CN108715452B - Desulfurization waste liquid pretreatment method for preparing high-purity sodium thiocyanate and sodium thiosulfate - Google Patents
Desulfurization waste liquid pretreatment method for preparing high-purity sodium thiocyanate and sodium thiosulfate Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 131
- 239000002699 waste material Substances 0.000 title claims abstract description 80
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 45
- 230000023556 desulfurization Effects 0.000 title claims abstract description 45
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 title claims abstract description 36
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 235000019345 sodium thiosulphate Nutrition 0.000 title claims abstract description 35
- 238000002203 pretreatment Methods 0.000 title description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 82
- 150000003839 salts Chemical class 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000005273 aeration Methods 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 33
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 15
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 70
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 58
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 30
- 239000011593 sulfur Substances 0.000 claims description 30
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 22
- 230000008025 crystallization Effects 0.000 claims description 22
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000004042 decolorization Methods 0.000 claims description 4
- 230000001360 synchronised effect Effects 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000013078 crystal Substances 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 230000008020 evaporation Effects 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 description 12
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000003712 decolorant Substances 0.000 description 3
- 238000007255 decyanation reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001640 fractional crystallisation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 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 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
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
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- 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 method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate comprises the following steps: the treating agent A is NaSO3And/or NaHSO3The treating agent B is NaHSO4And/or NH4SCN, or the treating agent is NaHSO3Or NaHSO3+NaSO3Adding the treating agent A into the desulfurization waste liquid step by step for preliminary pretreatment, discharging gas, aerating, filtering, preheating, decoloring and concentrating the liquid, adding the treating agent B for further pretreatment during concentration, discharging the gas, and then evaporating, concentrating, crystallizing and centrifuging to obtain low-impurity mixed salt; or synchronously adding the treating agent A + the treating agent B or the treating agent only during the pretreatment, and adding other steps step by step; the pretreatment time is 1-5h, the aeration temperature is 50-60 ℃, and the preheating temperature is 65-95 ℃. The method converts the impurities in the desulfurization waste liquid into valuable salts, and produces high-purity double salts.
Description
Technical Field
The invention relates to a pretreatment method of a desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate, belonging to the technical field of treatment of desulfurization waste liquid of a coking plant.
Background
At present, part of domestic coking plants adopt a PDS wet sodium method to carry out desulfurization and decyanation on coke oven gas and generate desulfurization and decyanation waste liquid. Due to the complexity and the variability of coal gas components of a coke-oven plant and the characteristics of a desulfurization and decyanation process, the desulfurization solution contains main components of sodium thiocyanate, sodium thiosulfate and sodium sulfate, and sometimes contains impurities such as high suspended sulfur, sodium carbonate, sodium bicarbonate, micro particles, solid particles and the like. For the treatment of the desulfurization waste liquid, a coke-oven plant generally adopts a method of vacuum concentration, then extraction concentration crystallization or fractional crystallization to respectively obtain mixed salts of sodium thiocyanate crystal salt, sodium thiosulfate and sodium sulfate, and the mixed salts are recycled, wherein the sodium thiocyanate and the sodium thiosulfate crystal salt are target products for recycling due to wide industrial application, but the purity and the quality of the two crystal salts obtained by the method are not high enough, the two crystal salts contain impurities such as sodium carbonate, sodium bicarbonate and the like, the sodium carbonate and the sodium bicarbonate are alkaline, the pH of the target products is influenced by the existence of the sodium thiocyanate and the sodium thiocyanate, and the application and the price of the sodium thiosulfate and the sodium thiocyanate are limited.
At present, the purity of the sodium thiocyanate and sodium thiosulfate crystal salt obtained by the method is 96-98.5 wt%, the market price is 3000 yuan/ton, and if the purity is increased by 0.5-1 wt%, the price can be increased to 4000 yuan/ton. The improvement of 1% purity seems not big a little, but more meticulous degree of difficulty is big more, to industrial actual production moreover, on the premise of how can strictly control the cost, guarantees not to introduce other impurity, gets rid of and converts impurity such as suspension sulphur, sodium carbonate, sodium bicarbonate in the desulfurization waste liquid, improves the purity of sodium thiocyanate and sodium thiosulfate, has very important realistic meaning.
Disclosure of Invention
Aiming at the problems that the purity of sodium thiocyanate and sodium thiosulfate crystal salt is not high and sodium carbonate and sodium bicarbonate impurities are contained, the invention provides a desulfurization waste liquid pretreatment method for preparing high-purity sodium thiocyanate and sodium thiosulfate.
The technical scheme of the invention is as follows:
a method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate is characterized in that a treating agent comprises a treating agent A and a treating agent B, wherein the treating agent A is Na2SO3And/or NaHSO3The treating agent B is NaHSO4And/or NH4SCN，
The treating agent A and the treating agent B are added step by step, and the method comprises the following steps:
adding a treating agent A into the desulfurization waste liquid for preliminary pretreatment, then aerating, filtering, preheating and decoloring the liquid, then adding the liquid into a reaction-concentration kettle, adding a treating agent B for further pretreatment, discharging gas, and then evaporating, concentrating, crystallizing and centrifuging to obtain low-impurity mixed salt;
or the treating agent A and the treating agent B are synchronously added, and the method comprises the following steps:
adding a treating agent A and a treating agent B into the desulfurization waste liquid for primary pretreatment, discharging gas, and carrying out aeration, filtration, preheating, decolorization, evaporative concentration, crystallization and centrifugation on the liquid to obtain low-impurity mixed salt;
the preliminary pretreatment time is 1-5h, the aeration temperature is 50-60 ℃, the time is 2-4h, the preheating temperature is 65-95 ℃, the temperature of the reaction-concentration kettle is more than 85 ℃, and the reaction time is 1-8 h.
A method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate is characterized in that a treating agent is NaHSO3Or NaHSO3+Na2SO3The method comprises the following steps:
adding the treating agent into the desulfurization waste liquid for preliminary pretreatment, discharging gas, and carrying out aeration, filtration, preheating, decoloration, evaporative concentration, crystallization and centrifugation on the liquid to obtain low-impurity mixed salt;
the preliminary pretreatment time is 1-5h, the aeration temperature is 50-60 ℃, the time is 2-4h, the preheating temperature is 65-95 ℃, the temperature of the reaction-concentration kettle is more than 85 ℃, and the reaction time is 1-2 h.
The treating agent A is Na2SO3The treating agent B is NH4SCN is added step by step, and the reaction time of the reaction-concentration kettle is 5-8 h.
When added step by step, Na2SO3The amount of the sulfur is 85 to 95 percent of the mole number of the sulfur in the waste liquid, NH4The amount of SCN is 85-95% of the mole number of sodium bicarbonate in the decolorized clear solution, and 2 × 85-2 × 95% of the mole number of sodium carbonate.
And (3) absorbing tail gas of the product ammonia gas of the reaction-concentration kettle, and condensing the evaporated steam.
The treating agent A is NaHSO3And/or Na2SO3The treating agent B is NaHSO4The adding mode is synchronous adding, and the reaction time of the reaction-concentration kettle is 1-2 h.
SynchronizationWhen added, total SO3 2-The amount of the sulfur in the waste liquid is 85 to 95 percent of the mole number of the sulfur in the waste liquid, and the total H+The amount of the sodium carbonate is 85 to 95 percent of the mole number of the sodium bicarbonate in the waste liquid and 2 × 85 to 2 × 95 percent of the mole number of the sodium carbonate.
And internally circulating the desulfurization waste liquid by a circulating liquid pump and/or mechanical stirring during the primary pretreatment.
And after decoloring, feeding the decolored clear liquid into a decolored clear liquid tank, wherein the decolored clear liquid tank is provided with a heat insulation layer.
The temperature of the reaction-concentration kettle is 85-100 ℃.
The invention has the beneficial technical effects that:
the invention relates to a method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate, which combines a novel concentration process through a primary pretreatment step and selects SO3 2-And/or HSO3 2-Treating agent A and having H+And/or NH4 +With SO or with treating agent B3 2-And H+The treating agent of two ions is used for preliminary pretreatment of the waste liquid, wherein Na2SO3And NaHSO3SO in (1)3 2-Converting the impurity sulfur in the waste liquid into the target product sodium thiosulfate, NaHSO under the proper condition4And NaHSO3H in (1)+And NH4NH in SCN4 +Sodium carbonate and sodium bicarbonate are converted into gas to be discharged, so that impurities in the desulfurization waste liquid are converted into valuable salts by using low-value materials through chemical reaction, and high-purity sodium thiocyanate crystal salt and high-purity sodium thiosulfate crystal salt are prepared. Preferably, the treating agent is Na2SO3+NaHSO3+NaHSO4Or Na2SO3+NaHSO4Or NaHSO3+NaHSO4Or Na2SO3+NaHSO3Or NaHSO3Synchronously adding during preliminary pretreatment SO as to ensure SO during preliminary pretreatment3 2-Mixing with waste liquid, and aerating at 50-60 deg.C with SO3 2-Is in full contact with sulfur and reactsShould be converted into Na2S2O3New impurities are avoided from being introduced, unconverted sulfur and other solids are filtered and removed together, and the purity of the sodium thiosulfate in the crystallized salt is higher; and make NaHSO4The reaction time with sodium carbonate and sodium bicarbonate is prolonged from the primary pretreatment to the concentration period, the reaction is more complete, and a small amount of carbon dioxide gas generated does not need to be recovered. More preferably, the treating agent is Na2SO3+NH4SCN, added step by step, Na2SO3During the pretreatment, sulfur is added, and NH is added4The SCN is added with the sodium carbonate and the sodium bicarbonate during concentration, namely a new concentration process is adopted, the reaction is carried out firstly and then the concentration is carried out, on one hand, the reaction and the concentration are more sufficient by virtue of higher temperature and pressure of a reaction-concentration kettle, the impurity removal effect is good, and the waste of NH caused by premature addition can be avoided4SCN, and ammonia gas generated by the reaction can be collected in a centralized manner, so that the environment pollution is avoided; on the other hand, the product is sodium thiocyanate, and the aim of improving the purity of the sodium thiocyanate crystal salt is fulfilled. In conclusion, low-impurity mixed salts can be obtained by this process.
The method comprises the steps of preliminary pretreatment, aeration, filtration, preheating, decoloration, concentration, crystallization and centrifugation in sequence, wherein Na is added during the preliminary pretreatment2SO3Or simultaneously or separately adding NaHSO3Removing sulfur and simultaneously removing sodium carbonate and sodium bicarbonate completely or partially; then aerating to remove the micro-particles and simultaneously providing a temperature and mixing condition suitable for the removal reaction; filtering to remove unconverted sulfur and other solid impurities; preheating before decoloring ensures higher temperature, so that unreacted treating agents are fully reacted on one hand, and complete decoloring is facilitated on the other hand; decoloring to remove impurities such as noble metals; the concentration can be carried out by a new concentration process, i.e. NaHSO4And/or NH4SCN is put into a reaction-concentration kettle, the SCN and the SCN are fully reacted by utilizing the higher temperature and pressure of the reaction-concentration kettle, the residence time in the reaction-concentration kettle is properly prolonged to fully react, sodium carbonate and sodium bicarbonate are intensively removed, evaporation concentration is carried out after the reaction, and then mixed salt with low impurity content can be obtained through crystallization and centrifugation. By the method of the inventionThe method not only solves the quality problem of the desulfurization waste liquid and brings high economic benefit for enterprises, but also has small modification to the existing traditional equipment, low cost and wide application prospect.
Preferably, the total SO in the treating agent is controlled3 2-The amount of the sulfur in the waste liquid is 85 to 95 percent of the mole number of the sulfur in the waste liquid, and the total H+Or NH4 +The amount of the sodium carbonate is 85 to 95 percent of the total mole number of the sodium bicarbonate in the decolored clear liquid, and the mole number of the sodium carbonate is 2 × 85 to 2 × 95 percent, so that the treating agent is not excessive.
Preferably, the product ammonia gas of the reaction-concentration kettle is subjected to tail gas absorption, and the evaporation gas is subjected to condensation treatment and recycling.
Preferably, the desulfurization waste liquid is internally circulated by a circulating liquid pump and/or mechanical stirring during primary pretreatment, so that the reaction speed is increased.
Preferably, after decolorization, the decolorized clear liquid enters a decolorized clear liquid tank, and the decolorized clear liquid tank is provided with a good heat insulation layer and can keep the temperature of the decolorized clear liquid at 65-95 ℃.
Preferably, the temperature of the reaction-concentration kettle is 85-100 ℃, so that reactants are in a micro-boiling state.
Preferably, the mixed salt is treated by a conventional refined salt extraction method, the mixed salt is firstly extracted, and then sodium thiocyanate, sodium thiosulfate and sodium sulfate crystalline salt are respectively obtained through concentration crystallization and dissolution crystallization, or the sodium thiocyanate, sodium thiosulfate and sodium sulfate crystalline salt are obtained through fractional crystallization and dissolution crystallization, the purity of the sodium thiocyanate crystalline salt is up to 98.5-99.0 wt%, and the purity of the sodium thiosulfate crystalline salt is 95-96 wt%.
Drawings
FIG. 1 is a process flow diagram of an embodiment of a desulfurization waste liquid pretreatment method of the present invention;
FIG. 2 is a schematic view of an apparatus according to an embodiment of the desulfurization waste liquid pretreatment method of the present invention.
The various reference numbers in the figures are listed below:
1-desulfurizing liquid delivery pump, 2-circulating liquid pump, 3-pretreatment tank, 4-aeration tank, 5-aeration air chamber, 6-plate frame filter, 7-decolorizing feed pump, 8-preheater, 9-decolorizing tower feed inlet, 10-decolorizing tower, 11-decolorizing tower inlet hole, 12-decolorizing tower clear liquid outlet, 13-decolorizing clear liquid tank, 14-reaction concentrating kettle feed pump, 15-reaction concentrating kettle clear liquid inlet, 16-reaction-concentrating kettle, 17-concentrating kettle manhole, 18-treating agent feed inlet, 19-reaction gas and evaporation gas outlet, 20-concentrated liquid outlet, 21-crystallizing kettle concentrated liquid inlet, 22-mixed salt crystallizing kettle, 23-centrifuge, 24-tail gas absorption tower and 25-evaporation gas cooler.
Detailed Description
In order that the invention may be readily understood, the invention will now be further described with reference to specific examples.
Example 1
The sulfur content in the waste liquid is 3g/L, the sodium carbonate content is 2g/L, and the sodium bicarbonate content is 5 g/L. The treating agent A is Na2SO3The treating agent B is NH4SCN, Na in per liter of waste liquid2SO3Is added in an amount of 11g, NH being present in each liter of waste liquid4SCN was added in an amount of 7.2g, and was added at the time of preliminary pretreatment and at the time of concentration, respectively.
As shown in fig. 1 and fig. 2, the method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate in the embodiment includes the following specific steps:
desulfurization waste liquid is squeezed into preliminary treatment groove 3 by desulfurization liquid delivery pump 1, to preliminary treatment groove 3 add treating agent A, directly drop into inside the desulfurization waste liquid, carry out 2 hours preliminary treatment, and the desulfurization waste liquid is circulated in order to realize intensive mixing by circulating liquid pump 2 during, makes treating agent and waste liquid contact and reaction abundant, improves the treatment rate. The desulfurized waste liquid after the preliminary pretreatment is sent into an aeration tank 4 for aeration treatment, small-particle solid impurities are driven by a bubble support to float upwards for removal after 4 hours of aeration, aeration gas is supplied by an aeration gas chamber 5, the aeration temperature is 50-60 ℃, the temperature is favorable for the reaction to be further and fully carried out, then the small-particle solid impurities enter a plate-and-frame filter 6 for filtering to remove unreacted solid sulfur and other solid impurities, then the small-particle solid impurities are sent into a preheater 8 for heating through a decoloration feeding pump 7, the temperature is controlled to be 85 +/-5 ℃, then the small-particle solid impurities flow into a decoloration tower 10 through a decoloration tower feeding port 9 and are decolored by activated carbon to remove heavy metals, a decolorant is put into a decoloration tower feeding port 11, decolored clear liquid flows out through a decoloration tower clear liquid outlet 12 and enters a decoloration clear liquid tank 13 for treatment. The decolored clear liquid is pumped into a clear liquid inlet 15 of the reaction concentration kettle by a feeding pump 14 of the reaction concentration kettle through a hole of the concentration kettle and enters a reaction-concentration kettle 16, the temperature of the clear liquid and a treating agent B added through a treating agent inlet 18 are firstly raised to 95 ℃ in the reaction-concentration kettle 16, the reaction time under the condition of micro boiling is controlled to be 4 hours, and the generated tail gas ammonia enters a tail gas absorption tower 24 for absorption treatment through a reaction gas and evaporation gas outlet 19; after the reaction, the reaction product enters a vacuum concentration stage, the evaporation steam is discharged from a reaction gas and evaporation steam outlet 19 and enters an evaporation steam cooler 25 for condensation, and the water is recycled after the treatment. The concentrated solution after concentration is discharged from a concentrated solution outlet 20 and enters a mixed salt crystallization kettle 22 through a crystallization kettle concentrated solution inlet 21 for crystallization; after crystallization, the mixed salt containing low impurities is obtained by centrifugation through a centrifuge 23. Extracting and filtering the mixed salt, concentrating, crystallizing and centrifuging the extract liquor to obtain sodium thiocyanate crystal salt with the purity of 99.0 wt%; dissolving, crystallizing and centrifuging filter residues to obtain sodium thiosulfate and sodium sulfate, and separating sodium sulfate to obtain sodium thiosulfate crystal salt with the purity of 95.8 wt%.
In addition, when the internal components of the reaction-concentration still 16 require maintenance and repair, a worker enters through the concentration still manhole 17.
The equations for the chemical reactions that mainly occur in the above process are as follows:
NH4SCN+NaHCO3＝NH3↑+CO2↑+H2O+NaSCN
2NH4SCN+Na2CO3＝2NH3↑+CO2↑+H2O+2NaSCN。
example 2
This example is different from example 1 in NH4Change of SCN to NaHSO4NaHSO per liter of waste liquid4Adding amount ofIt was 11.5 g. The purity of the obtained sodium thiocyanate crystal salt is 98.6 wt%; the purity of the sodium thiosulfate crystalline salt was 95.4 wt%.
The equations for the chemical reactions that mainly occur in the above process are as follows:
NaHSO4+NaHCO3＝CO2↑+H2O+Na2SO4
2NaHSO4+Na2CO3＝CO2↑+H2O+2Na2SO4。
example 3
The sulfur content in the waste liquid is 3g/L, the sodium carbonate content is 2g/L, and the sodium bicarbonate content is 5 g/L. The treating agent is the same as the treating agent in the embodiment 2, but the adding time of the treating agent is different, the treating agent is synchronously added during the primary pretreatment, the flow and the device can refer to the figures 1 and 2, and the specific steps are as follows:
the desulfurization waste liquid is pumped into a pretreatment tank 3 by a desulfurization liquid delivery pump 1, and a treating agent Na is added into the pretreatment tank 32SO3And NaHSO4Inside directly dropping into desulfurization waste liquid, carrying out 2 hours preliminary treatment, the desulfurization waste liquid is circulated in order to realize the intensive mixing by circulating liquid pump 2 during to mechanical stirring has in the treatment trough 3, makes the treating agent and waste liquid contact and reaction abundant, improves the treatment rate. The desulfurized waste liquid after the primary pretreatment is sent into an aeration tank 4 for aeration treatment, small-particle solid impurities are driven by a bubble support to float upwards for removal after 4 hours of aeration, aeration gas is supplied by an aeration gas chamber 5, the aeration temperature is 50-60 ℃, the reaction is favorably and fully carried out, then the aeration gas enters a plate-and-frame filter 6 for filtering and removing unreacted solid sulfur and other solid impurities, then the aeration gas is sent into a preheater 8 for heating by a decoloration feeding pump 7, the temperature is controlled to be 85 +/-5 ℃, then the aeration gas flows into a decoloration tower 10 through a decoloration tower feed inlet 9 for decoloration by activated carbon to remove heavy metals, a decolorant is put into the inlet 11 of the decoloration tower, decolored clear liquid after decoloration flows out through a decoloration tower clear liquid outlet 12 and enters a decolored clear liquid tank 13Has good heat insulating layer to maintain the temperature of the decolorized clear liquid. The decolored clear liquid is pumped into a clear liquid inlet 15 of the reaction concentration kettle by a feeding pump 14 of the reaction concentration kettle and enters a reaction-concentration kettle 16, the temperature in the reaction-concentration kettle 16 is firstly raised to 95 ℃, the reaction time is 1 hour under the condition of micro boiling, after the reaction, the clear liquid enters a vacuum concentration stage, the evaporation gas is discharged from a reaction gas outlet 19 and an evaporation gas outlet 19 and enters an evaporation gas cooler 25 for condensation, and the water is recycled after the treatment. The concentrated solution after concentration is discharged from a concentrated solution outlet 20 and enters a mixed salt crystallization kettle 22 through a crystallization kettle concentrated solution inlet 21 for crystallization; after crystallization, the mixed salt containing low impurities is obtained by centrifugation through a centrifuge 23. Extracting and filtering the mixed salt, concentrating, crystallizing and centrifuging the extract liquor to obtain sodium thiocyanate crystal salt with the purity of 98.6 wt%; dissolving, crystallizing and centrifuging filter residues to obtain sodium thiosulfate and sodium sulfate, and separating sodium sulfate to obtain sodium thiosulfate crystal salt with the purity of 96.0 wt%.
The chemical reactions that mainly take place in the above process are referred to example 2.
Example 4
The sulfur content in the waste liquid is 3g/L, the sodium carbonate content is 2g/L, the sodium bicarbonate content is 5g/L, the treating agent is the same as that in the example 1, and Na is contained in each liter of the waste liquid2SO3Is added in an amount of 11g, NH being present in each liter of waste liquid4The SCN was added in an amount of 7.2g, except that the treatment agent was added at a different time and simultaneously in the preliminary pretreatment, and the specific procedure was similar to that in example 3 and will not be repeated here.
The purity of the sodium thiocyanate crystal salt is 98.9 wt%; the purity of the sodium thiosulfate crystalline salt was 95.2 wt%.
The chemical reactions that mainly take place in the above process are referred to example 1.
Example 5
The sulfur content in the waste liquid is 3g/L, the sodium carbonate content is 2g/L, the sodium bicarbonate content is 5g/L, and the treating agent is NaHSO3The addition amount is 10g added into each liter of waste liquid, and the addition amount is added during primary pretreatment, and the method comprises the following specific steps:
the desulfurization waste liquid is pumped into a pretreatment tank 3 by a desulfurization liquid delivery pump 1, and a treating agent NaHSO is added into the pretreatment tank 33Inside directly throwing into the desulfurization waste liquid, carry out 2 hours preliminary treatment, the desulfurization waste liquid is circulated by circulating liquid pump 2 in order to realize intensive mixing during, makes the contact of treating agent and waste liquid and reacts fully, improves the treatment rate. The desulfurized waste liquid after the preliminary pretreatment is sent into an aeration tank 4 for aeration treatment, small-particle solid impurities are driven by a bubble support to float upwards for removal after 4 hours of aeration, aeration gas is supplied by an aeration gas chamber 5, the aeration temperature is 50-60 ℃, the reaction is favorably and fully carried out, then the aerated gas enters a plate-and-frame filter 6 for filtering and removing unreacted solid sulfur and other solid impurities, then the aerated gas is sent into a preheater 8 for heating through a decoloration feeding pump 7, the temperature is controlled to be 85 +/-5 ℃, then the aerated gas flows into a decoloration tower 10 through a decoloration tower feeding port 9 and is decolored by activated carbon to remove heavy metals, a decolorant is put in through a decoloration tower inlet hole 11, decolored clear liquid after decoloration flows out through a decoloration tower clear liquid outlet 12 and enters a decolored clear liquid tank 13 for treatment, the surface of the decoloration tank 13. The decolored clear liquid is pumped into a clear liquid inlet 15 of the reaction concentration kettle by a feeding pump 14 of the reaction concentration kettle and enters a reaction-concentration kettle 16, the temperature in the reaction-concentration kettle 16 is firstly raised to 95 ℃, the clear liquid directly enters a vacuum concentration stage under the condition of micro boiling, the evaporation steam is discharged from a reaction gas and evaporation steam outlet 19 and enters an evaporation steam cooler 25 for condensation, and the return water is reused after the treatment. The concentrated solution after concentration is discharged from a concentrated solution outlet 20 and enters a mixed salt crystallization kettle 22 through a crystallization kettle concentrated solution inlet 21 for crystallization; after crystallization, the mixed salt containing low impurities is obtained by centrifugation through a centrifuge 23. Extracting and filtering the mixed salt, concentrating, crystallizing and centrifuging the extract liquor to obtain the sodium thiocyanate crystal salt with the purity of 98.6 wt%; dissolving, crystallizing and centrifuging filter residues to obtain sodium thiosulfate and sodium sulfate, and separating sodium sulfate to obtain sodium thiosulfate crystal salt with the purity of 95.7 wt%.
The equations for the chemical reactions that mainly occur in the above process are as follows:
2NaHSO3+Na2CO3＝2Na2SO3+H2O+CO2↑
NaHSO3+NaHCO3＝Na2SO3+H2O+CO2↑
example 6
The sulfur content in the waste liquid is 3g/L, the sodium carbonate content is 2g/L, the sodium bicarbonate content is 5g/L, and the treating agents are A: na (Na)2SO3+NaHSO3And the treating agent B: NH (NH)4SCN, the addition amount of each liter of waste liquid is 7.0g, 4.0g and 4.5g respectively, Na2SO3+NaHSO3In the pretreatment, NH is added simultaneously4SCN was added at concentration. The purity of the obtained sodium thiocyanate crystal salt is 98.8 wt%; the purity of the sodium thiosulfate crystalline salt was 95.8 wt%.
The equations for the chemical reactions that mainly occur in the above process are as follows:
2NaHSO3+Na2CO3＝2Na25O3+H2O+CO2↑
NaHSO3+NaHCO3＝Na2SO3+H2O+CO2↑
NH4SCN+NaHCO3＝NH3↑+CO2↑+H2O+NaSCN
2NH4SCN+Na2CO3＝2NH3↑+CO2↑+H2O+2NaSCN。
example 7
The sulfur content in the waste liquid is 3g/L, the sodium carbonate content is 2g/L, the sodium bicarbonate content is 5g/L, and the treating agent A: is Na2SO3+ NaHSO3And the treating agent B: NaHSO4The addition amount of each liter of waste liquid is respectively 4g, 6.0g and 4.5g, and the addition mode is synchronous addition during pretreatment. The purity of the obtained sodium thiocyanate crystal salt is 98.7 wt%; the purity of the sodium thiosulfate crystalline salt was 95.5 wt%.
2NaHSO3+Na2CO3＝2Na2SO3+H2O+CO2↑
NaHSO3+NaHCO3＝Na2SO3+H2O+CO2↑
NaHSO4+NaHCO3＝CO2↑+H2O+Na2SO4
2NaHSO4+Na2CO3＝CO2↑+H2O+2Na2SO4。
TABLE 1 Experimental data
As is clear from the experimental data in Table 1, the purity of the sodium thiocyanate crystal salt is as high as more than 98.5 wt% and the purity of the sodium thiosulfate crystal salt is as high as 95-96 wt% by using the desulfurization waste liquid pretreatment method of the invention.
It is pointed out here that the above description is helpful for the person skilled in the art to understand the content of the invention, but does not limit the scope of protection of the invention. Any such equivalents, modifications and/or omissions as may be made without departing from the spirit and scope of the invention may be resorted to.
Claims (10)
1. A method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate is characterized in that a treating agent comprises a treating agent A and a treating agent B, wherein the treating agent A is Na2SO3And/or NaHSO3The treating agent B is NaHSO4Or NH4SCN，
The treating agent A and the treating agent B are added step by step, and the method comprises the following steps:
adding a treating agent A into the desulfurization waste liquid for preliminary pretreatment, then aerating, filtering, preheating and decoloring the liquid, then adding the liquid into a reaction-concentration kettle, adding a treating agent B for further pretreatment, discharging gas, and then evaporating, concentrating, crystallizing and centrifuging to obtain low-impurity mixed salt;
or the treating agent A and the treating agent B are synchronously added, and the method comprises the following steps:
adding a treating agent A and a treating agent B into the desulfurization waste liquid for primary pretreatment, discharging gas, and carrying out aeration, filtration, preheating, decolorization, evaporative concentration, crystallization and centrifugation on the liquid to obtain low-impurity mixed salt;
the preliminary pretreatment time is 1-5h, the aeration temperature is 50-60 ℃, the time is 2-4h, the preheating temperature is 65-95 ℃, the temperature of the reaction-concentration kettle is more than 85 ℃, and the reaction time is 1-8 h;
total SO in treating agent3 2-The amount of the sulfur in the waste liquid is 85 to 95 percent of the mole number of the sulfur in the waste liquid, and the total H in the treating agent+Or NH4 +The amount of the sodium carbonate is 85 to 95 percent of the mole number of the sodium bicarbonate in the waste liquid and 2 × 85 to 2 × 95 percent of the mole number of the sodium carbonate.
2. A method for pretreating desulfurization waste liquid for preparing high-purity sodium thiocyanate and sodium thiosulfate is characterized in that a treating agent is NaHSO3Or NaHSO3+Na2SO3The method comprises the following steps:
adding the treating agent into the desulfurization waste liquid for preliminary pretreatment, discharging gas, and carrying out aeration, filtration, preheating, decoloration, evaporative concentration, crystallization and centrifugation on the liquid to obtain low-impurity mixed salt;
the preliminary pretreatment time is 1-5h, the aeration temperature is 50-60 ℃, the time is 2-4h, the preheating temperature is 65-95 ℃, the temperature of the reaction-concentration kettle is more than 85 ℃, and the reaction time is 1-2 h;
total SO in treating agent3 2-The amount of the sulfur in the waste liquid is 85 to 95 percent of the mole number of the sulfur in the waste liquid, and the total H in the treating agent+The amount of the sodium carbonate is 85 to 95 percent of the mole number of the sodium bicarbonate in the waste liquid and 2 × 85 to 2 × 95 percent of the mole number of the sodium carbonate.
3. The method according to claim 1, characterized in that the treating agent A is Na2SO3The treating agent B is NH4SCN is added step by step, and the reaction time of the reaction-concentration kettle is 5-8 h.
4. The method according to claim 3, wherein Na is2SO3The amount of the sulfur is 85 to 95 percent of the mole number of the sulfur in the waste liquid, NH4The amount of SCN is 85-95% of the mole number of sodium bicarbonate in the decolorized clear solution, and 2 × 85-2 × 95% of the mole number of sodium carbonate.
5. The method according to claim 1 or 3, characterized in that the product ammonia gas of the reaction-concentration kettle is subjected to tail gas absorption, and the evaporated steam is subjected to condensation treatment.
6. The method according to claim 1, characterized in that the treating agent A is NaHSO3And/or Na2SO3The treating agent B is NaHSO4The adding mode is synchronous adding, and the reaction time of the reaction-concentration kettle is 1-2 h.
7. The method of claim 6, wherein the total SO in the treating agent is3 2-The amount of the sulfur in the waste liquid is 85 to 95 percent of the mole number of the sulfur in the waste liquid, and the total H in the treating agent+The amount of the sodium carbonate is 85 to 95 percent of the mole number of the sodium bicarbonate in the waste liquid and 2 × 85 to 2 × 95 percent of the mole number of the sodium carbonate.
8. The method according to claim 1 or 2, characterized in that the desulfurized waste liquid is internally circulated by means of a circulating liquid pump and/or mechanical agitation during said preliminary pretreatment.
9. The method according to claim 1 or 2, characterized in that after the decolorization, the decolorized liquor enters a decolorized liquor tank, which has an insulating layer.
10. The method according to claim 1 or 2, characterized in that the temperature of the reaction-concentration tank is 85 ℃ to 100 ℃.
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| JPS5493669A (en) * | 1977-12-14 | 1979-07-24 | Toray Ind Inc | Treating method for desulfurized waste liquid of coke oven gas |
| CN103663496A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving purity of sodium thiocyanate in coking and desulfurizing waste liquid |
| CN103663497A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid |
| CN104925830A (en) * | 2015-07-10 | 2015-09-23 | 安徽工业大学 | Chemical treatment method for extracting sodium thiocyanate from coked desulfurization waste solution |
| CN107128950A (en) * | 2017-07-13 | 2017-09-05 | 江苏沂州煤焦化有限公司 | The apparatus and method that refined salt is extracted in the waste liquid produced from wet method ISS J desulfurization |
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| JPS5493669A (en) * | 1977-12-14 | 1979-07-24 | Toray Ind Inc | Treating method for desulfurized waste liquid of coke oven gas |
| CN103663496A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving purity of sodium thiocyanate in coking and desulfurizing waste liquid |
| CN103663497A (en) * | 2013-09-24 | 2014-03-26 | 北京艾思合众环保科技有限公司 | Method for improving whiteness of sodium thiocyanate in coking desulfurization waste liquid |
| CN104925830A (en) * | 2015-07-10 | 2015-09-23 | 安徽工业大学 | Chemical treatment method for extracting sodium thiocyanate from coked desulfurization waste solution |
| CN107128950A (en) * | 2017-07-13 | 2017-09-05 | 江苏沂州煤焦化有限公司 | The apparatus and method that refined salt is extracted in the waste liquid produced from wet method ISS J desulfurization |
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