CN108715452A - A kind of desulfurization waste liquor preprocess method of high-purity sodium sulfocyanate and sodium thiosulfate - Google Patents
A kind of desulfurization waste liquor preprocess method of high-purity sodium sulfocyanate and sodium thiosulfate Download PDFInfo
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- CN108715452A CN108715452A CN201810837769.7A CN201810837769A CN108715452A CN 108715452 A CN108715452 A CN 108715452A CN 201810837769 A CN201810837769 A CN 201810837769A CN 108715452 A CN108715452 A CN 108715452A
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- 239000002699 waste material Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 45
- 230000023556 desulfurization Effects 0.000 title claims abstract description 43
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 title claims abstract description 35
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 title claims abstract description 34
- 235000019345 sodium thiosulphate Nutrition 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 77
- 239000007788 liquid Substances 0.000 claims abstract description 77
- 150000003839 salts Chemical class 0.000 claims abstract description 55
- 239000012535 impurity Substances 0.000 claims abstract description 29
- 238000002425 crystallisation Methods 0.000 claims abstract description 27
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 238000005273 aeration Methods 0.000 claims abstract description 21
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 14
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005119 centrifugation Methods 0.000 claims abstract description 9
- 230000001360 synchronised effect Effects 0.000 claims abstract description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 46
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 17
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000005864 Sulphur Substances 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000007792 addition Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 238000004061 bleaching Methods 0.000 description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 235000017550 sodium carbonate Nutrition 0.000 description 12
- 229940001593 sodium carbonate Drugs 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical group [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000007255 decyanation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- -1 molecule Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000009307 diakinesis Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/20—Thiocyanic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
- Treating Waste Gases (AREA)
Abstract
A kind of desulfurization waste liquor preprocess method of the sodium sulfocyanate and sodium thiosulfate of high-purity, includes the following steps：Inorganic agent A is NaSO3And/or NaHSO3, inorganic agent B is NaHSO4And/or NH4SCN or inorganic agent are NaHSO3Or NaHSO3+NaSO3, substep addition, into desulfurization waste liquor, addition inorganic agent A is tentatively pre-processed, gas is discharged, and through aeration, filtering, preheating, decoloration, concentration, when concentration is added inorganic agent B and further pre-processes liquid, gas is discharged, and then re-evaporation concentration, crystallization, centrifugation obtains low impurity mixed salt；Or it is synchronous be added, inorganic agent A+ inorganic agents B or inorganic agent are only added in pretreatment, the step of other steps are added with substep；Pretreatment time is 1-5h, is aerated 50-60 DEG C of temperature, and preheating temperature is 65-95 DEG C.This method converts desulfurization waste liquor impurity to valuable salt, produces two salt of high-purity.
Description
Technical field
The present invention relates to the desulfurization waste liquor preprocess methods of a kind of high-purity sodium sulfocyanate and sodium thiosulfate, belong to
Coke-oven plant's field of desulfurization waste liquid treatment technology.
Background technology
Some Domestic coke-oven plant carries out desulfuration and decyanation using PDS wet type sodium methods to coke-stove gas at present, and it is de- to generate desulfurization
Cyanogen waste liquid.Due to the complexity of coke-oven plant's gas composition, the characteristic of variability and desulfuration and decyanation process, cause in doctor solution not only
Containing main component sodium sulfocyanate, sodium thiosulfate and sodium sulphate, sometimes with high suspension sulphur, sodium carbonate, sodium bicarbonate,
The impurity such as molecule, solid particle.Processing for desulfurization waste liquor, coke-oven plant generally using being first concentrated in vacuo, then pass through again
Extract condensing crystallizing or Steppecd crystallization, respectively obtain sodium sulfocyanate crystal salt, sodium thiosulfate, sodium sulphate mixed salt, recycling
Recycling, wherein sodium sulfocyanate and sodium thiosulfate crystal salt are the target products recycled since industrial use is extensive, but
It is that above two crystallization purity salt, quality that this method obtains are not high enough, containing the impurity such as sodium carbonate and sodium bicarbonate, and carbon
The aobvious alkalinity of sour sodium and sodium bicarbonate, its presence also influence the pH of target product, limit sodium thiosulfate and sodium sulfocyanate
Purposes and price.
Currently, the purity of sodium sulfocyanate and sodium thiosulfate crystal salt that this method obtains is 96-98.5wt%, market price
Lattice are 3000 yuan/ton, and if improving the purity of 0.5-1wt%, price can be increased to 4000 yuan/ton.1% purity
It is little that raising seems amplitude, but finer difficulty is bigger, and for industrial actual production, how strictly control at
Under the premise of this, guarantee does not introduce other impurity, removal and suspension sulphur, sodium carbonate, sodium bicarbonate etc. in conversion desulfurization waste liquor
Impurity improves the purity of sodium sulfocyanate and sodium thiosulfate, is of great practical significance.
Invention content
Not high, the asking containing sodium carbonate and sodium bicarbonate impurity for sodium sulfocyanate and sodium thiosulfate crystallization purity salt
Topic, the present invention provide a kind of desulfurization waste liquor preprocess method of the sodium sulfocyanate and sodium thiosulfate of high-purity.
Technical scheme of the present invention：
A kind of desulfurization waste liquor preprocess method of the sodium sulfocyanate and sodium thiosulfate of high-purity, it is characterised in that place
Reason agent includes inorganic agent A and inorganic agent B, and wherein inorganic agent A is Na2SO3And/or NaHSO3, inorganic agent B is NaHSO4And/or
NH4SCN,
Inorganic agent A and inorganic agent B substeps are added, and include the following steps：
Inorganic agent A is added into desulfurization waste liquor to carry out after tentatively pre-processing, liquid is through aeration, filtering, preheating, decoloration, so
Be added in reaction-concentration kettle afterwards, and inorganic agent B be added and further pre-processes, gas discharge, then re-evaporation concentration, crystallization, from
Gains in depth of comprehension are to low impurity mixed salt；
Or inorganic agent A additions synchronous with inorganic agent B, include the following steps：
Inorganic agent A and inorganic agent B is added into desulfurization waste liquor tentatively to be pre-processed, gas discharge, liquid is through aeration, mistake
Filter, preheating, decoloration, evaporation and concentration, crystallization, centrifugation obtain low impurity mixed salt；
The preliminary pretreated time is 1-5h, 50-60 DEG C of the temperature of the aeration, time 2-4h, the preheating
Temperature be 65-95 DEG C, the temperature of the reaction-concentration kettle is 85 DEG C or more, reaction time 1-8h.
A kind of desulfurization waste liquor preprocess method of the sodium sulfocyanate and sodium thiosulfate of high-purity, it is characterised in that place
Reason agent is NaHSO3Or NaHSO3+Na2SO3, include the following steps：
The inorganic agent is added into desulfurization waste liquor tentatively to be pre-processed, gas discharge, liquid through aeration, filtering, in advance
Heat, decoloration, evaporation and concentration, crystallization, centrifugation obtain low impurity mixed salt；
The preliminary pretreated time is 1-5h, 50-60 DEG C, time 2-4h of the aeration temperature, the preheating
Temperature is 65-95 DEG C, and the temperature of the reaction-concentration kettle is 85 DEG C or more, reaction time 1-2h.
The inorganic agent A is Na2SO3, the inorganic agent B is NH4SCN, feed postition are that substep is added, reaction-concentration kettle
Reaction time be 5-8h.
When substep is added, Na2SO3Amount be waste liquid in sulphur molal quantity 85-95%, NH4The amount of SCN is that decoloration is clear
The 85%~95% of the molal quantity of sodium bicarbonate in liquid, 2 × 85%~2 × the 95% of the molal quantity of sodium carbonate.
The products gaseous ammonia of the reaction-concentration kettle is subjected to tail gas absorption, evaporation vapour carries out condensation process.
The inorganic agent A is NaHSO3And/or Na2SO3, the inorganic agent B is NaHSO4, feed postition is synchronous addition,
The reaction time of the reaction-concentration kettle is 1-2h.
When synchronous addition, total SO3 2-Amount be waste liquid in sulphur molal quantity 85-95%, total H+Amount be waste liquid in carbon
The 85%~95% of the molal quantity of sour hydrogen sodium, 2 × 85%~2 × the 95% of the molal quantity of sodium carbonate.
Desulfurization waste liquor is set to carry out interior cycle by recycle liquid pump and/or mechanical agitation in the preliminary pretreatment.
After decoloration, decoloration clear liquid enters decoloration Clear liquid tank, and the decoloration Clear liquid tank has insulating layer.
The temperature of the reaction-concentration kettle is 85 DEG C -100 DEG C.
The advantageous effects of the present invention：
The present invention is a kind of desulfurization waste liquor preprocess method of the sodium sulfocyanate and sodium thiosulfate of high-purity, is passed through
The method that preliminary pre-treatment step combines new concentration technology, selecting has SO3 2-And/or HSO3 2-Inorganic agent A and have H+
And/or NH4 +Inorganic agent B or there is SO simultaneously3 2-And H+The inorganic agent of two kinds of ions tentatively pre-processes waste liquid, wherein Na2SO3
And NaHSO3In SO3 2-Convert the sulfur impurity in waste liquid to target product sodium thiosulfate, NaHSO under proper condition4With
NaHSO3In H+And NH4NH in SCN4 +Sodium carbonate and sodium bicarbonate are converted to gas discharge, to pass through chemical reaction
It converts the impurity in desulfurization waste liquor to valuable salt with the material of low value, prepares the sodium sulfocyanate crystal salt of high-purity
With sodium thiosulfate crystal salt.Preferably, inorganic agent Na2SO3+NaHSO3+NaHSO4Or Na2SO3+NaHSO4Or NaHSO3+
NaHSO4Or Na2SO3+NaHSO3Or NaHSO3, synchronize and be added in preliminary pretreatment so that SO when preliminary pretreatment3 2-With waste liquid
It is sufficiently mixed and reacts, in aeration, SO under 50-60 DEG C of higher temperature3 2-It comes into full contact with and reacts with sulphur, be converted into
Na2S2O3, avoid introducing new impurity, unconverted sulphur is filtered to remove together with other solids, sodium thiosulfate in crystal salt
Purity higher；And make NaHSO4With the reaction time of sodium carbonate and sodium bicarbonate diakinesis is extended to from preliminary pretreatment
Between, reaction is more abundant, and a small amount of carbon dioxide gas of generation is without recycling.It is furthermore preferred that inorganic agent is Na2SO3+NH4SCN, point
Step is added, Na2SO3It is added in pretreatment and handles sulphur, and NH4Processing sodium carbonate and sodium bicarbonate is added in concentration in SCN, i.e.,
New concentration technology is used, first reacts and concentrates again, on the one hand, by the higher temperature and pressure of reaction-concentration kettle so that two
Person reacts more abundant, good impurity removing effect, can also avoid being added too early and wasting NH4SCN, and the ammonia for reacting generation can collect
Middle collection avoids pollution environment；On the other hand, product is sodium sulfocyanate, realizes the purpose for improving sodium sulfocyanate crystallization purity salt.
In short, low impurity mixed salt can be obtained by this method.
Method of the invention includes preliminary pretreatment successively, is aerated, filters, preheating, decoloration, concentration, crystallizing and centrifuge,
Na is added when preliminary pretreatment2SO3Or it synchronizes and is added or is individually added into NaHSO3, go completely or partially to remove carbon elimination while sulphur removal
Sour sodium and sodium bicarbonate；Then it is aerated, the temperature and blended sliver of a suitable elimination reaction is provided while removing molecule
Part；The unconverted sulphur of filtering and removing and other solid impurities；Preheating ensures higher temperature before decoloration, on the one hand so that unreacted
Inorganic agent fully reacts, and it is complete to be on the other hand conducive to decoloration；Decoloration removes the impurity such as noble metal；New concentration can be used when concentration
Technique, i.e., by NaHSO4And/or NH4SCN is put into reaction-concentration kettle, utilizes the higher temperature and pressure of reaction-concentration kettle
Make the two fully reaction, and the residence time in reaction-concentration kettle is appropriately extended, make its reaction fully, concentrates removal carbonic acid
Sodium and sodium bicarbonate, re-evaporation concentrates after reaction, and then crystallized, centrifugation can be obtained the mixed salt of low impurity content.Pass through this
The method of invention not only solves desulfurization waste liquor quality problems, brings high economic benefit for enterprise, and to existing traditional equipment
It is transformed small, at low cost, is with a wide range of applications.
Preferably, total SO in control process agent3 2-Amount be waste liquid in sulphur molal quantity 85-95%, total H+Or NH4 +
Amount be decolourize clear liquid in sodium bicarbonate total amount molal quantity 85%~95%, 2 × 85%~the 2 of the molal quantity of sodium carbonate
× 95% so that inorganic agent is not excessive.
Preferably, the products gaseous ammonia of reaction-concentration kettle is subjected to tail gas absorption, evaporation vapour carries out condensation process recycling profit
With.
Preferably, so that desulfurization waste liquor is carried out interior cycle by recycle liquid pump and/or mechanical agitation in preliminary pretreatment, increase
Add reaction speed.
Preferably, after decoloration, the decoloration clear liquid enters decoloration Clear liquid tank, and the decoloration Clear liquid tank has good heat preservation
Layer, it is 65-95 DEG C that can keep the temperature of decoloration clear liquid.
Preferably, the temperature of the reaction-concentration kettle is 85 DEG C -100 DEG C, and it is micro-boiling state to make reactant.
Preferably, mixed salt is handled using conventional refined salt extracting method, mixed salt extracted first, then concentrated crystallization and molten
Solution crystallization respectively obtains sodium sulfocyanate, sodium thiosulfate and sulfate crystal salt, or is obtained through fractional crystallization and dissolving crystallized method
Purity to sodium sulfocyanate, sodium thiosulfate and sulfate crystal salt, sodium sulfocyanate crystal salt is up to 98.5-99.0wt%, sulphur
The purity of sodium thiosulfate crystal salt is 95-96wt%.
Description of the drawings
Fig. 1 is the process flow chart of the embodiment of the desulfurization waste liquor preprocess method of the present invention；
Fig. 2 is the schematic device of the embodiment of the desulfurization waste liquor preprocess method of the present invention.
Each label lists as follows in figure：
1- doctor solution delivery pumps, 2- recycle liquid pumps, 3- pretreatment tanks, the aeration tanks 4-, 5- are aerated gas chamber, 6- plate-frame filterings
Machine, 7- decoloration feeding pumps, 8- preheaters, 9- bleaching tower feed inlets, 10- bleaching towers, 11- bleaching towers enter hole, and 12- bleaching towers are clear
Liquid exports, 13- decoloration Clear liquid tanks, and 14- reacts concentration kettle feeding pump, and 15- reacts concentration kettle clear liquid inlet, 16- reactions-dense
Contracting kettle, 17- concentration kettle manholes, 18- inorganic agent feed inlets, 19- reaction gas and evaporation vapor outlet, 20- concentrated solution outlets, 21- knots
Brilliant kettle concentrate entrance, 22- mixed salt crystallization kettles, 23- centrifuges, 24- tail gas absorbers, 25- evaporate vapour cooler.
Specific implementation mode
In order to make present invention may be readily understood, in conjunction with specific embodiment, the present invention will be further elaborated.
Embodiment 1
Sulfur content is 3g/L in waste liquid, and carbonate content 2g/L, sodium bicarbonate content is 5g/L.Inorganic agent A is
Na2SO3, inorganic agent B is NH4SCN, Na in every liter of waste liquid2SO3Additive amount be 11g, NH in every liter of waste liquid4The additive amount of SCN is
7.2g is added in preliminary pretreatment and when concentration respectively.
Shown in Fig. 1 and Fig. 2, a kind of high-purity sodium sulfocyanate of the present embodiment and the desulfurization waste liquor of sodium thiosulfate are pre-
Processing method is as follows：
Desulfurization waste liquor squeezes into pretreatment tank 3 by doctor solution delivery pump 1, and inorganic agent A is added to pretreatment tank 3, direct plunges into
To inside desulfurization waste liquor, preliminary pretreatment in 2 hours is carried out, during which desulfurization waste liquor is recycled by recycle liquid pump 2 and fully stirred to realize
It mixes, so that inorganic agent is contacted with waste liquid and react abundant, improve processing speed.It is sent into aeration through preliminary pretreated desulfurization waste liquor
Pond 4 carries out Air Exposure, is aerated 4 hours, and solid small particles impurity is driven by bubble bracketing to float and remove, and aerating gas is by exposing
Gas gas chamber 5 supplies, and aeration temperature is 50-60 DEG C, which is conducive to reaction and further fully carries out, subsequently into plate-frame filtering
The filtering of machine 6 removes unreacted solid sulfur and other solid impurities, then is sent into preheater 8 through the feeding pump 7 that decolourizes and heats, temperature
Then control flows into bleaching tower 10 through bleaching tower feed inlet 9 and removes removing heavy metals through activated carbon decolorizing at 85 ± 5 DEG C, decolorising agent by
Bleaching tower enters the input of hole 11, and the decoloration clear liquid after decoloration is flowed out through bleaching tower purified liquor outlet 12, waits locating into decoloration Clear liquid tank 13
Reason, 13 surface of decoloration Clear liquid tank have good insulating layer, can keep the temperature of decoloration clear liquid.Clear liquid decolourize by reaction concentration kettle
14 concentrated kettle of feeding pump enters hole and gets to reaction concentration kettle clear liquid inlet 15 and enter reaction-concentration kettle 16, and through inorganic agent
The inorganic agent B that feed inlet 18 is added first carries out being warming up to 95 DEG C in reaction-concentration kettle 16, controls and is reacted under micro-boiling situation
4 hours time, the reacted gas of tail gas ammonia and evaporation vapor outlet 19 of generation enter 24 absorption of tail gas absorber and handle；Reaction
Afterwards, into the stage of vacuum concentration, evaporation vapour is discharged by reaction gas and evaporation vapor outlet 19, and it is cold to enter evaporation vapour cooler 25
Solidifying, pending rear return water recycles.Concentrate after concentration is discharged by concentrated solution outlet 20, crystallized kettle concentrate entrance 21 into
Enter and is crystallized in mixed salt crystallization kettle 22；After crystallization the mixed salt containing low impurity is centrifuged to obtain through centrifuge 23.Mixed salt again through extracting, filtering,
Extract liquor is concentrated, crystallization, centrifuges, and obtains sodium sulfocyanate crystal salt, purity 99.0wt%；Filter residue is through dissolving, crystallization, centrifugation
Sodium thiosulfate and sodium sulphate are obtained, then isolates sodium sulphate and obtains sodium thiosulfate crystal salt, purity 95.8wt%.
In addition, when 16 internal part of reaction-concentration kettle needs to overhaul and safeguard, staff passes through concentration kettle manhole 17
Into.
The equation of the chemical reaction mainly occurred in the above process is as follows：
NH4SCN+NaHCO3=NH3↑+CO2↑+H2O+NaSCN
2NH4SCN+Na2CO3=2NH3↑+CO2↑+H2O+2NaSCN。
Embodiment 2
The present embodiment is NH with 1 difference of embodiment4SCN changes into NaHSO4, NaHSO in every liter of waste liquid4Additive amount is
11.5g.The purity of obtained sodium sulfocyanate crystal salt is 98.6wt%；The purity of sodium thiosulfate crystal salt is 95.4wt%.
The equation of the chemical reaction mainly occurred in the above process is as follows：
NaHSO4+NaHCO3=CO2↑+H2O+Na2SO4
2NaHSO4+Na2CO3=CO2↑+H2O+2Na2SO4。
Embodiment 3
Sulfur content is 3g/L in waste liquid, and carbonate content 2g/L, sodium bicarbonate content is 5g/L.Inorganic agent and embodiment
2 is identical, but time difference is added in inorganic agent, synchronizes and is added in preliminary pretreatment, and flow and device can refer to Fig. 1 and Fig. 2, tool
Steps are as follows for body：
Desulfurization waste liquor squeezes into pretreatment tank 3 by doctor solution delivery pump 1, and inorganic agent Na is added to pretreatment tank 32SO3With
NaHSO4, be directly thrown into inside desulfurization waste liquor, carry out preliminary pretreatment in 2 hours, during which desulfurization waste liquor is followed by recycle liquid pump 2
Ring is sufficiently stirred with realizing, and has mechanical agitation in treatment trough 3, so that inorganic agent is contacted with waste liquid and is reacted abundant, improves
Processing speed.It is sent into aeration tank 4 through preliminary pretreated desulfurization waste liquor and carries out Air Exposure, is aerated 4 hours, solid small particles
Impurity is driven by bubble bracketing to float and removes, and aerating gas is supplied by aeration gas chamber 5, and aeration temperature is 50-60 DEG C, is conducive to
Reaction further fully carries out, and is filtered subsequently into flame filter press 6 and removes unreacted solid sulfur and other solid impurities,
It is sent into preheater 8 through the feeding pump 7 that decolourizes again to heat, temperature is controlled at 85 ± 5 DEG C, is then flowed into and is decolourized through bleaching tower feed inlet 9
Tower 10 goes removing heavy metals, decolorising agent to enter hole 11 by bleaching tower and put into through activated carbon decolorizing, and the decoloration clear liquid after decoloration is through bleaching tower
Purified liquor outlet 12 flows out, pending into decoloration Clear liquid tank 13, and 13 surface of decoloration Clear liquid tank has good insulating layer, can keep
The temperature of decoloration clear liquid.Decoloration clear liquid is got to reaction concentration kettle clear liquid inlet 15 by reaction concentration kettle feeding pump 14 and is entered anti-
- concentration kettle 16 is answered, 95 DEG C is first warming up in reaction-concentration kettle 16, controls under micro-boiling situation, 1 hour reaction time, reaction
Afterwards, into the stage of vacuum concentration, evaporation vapour is discharged by reaction gas and evaporation vapor outlet 19, and it is cold to enter evaporation vapour cooler 25
Solidifying, pending rear return water recycles.Concentrate after concentration is discharged by concentrated solution outlet 20, crystallized kettle concentrate entrance 21 into
Enter and is crystallized in mixed salt crystallization kettle 22；After crystallization the mixed salt containing low impurity is centrifuged to obtain through centrifuge 23.Mixed salt again through extracting, filtering,
Extract liquor is concentrated, crystallization, centrifuges, and obtains sodium sulfocyanate crystal salt, purity 98.6wt%；Filter residue is through dissolving, crystallization, centrifugation
Sodium thiosulfate and sodium sulphate are obtained, then isolates sodium sulphate and obtains sodium thiosulfate crystal salt, purity 96.0wt%.
The chemical reaction mainly occurred in the above process is with reference to embodiment 2.
Embodiment 4
Sulfur content is 3g/L in waste liquid, and carbonate content 2g/L, sodium bicarbonate content is 5g/L, inorganic agent and embodiment
1 is identical, Na in every liter of waste liquid2SO3Additive amount be 11g, NH in every liter of waste liquid4The additive amount of SCN is 7.2g, the difference is that place
The addition time for managing agent is different, synchronizes and is added in preliminary pretreatment, specific steps are similar to Example 3, do not repeat to retouch herein
It states.
The purity of sodium sulfocyanate crystal salt is 98.9wt%；The purity of sodium thiosulfate crystal salt is 95.2wt%.
The chemical reaction mainly occurred in the above process is with reference to embodiment 1.
Embodiment 5
Sulfur content is 3g/L in waste liquid, and carbonate content 2g/L, sodium bicarbonate content is 5g/L, and inorganic agent is
NaHSO3, additive amount is that 10g is added in every liter of waste liquid, is added, is as follows in preliminary pretreatment：
Desulfurization waste liquor squeezes into pretreatment tank 3 by doctor solution delivery pump 1, and inorganic agent NaHSO is added to pretreatment tank 33, directly
It puts into inside desulfurization waste liquor, carries out preliminary pretreatment in 2 hours, during which desulfurization waste liquor is recycled by recycle liquid pump 2 and filled with realizing
Divide stirring, so that inorganic agent is contacted with waste liquid and react abundant, improve processing speed.It is sent into through preliminary pretreated desulfurization waste liquor
Aeration tank 4 carries out Air Exposure, is aerated 4 hours, and solid small particles impurity is driven by bubble bracketing to float and remove, and is aerated gas
Body is supplied by aeration gas chamber 5, and aeration temperature is 50-60 DEG C, is conducive to reaction and is further fully carried out, subsequently into plate-frame filtering
The filtering of machine 6 removes unreacted solid sulfur and other solid impurities, then is sent into preheater 8 through the feeding pump 7 that decolourizes and heats, temperature
Then control flows into bleaching tower 10 through bleaching tower feed inlet 9 and removes removing heavy metals through activated carbon decolorizing at 85 ± 5 DEG C, decolorising agent by
Bleaching tower enters the input of hole 11, and the decoloration clear liquid after decoloration is flowed out through bleaching tower purified liquor outlet 12, waits locating into decoloration Clear liquid tank 13
Reason, 13 surface of decoloration Clear liquid tank have good insulating layer, can keep the temperature of decoloration clear liquid.Clear liquid decolourize by reaction concentration kettle
Feeding pump 14 gets to reaction concentration kettle clear liquid inlet 15 and enters reaction-concentration kettle 16, is first risen in reaction-concentration kettle 16
Temperature is controlled to 95 DEG C under micro-boiling situation, is directly entered the vacuum concentration stage, evaporation vapour is by reaction gas and evaporation vapor outlet 19
Discharge, and enter evaporation vapour cooler 25 and condense, pending rear return water recycles.Concentrate after concentration is by concentrated solution outlet 20
Discharge, crystallized kettle concentrate entrance 21, which enters in mixed salt crystallization kettle 22, to be crystallized；Centrifuge containing low miscellaneous through centrifuge 23 after crystallization
The mixed salt of matter.Mixed salt is again through extracting, filtering, and extract liquor is concentrated, crystallization, centrifuges, and the purity for obtaining sodium sulfocyanate crystal salt is
98.6wt%；Filter residue obtains sodium thiosulfate and sodium sulphate through dissolving, crystallization, centrifugation, then isolates sodium sulphate and obtain thio sulphur
Sour sodium crystal salt, purity 95.7wt%.
The equation of the chemical reaction mainly occurred in the above process is as follows：
2NaHSO3+Na2CO3=2Na2SO3+H2O+CO2↑
NaHSO3+NaHCO3=Na2SO3+H2O+CO2↑
Embodiment 6
Sulfur content is 3g/L in waste liquid, and carbonate content 2g/L, sodium bicarbonate content is 5g/L, inorganic agent A：
Na2SO3+NaHSO3, inorganic agent B：NH4SCN, additive amount is respectively 7.0g, 4.0g and 4.5g, Na in every liter of waste liquid2SO3+
NaHSO3It synchronizes and is added in pretreatment, and NH4SCN is added in concentration.The purity for obtaining sodium sulfocyanate crystal salt is
98.8wt%；The purity of sodium thiosulfate crystal salt is 95.8wt%.
The equation of the chemical reaction mainly occurred in the above process is as follows：
2NaHSO3+Na2CO3=2Na25O3+H2O+CO2↑
NaHSO3+NaHCO3=Na2SO3+H2O+CO2↑
NH4SCN+NaHCO3=NH3↑+CO2↑+H2O+NaSCN
2NH4SCN+Na2CO3=2NH3↑+CO2↑+H2O+2NaSCN。
Embodiment 7
Sulfur content is 3g/L in waste liquid, and carbonate content 2g/L, sodium bicarbonate content is 5g/L, inorganic agent A：For
Na2SO3+ NaHSO3, inorganic agent B：NaHSO4, additive amount is respectively 4g, 6.0g and 4.5g in every liter of waste liquid, feed postition be
It synchronizes and is added when pretreatment.The purity for obtaining sodium sulfocyanate crystal salt is 98.7wt%；The purity of sodium thiosulfate crystal salt is
95.5wt%.
2NaHSO3+Na2CO3=2Na2SO3+H2O+CO2↑
NaHSO3+NaHCO3=Na2SO3+H2O+CO2↑
NaHSO4+NaHCO3=CO2↑+H2O+Na2SO4
2NaHSO4+Na2CO3=CO2↑+H2O+2Na2SO4。
1. experimental data of table
From the experimental data of table 1 it should be apparent that using desulfurization waste liquor preprocess method of the invention, sodium sulfocyanate
Crystallization purity salt is up to 98.5wt% or more, and sodium thiosulfate crystallization purity salt is up to 95-96wt%.
It is hereby stated that described above contribute to those skilled in the art understand that present disclosure, but not limit this hair
Bright protection domain.It is any that equivalent replacement described above, modification are improved and/or deleted without disengaging substantive content of the present invention
Numerous conform to the principle of simplicity and the implementation carried out, each fall within protection scope of the present invention.
Claims (10)
1. a kind of sodium sulfocyanate of high-purity and the desulfurization waste liquor preprocess method of sodium thiosulfate, it is characterised in that processing
Agent includes inorganic agent A and inorganic agent B, and wherein inorganic agent A is Na2SO3And/or NaHSO3, inorganic agent B is NaHSO4And/or
NH4SCN,
Inorganic agent A and inorganic agent B substeps are added, and include the following steps：
Inorganic agent A is added into desulfurization waste liquor to carry out after tentatively pre-processing, then liquid adds through aeration, filtering, preheating, decoloration
Enter in reaction-concentration kettle, and inorganic agent B is added and further pre-processes, gas discharge, then re-evaporation is concentrated, crystallizes, centrifuged
To low impurity mixed salt；
Or inorganic agent A additions synchronous with inorganic agent B, include the following steps：
Into desulfurization waste liquor be added inorganic agent A and inorganic agent B tentatively pre-processed, gas be discharged, liquid through aeration, filtering,
Preheating, decoloration, evaporation and concentration, crystallization, centrifugation obtain low impurity mixed salt；
The preliminary pretreated time is 1-5h, 50-60 DEG C of the temperature of the aeration, time 2-4h, the temperature of the preheating
Degree is 65-95 DEG C, and the temperature of the reaction-concentration kettle is 85 DEG C or more, reaction time 1-8h.
2. a kind of sodium sulfocyanate of high-purity and the desulfurization waste liquor preprocess method of sodium thiosulfate, it is characterised in that processing
Agent is NaHSO3Or NaHSO3+Na2SO3, include the following steps：
The inorganic agent is added into desulfurization waste liquor tentatively to be pre-processed, gas discharge, liquid is through aeration, filtering, preheating, de-
Color, evaporation and concentration, crystallization, centrifugation obtain low impurity mixed salt；
The preliminary pretreated time is 1-5h, 50-60 DEG C, time 2-4h of the aeration temperature, the temperature of the preheating
It it is 65-95 DEG C, the temperature of the reaction-concentration kettle is 85 DEG C or more, reaction time 1-2h.
3. according to the method described in claim 1, it is characterized in that the inorganic agent A is Na2SO3, the inorganic agent B is
NH4SCN, feed postition are that substep is added, and the reaction time of reaction-concentration kettle is 5-8h.
4. according to the method described in claim 3, it is characterized in that Na2SO3Amount be waste liquid in sulphur molal quantity 85-
95%, NH4The amount of SCN be decolourize clear liquid in sodium bicarbonate molal quantity 85%~95%, the molal quantity of sodium carbonate 2 ×
85%~2 × 95%.
5. method according to claim 1 or 3, it is characterised in that by the products gaseous ammonia of the reaction-concentration kettle into end of line
Aspiration, evaporation vapour carry out condensation process.
6. according to the method described in claim 1, it is characterized in that the inorganic agent A is NaHSO3And/or Na2SO3, the place
It is NaHSO to manage agent B4, feed postition is synchronous addition, and the reaction time of the reaction-concentration kettle is 1-2h.
7. the method according to claim 2 or 6, it is characterised in that total SO3 2-Amount be the sulphur in waste liquid molal quantity
85-95%, total H+Amount be waste liquid in sodium bicarbonate molal quantity 85%~95%, the 2 × 85% of the molal quantity of sodium carbonate
~2 × 95%.
8. method according to claim 1 or 2, it is characterised in that in the preliminary pretreatment by recycle liquid pump and/
Or mechanical agitation makes desulfurization waste liquor carry out interior cycle.
9. method according to claim 1 or 2, it is characterised in that after decoloration, decoloration clear liquid enters decoloration Clear liquid tank, described
Clear liquid tank of decolourizing has insulating layer.
10. method according to claim 1 or 2, it is characterised in that the temperature of the reaction-concentration kettle is 85 DEG C -100
℃。
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| CN116899313A (en) * | 2023-05-05 | 2023-10-20 | 河南殷之都环保科技有限公司 | A device and process for preparing sodium thiocyanate by coking ammonium thiocyanate |
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