CN109876630A - A method of sulfur dioxide flue gas is administered with alkaline scrap material and recycles tin antimony metal and sodium sulfite crystal - Google Patents
A method of sulfur dioxide flue gas is administered with alkaline scrap material and recycles tin antimony metal and sodium sulfite crystal Download PDFInfo
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Abstract
The present invention relates to a kind of methods administered sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystal, by broken dissolution alkaline scrap material and filter, obtain NaOH, Na2SnO3、Na3SbO4Mixed solution and filter residue, SO contained by flue gas of the mixed solution in absorption equipment with industrial discharge2Absorbing reaction is carried out, SO in flue gas is made2Content reaches discharge standard, during absorbing reaction, also obtains Sn (OH)4With Sb (OH)5Solid sediment and Na2SO3The mixed serum of solution is implemented to be separated by solid-liquid separation, obtains Sn (OH) to slurries4With Sb (OH)5Solid sediment and Na2SO3Solution.By filter residue and Sn (OH)4With Sb (OH)5Solid sediment is added reduction coal and passes through high temperature reduction melting, tin antimony metal and smelting slag is obtained, further to Na2SO3Solution is evaporated concentration and separation, obtains sodium sulfite crystal.The present invention has process flow short, and the tin antimony metal rate of recovery is high, realizes waste treatment and waste, the advantages such as production process clean and environmental protection.
Description
Technical field
The present invention relates to a kind of with alkaline scrap material improvement sulfur dioxide flue gas and recycles tin antimony metal and sodium sulfite crystal
Method, belong to industrial waste gas controlling waste residue and valuable metal recovery field.
Background technique
Currently, there are Some Enterprises during fire refining of crude lead, first carrying out condensation copper removal and adding sulphur copper removal, nitre is added
Sour sodium and sodium carbonate aoxidize while slag making removes tin and antimony, output tin antimony alkaline residue；In addition, waste lead acid battery recycling enterprise
Industry is also added sodium nitrate and sodium carbonate carries out reduction melting, output tin antimony alkaline residue in carrying out lead pig regeneration smelting process.Tin
Antimony alkaline residue contains Pb20~30%, Sn5~10%, Sb10~15%, Na2O10~30%.
Tin antimony alkaline residue is incorporated 15~20% anthracite and 3~6% lime stone, carries out reduction melting, output at high temperature
Metal alloy containing Pb65%, Sn15%, Sb20%, while output contains Sn1~4%, Sb2~8%, Na2The secondary alkali of O15~35%
Slag.In the second caustic sludge, main component is sodium antimonate, sodium stannate, sodium metasilicate, free sodium oxide molybdena；In addition, due in melting
Journey, silica, calcium oxide, aluminium oxide, magnesia, ferrous oxide when being liquefied reduction melting in coal tar ash etc., therefore,
In the second caustic sludge, also containing ingredients such as sodium metasilicate, sodium metaaluminate, calcium antimonate, metaantimmonic acid magnesium, aluminium oxide, ferrous oxides.
The valuable metal tin that is contained due to the second caustic sludge, antimony grade are low, thus do not have directly development and utilization economically
Value.Although the valuable metal tin that the second caustic sludge contains, antimony grade are low, many harmful components are all dissolved in this alkaline residue
Water, can directly polluted source and soil, therefore can only be deposited in Anti-lost, it is anti-raise in the cinder field spread, form waste residue.It is this secondary
Alkaline residue is commonly called as alkaline scrap material, if cannot get harmless treatment, stacks anyway, is all permanent pollution hidden trouble.
There are Some Enterprises by alkaline scrap material, for the neutralisation treatment of Sewage from Sulphuric Acid Plants, it is expected that reaching the treatment of wastes with processes of wastes against one another and taking into account back
Tin antimony metal is received, such as is used for the sulfuric acid gas cleaning sewage treatment of the sulfuric acid gas cleaning sewage treatment of zinc abstraction, Copper making,
But application effect is undesirable, and there are two main problems, first is that the metabisulfite solution obtained after neutralizing, needs to carry out at concentration again
Reason, when concentration, consume a large amount of steam, and sodium sulphate product price is very low, second is that the solution after neutralizing, arsenic, cadmium are strictly exceeded,
Sodium sulphate product can not meet product quality requirement.
There are also enterprises referring to the mode of sodium metaaluminate production aluminium hydroxide, using in carbon dioxide gas and alkaline scrap material,
It is expected to obtain the hydroxide precipitating of sodium carbonate liquor and tin, antimony, alkali is recycled, in a manner of soda ash finally with solid sediment side
Formula recycles tin antimony metal.But the application effect of this mode is also undesirable, and main cause is that the aqueous solution acidity of carbon dioxide is very
It is weak, cause reaction speed very slow, reaction efficiency is very low, and most tin antimony can not be with hydroxide precipitation form output, can not
Achieve the purpose that recycle tin antimony metal.
To sum up, merely from the point of view of economic benefit, valuable metal and its are extracted in the alkaline scrap material low from valuable metal grade
His industrial chemicals cannot all obtain satisfactory effect in a conventional method and technological means.And on the other hand, in many rows
It puts in the manufacturing enterprise containing sulfur dioxide flue gas, to make flue gas qualified discharge, a large amount of moneys is expended again to the desulfurized treatment of flue gas
Source and financial resources.Therefore, during using alkaline scrap material recycling valuable metal and other industrial chemicals, if not increasing too
More costs do not expend or only in the case where other resources of limited consuming, for effectively administering sulfur dioxide flue gas, can make
Alkaline scrap material realizes harmless treatment and resource utilization, really realizes waste treatment and waste, this has just been not only earthshaking
Social benefit, practical there has also been significant economic benefits.
Following patent document related to the present invention is found by country's retrieval:
102351360 A of application publication number CN applies for publication date 2012.02.15.
Method of the synthetical recovery containing arsenic alkali solution and form waste gas of sulfur dioxide, comprising the following steps: (1) containing arsenic alkali solution at room temperature
In be passed through form waste gas of sulfur dioxide, reduction reaction 2-6 hours, until the pH value of solution is 3-5, stop ventilation；By high price antimony and high price
Arsenic is reduced to low price antimony and arsenic；(2) it filters: the filter residue containing antimony is returned into antimony regulus system；Arsenic mixed sulfate solution will be contained to exist
It is concentrated by evaporation, crystallizes at a temperature of 100-110 DEG C, it is dry, obtain the solid of mixed sulfate containing arsenic；(3) arsenic mixing sulfuric acid will be contained
Salt solid, in 500-800 DEG C of volatilization arsenic trioxide, is collected by the prior art under air-proof condition, arsenic trioxide is recycled in cooling；
The reduction coal of mixed sulfate weight 30-50% is added when mixed sulfate becomes white shape material, mixes, is warming up to 900-
It 1100 DEG C, reacts 2-6 hours, obtains sulfide black-ash；(4) according to the prior art, sulfide black-ash is processed into technical grade vulcanized sodium
Or sodium hydrogensulfite.
The above method is inhaled during containing the compound for recycling arsenic in arsenic alkali solution also with containing form waste gas of sulfur dioxide
Receive reaction, also used during subsequent recovery and carry out high temperature reduction as the coal of reducing agent, but in application method, using setting
In standby, related data with the present invention compare obvious differences, in particular, process object (reactant) of the invention, acquisition pair
As (product) and to solve the problems, such as different with the above method from the overall goal to be reached.
Summary of the invention
The technical problem to be solved in the present invention: first is that Na contained by alkaline scrap material2O、Na2SnO、Na3SbO4To SO in flue gas2Have
Effect, which absorbs, realizes flue gas qualified discharge problem, second is that valuable material tin antimony metal is effectively recycled with sodium sulfite crystal, Jin Ershi
Existing alkaline scrap material harmless treatment and resource utilization problem.
In view of the above-mentioned problems, technical solution proposed by the present invention is:
A method of sulfur dioxide flue gas is administered with alkaline scrap material and recycles tin antimony metal and sodium sulfite crystal comprising with
Lower step:
(1), it dissolves alkaline scrap material: Na will be contained2O、Na2SnO、Na3SbO4Alkaline scrap material, be crushed, added water and stirred, to molten
It is filtered after solution, obtains filter residue and containing OH- 、Na+、SnO3 2-、SbO4 3- NaOH, Na2SnO3、Na3SbO4Mixed solution；
(2), sulfur dioxide flue gas: NaOH, Na that step 1 is obtained is administered2SnO3、Na3SbO4Absorption equipment is added in mixed solution
Absorb the SO in flue gas2, so that the flue gas SO after absorbing2Content reaches discharge standard；Meanwhile the absorption process generates Sn (OH)4
With Sb (OH)5Solid sediment and Na2SO3Solution mixed serum；
(3), it recycles tin antimony metal: the mixed serum being subjected to solid and liquid separation, obtains Sn (OH)4With Sb (OH)5Solid sediment
And Na2SO3Solution, by Sn (OH)4With Sb (OH)5After solid sediment and the mixing of the filter residue of step (1) output, then it is incorporated coal,
Reduction melting under high temperature makes Sn (OH)4With Sb (OH)5Reduction reaction is carried out with C contained in coal, Sn, Sb is generated, obtains tin antimony
Alloy product and smelting slag；
(4), sodium sulfite production: the Na of step (3) output2SO3Solution is cooled down again after being concentrated by evaporation, is obtained
To sodium sulfite crystalline substance liquid mixture；Sodium sulfite crystal is obtained by separating sodium sulfite crystalline substance liquid mixture, and is still contained
The mother liquor of sodium sulfite ingredient；Mother liquor containing sodium sulfite is remake into evaporation and concentration and separation, is further obtained from mother liquor
Sodium sulfite crystal；
Step (1) is described to contain Na2O、Na2SnO3、Na3SbO4Alkaline scrap material, wherein Na2O, Sn, Sb mass content is respectively are as follows:
Na2O:15~35%, Sn:1~4%, Sb:2~8%.
Step (1) the broken alkaline scrap material, when being dissolved in water, liquid-solid ratio is 2:1-4:1, whipping temp
It is 50~70 DEG C, dissolution time is 6~12 hours.
Step (1) is described to contain Na2O、Na2SnO、Na3SbO4The ionization equation being dissolved in water are as follows:
Na2O+H2O=2Na++2OH-
Na2SnO3=2Na++SnO3 2-
Na3SbO4=3Na++SbO4 3- 。
Described obtained NaOH, the Na of step (1)2SnO3、Na3SbO4、H2O mixed solution, NaOH, Sn, Sb concentration are respectively are as follows:
NaOH:95~113g/L, Sn:5~10g/L, Sb:10~20g/L.
Step (2) absorption equipment is absorption tower；By NaOH, Na2SnO3、Na3SbO4、H2O mixed solution is on absorption tower
SO in interior absorption flue gas2When, absorbing temperature is 50~70 DEG C, and absorption process liquid gas weight ratio is 2:1~10:1, absorbs series 1
~3 grades.
In the step (2), by NaOH, Na2SnO3、Na3SbO4、H2O mixed solution absorbs in flue gas in absorption tower
SO2The chemical equation of Shi Fasheng is as follows:
SO2+H2O=H2SO3
H2SO3+2NaOH =Na2SO3+2H2O
H2SO3+Na2SnO3+H2O =Na2SO3+Sn(OH)4↓
3H2SO3+2Na3SbO4+2H2O =3Na2SO3+2Sb(OH)5↓ 。
In the step (3), Sn (OH)4With Sb (OH)5After solid sediment and filter residue mixing, then it is incorporated coal, coal therein is
A kind of anthracite, the anthracite and Sn (OH) of supplying4With Sb (OH)5The ratio by mass ratio of solid sediment is 10~20%；Institute
Stating high temperature is 1200~1300 DEG C.
Step (3) Sn (OH) 4 and Sb (OH)5Reduction reaction, reaction equation are carried out with C contained in coal are as follows:
Sn(OH)4+C=Sn↓+2H2O↑+CO2↑
2Sb(OH)5+3C=2Sb↓+5H2O↑+CO+2CO2↑。
The invention has the advantages that
1, process flow is short.Only there are four steps for entire technical process, and first step is by effective alkalinity in alkaline scrap material
Substance is dissolved in water, is that utilizing for alkaline scrap material creates primary condition；Second step is the core step that alkaline scrap material utilizes
Suddenly, will there is the alkaline matter for absorbing SO 2 from fume ability in alkaline scrap material, with sulfur dioxide or acid acid in flue gas
Property sulfurous acid solution reaction, achieve the purpose that using alkali, while by the tin antimony metal oxide basic salt in alkaline scrap material, turn
Become metal hydroxides, creates primary condition for recycling tin antimony metal；Third step is the recycling of tin antimony metal, recycles tin
Antimony metal can increase the economic benefit of project；4th step, is changed into sodium sulfite product for sodium sulfite solution.
2, alkali and the tin antimony metal rate of recovery are high.In the removal process of alkali, it will be dissolvable in water the sodium salt of water first, as far as possible
It is dissolved in water, secondly using sulfur dioxide or the middle strong acidity of sulfurous acid, quickly, is efficiently reacted with alkaline sodium salt, generates sulfurous
Acid sodium solution converts sodium sulfite solution to finally by physical process the sodium sulfite product of market value；In tin antimony
In metal recovery process, the tin-antimony oxide for being dissolvable in water water is formed by strong base-weak acid salt first, is dissolved in water as far as possible,
Secondly using sulfur dioxide or the middle strong acidity of sulfurous acid, tin-antimony oxide is formed by strong base-weak acid salt, neutralize anti-
It answers, tin antimony metal oxide is made to be formed by strong base-weak acid salt, be converted into corresponding hydroxide precipitating, also finally by high temperature
The hydroxide precipitation slag of tin antimony metal is reduced to metallic tin and metallic antimony by former melting, and is ultimately formed with higher additional
The metal alloy product of value.Alkali and tin antimony recovery are high, also create reasonable economic benefit for project implementation.
3, it realizes waste treatment and waste.Alkaline scrap material of the present invention is a kind of dangerous waste residue of smelting in itself, stacks management meeting
Cause environmental pollution at any time, there are higher environmental pollution hidden danger；And the sulfur dioxide in flue gas, it is the main source for causing acid rain
Head product, is one of primary pollution source of flue gas, is the harmful substance that must be administered.Sulfur dioxide cigarette is administered using alkaline scrap material
Gas can eliminate two kinds of pollutants of alkaline scrap material and SO 2 from fume simultaneously, and its product is finally changed into tin pewter
Product and sodium sulfite product do not generate secondary pollution while that is, two kinds of pollutants are effectively administered, and have reached two kinds of dirts
The purpose for contaminating object resource utilization, realizes the treatment of wastes with processes of wastes against one another.
4, production process clean and environmental protection.Four technical process that the present invention uses, without external waste discharge, alkaline scrap material
The tap water used is dissolved, after being converted into sodium hydroxide-sodium stannate-metaantimmonic acid sodium solution, during administering sulfur dioxide cigarette,
It is converted into sodium sulfite solution, for sodium sulfite solution after being concentrated by evaporation, extra water evaporate into atmosphere in the form of water vapour
In, water vapour is a kind of nontoxic clean gas, is not polluted the environment；Four technical process, do not discharge waste residue externally,
The tin antimony hydroxide precipitating filter residue for crossing filter residue and SO 2 from fume improvement output of course of dissolution, all returns to high temperature reductions
Melting, while recycling tin antimony metal, slag passes through complete melt process, is converted into ordinary solid waste residue, without toxic, is
Cement industry raw material；The gas of high temperature reduction melting output, main ingredient are nitrogen, oxygen and carbon dioxide, are controlled by absorption
After reason, meets discharge standard and require to carry out qualified discharge.As it can be seen that production process clean and environmental protection of the present invention, effective protection environment.
Detailed description of the invention
Fig. 1 is that a kind of administered with alkaline scrap material of the present invention and recycles tin antimony metal and sulfurous acid at sulfur dioxide flue gas
The process flow chart of the method for sodium crystal.
Specific embodiment
To illustrate feature and its application effect of the invention convenient for clearer, overall solution first is made to embodiment of the present invention
Analysis.
Firstly, alkaline scrap material is leached with water, sodium stannate, sodium antimonate, free sodium oxide molybdena dissolution in alkaline scrap material
Yu Shuizhong.Practical alkaline scrap material also contains sodium metasilicate, and sodium metasilicate is also dissolved in the water.And ferrous oxide, oxygen in alkaline scrap material
It is insoluble to change magnesium, calcium oxide etc..After filtering is separated by solid-liquid separation, obtain with NaOH, Na2SnO3、Na3SbO4And Na2SiO3
For major solute mixed solution and be not dissolved in water cross filter residue.
Then, with NaOH, Na2SnO3、Na3SbO4And Na2SiO3For the mixed solution of major solute, absorb in flue gas
SO2, SO in flue gas2After being dissolved in water, sulfurous acid is generated.Sulfurous acid is medium strong acid, output hydrogen ion after ionization, ionization
The hydrogen ion of output is reacted with mixed solution, generates the corresponding hydroxide Sn (OH) for being not dissolved in water respectively4、Sb(OH)5、
Si(OH)4Deng.Meanwhile the sodium ion in mixed solution generates the Na for being dissolved in water in conjunction with inferior sulfate radical2SO3(i.e. sulfurous acid
Sodium).Wherein, sodium metasilicate and reacting for sulfurous acid are as follows:
H2SO3+Na2SiO3+H2O =Na2SO3+Si(OH)4↓
In this way, containing NaOH, Na2SnO3、Na3SbO4And Na2SiO3Pass through in absorption flue gas for the mixed solution of major solute
SO2Afterwards, the sodium salt in mixed solution is changed into sodium sulfite solution and is not dissolved in the hydroxide precipitating of water, through solid-liquid point
From obtaining sodium sulfite solution and solid sediment.
Then, to the solid sediment for crossing filter residue and smoke gas treatment of alkaline scrap material dissolution, it is incorporated anthracite together, in height
Temperature is lower to carry out reduction melting, recycles to tin antimony metal.Stannic hydroxide, hydroxide during reduction melting, in filter residue
Antimony is reduced to metallic tin and metallic antimony, and forms metal alloy product；Silicon hydroxide, aluminium hydroxide in filter residue etc. are decomposed into
Silica, aluminium oxide melt mutually together with calcium oxide, ferrous oxide etc., form clinker.
Tin antimony metal has not only effectively been recycled in reduction melting, meanwhile, filter residue has also been subjected to complete melting and has been handled, has made to filter
Slag is thoroughly changed into ordinary solid waste, can be used as cement raw.
The Na of above process output2SO3Solution cools down again after being concentrated by evaporation, obtains sodium sulfite crystalline substance liquid mixture；
Sodium sulfite crystal is obtained by separating sodium sulfite crystalline substance liquid mixture, and the mother liquor still containing sodium sulfite ingredient；It will
Mother liquor containing sodium sulfite remakes evaporation and concentration and centrifuge separation, and sodium sulfite crystal is further obtained from mother liquor.Sulfurous
Sour sodium crystal is a kind of industrial sodium salt.
In the above process, since the alkaline scrap material is the secondary alkali for having already passed through a tin antimony melting and being extracted
Slag, Na2O、Na2SnO、Na3SbO4Middle Na2O, the mass content of Sn, Sb is only are as follows: Na2O:15~35%, Sn:1~4%, Sb:2~
8%。
In the above process, when being dissolved in water broken alkaline scrap material, liquid-solid ratio is 2:1-4:1, and whipping temp is
50~70 DEG C, dissolution time is 6~12 hours.
It is described to contain Na in the above process2O、Na2SnO3、Na3SbO4The ionization equation being dissolved in water are as follows:
Na2O+H2O=2Na++2OH-
Na2SnO3=2Na++SnO3 2-
Na3SbO4=3Na++SbO4 3-。
In the above process, obtained NaOH, Na2SnO3、Na3SbO4In mixed solution, the concentration of contained NaOH, Sn, Sb are as follows:
NaOH:95~113g/L, Sn:5~10g/L, Sb:10~20g/L.
In the above process:
The absorption equipment includes absorption tower；
Described 1~3 grade of absorption series refers to, when using tower is absorbed, according to SO 2 from fume content height, is inhaled
The series for receiving reaction is divided into following three kinds of situations:
Under the lower situation of SO 2 from fume content, absorbed using single-stage absorption tower.
Under the higher situation of SO 2 from fume content, the second level being composed in series by two level-one, second level absorption towers is used
Absorption system is absorbed.Under this situation: flue gas enters from first stage tower, discharges after first stage tower, second level tower absorb from second level tower；
Contain NaOH, Na2SnO3、Na3SbO4Mixed solution is added from second absorption tower, anti-through absorb with sulfur dioxide in flue gas
Ying Hou, partially continues cycling through utilization in two-level absorption tower, and another part open circuit enters first grade absorption tower and carries out absorbing reaction.
In the case of SO 2 from fume content is high, carried out using the three-level absorption system that three absorption towers are composed in series
It absorbs；Under this situation: flue gas enters from first stage tower, discharges after first stage tower, second level tower, three-level tower absorb from three-level tower；Contain
NaOH、Na2SnO3、Na3SbO4Mixed solution is added from third absorption tower, after carrying out absorbing reaction with sulfur dioxide in flue gas,
Part continues cycling through utilization in three-level absorption tower, and another part open circuit enters two-level absorption tower and carries out absorbing reaction, in second level
After the reaction of absorption tower, utilization is partially continued cycling through in two-level absorption tower, another part open circuit enters first grade absorption tower and inhaled
Receive reaction.
Described NaOH, Na2SnO3、Na3SbO4、H2O mixed solution absorbs SO in flue gas in absorption tower2When, absorb temperature
It is 50~70 DEG C, absorption process liquid, gas weight ratio are 2:1~10:1.
In the above process, described NaOH, Na2SnO3、Na3SbO4Mixed solution absorbs SO in flue gas in absorption tower2Shi Fa
Raw chemical equation is as follows:
SO2+H2O=H2SO3
H2SO3+2NaOH =Na2SO3+2H2O
H2SO3+Na2SnO3+H2O =Na2SO3+Sn(OH)4↓
3H2SO3+2Na3SbO4+2H2O =3Na2SO3+2Sb(OH)5↓
In the above process, the Sn (OH)4With Sb (OH)5Solid sediment is incorporated anthracite, by weight, anthracitic supplying
Ratio is 10~20%；The high temperature is temperature of the control at 1200~1300 DEG C；Reduction melting at these elevated temperatures makes Sn (OH)4
With Sb (OH)5It is restored with C contained in anthracite, obtains tin pewter product and smelting slag.
In the above process, the Sn (OH)4With Sb (OH)5It is restored with C contained in anthracite, reduction reaction side
Formula are as follows:
Sn(OH)4+C=Sn↓+2H2O↑+CO2↑
2Sb(OH)5+3C=2Sb↓+5H2O↑+CO+2CO2↑
So far, lead to a present invention, valuable metal tin antimony and sodium sulfite crystal are effectively recycled in alkaline scrap material, the oxygen contained
SiClx, aluminium oxide are formed together the clinker that can be used for cement producting material with calcium oxide, ferrous oxide etc..Meanwhile it only consuming
Take under the smaller cost of the resources such as limited amount water and anthracite, be also governed sulfur dioxide flue gas, alkaline scrap material obtains
Harmless treatment.
In the following, being done by specific embodiment to embodiments of the present invention detailed further.
Embodiment 1
The present embodiment is that a kind of administered with alkaline scrap material of the present invention and recycles tin antimony metal and sulfurous at sulfur dioxide flue gas
First example of the method for sour sodium crystal:
(1), alkaline scrap material dissolves: will contain Na2The alkaline scrap material 20t of O15%, Sn1%, Sb2% carry out being crushed to granularity≤10mm；
Then in 75m3Leaching tanks in, be added 40m3Tap water opens leaching tanks blender, and it is useless to be gradually added broken 20t alkalinity
Slag is warming up to 50 DEG C, and the alkaline matter of alkaline scrap material and free sodium oxide molybdena is made to be dissolved in water, after dissolving 6h, is carried out with filter press
Filtering, obtains hygrometric state filter residue 18t and concentration is respectively NaOH:95g/L, Sn:5g/L, Sb:10g/L, the NaOH of Si:10g/L,
Na2SnO3、Na3SbO4、Na2SiO3Mixed solution 36m3；Hygrometric state filter residue enters step (3) processing, and mixed solution enters step (2)
Processing.
(2), administer sulfur dioxide flue gas: by concentration be NaOH:95g/L, Sn:5g/L, Sb:10g/L, Si:10g/L's
NaOH、Na2SnO3、Na3SbO4、Na2SiO3Mixed solution 36m3, by 0.375m3Φ is continuously added in the speed of/h in 96h
In the single-stage absorption tower of 2800mm × H12000mm, carry out absorbing flow being 45000Nm3/h、SO2Content 2000mg/Nm3Cigarette
Gas, absorption process temperature are 50 DEG C, and absorption process conveys circulation solution, solution internal circulating load 100m with the pump of 22kW3/ h, absorbed
Journey liquid gas weight ratio is 2:1；Flue gas SO after absorption2Content 46mg/Nm3, reach national emission standard, carry out qualified discharge；It inhales
The Sn (OH) that receipts process generates4、Sb(OH)5、Si(OH)4Solid sediment and Na2SO3Solution mixed serum, every 96h filter press
It is filtered separation mixed serum 36m3, be separated by filtration every time, obtain aqueous 29% hygrometric state filter residue 3.32t and contain
Na2SO3The solution 34.1m of 215g/L3；The dry slag of hygrometric state filter residue contains Sn7.35%, Sb14.68%, enters step (3) processing, contains
Na2SO3The solution of 215g/L enters step (4) processing.
(3), tin antimony metal recycles: the 18t hygrometric state filter residue of step (1) output and the 3.32t of step (2) output contain Sn, contain
The total 21.32t of Sb hygrometric state filter residue is gone back by weight 10% supplying anthracite 2.13t into reverberatory furnace and at 1200 DEG C
Former melting 6h obtains tin the antimony metal alloy product 0.45t and smelting slag 15.6t containing Sn35%, Sb65%；Tin antimony metal alloy
Product 0.45t, smelting slag 15.6t is as cement industry raw material.
(4), sodium sulfite production: the solution 34.1m containing Na2SO3215g/L of step (2) output3, by single-action
After evaporator is evaporated concentration, obtain containing Na2SO3500g/L solution 14.7m3, then by 14.7m3Concentrate is pressed from both sides with water-cooled
Set enamel still is cooled to 40 DEG C, obtains sodium sulfite crystalline substance liquid mixture；After brilliant liquid mixture is separated with centrifugal separator, produce
Sodium sulfite crystal 3.52t and concentration are Na out2SO3: the mother liquor 13.4m of 285g/L3；The evaporation that mother liquor returns to this step is dense
Contracting post carries out second of circulating and evaporating concentration, obtains sodium sulfite product 3.52t.
Embodiment 2
The present embodiment is that a kind of administered with alkaline scrap material of the present invention and recycles tin antimony metal and sulfurous at sulfur dioxide flue gas
Second example of the method for sour sodium crystal:
(1), alkaline scrap material dissolves: by the alkaline scrap material 30t containing Na2O25%, Sn2.5%, Sb5%, be crushed to granularity≤
10mm；Then in 150m3Leaching tanks in, be added 90m3Tap water opens leaching tanks blender, is gradually added in leaching tanks broken
30t alkaline scrap material after broken, is warming up to 60 DEG C, and the alkaline matter of alkaline scrap material and free sodium oxide molybdena is made to be dissolved in water, dissolves 9h
Afterwards, it is filtered with filter press, obtains hygrometric state filter residue 18.8t and concentration is NaOH:107g/L, Sn:8.3g/L, Sb:16.6g/
NaOH, Na of L, Si:8g/L2SnO3、Na3SbO4、Na2SiO3Mixed solution 84m3；Hygrometric state filter residue enters step (3) processing, mixes
It closes solution and enters step (2) processing.
(2), it administers sulfur dioxide flue gas: being NaOH:107g/L, Sn:8.3g/L, Sb:16.6g/L, Si:8g/L by concentration
NaOH, Na2SnO3、Na3SbO4、Na2SiO3Mixed solution 84m3, by 3.5m3The speed of/h is continuously interior for 24 hours to be added Φ 3500mm
In the second level absorption tower of the two-stage absorption system of × H14000mm, carry out absorbing flow being 70000Nm3/h、SO2Content
6000mg/Nm3Flue gas, absorption process temperature is 60 DEG C, and every grade of absorption tower of absorption process conveys solution with the circulating pump of 75kW,
Solution internal circulating load 400m3/ h, absorption process liquid gas weight ratio are 5:1；Flue gas SO after absorption2Content 60mg/Nm3, reach country
Discharge standard carries out qualified discharge；The Sn (OH) that absorption process generates4、Sb(OH)5、Si(OH)4Solid sediment and Na2SO3It is molten
Liquid mixed serum separates mixed serum 84m per being filtered for 24 hours with filter press3, it is separated by filtration every time, obtains aqueous 27.5%
Hygrometric state filter residue 7.98t and contain Na2SO3The solution 81.9m of 234g/L3；The dry slag of hygrometric state filter residue contains Sn11.85%, Sb23.68%, enters
Step (3) processing, contains Na2SO3The solution of 234g/L enters step (4) processing.
(3), tin antimony metal recycles: the 18.8t hygrometric state filter residue of step (1) output and the 7.98t of step (2) output containing Sn,
The total 26.78t of the filter residue of hygrometric state containing Sb, by weight 15% supplying anthracite 4.02t, into Australia Si Maite and at 1250 DEG C into
Row reduction melting 9h obtains tin the antimony metal alloy product 1.81t and smelting slag 19.3t containing Sn36%, Sb64%；Tin antimony metal
Alloy product 1.81t, smelting slag 19.3t is as cement industry raw material.
(4), sodium sulfite production: step (2) output contains Na2SO3The solution 81.9m of 234g/L3, by two effects
After evaporator is evaporated concentration, obtain containing Na2SO3550g/L solution 34.8m3, then by 34.8m3Concentrate is pressed from both sides with water-cooled
Set enamel still is cooled to 50 DEG C, obtains sodium sulfite crystalline substance liquid mixture；After brilliant liquid mixture is separated with centrifugal separator, produce
Sodium sulfite crystal 10.65t and concentration are Na out2SO3: the mother liquor 30.3m of 280g/L3；The evaporation that mother liquor returns to this step is dense
Contracting post carries out second of circulating and evaporating concentration, obtains sodium sulfite product 10.65t.
Embodiment 3
The present embodiment is that a kind of administered with alkaline scrap material of the present invention and recycles tin antimony metal and sulfurous at sulfur dioxide flue gas
The third example of the method for sour sodium crystal:
(1), alkaline scrap material dissolves: will contain Na2O35%, the alkaline scrap material 75t of Sn4%, Sb8%, be crushed to granularity≤
10mm；Then in 1 500m3Dense formula leaching tanks in, be added 300m3Tap water opens dense formula leaching tanks blender, by
Step broken 75t alkaline scrap material is added in dense formula leaching tanks, be warming up at 70 DEG C, make alkaline scrap material alkaline matter and
Free sodium oxide molybdena is dissolved in water, dissolves 12h, is filtered with filter press, obtains hygrometric state filter residue 33.75t and concentration is NaOH:113g/
NaOH, Na of L, Sn:10g/L, Sb:20g/L, Si:5g/L2SnO3、Na3SbO4、Na2SiO3Mixed solution 291m3；Hygrometric state filter residue
(3) processing is entered step, mixed solution enters step (2) processing.
(2), administer sulfur dioxide flue gas: by concentration be NaOH:113g/L, Sn:10g/L, Sb20g/L, Si5g/L's
NaOH、Na2SnO3、Na3SbO4、Na2SiO3Mixed solution 291m3, by 18.375m3The speed of/h is continuously interior for 24 hours to be added Φ
In the third level absorption tower of the three-level absorption system of 4200mm × H15000mm, carry out absorbing flow being 100000Nm3/h、SO2Contain
Measure 15000mg/Nm3Flue gas, absorption process temperature be 70 DEG C, every grade of absorption tower of absorption process is defeated with the circulating pump of 2 132kW
Send solution, solution internal circulating load 1400m3/ h, absorption process liquid gas weight ratio are 10:1；Flue gas SO after absorption2Content 75mg/
Nm3, reach national emission standard, carry out qualified discharge；The Sn (OH) that absorption process generates4、Sb(OH)5、Si(OH)4Solid is heavy
Starch and Na2SO3Solution mixed serum, every 8h are filtered separation mixed serum 97m with filter press3, it is separated by filtration, obtains every time
To aqueous 26.9% hygrometric state filter residue 9.14t and contain Na2SO3The solution 94.5m of 242g/L3, every filter 23 time is a filtering week
Phase, each output filter cycle obtain aqueous 26.9% hygrometric state filter residue 27.42t and containing Na2SO3The solution 284m of 242g/L3；It is wet
The dry slag of state filter residue contains Sn13.37%, Sb26.59%, enters step (3) processing, contains Na2SO3The solution of 242g/L enters step (4)
Processing.
(3), tin antimony metal recycles: the 33.75t hygrometric state filter residue of step (1) output and the 27.42t of step (2) output contain
Sn, the total 61.17t of the filter residue of hygrometric state containing Sb, by weight 20% supplying anthracite 12.23t, into side-blown converter and at 1300 DEG C
Reduction melting 12h is carried out, tin the antimony metal alloy product 7.45t and smelting slag 51.8t containing Sn36%, Sb64% are obtained；Tin antimony
Metal alloy product 7.45t direct marketing, smelting slag 51.8t is as cement industry raw material.
(4), sodium sulfite production: step (2) output contains Na2SO3The solution 284m of 242g/L3, steamed by triple effect
After hair device is evaporated concentration, obtain containing Na2SO3600g/L solution 114.5m3, then by 114.5m3Concentrate is pressed from both sides with water-cooled
Set enamel still is cooled to 60 DEG C, obtains sodium sulfite crystalline substance liquid mixture；After brilliant liquid mixture is separated with centrifugal separator, produce
Sodium sulfite crystal 40.91t and concentration are Na out2SO3: the mother liquor 98.2m of 280g/L3；The evaporation that mother liquor returns to this step is dense
Contracting post carries out second of circulating and evaporating concentration, obtains sodium sulfite product 40.91t.
It will be apparent that without departing from the principles of the present invention, several improvement or modification made are regarded as this
The protection scope of invention.
Claims (9)
1. a kind of method administered sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystal, feature
Be the following steps are included:
(1), it dissolves alkaline scrap material: Na will be contained2O、Na2SnO、Na3SbO4Alkaline scrap material, be crushed, added water and stirred, it is to be dissolved
After filter, obtain filter residue and containing OH- 、Na+、SnO3 2-、SbO4 3- NaOH, Na2SnO3、Na3SbO4Mixed solution；
(2), sulfur dioxide flue gas: NaOH, Na that step 1 is obtained is administered2SnO3、Na3SbO4Absorption equipment is added in mixed solution
Absorb the SO in flue gas2, so that the flue gas SO after absorbing2Content reaches discharge standard；Meanwhile the absorption process generates Sn (OH)4
With Sb (OH)5Solid sediment and Na2SO3Solution mixed serum；
(3), it recycles tin antimony metal: the mixed serum being subjected to solid and liquid separation, obtains Sn (OH)4With Sb (OH)5Solid sediment
And Na2SO3Solution, by Sn (OH)4With Sb (OH)5After solid sediment and the mixing of the filter residue of step (1) output, then it is incorporated coal,
Reduction melting under high temperature makes Sn (OH)4With Sb (OH)5Reduction reaction is carried out with C contained in coal, Sn, Sb is generated, obtains tin antimony
Alloy product and smelting slag；
(4), sodium sulfite production: by the Na of step (3) output2SO3Solution is cooled down again after being concentrated by evaporation, is obtained
To sodium sulfite crystalline substance liquid mixture；Sodium sulfite crystal is obtained by separating sodium sulfite crystalline substance liquid mixture, and is still contained
The mother liquor of sodium sulfite ingredient；Mother liquor containing sodium sulfite is remake into evaporation and concentration and separation, is further obtained from mother liquor
Sodium sulfite crystal.
2. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, which is characterized in that step (1) is described to contain Na2O、Na2SnO3、Na3SbO4Alkaline scrap material, wherein Na2O、Sn、Sb
Mass content is respectively are as follows: Na2O:15~35%, Sn:1~4%, Sb:2~8%.
3. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, which is characterized in that step (1) the broken alkaline scrap material, when being dissolved in water, liquid-solid ratio is 2:1-
4:1, whipping temp are 50~70 DEG C, and dissolution time is 6~12 hours.
4. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, which is characterized in that step (1) is described to contain Na2O、Na2SnO、Na3SbO4The ionization equation being dissolved in water are as follows:
Na2O+H2O=2Na++2OH-
Na2SnO3=2Na++SnO3 2-
Na3SbO4=3Na++SbO4 3- 。
5. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, which is characterized in that described obtained NaOH, the Na of step (1)2SnO3、Na3SbO4Mixed solution, NaOH, Sn, Sb
Concentration is respectively are as follows: NaOH:95~113g/L, Sn:5~10g/L, Sb:10~20g/L.
6. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, it is characterised in that:
Step (2) absorption equipment is absorption tower；By NaOH, Na2SnO3、Na3SbO4Mixed solution absorbs cigarette in absorption tower
SO in gas2When, absorbing temperature is 50~70 DEG C, and absorption process liquid gas weight ratio is 2:1~10:1, absorbs 1~3 grade of series.
7. according to claim 1 or 6 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sulfurous acid
The method of sodium crystal, which is characterized in that in the step (2), by NaOH, Na2SnO3、Na3SbO4, mixed solution absorbing
SO in flue gas is absorbed in tower2The chemical equation of Shi Fasheng is as follows:
SO2+H2O=H2SO3
H2SO3+2NaOH =Na2SO3+2H2O
H2SO3+Na2SnO3+H2O =Na2SO3+Sn(OH)4↓
3H2SO3+2Na3SbO4+2H2O =3Na2SO3+2Sb(OH)5↓ 。
8. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, which is characterized in that in the step (3), Sn (OH)4With Sb (OH)5After solid sediment and filter residue mixing, then match
The coal entered is anthracite, the anthracite and Sn (OH) of supplying4With Sb (OH)5The ratio by mass ratio of solid sediment be 10~
20%；The high temperature is 1200~1300 DEG C.
9. according to claim 1 administer sulfur dioxide flue gas with alkaline scrap material and recycle tin antimony metal and sodium sulfite crystalline substance
The method of body, which is characterized in that step (3) described Sn (OH)4With Sb (OH)5Reduction reaction is carried out with C contained in coal, it is anti-
Answer equation are as follows:
Sn(OH)4+C=Sn↓+2H2O↑+CO2↑
2Sb(OH)5+3C=2Sb↓+5H2O↑+CO+2CO2↑。
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| CN112607751A (en) * | 2020-12-31 | 2021-04-06 | 耒阳市焱鑫有色金属有限公司 | Method for re-dissolving, freezing and purifying mixed salt containing arsenic, sodium sulfite and sodium sulfate |
| CN114506865A (en) * | 2020-10-29 | 2022-05-17 | 中国石油化工股份有限公司 | Aluminum hydroxide and method for preparing aluminum hydroxide by carbonization method |
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