continuously to temperature and be 35 DEG C (contains sulfuric acid and ferrous sulfate, and taking the gross weight of described waste sulfuric acid solution as benchmark, the content of sulfuric acid is 18 % by weight, the content of ferrous sulfate is 2.5 % by weight) in, until when in described waste sulfuric acid solution, the concentration of sulfuric acid reaches 48 % by weight, described waste sulfuric acid solution is carried out to suction filtration, then the solid product ferrous sulfate obtaining is carried out to calcination processing, and above-mentioned waste gas is continued to pass in the filtrate obtaining, until obtain the sulphuric acid soln that concentration is 80 % by weight, and this sulphuric acid soln is used for to acidolysis ilmenite concentrate.
Embodiment 4
This embodiment is for illustrating the treatment process of waste sulfuric acid solution provided by the invention.
According to the method for embodiment 1, the crystal water in green vitriol is removed, different, the consumption of the ferrous sulfate monohydrate mixing with the green vitriol of crystal water to be removed is 4 weight parts, obtains anhydrous slufuric acid ferrous iron.Result shows, in rotary kiln, do not occur fouling, wall sticking phenomenon, the production capacity of rotary kiln be 11kg anhydrous slufuric acid ferrous iron/hour, obtain the sulphuric acid soln that concentration is 80 % by weight, and by this sulphuric acid soln for acidolysis ilmenite concentrate.
Embodiment 5
This embodiment is for illustrating the treatment process of waste sulfuric acid solution provided by the invention.
According to the method for embodiment 1, the crystal water in green vitriol is removed, different, in the process that removes crystal water, in rotary kiln, do not pass into continuously temperature and be the air of 30 DEG C, obtain anhydrous slufuric acid ferrous iron.Result shows, in rotary kiln, do not occur fouling, wall sticking phenomenon, the production capacity of rotary kiln be 8kg anhydrous slufuric acid ferrous iron/hour, obtain the sulphuric acid soln that concentration is 80 % by weight, and by this sulphuric acid soln for acidolysis ilmenite concentrate.
Comparative example 1
This comparative example is for illustrating the reference treatment process of waste sulfuric acid solution.
Method according to embodiment 4 is processed waste sulfuric acid solution, different, and in step (2), the first contact makes the concentration of sulfuric acid in waste sulfuric acid solution reach 35 % by weight.As a result, after continuing to pass into described gas, in solution, sulfuric acid concentration can only increase to 60 % by weight.
As can be seen from the above results, adopt method provided by the invention can make waste sulfuric acid solution be able to purifying and can be re-used, thereby not only effectively utilized useless raw material, but also can alleviate the pressure that environment is caused, have prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. the treatment process of a waste sulfuric acid solution, described waste sulfuric acid solution contains sulfuric acid and ferrous sulfate, and taking the gross weight of described waste sulfuric acid solution as benchmark, in described waste sulfuric acid solution, the concentration of sulfuric acid is not higher than 20 % by weight, it is characterized in that, the method comprises the crystal water in green vitriol is removed to rear calcining, and the waste gas that obtains after calcining is carried out to first with described waste sulfuric acid solution contact, until the concentration of sulfuric acid reaches 45-50 % by weight in described waste sulfuric acid solution, then described waste sulfuric acid solution is carried out to solid-liquid separation, and the continuation of the filtrate that obtains is carried out to second with described waste gas contact.
2. treatment process according to claim 1, wherein, taking the gross weight of pending waste sulfuric acid solution as benchmark, in pending waste sulfuric acid solution, the concentration of sulfuric acid is 17-20 % by weight, the concentration of ferrous sulfate is 2-3 % by weight.
3. treatment process according to claim 1 and 2, wherein, the method that the crystal water in described green vitriol is removed comprises described green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid is ferrous mixes and be dried to remove crystal water.
4. treatment process according to claim 3, wherein, taking the described green vitriol of 100 weight parts as benchmark, total consumption of described ferrous sulfate monohydrate and anhydrous slufuric acid ferrous iron is 20-45 weight part.
5. treatment process according to claim 4, wherein, described dry temperature is 60-350 DEG C.
6. treatment process according to claim 5, wherein, described dry mode is first by the mixture of green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron dry 1-5 hour at 60-80 DEG C, again temperature is risen to 100-150 DEG C of dry 1-5 hour, and then temperature is risen to 300-350 DEG C of dry 1-5 hour.
7. according to the treatment process described in any one in claim 4-6, wherein, the method that the crystal water in described green vitriol is removed is also included in when the mixture of described green vitriol and ferrous sulfate monohydrate and/or anhydrous slufuric acid ferrous iron is dried, and passes into flowing air.
8. treatment process according to claim 7, wherein, the temperature of described air is 20-350 DEG C; Taking the green vitriol of 1kg crystal water to be removed as benchmark, the flow of described air is 0.1-5m
3/ h.
9. treatment process according to claim 1 and 2, wherein, described waste sulfuric acid solution and green vitriol are waste sulfuric acid solution and the green vitriol that adopts method for producing gtitanium dioxide with sulphuric acid by-product.
10. treatment process according to claim 1 and 2, wherein, the method also comprises the sulphuric acid soln obtaining after processing for dissolving ilmenite concentrate to prepare titanium dioxide.
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| CN109941974A (en) * | 2019-04-29 | 2019-06-28 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for cobalt chloride processing titanium dioxide waste acid by sulfuric acid process |
| CN110040698A (en) * | 2019-05-17 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | The method of magnesium sulfate processing titanium dioxide waste acid by sulfuric acid process |
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| 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 |
| CN102910594A (en) * | 2012-11-06 | 2013-02-06 | 黄正源 | Method for concentrating waste sulfuric acid by utilizing waste heat of titanium dioxide calcinator |
| CN102923674A (en) * | 2012-11-28 | 2013-02-13 | 四川龙蟒钛业股份有限公司 | Recycling method of ferrous-sulfate-containing by-product generated in titanium dioxide production process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109941974A (en) * | 2019-04-29 | 2019-06-28 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for cobalt chloride processing titanium dioxide waste acid by sulfuric acid process |
| CN110040698A (en) * | 2019-05-17 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | The method of magnesium sulfate processing titanium dioxide waste acid by sulfuric acid process |
| CN110040698B (en) * | 2019-05-17 | 2022-07-29 | 成都先进金属材料产业技术研究院股份有限公司 | Method for treating titanium dioxide waste acid by using magnesium sulfate |
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