CN207129963U - The device of refined salt is extracted from waste liquid caused by wet method ISS J desulfurization - Google Patents

The device of refined salt is extracted from waste liquid caused by wet method ISS J desulfurization Download PDF

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CN207129963U
CN207129963U CN201720848785.7U CN201720848785U CN207129963U CN 207129963 U CN207129963 U CN 207129963U CN 201720848785 U CN201720848785 U CN 201720848785U CN 207129963 U CN207129963 U CN 207129963U
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kettle
sodium
separation
sulphur cyanogen
crude salt
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张五洲
何相君
张德亮
臧未
臧未一
陈嘉梁
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Ningbo Zhongke Far East Catalytic Engineering Technology Co Ltd
JIANGSU YIZHOU COAL COKING Co Ltd
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Ningbo Zhongke Far East Catalytic Engineering Technology Co Ltd
JIANGSU YIZHOU COAL COKING Co Ltd
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Abstract

The utility model discloses a kind of device that refined salt is extracted from waste liquid caused by wet method ISS J desulfurization, the device includes crude salt dry component, sodium sulfocyanate separation and purification component, sodium thiosulfate separation and purification component, sodium sulphate separation and purification component and solvent recovery component；Crude salt dry component includes desulfurization waste liquor tank, heat exchanger, evaporating kettle, crystallization kettle and centrifuge；Sodium sulfocyanate separation and purification component includes dissolution kettle, filter-pressing cauldron, evaporating kettle, crystallization kettle, centrifuge, drying machine and packing machine；Sodium thiosulfate separation and purification component includes dissolution kettle, condensate drum, filter-pressing cauldron, crystallization kettle, centrifuge and packing machine；Sodium sulphate separation and purification component includes dissolution kettle, concentrated sulfuric acid head tank, evaporating kettle, centrifuge, drying machine and packing machine；Apparatus and method of the present utility model, it pollutes waste liquid caused by the desulphurization system of environment to script and thoroughly handles and be produced as technical grade product, is truly realized wastewater zero discharge and turns waste into wealth.

Description

The device of refined salt is extracted from waste liquid caused by wet method ISS-J desulfurization
Technical field
The utility model belongs to technical field of coal chemical industry, and in particular to one kind is from waste liquid caused by wet method ISS-J desulfurization Extract the device of refined salt.
Background technology
Under increasingly strict waste gas emission standard, desulfurization waste liquor discharge capacity will be increasing, environmental pollution and environment Being born caused by improvement also can increasingly weigh, and how to efficiently solve desulfurization waste liquor emission problem already turns into the weight of chemical field Big problem.
In wet method ISS-J desulfurization, the hydrogen sulfide, hydrogen cyanide in coke-stove gas are while removing is obtained, unavoidably Side reaction occurs for ground, can generate the inorganic salts such as sodium sulfocyanate, sodium thiosulfate and sodium sulphate；When inorganic salt accumulation to a certain extent When (general total content is more than 300g/L), desulfuration efficiency meeting degradation, therefore, it is necessary to periodically outer arrange doctor solution.Due to sulphur cyanogen Hydrochlorate has strong toxicity to crops and microorganism, it is impossible to biological dephenolize system is directly discharged into as other industrial wastewaters and is entered Row harmless treatment, and sulfate and thiosulfate are then different from rhodanate in the waste water, to the work of crop and microorganism With on the contrary, easily causing the eutrophication of environment into environment；Simultaneously as the waste water salt content is high, and these salt Solubility is again very high, the waste liquid using common process for treating industrial waste water significant discomfort with processing wet method ISS-J desulfurization.
Most domestic coke-oven plant has two kinds to the processing method of ISS-J desulfurization waste liquors at present：First, desulfurization waste liquor is matched somebody with somebody Enter in coal and handled, it is big to equipment corrosion；It is actually prior and although this method solves the place to go of desulfurization waste liquor It is sulphur system circulation in mixed coal, coal gas, doctor solution, does not dispose really, also increases the processing load of desulfurizer, The doctor solution of replacing is easier to generate secondary salt, reduces desulfuration efficiency；Desulfurization waste liquor, which enters in coke, simultaneously can increase coke Sulfur content, coke quality is caused to decline.Second, carrying out salt extraction processing to desulfurization waste liquor, the salt in desulfurization waste liquor is extracted Come, recycled；This method can not only reduce the discharge of desulfurization waste liquor, can also reclaim a large amount of valuable chemical industry Product, there is significant economic benefit and environmental benefit.But the use of the enterprise of salt equipment is not at present a lot, and domestic desulfurization Waste liquid salt extraction system simply extracts mixed salt or sodium sulfocyanate, sodium thiosulfate nearly all without advanced treating is carried out, remaining useless Water still needs to outer row, therefore can cause certain environmental pollution.
Utility model content
The purpose of this utility model be to provide one kind waste liquid caused by wet method ISS-J desulfurization can be carried out thoroughly processing, Realize wastewater zero discharge and can be with the device of the sodium sulfocyanate of by-product technical grade, sodium thiosulfate and sodium sulphate product.
In order to achieve the above object, scheme is used by the utility model：
It is a kind of from waste liquid caused by wet method ISS-J desulfurization extract refined salt device, the device include crude salt dry component, Sodium sulfocyanate separation and purification component, sodium thiosulfate separation and purification component, sodium sulphate separation and purification component and solvent recovery cycle Component；Crude salt dry component is transferred to from waste liquid caused by wet method ISS-J sulfur removal technologies to be handled, and is handled through crude salt dry component Material afterwards is transferred in sodium sulfocyanate separation and purification component, on the one hand sodium sulfocyanate separation and purification component separates partial material after Sodium thiosulfate separation and purification component is transferred to, technical grade sodium sulfocyanate product on the other hand can be produced from filtrate simultaneously will be useless Liquid is recycled back in desulfurization waste liquor tank, and sodium thiosulfate separation and purification component from sodium sulfocyanate separation and purification component to conveying the thing of coming Material carries out processing and produces sodium thiosulfate product and further another part material is transferred in sodium sulphate separation and purification component, sulphur Sour sodium separation and purification component is handled the material being transferred to produce sodium sulphate product, and solvent recovery component is to by sodium sulfocyanate Methanol caused by evaporation is recycled in separation and purification component and sodium sulphate separation and purification component.
The crude salt dry component includes desulfurization waste liquor tank, crude salt heat exchanger, crude salt evaporating kettle, the crude salt knot being sequentially connected Brilliant kettle and crude salt centrifuge, desulfurization waste liquor tank are connected with the waste liquid outlet of desulphurization system；Waste liquid is transferred to as caused by sulfur removal technology Decolorization is carried out in desulfurization waste liquor tank, activated carbon is added and stirs to be decolourized；Filtered after decolouring, filter residue returns to coal Factory's (delivering to coke oven) and filtrate are pumped into crude salt evaporating kettle after being preheated via crude salt heat exchanger, and stirring is provided with crude salt evaporating kettle Device and inner coil pipe, low-pressure steam is passed through to be evaporated to filtrate to inner coil pipe, the concentrate after evaporation is flowed into thick by potential difference In salt crystallization kettle；Crude salt crystallization kettle has agitating device and external jacket, and recirculated cooling water is passed through into external jacket with to concentrate Crystallisation by cooling is carried out, the crude salt suspension after crystallization is centrifuged by potential difference into crude salt centrifuge, thick after having centrifuged Salt expects to be delivered in crude salt dissolution kettle by crude salt conveying worm admittedly；
The sodium sulfocyanate separation and purification component include be sequentially connected crude salt dissolution kettle, crude salt filter-pressing cauldron, sulphur cyanogen evaporation Kettle, sulphur cyanogen crystallization kettle, sulphur cyanogen centrifuge, sulphur cyanogen drying machine and sodium sulfocyanate packing machine；Crude salt dissolution kettle and crude salt centrifuge Gu material outlet is connected, the solid material of crude salt filter-pressing cauldron exports and is connected to thio dissolution kettle, filtrate (liquid is connected to sulphur cyanogen evaporating kettle；Sulphur The solid material outlet of cyanogen centrifuge is connected to sulphur cyanogen drying machine and purified liquor outlet is connected to desulfurization waste liquor tank.Crude salt dissolution kettle is half ground Following formula arranges, its bottom be provided with heating steam pipe coil, it is internal be provided with agitating device, by crude salt drier Lai crude salt and methanol Stirring and dissolving；The sodium sulfocyanate methanol solution dissolved delivers to crude salt filter-pressing cauldron by crude salt solution transfer pump and carries out separation of solid and liquid, The filter residue solid (sodium thiosulfate and sodium sulphate) come is press-filtered out to be transferred in thio dissolution kettle, and (sodium sulfocyanate methanol is molten for filtrate Liquid) be pumped to sulphur cyanogen evaporating kettle and be evaporated processing, the methanol gas that evaporated on top comes out through over cure cyanogen evaporating heat exchanger and Recycled after the condensation of sulphur cyanogen condenser；Concentrate after evaporation enters sulphur cyanogen crystallization kettle and carries out crystallisation by cooling, after crystallization Sodium sulfocyanate methanol slurry is centrifuged by potential difference into sulphur cyanogen centrifuge, and the clear liquid being centrifuged out returns as supplement water Desulfurization waste liquor tank, the solid material (sodium sulfocyanate) for centrifuging to obtain are dried into sulphur cyanogen drying machine, and sodium sulfocyanate is obtained after drying The sodium sulfocyanate product of purity more than 99.8%, methanol content ＜ 0.02%, packaging and storage is carried out into sodium sulfocyanate packing machine.
The sodium thiosulfate separation and purification component include be sequentially connected thio dissolution kettle, condensate drum, thio press filtration Kettle, thio crystallization kettle, thio centrifuge and sodium thiosulfate packing machine；Condensate drum is used to supplement condensation into thio dissolution kettle Liquid (such as water), and the outlet of the solid material of thio filter-pressing cauldron is connected to sodium sulphate dissolution kettle filtrate (liquid and is connected to thio crystallization kettle. Condensate liquid is added into thio dissolution kettle dissolving is stirred to solid (mixture of sodium thiosulfate and sodium sulphate), dissolved Solidliquid mixture thio filter-pressing cauldron be delivered to by thio delivery pump carry out separation of solid and liquid, being press-filtered out the filter residue that comes, (sodium sulphate is solid Body) enter sodium sulphate dissolution kettle, and filtrate (sodium thiosulfate solution) enters thio Clear liquid tank and adds activated carbon thereto With adsorbing contaminant, then via being transferred to thio filtrate tank after active carbon filter removal activity charcoal, then through thio filtrate delivery pump Sodium thiosulfate solution is delivered to thio crystallization kettle, the inner coil pipe that recirculated cooling water is passed through to thio crystallization kettle is cooled Crystallization, the sodium thiosulfate suspension after crystallization are centrifuged into thio centrifuge, and the clear liquid being centrifuged out is as benefit Water-filling returns to desulfurization waste liquor tank, and centrifugation obtains water content ＜ 2% sodium thiosulfate product, entered into sodium thiosulfate packing machine Row packaging and storage.
The sodium sulphate separation and purification component include be sequentially connected sodium sulphate dissolution kettle, concentrated sulfuric acid head tank, sodium sulphate Evaporating kettle, sodium sulphate centrifuge, sodium sulphate drying machine and sodium sulphate packing machine, concentrated sulfuric acid head tank are connected to sodium sulphate dissolving Kettle.The concentrated sulfuric acid is added drop-wise in sodium sulphate dissolution kettle by sulfuric acid high position tank by proportioning and controls the pH value of solution to treat molten in 6-7 Sodium thiosulfate in liquid is oxidized to after it has filtered particulate matter by sodium sulphate delivery pump after sodium sulphate via filtered over sodium sulfate device It is pumped into sodium sulphate Clear liquid tank, then is evaporated its pump to sodium sulphate evaporating kettle through sodium sulphate clear liquid pump, the sulfuric acid being evaporated Sodium concentrate is centrifuged by potential difference into sodium sulphate centrifuge, and the sodium sulphate for centrifuging to obtain expects that entering sodium sulphate dries admittedly Machine is dried, and water content ＜ 0.2% sodium sulphate product is obtained after drying, and packaging and storage is carried out into sodium sulphate packing machine.
The solvent recovery cycle component includes Methanol Recovery cycling element and Water Sproading cycling element, Methanol Recovery circulation Unit mainly includes：Condenser, qualified methanol tank, air-introduced machine, absorption tower, circulating pump, unqualified methanol tank, methanol fractionation system And associated pipe, two sections of fillers are set in absorption tower.The methanol gas evaporated is condensed into liquid by condenser, is transferred to Stored for future use in qualified methanol tank；And methanol gas may also be contained in uncontrollable discharge gas caused by each equipment operation breathing Body, it is delivered to absorption tower through air-introduced machine and absorbed, air-introduced machine is transported to the bottom of towe on absorption tower, is set in absorption tower The effect that two sections of fillers and enhancing absorb；Gas containing methanol is entered by bottom of towe, and the fresh water sprayed into tower top inversely connects Touch and absorbed, circulated fresh water circulated sprinkling to absorption tower, it is unqualified that circulating pump sets side line to be delivered to methanol solution In methanol tank；The methanol of low concentration is pumped to methanol fractionation system by unqualified methanol, and it is qualified that the complete methanol of rectifying is delivered to again It is standby in methanol tank.
The Water Sproading cycling element includes：Condenser, condensate drum and heat exchanger；From caused by the evaporation of crude salt evaporating kettle Vapor enter condenser in is condensed into aqueous water, be then transferred in condensate drum store it is standby；By its pump when needing to use Go out, 95 DEG C are heated to subsequently into being used in thio dissolution kettle by heat exchanger.
The device is that waste liquid caused by wet method ISS-J desulfurization can be carried out thoroughly to handle and therefrom extract technical grade sulphur cyanogen The device of sour sodium, sodium thiosulfate and sodium sulphate product, waste liquid caused by its desulphurization system to script pollution environment pass through molten Agent method realizes the thorough processing of three kinds of refined salt after using the series of process flow processings such as fractional crystallization and is produced as work Industry level product, caused vapor reuse water circulation unit in evaporating concentration process, the clear liquid after salt extraction return as supplement water In desulphurization system, the methanol loop as sodium sulfocyanate extractant uses, so as to be truly realized wastewater zero discharge；And extract Sodium sulfocyanate, sodium thiosulfate and sodium sulphate product supply other industrial unit production and applications, being truly realized turns waste into wealth.
Preferably, the crude salt dry component also includes crude salt drier, and the crude salt drier entrance is connected to crude salt Centrifuge and exporting be connected to crude salt dissolution kettle (i.e. by crude salt drier be installed on former crude salt centrifuge and crude salt dissolution kettle it Between).Because the crude salt after centrifugation expects to contain a small amount of water admittedly, therefore crude salt drier is set to carry out crude salt after crude salt centrifuge Expansion drying is to improve follow-up sodium sulfocyanate product quality.Crude salt after centrifugation is expected to be delivered to slightly by crude salt conveying worm admittedly Salt drier carries out expansion drying, and water content in crude salt is reduced into less than 1%, most preferably, by crude salt moisture content control after drying System is sent into crude salt dissolution kettle by potential difference in ＜ 0.5%, dried crude salt and carries out sodium sulfocyanate refinement processing.
Preferably, the sodium sulfocyanate separation and purification component also includes subsider, and the entrance of the subsider is connected to slightly The filtrate (liquid of salt filter-pressing cauldron, its outlet is connected to sulphur cyanogen evaporating kettle, and (i.e. subsider is arranged at former crude salt filter-pressing cauldron and sulphur cyanogen and steamed Between hair kettle).The sodium sulfocyanate methanol solution obtained by crude salt filter-pressing cauldron press filtration is first transferred to subsider and carries out further solid-liquid Sedimentation separation, the sulphur cyanogen methanol solution after sedimentation separation is handled are pumped in sulphur cyanogen evaporating kettle by sedimentation clear liquid.
Preferably, the sodium sulfocyanate separation and purification component also includes sulphur cyanogen first separation component and sulphur cyanogen secondary separation group Part；The sulphur cyanogen first separation component includes mother liquid evaporation kettle of sulphur cyanogen, mother liquor crystallization kettle of sulphur cyanogen, sulphur cyanogen mother liquor Centrifuge, sulphur cyanogen drying machine and sodium sulfocyanate packing machine；The sulphur cyanogen secondary separation component includes sulphur cyanogen secondary mother liquid evaporating kettle, The concentrated solution outlet of sulphur cyanogen secondary mother liquid evaporating kettle is connected to desulfurization waste liquor tank；The entrance of mother liquid evaporation kettle of sulphur cyanogen is connected to The purified liquor outlet of sulphur cyanogen centrifuge, and the outlet of the solid material of mother liquor centrifuge of sulphur cyanogen is connected to sulphur cyanogen drying machine purified liquor outlet company It is connected to sulphur cyanogen secondary mother liquid evaporating kettle.
The clear liquid (mother liquor of sulphur cyanogen) that sulphur cyanogen centrifuge comes out enters mother liquor tank of sulphur cyanogen, mother liquor of sulphur cyanogen Tank adds sulphur mother liquor tank adsorbing contaminant of cyanogen with heating steam pipe coil and agitating device, by activated carbon, after stirring and adsorbing Mother liquor of sulphur cyanogen and Mixture of Activated Carbon through mother liquor delivery pump of sulphur cyanogen be delivered to sulphur cyanogen active carbon filter remove Enter decolouring Clear liquid tank after activated carbon, it is once female that mother liquor of sulphur cyanogen in decolouring Clear liquid tank is delivered to sulphur cyanogen by decolouring clear liquid pump Liquid evaporating kettle is evaporated processing, and the methanol gas of evaporated on top reclaims after the mother liquor condenser condensation of over cure cyanogen, and The sulphur cyanogen methanol concentrate being evaporated enters mother liquor crystallization kettle of sulphur cyanogen and carries out crystallisation by cooling, the sulphur cyanogen methanol slurry after crystallization It is centrifuged by potential difference into mother liquor centrifuge of sulphur cyanogen, the clear liquid that mother liquor centrifuge of sulphur cyanogen is come out (i.e. sulphur cyanogen secondary mother liquid) is transferred in sulphur cyanogen secondary mother liquid tank, and the sodium sulfocyanate that centrifugation is obtained expects to be transferred to sulphur cyanogen drying machine admittedly It is dried, ＜ containing methanol 0.2% sodium sulfocyanate enters sulphur cyanogen packing machine progress packaging and storage after drying.Sulphur cyanogen secondary mother liquid Sulphur cyanogen secondary mother liquid evaporating kettle is delivered to through sulphur cyanogen secondary mother liquid delivery pump be evaporated processing, the first of evaporating kettle evaporated on top again Alcohol gas reclaims after the condensation of over cure cyanogen secondary mother liquid condenser, and the sodium sulfocyanate supplying process water being evaporated forms suspension Desulfurization waste liquor tank is delivered into doctor solution underground tank, then through doctor solution submerged pump.
Preferably, in the dissolution kettle and sodium thiosulfate separation and purification component in the sodium sulfocyanate separation and purification component Dissolution kettle has identical structure (being respectively provided with Weighing mechanism, online density measuring mechanism, rabbling mechanism and heating arrangements etc.), steams Hair bottom portion is provided with weighing spring within precision ± 0.5kg, the weighing spring be evenly distributed on dissolution kettle bottom and It uses flexible pipe to be connected to dissolution kettle；Dissolution kettle middle and lower part side is provided with on-line densimeter, on-line densimeter and methanol line On flow control valve electrical connection；Flushing pipe is installed on more preferably described on-line densimeter, when being used for a long time with prevention Salt particle can be rich long-pending inaccurate in resulting in blockage or measuring on pipeline or densitometer.
The mixed salt (i.e. crude salt is expected admittedly) that the step dried through crude salt is dried to obtain is delivered to the sodium sulfocyanate separation and purification Mixed salt is weighed during dissolution kettle in component, at the same the sodium sulfocyanate content in mixed salt need to be detected it is (former in desulfurization Under conditions of expecting that gas and desulphurization catalyst are stable, the measure of sodium sulfocyanate content only need to be in initial measure once), according to title Sodium sulfocyanate content meter in the mixed salt that mixed salt quality and combination in the dissolution kettle restored are measured calculates required first Alcohol amount, then toward adding methanol in dissolution kettle and carrying out stirring and dissolving, in stirring and dissolving by being installed on dissolution kettle middle and lower part The density data signal measured is simultaneously sent to the Flow-rate adjustment in methanol line by the on-line densimeter measurement solution density of side Valve and methanol solution density when being adjusted to the aperture of regulating valve (open big or turn down) and controlling dissolving.It is stripped of thiocyanic acid Need to carry out the mixed salt for adding dissolution kettle when the mixed salt of sodium is delivered in the dissolution kettle in sodium thiosulfate separation and purification component Weigh, combining the sodium thiosulfate content in the mixed salt measured according to the quality of mixed salt in the dissolution kettle for weighing to obtain calculates Hot water amount is needed, then dissolving is stirred toward addition hot water in dissolution kettle, in stirring and dissolving by being installed in dissolution kettle The density data signal measured is simultaneously sent to the flow on hot water piping by the on-line densimeter measurement solution density of lower side Regulating valve and solution density when being adjusted to the aperture of regulating valve (open big or turn down) and controlling the water to dissolve.
The flow control valve of dissolution kettle in sodium sulfocyanate separation and purification component will by weighing spring and on-line densimeter The density domination of sodium sulfocyanate methanol solution is in 1.03-1.05kg/cm3；Dissolution kettle in sodium thiosulfate separation and purification component Flow control valve by weighing spring and on-line densimeter by the density domination of hypo solution in 1.6-1.65kg/ cm3。
Preferably, the thiocyanic acid in the mixed salt evaporating kettle and sodium sulfocyanate separation and purification component in the crude salt dry component Sodium evaporating kettle also include evaporation adjusting means, the adjusting means by Trunk Line switch valve, by-pass regulating valve, liquid level gauge, on Portion's steam valve and lower steam valve composition.
It is fast that mixed salt evaporating kettle in crude salt dry component also includes the evaporation that evaporation adjusting means is used for mixed salt evaporating kettle Rate and evaporation capacity are controlled：Liquid level and enter the steam flow of evaporating kettle by controlling mixed salt evaporating kettle feed rate, in kettle To control the evaporation rate of evaporating kettle and evaporation capacity：Steam pipe coil inside mixed salt evaporating kettle is divided into two sections, epimere coil pipe More than the middle part of evaporation kettle barrel, using the form of inside and outside two layers distribution, its spacing is the outer tube clear distance of two layers of coil pipe 50mm；Hypomere coil pipe is located at the middle and lower part of cylinder, consistent with the distribution form on top.Carried out by the steam gone out by evaporating kettle The mixed salt solution of preheating adds evaporating kettle, 60- of the mixed salt solution to be added in evaporating kettle to evaporating kettle capacity by Trunk Line During 70% liquid level, mixed salt solution Trunk Line switch valve is closed, while by-pass regulating valve is opened, liquid level gauge (preferably double flange differential pressures Liquid level gauge) liquid level data signal is sent to the flow control valve on by-pass mixed salt solution pipeline in time, so as to regulating valve Aperture and switch are controlled with size；When being evaporated to solution level less than 50%, the steam on evaporating kettle top is closed, only Open the steam of bottom；It can so meet to evaporate required heating surface (area) (HS, and can saves steam consumption quantity when amount of solution is few.
Sodium sulfocyanate evaporating kettle in sodium sulfocyanate separation and purification component also includes evaporation adjusting means and is used for sulphur cyanogen The evaporation rate and evaporation capacity of evaporating kettle are controlled；Liquid level and enter by controlling sodium sulfocyanate evaporating kettle feed rate, in kettle Enter the steam flow of evaporating kettle to control the evaporation rate of evaporating kettle and evaporation capacity, the steam pipe coil inside mixed salt evaporating kettle is divided into Two sections, epimere coil pipe is more than the middle part of evaporation kettle barrel, using the form of inside and outside two layers distribution, two layers of its spacing The outer tube clear distance 50mm of coil pipe；Hypomere coil pipe is located at the middle and lower part of cylinder, consistent with the distribution form on top.It is stripped of thio sulphur Sour sodium, the sodium sulfocyanate methanol solution of sodium sulphate are added in evaporating kettle by Trunk Line, the mixed salt solution to be added in evaporating kettle To evaporating kettle capacity 60-70% liquid levels when, mixed salt solution Trunk Line switch valve close, while by-pass regulating valve open, liquid level Liquid level data signal is sent to the Flow-rate adjustment on by-pass mixed salt solution pipeline by meter (preferably double flange differential pressure levelmeters) in time Valve, so as to which the aperture to regulating valve and switch are controlled with size；When being evaporated to solution level less than 50%, by evaporating kettle The steam on top is closed, and only opens the steam of bottom；It can so meet to evaporate required heating surface (area) (HS, and can is in amount of solution few time Save steam consumption quantity.
A kind of method that refined salt is extracted from waste liquid caused by wet method ISS-J desulfurization, this method comprise the following steps：
The step that S11 crude salts are dried：
Activated carbon is added into desulfurization waste liquor and carries out decolorization, is filtered after the completion of decolorization, and filter residue is returned Return after coal works and filtrate then preheat via crude salt heat exchanger to be pumped into crude salt evaporating kettle and be evaporated concentration, the concentration after concentration Liquid is flowed into crude salt crystallization kettle by potential difference and carries out crystallisation by cooling, and then the crude salt suspension after crystallization is centrifuged, and To centrifuge obtained crude salt expect to be transferred to admittedly it is standby in crude salt dissolution kettle；More preferably, the condition of decolorization is：Activated carbon dosage 2 ‰ -2%, 35~40 DEG C of temperature of charge, stir 6 hours；
The step of S12 sodium sulfocyanate separation and purifications：
Methanol is added into crude salt dissolution kettle and is stirred dissolving, by after stirring and dissolving after 40~60 DEG C of stirring and dissolving 4h Material is transferred to crude salt filter-pressing cauldron and carries out press filtration processing, and the sodium thiosulfate and solid sodium sulfate obtained after press filtration is transferred to thio dissolving Kettle, and the methanol solution of sodium sulfocyanate is transferred to sulphur cyanogen evaporating kettle, is steamed by evaporation time 6h, 120 DEG C of evaporating temperature condition Hair processing；The methanol gas that sulphur cyanogen evaporating kettle evaporated on top comes out is after over cure cyanogen evaporating heat exchanger and the condensation of sulphur cyanogen condenser Recovery, sodium sulfocyanate methanol concentrate enter sulphur cyanogen crystallization kettle and carry out crystallisation by cooling, and crystallization condition is：Crystallization time 1.5h, knot Brilliant temperature 50 C or so；Sodium sulfocyanate methanol slurry after crystallization is centrifuged into sulphur cyanogen centrifuge, clear after centrifugation Liquid is returned in desulfurization waste liquor tank, and sodium sulfocyanate expects that (the solid material obtained after centrifuging) is then done into sulphur cyanogen drying machine admittedly It is dry, it is dried to obtain sodium sulfocyanate product；
S13 sodium thiosulfate separation and purifications：
Condensate liquid is added into thio dissolution kettle dissolving is stirred to the mixture of sodium thiosulfate and solid sodium sulfate, Control solution density 1600kg/m3, 80 DEG C of temperature be stirred dissolving, be then sent to thio filter-pressing cauldron and carry out separation of solid and liquid, The filter residue (solid sodium sulfate) for being press-filtered out is entered into sodium sulphate dissolution kettle, and filtrate (sodium thiosulfate solution) is then transferred to sulphur For Clear liquid tank；Activated carbon is added to the impurity in thio Clear liquid tank absorption sodium thiosulfate solution, then via activated carbon Thio filtrate tank is transferred to after filter removal activity charcoal, then is delivered to thio crystallization kettle through thio filtrate delivery pump and carries out cooling knot Crystalline substance, sodium thiosulfate suspension is centrifuged after crystallizing 24h, the clear liquid after centrifugation returns to desulfurization waste liquor tank, centrifuges To sodium thiosulfate product；
The step of S14 sodium sulphate separation and purifications：
It is added dropwise to sodium sulphate dissolution kettle in the concentrated sulfuric acid to pH value 6-7, the sodium thiosulfate in sodium sulphate dissolution kettle to be done Oxidation after, be transferred in sodium sulphate Clear liquid tank, then deliver to sodium sulphate evaporating kettle and be evaporated, evaporate after metabisulfite solution is filtered At 120 DEG C, the sodium sulphate concentrate after evaporation is centrifuged temperature control, after the solid material (sodium sulphate) for centrifuging to obtain is dried Obtain sodium sulphate product；
The step of S15 solvent recovery cycles：
Recovery circulation and the recovery of water of the step of solvent recovery cycle including methanol circulate, the step of the recovery circulation of methanol Suddenly comprise the following steps：The methanol gas evaporated is condensed into liquid by condenser, it is qualified to be then transferred to liquid methanol Stored for future use in methanol tank.And may also contain methanol gas in uncontrollable discharge gas caused by each equipment operation breathing, will It is delivered to absorption tower through air-introduced machine and absorbed, and air-introduced machine is transported to the bottom of towe on absorption tower, and two sections are set in absorption tower Filler is to strengthen assimilation effect；Gas containing methanol is entered by bottom of towe, is inhaled with reverse contact of the fresh water that tower top sprays into Receive, fresh water circulated sprinkling to absorption tower, circulating pump are set side line that methanol solution is delivered into unqualified methanol tank by circulating pump In；The methanol of low concentration is pumped to methanol fractionation system by unqualified methanol, and the complete methanol of rectifying delivers to qualified methanol tank again In it is standby.
The step of Water Sproading circulation, includes：Vapor caused by being evaporated from crude salt evaporating kettle is imported in condenser, Condense the steam into aqueous water, be then transferred in condensate drum store it is standby；Pumped out when needing to use, by heat exchanger by its 95 DEG C are heated to subsequently into being used in thio dissolution kettle.
This method is that waste liquid caused by wet method ISS-J desulfurization can be carried out thoroughly to handle and therefrom extract technical grade sulphur cyanogen The method of sour sodium, sodium thiosulfate and sodium sulphate product, waste liquid caused by its desulphurization system to script pollution environment pass through molten Agent method realizes the thorough processing of three kinds of refined salt after using the series of process flow processings such as fractional crystallization and is produced as work Industry level product, caused vapor reuse water circulation unit in evaporating concentration process, the clear liquid after salt extraction return as supplement water In desulphurization system, the methanol loop as sodium sulfocyanate extractant uses, so as to be truly realized wastewater zero discharge；And extract Sodium sulfocyanate, sodium thiosulfate and sodium sulphate product supply other industrial unit production and applications, being truly realized turns waste into wealth.
Preferably, the step of also including expansion drying in the step that the S11 crude salts are dried；Because the crude salt after centrifugation is consolidated Material contains a small amount of water, therefore the crude salt after centrifugation is preferably expected into being delivered to crude salt drier by crude salt conveying worm is flashed admittedly Dry, to improve follow-up sodium sulfocyanate product quality.Crude salt after centrifugation is expected admittedly to be delivered to crude salt by crude salt conveying worm Drier carries out expansion drying, and water content in crude salt is reduced into less than 1%, most preferably, crude salt moisture content ＜ after drying 0.5%；Crude salt after expansion drying is sent into standby in crude salt dissolution kettle by potential difference.
Preferably, the step of S12 sodium sulfocyanates separation and purification also includes the step of sedimentation separation, by the sulphur after press filtration The methanol solution of Zassol carries out sedimentation separation processing first before sulphur cyanogen evaporating kettle is transferred to, by the methanol solution of sodium sulfocyanate It is pumped into subsider and carries out solid-liquid sedimentation separation, by the sulphur cyanogen methanol solution through sedimentation separation by sedimentation clear liquid pump after sedimentation 24h Enter in sulphur cyanogen evaporating kettle.
Further, the clear liquid after the centrifugation in the step of S12 sodium sulfocyanates separation and purification is through first separation And returned again to after the processing of the step of double evaporation-cooling in doctor solution system；The step of first separation, includes：Sulphur cyanogen after centrifugation One time mother liquor enters in mother liquor tank of sulphur cyanogen, adds activated carbon to mother liquor of sulphur cyanogen, takes off mixture after stirring and adsorbing 4h Except being transferred to after activated carbon in decolouring Clear liquid tank, to mother liquor of sulphur cyanogen in decolouring Clear liquid tank by evaporation time 6h, evaporating temperature 120 DEG C are evaporated processing, evaporate obtained Methanol Recovery；Then by sulphur cyanogen methanol concentrate by crystallization time 1.5h, crystallization Temperature 50 C or so carries out crystallisation by cooling, and processing is centrifuged in the sulphur cyanogen methanol slurry after crystallization, the sulphur that centrifugation is obtained Cyanogen secondary mother liquid is transferred to sulphur cyanogen secondary mother liquid tank, and the sodium sulfocyanate obtained to centrifugation expects processing is dried admittedly, after drying To sodium sulfocyanate product；The step of double evaporation-cooling, includes：Secondary steaming is carried out 120 DEG C in evaporating temperature to sulphur cyanogen secondary mother liquid Hair processing, the methanol gas recovery of evaporating kettle evaporated on top, the sodium sulfocyanate for evaporating to obtain are incorporated process water and form suspension It is pumped in desulfurization waste liquor tank.
Further, the sodium sulfocyanate in the step of S12 sodium sulfocyanates separation and purification expects dry step and one admittedly Sodium sulfocyanate in the step of secondary separation expects dry step using same sulphur cyanogen drier or respectively using respective admittedly Sulphur cyanogen drier；I.e. S12 sodium sulfocyanates separation and purification the step of can there is a sulphur cyanogen drier to be used in conjunction with for two steps, Two sulphur cyanogen driers can be provided with and be used respectively for two steps, consider the latter more preferably.
Preferably, methods described also includes：
The step of methanol solution density is controlled when in the step of S12 sodium sulfocyanates separation and purification to dissolving： The density of sodium sulfocyanate methanol solution is strict controlled in by 1.03-1.05kg/ by weight method and the method for online density measuring cm3；The mixed salt (i.e. crude salt is expected admittedly) that the step dried through crude salt is dried to obtain is weighed when being delivered to dissolution kettle to mixed salt, together When mixed salt in sodium sulfocyanate content need to be detected (under conditions of desulfurization material gas and desulphurization catalyst are stable, sulphur cyanogen The measure of sour sodium content only need to be in initial measure once), weigh be by installed in dissolution kettle bottom installation accuracy ± What the weighing spring within 0.5kg was completed, weighing spring is evenly distributed on device bottom and it uses flexible pipe to be connected to dissolving Kettle；Sodium sulfocyanate content meter in the mixed salt that mixed salt quality and combination in the dissolution kettle for weighing to obtain are measured calculates institute The quantity of methyl alcohol needed, then toward adding methanol in dissolution kettle and carrying out stirring and dissolving, in stirring and dissolving by being installed on dissolving The density data signal measured is simultaneously sent in methanol line by the on-line densimeter measurement solution density of kettle middle and lower part side Flow control valve and methanol solution density when being adjusted to the aperture of regulating valve (open big or turn down) and controlling dissolving；It is preferred that Ground, flushing pipe is installed on on-line densimeter, when being used for a long time with prevention salt particle can rich product on pipeline or densitometer And result in blockage or measure and be inaccurate.Methanol usage when in above-mentioned steps by strictly controlling dissolving will control solution density to exist 1030~1050kg/m3, more preferably, solution temperature control is at 40~60 DEG C or so (most preferably 50 DEG C or so) during dissolving, simultaneously The methanol of volatilization is subjected to tail gas recycle to reduce methanol consumption, so as to reduce production cost.
Preferably, methods described also includes：
The step that solution density when being dissolved in the step of S13 sodium thiosulfate separation and purification to water is controlled Suddenly：The density of hypo solution is controlled to take off in 1.6-1.65kg/cm3 by weight method and the method for online density measuring Need to weigh to the mixed salt for adding dissolution kettle except the mixed salt of sodium sulfocyanate is delivered to when in dissolution kettle, it is to pass through peace to weigh What weighing spring within the precision ± 0.5kg of dissolution kettle bottom was completed, weighing spring be evenly distributed on device bottom and It uses flexible pipe to be connected to dissolution kettle；Sulphur in the mixed salt measured is combined according to the quality of mixed salt in the dissolution kettle for weighing to obtain Sodium thiosulfate content meter, which calculates, needs hot water amount, then dissolving is stirred toward addition hot water in dissolution kettle, in stirring and dissolving On-line densimeter by being installed on dissolution kettle middle and lower part side measures solution density and sends the density data signal measured When being adjusted to the flow control valve on hot water piping to the aperture of regulating valve (open big or turn down) and controlling the water to dissolve Solution density；Preferably, flushing pipe is installed, the rich product of salt particle meeting is in pipe when being used for a long time with prevention on on-line densimeter Result in blockage or measure on road or densitometer and be inaccurate.
Preferably, methods described also includes：
The step being controlled in the step that the S11 crude salts are dried to the evaporation rate and evaporation capacity of mixed salt evaporating kettle Suddenly：Liquid level and enter the steam flow of evaporating kettle to control the steaming of evaporating kettle by controlling mixed salt evaporating kettle feed rate, in kettle Send out speed and evaporation capacity：The mixed salt solution preheated by the steam gone out by evaporating kettle adds evaporating kettle by Trunk Line, treats Be added to mixed salt solution in evaporating kettle to evaporating kettle capacity 60-70% liquid levels when, close mixed salt solution Trunk Line switch valve, By-pass regulating valve is opened simultaneously, liquid level data signal is sent to by-pass in time and mixed by liquid level gauge (preferably double flange differential pressure levelmeters) Flow control valve on salting liquid pipeline, so as to which the aperture to regulating valve and switch are controlled with size；When being evaporated to solution When liquid level is less than 50%, the steam on evaporating kettle top is closed, only opens the steam of bottom.It can so meet to evaporate required heating Area, and can save steam consumption quantity when amount of solution is few.
Preferably, methods described also includes：
The evaporation rate and evaporation capacity of sulphur cyanogen evaporating kettle are controlled in the step of S12 sodium sulfocyanates separation and purification The step of processed：Liquid level and enter the steam flow of evaporating kettle to control by controlling sodium sulfocyanate evaporating kettle feed rate, in kettle The evaporation rate and evaporation capacity of evaporating kettle, it is stripped of sodium thiosulfate, the sodium sulfocyanate methanol solution of sodium sulphate is added by Trunk Line Enter in evaporating kettle, during the 60-70% liquid levels of the mixed salt solution to be added in evaporating kettle to evaporating kettle capacity, close mixed salt solution Trunk Line switch valve, while by-pass regulating valve is opened, liquid level gauge (preferably double flange differential pressure levelmeters) in time believes liquid level data The flow control valve number being sent on by-pass mixed salt solution pipeline, so as to which the aperture to regulating valve and switching is controlled with size System；When being evaporated to solution level less than 50%, the steam on evaporating kettle top is closed, only opens the steam of bottom；So can Meet heating surface (area) (HS needed for evaporation, and can saves steam consumption quantity when amount of solution is few.
Most domestic coke-oven plant is live by the individual of operator to waste treatment process caused by ISS-J desulfurization at present Experience and field observation are operated, so that the quantity of solvent that is added during dissolving it is more or less, time for being concentrated by evaporation it is long or It is short can not accurate judgement, cause the refined salt product purity that extracts not enough or the comparatively high consumption in operating process；Above-mentioned is each Rate-determining steps (i.e. control method) solve the difficulty artificially judged in live actual mechanical process or error, reach energy-conservation and carry The purpose of high product quality, it has very useful directive significance to execute-in-place.
Waste liquid caused by ISS-J desulfurization can be handled the utility model discloses one kind and therefrom extract technical grade The apparatus and method of sodium sulfocyanate, sodium thiosulfate and sodium sulphate product, it is polluted to script caused by the desulphurization system of environment Waste liquid using the thorough processing that three kinds of refined salt is realized after the series of process flow processings such as fractional crystallization and is incited somebody to action by solvent method It is produced as technical grade product；Wherein, sodium sulfocyanate product content reaches 99.8%, meets HG/T3812-2006 industry sulphur cyanogen Sour sodium high-class product standard, sodium thiosulfate product purity reach more than 98%, meet HG/T2328-2006 industry sodium thiosulfate Grade A standard；Above-mentioned sodium sulfocyanate, sodium thiosulfate and sodium sulphate product supplies other industrial unit production and applications, really Accomplish to turn waste into wealth.Also, caused vapor is recycled by Water Sproading cycling element in evaporating concentration process, salt extraction Clear liquid afterwards is returned in desulfurization waste liquor tank as supplement water, and the methanol as sodium sulfocyanate extractant is circulated by Methanol Recovery Unit recycles, so as to be truly realized wastewater zero discharge.
Brief description of the drawings
Fig. 1 is the connection diagram of device of the present utility model.
Wherein, 1, crude salt dry component, 2, sodium sulfocyanate separation and purification component, 3, sodium thiosulfate separation and purification component, 4th, sodium sulphate separation and purification component, 11, desulfurization waste liquor tank, 12, crude salt heat exchanger, 13, crude salt evaporating kettle, 14, crude salt crystallization kettle, 15th, crude salt centrifuge, 16, crude salt drier, 21, crude salt dissolution kettle, 22, crude salt filter-pressing cauldron, 23, subsider, the evaporation of 24 sulphur cyanogen Kettle, 25, sulphur cyanogen crystallization kettle, 26, sulphur cyanogen centrifuge, 27, sulphur cyanogen drying machine, 28, sulphur cyanogen first separation component, 29, sulphur cyanogen it is secondary Separation assembly, 31, thio dissolution kettle, 211, qualified methanol tank, 311, condensate drum, 32, thio filter-pressing cauldron, 33, thio crystallization Kettle, 34, thio centrifuge, 41, sodium sulphate dissolution kettle, 411, concentrated sulfuric acid head tank, 42, sodium sulphate evaporating kettle, 43, sodium sulphate Centrifuge, 44, sodium sulphate drying machine；281st, mother liquid evaporation kettle of sulphur cyanogen, 282, mother liquor crystallization kettle of sulphur cyanogen, 283, sulphur cyanogen Mother liquor centrifuge, 284, sulphur cyanogen drying machine, 291 sulphur cyanogen secondary mother liquid evaporating kettles.
Embodiment
In order that the utility model may be better understood in those skilled in the art, so as to protection model of the present utility model Enclose and make clearer limitation, structures and methods of the present utility model are described in detail below in conjunction with the accompanying drawings.
A kind of device that refined salt is extracted from waste liquid caused by wet method ISS-J desulfurization, the device include crude salt dry component 1st, sodium sulfocyanate separation and purification component 2, sodium thiosulfate separation and purification component 3, sodium sulphate separation and purification component 4 and solvent recovery Component (not shown)；Waste liquid caused by sulfur removal technology from the catalysis of wet method ISS-J types desulphurization catalyst is transferred to crude salt and dried Component 1 is handled, and the material after the processing of crude salt dry component 1 is transferred in sodium sulfocyanate separation and purification component 2；Sodium sulfocyanate The one side of separation and purification component 2 is transferred to sodium thiosulfate separation and purification component 3 after partial material (filter residue after press filtration) is separated, On the other hand technical grade sodium sulfocyanate product can be produced from the filtrate after press filtration while partially liq is recycled back to crude salt and done Dry component 1；Sodium thiosulfate separation and purification component 3 from sodium sulfocyanate separation and purification component 2 to conveying the material come (after press filtration Filter residue) handle and therefrom produce sodium thiosulfate product and a part of liquid circulation is returned into crude salt dry component 1 simultaneously, go forward side by side Partial material (filter residue after press filtration) is transferred in sodium sulphate separation and purification component 4 by one step；Sodium sulphate separation and purification component 4 is to turning The material entered carries out processing and produces sodium sulphate product and a part of liquid circulation is returned into crude salt dry component 1；Solvent recovery component Component is withdrawn including Methanol Recovery component and water, solvent recovery component is used to steam caused methanol gas in whole system or water Gas is recycled, with the purpose for reducing cost He realizing wastewater zero discharge.
The crude salt dry component 1 mainly includes desulfurization waste liquor tank 11, crude salt heat exchanger 12, crude salt evaporating kettle 13, crude salt Crystallization kettle 14 and crude salt centrifuge 15；Desulfurization waste liquor tank 11 is connected with desulphurization system to receive the desulfurization come from desulphurization system conveying Waste liquid, the waste liquid as caused by sulfur removal technology, which is transferred in desulfurization waste liquor tank 11, carries out decolorization, adds activated carbon and stirs to enter Row decolorization；Filtered after decolouring, filter residue is returned after coal works (delivering to coke oven) and filtrate preheats via crude salt heat exchanger 12 Be pumped into crude salt evaporating kettle 13, agitating device and inner coil pipe be provided with crude salt evaporating kettle 13, to inner coil pipe be passed through low-pressure steam with Evaporation is stirred to filtrate, the concentrate after evaporation is flowed into crude salt crystallization kettle 14 by potential difference, and the water vapour being evaporated Water station recovery is transferred to after water withdraws component condensation；Crude salt crystallization kettle 14 has agitating device and external jacket, leads into external jacket Enter recirculated cooling water to carry out crystallisation by cooling to concentrate, the crude salt suspension after crystallization is entered by potential difference into crude salt centrifuge 15 Row centrifuges, and the crude salt after having centrifuged expects to be delivered in crude salt dissolution kettle 21 by crude salt conveying worm admittedly, and clear liquid then returns In desulfurization waste liquor tank 11.
The sodium sulfocyanate separation and purification component 2 mainly includes crude salt dissolution kettle 21, crude salt filter-pressing cauldron 22, sulphur cyanogen evaporating kettle 24th, sulphur cyanogen crystallization kettle 25, sulphur cyanogen centrifuge 26, sulphur cyanogen drying machine 27 and sodium sulfocyanate packing machine (not shown)；Crude salt is molten The solid material of solution kettle 21 and crude salt centrifuge 15, which exports, to be connected to receive dried crude salt solid, by qualified methanol tank 211 Methanol enters in crude salt dissolution kettle 21 to be dissolved to crude salt, and the solid material outlet of crude salt filter-pressing cauldron 22 is connected to thio dissolution kettle 31st, filtrate (liquid is connected to sulphur cyanogen evaporating kettle 24 so as to which the crude salt mixture after methanol is dissolved carries out separation of solid and liquid and by solid Material is transferred in sodium thiosulfate separation and purification component 3 and liquid material then continues to locate in sodium sulfocyanate separation and purification component 2 Reason；The solid material outlet of sulphur cyanogen centrifuge 26 is connected to sulphur cyanogen drying machine 27 and purified liquor outlet is connected to desulfurization waste liquor tank 11, and then Realize the extraction of sodium sulfocyanate and the circulation of waste liquid.Crude salt dissolution kettle 21 arranges that its bottom is provided with heating and steamed for semi-underground type Vapour coil pipe, it is internal be provided with agitating device, by crude salt centrifuge 15 crude salt and methanol stirring and dissolving；The sodium sulfocyanate dissolved Methanol solution delivers to crude salt filter-pressing cauldron 22 by crude salt solution transfer pump and carries out separation of solid and liquid, is press-filtered out the solid (thiosulfuric acid come Sodium and sodium sulphate) it is transferred in thio dissolution kettle 31, and filtrate (sodium sulfocyanate methanol solution) is pumped to sulphur cyanogen evaporating kettle 24 and carried out Evaporation process, the methanol gas that evaporated on top comes out are transferred to first after over cure cyanogen evaporating heat exchanger and the condensation of sulphur cyanogen condenser The qualified recycling can of alcohol or the unqualified recycling can of methanol are recycled；Concentrate after evaporation is carried out into sulphur cyanogen crystallization kettle 25 Crystallisation by cooling, the sodium sulfocyanate methanol slurry after crystallization are centrifuged into sulphur cyanogen centrifuge 26 by potential difference, are centrifuged out Clear liquid returned as supplement water in desulfurization waste liquor tank 11, and centrifuge obtained solid material (sodium sulfocyanate) and then enter sulphur cyanogen drying machine 27 are dried, and obtain sodium sulfocyanate purity more than 98% and methanol content ＜ 0.2% sodium sulfocyanate product after drying, it enters Enter sodium sulfocyanate packing machine and carry out packaging and storage.
More preferably, it is handled because crude salt adds methanol in crude salt dissolution kettle, passes through above-mentioned evaporation, crystallization With still contain a certain amount of methanol in the clear liquid after centrifugation, if be recycled directly back to desulfurization waste liquor tank can to subsequent treatment produce it is unfavorable Influence, thus the sodium sulfocyanate separation and purification component also includes sulphur cyanogen first separation component 28 and sulphur cyanogen secondary separation component 29.The sulphur cyanogen first separation component 28 mainly includes mother liquor tank (not shown) of sulphur cyanogen, sulphur cyanogen mother liquid evaporation Kettle 281, mother liquor crystallization kettle 282 of sulphur cyanogen, mother liquor centrifuge 283 of sulphur cyanogen, sulphur cyanogen drying machine 284 and packing machine are (in figure It is not shown)；The sulphur cyanogen secondary separation component 29 includes sulphur cyanogen secondary mother liquid evaporating kettle 291, sulphur cyanogen secondary mother liquid evaporating kettle 291 Concentrated solution outlet be connected to desulfurization waste liquor tank 11；The entrance of mother liquid evaporation kettle 281 of sulphur cyanogen is connected to sulphur cyanogen centrifuge 26 Purified liquor outlet, and the outlet of the solid material of mother liquor centrifuge 283 of sulphur cyanogen is connected to the purified liquor outlet of sulphur cyanogen drying machine 284 and is connected to The entrance of sulphur cyanogen secondary mother liquid evaporating kettle 291.
The clear liquid (mother liquor of sulphur cyanogen) that sulphur cyanogen centrifuge 26 is centrifuged out enters mother liquor tank of sulphur cyanogen, and sulphur cyanogen is once female Activated carbon is added sulphur mother liquor tank adsorbing contaminant of cyanogen, stirring and adsorbing by flow container with heating steam pipe coil and agitating device Mother liquor of sulphur cyanogen and Mixture of Activated Carbon afterwards is delivered to sulphur cyanogen active carbon filter through mother liquor delivery pump of sulphur cyanogen and taken off Except decolouring Clear liquid tank is entered after activated carbon, mother liquor of sulphur cyanogen in decolouring Clear liquid tank is delivered to sulphur cyanogen once by decolouring clear liquid pump Mother liquid evaporation kettle 281 is evaporated processing, and the methanol gas of evaporated on top is returned after the mother liquor condenser condensation of over cure cyanogen Receive, and the sulphur cyanogen methanol concentrate being evaporated enters mother liquor crystallization kettle 282 of sulphur cyanogen and carries out crystallisation by cooling, the sulphur cyanogen after crystallization Methanol slurry is centrifuged by potential difference into mother liquor centrifuge 283 of sulphur cyanogen, by mother liquor centrifuge 283 of sulphur cyanogen from The clear liquid (i.e. sulphur cyanogen secondary mother liquid) that the heart comes out is transferred in sulphur cyanogen secondary mother liquid tank 291, and the sodium sulfocyanate that centrifugation is obtained is consolidated Material is transferred to sulphur cyanogen drying machine and is dried, and ＜ containing methanol 0.2% sodium sulfocyanate is packed into sulphur cyanogen packing machine after drying Storage.Sulphur cyanogen secondary mother liquid is delivered to sulphur cyanogen secondary mother liquid evaporating kettle 291 through sulphur cyanogen secondary mother liquid delivery pump again and is evaporated place Reason, the methanol gas of evaporated on top reclaim after the condensation of over cure cyanogen secondary mother liquid condenser, the sodium sulfocyanate supplying being evaporated Process water forms suspension and enters doctor solution underground tank, then delivers to desulfurization waste liquor tank 11 through doctor solution submerged pump.
Not only can once it divide in sulphur cyanogen after over cure cyanogen first separation component 28 and sulphur cyanogen secondary separation component 29 are handled Yield is improved from extra sodium sulfocyanate product is obtained in component 28, after can also the methanol in solution fully be evaporated again Desulfurization waste liquor tank 11 is recycled back to, to avoid methanol to the adverse effect of follow-up liquid waste processing and the loss of methanol can be reduced, It is to kill two birds with one stone.
The sodium thiosulfate separation and purification component 3 mainly includes thio dissolution kettle 31, condensate drum 311, thio press filtration Kettle 32, thio crystallization kettle 33, thio centrifuge 34 and sodium thiosulfate packing machine (not shown)；Condensate drum 311 is used for Condensate liquid (such as water) is supplemented into thio dissolution kettle 31, the solid material outlet of thio filter-pressing cauldron 32 is connected to sodium sulphate dissolution kettle 41 And filtrate (liquid is connected to thio crystallization kettle 33, so as to be carried out according to the difference of sodium thiosulfate and sodium sulphate solubility to both Separation, sodium sulphate is transferred in sodium sulphate separation and purification component and hypo solution then continues to separate essence in sodium thiosulfate Handled in component 3 processed.Added into thio dissolution kettle 31 95 DEG C of condensate liquid (be preferably water) to solid (sodium thiosulfate and The mixture of sodium sulphate) dissolving is stirred, the solidliquid mixture dissolved is delivered to thio filter-pressing cauldron 32 by thio delivery pump Separation of solid and liquid is carried out, the filter residue (solid sodium sulfate) come is press-filtered out and enters sodium sulphate dissolution kettle 41, and filtrate (sodium thiosulfate water Solution) enter thio Clear liquid tank and add activated carbon thereto with adsorbing contaminant, then via active carbon filter removal activity Thio filtrate tank is transferred to after charcoal, then sodium thiosulfate solution is delivered to thio crystallization kettle 33 through thio filtrate delivery pump, will The inner coil pipe that recirculated cooling water is passed through thio crystallization kettle 33 carries out decrease temperature crystalline, and the sodium thiosulfate suspension after crystallization enters sulphur It is centrifuged for centrifuge 34, the clear liquid being centrifuged out returns to desulfurization waste liquor tank 11 as supplement water, and centrifugation obtains aqueous ＜ 2% sodium thiosulfate product is measured, packaging and storage is carried out into sodium thiosulfate packing machine.
The sodium sulphate separation and purification component 4 includes sodium sulphate dissolution kettle 41, concentrated sulfuric acid head tank 411, sodium sulphate evaporation Kettle 42, sodium sulphate centrifuge 43, sodium sulphate drying machine 44 and sodium sulphate packing machine (not shown), concentrated sulfuric acid head tank 411 It is connected to sodium sulphate dissolution kettle 41.The concentrated sulfuric acid is added drop-wise in sodium sulphate dissolution kettle 41 simultaneously by sulfuric acid high position tank 411 by proportioning Control solution pH value 6-7, after the sodium thiosulfate in solution is oxidized to sodium sulphate sodium sulphate delivery pump by it via sulfuric acid Sodium filter is pumped into sodium sulphate Clear liquid tank after having filtered particulate matter, then through sodium sulphate clear liquid pump by its pump to sodium sulphate evaporating kettle 42 are evaporated, and the sodium sulphate concentrate being evaporated is centrifuged by potential difference into sodium sulphate centrifuge 43, and centrifugation obtains Sodium sulphate expect to dry into sodium sulphate drying machine 44 admittedly, dry after obtain water content ＜ 0.2% sodium sulphate product, into sulphur Sour sodium packing machine carries out packaging and storage.
The solvent recovery cycle component includes Methanol Recovery cycling element and Water Sproading cycling element, Methanol Recovery circulation Unit mainly includes：Condenser (be matched with different evaporating kettles can be respectively can also be same condenser), it is qualified Methanol tank, air-introduced machine, absorption tower, circulating pump, unqualified methanol tank, methanol fractionation system and associated pipe, set in absorption tower Put two sections of fillers.By the methanol gas evaporated (sulphur cyanogen evaporating kettle, mother liquid evaporation kettle of sulphur cyanogen, the evaporation of sulphur cyanogen secondary mother liquid Kettle etc.) after condenser condenses, it is transferred in qualified methanol tank and stores.And uncontrollable discharge caused by each equipment operation breathing Methanol gas may also be contained in gas, it is delivered into absorption tower through air-introduced machine is absorbed, and air-introduced machine is transported to suction The bottom of towe of tower is received, two sections of fillers are set in absorption tower, the gas containing methanol is entered by bottom of towe, and the fresh water sprayed into tower top is inverse Absorbed to contact, circulate and set side line to be delivered to methanol solution not fresh water circulated sprinkling to absorption tower, circulating pump In qualified methanol tank；The methanol of low concentration is pumped to methanol fractionation system by unqualified methanol, and the complete methanol of rectifying is delivered to again It is standby in qualified methanol tank.
The Water Sproading cycling element includes：Condenser, condensate drum and heat exchanger；From caused by the evaporation of crude salt evaporating kettle Vapor enter condenser in is condensed into aqueous water, be then transferred in condensate drum store it is standby；By its pump when needing to use Go out, 95 DEG C are heated to subsequently into being used in thio dissolution kettle by heat exchanger.
In certain embodiments, the crude salt dry component also includes crude salt drier 16, and the crude salt drier 16 enters Mouth is connected to crude salt centrifuge 15 and outlet is connected to crude salt dissolution kettle 21 and (crude salt drier is installed on into former crude salt centrifuge Between crude salt dissolution kettle).Because the crude salt after centrifugation expects to contain a small amount of water admittedly, therefore crude salt is set to do after crude salt centrifuge Dry device carries out expansion drying to improve follow-up sodium sulfocyanate product quality to crude salt.Crude salt after centrifugation is expected by crude salt spiral admittedly Conveyer is delivered to crude salt drier and carries out expansion drying, and water content in crude salt is reduced into less than 1%, most preferably, after drying Crude salt moisture control is sent into progress sodium sulfocyanate in crude salt dissolution kettle by potential difference and refined in ＜ 0.5%, dried crude salt Workshop section is handled.
In further embodiments, the sodium sulfocyanate separation and purification component also includes subsider 23, the subsider 33 Entrance be connected to the filtrate (liquid of crude salt filter-pressing cauldron 22, purified liquor outlet is connected to the entrance of sulphur cyanogen evaporating kettle 24 (i.e. subsider is set It is placed between former crude salt filter-pressing cauldron and sulphur cyanogen evaporating kettle), the solid material for settling to obtain in subsider 33 is then transferred to thio dissolution kettle 31 Middle carry out subsequent treatment；It can further make the separation of solid and liquid of crude salt more abundant by the sedimentation separation of subsider.
In some preferred embodiments, the bottom of the crude salt dissolution kettle 21 is additionally provided with weighing spring, crude salt dissolution kettle 21 Middle and lower part side is provided with on-line densimeter；The pipeline that weighing spring is connected with crude salt dissolution kettle 21 uses flexible pipe to be connected to mitigate The weight and material that pipeline itself is brought flow through impulse force caused by pipeline and equipment weighed the influence brought；The bullet of weighing of installation Within the precision ± 0.5kg of spring, dissolve and no influence of being weighed on spring is vibrated caused by stirring, and the weighing spring installed need to be equal It is even to be distributed in device bottom.The on-line densimeter for being installed on dissolution kettle middle and lower part side is used to measure solution density and will measured Flow control valve that density data signal is sent in methanol line and the aperture (open big or turn down) of regulating valve is adjusted And methanol solution density when controlling dissolving.More preferably, flushing pipe is installed, when being used for a long time with prevention on on-line densimeter Salt particle can be rich long-pending inaccurate in resulting in blockage or measuring on pipeline or densitometer.Most preferably, by strictly controlling methanol to use Amount, and control solution density is controlled on 40~60 DEG C or so (most preferably 50 DEG C of left sides in 1030~1050kg/m3, solution temperature It is right), while the methanol of volatilization is subjected to tail gas recycle to reduce methanol consumption, so as to reduce production cost.
The bottom of the thio dissolution kettle 31 is provided with weighing spring and its underpart side is provided with on-line densimeter；Weigh bullet The pipeline that spring and equipment dissolution kettle are connected is connected using flexible pipe, and pipeline is flowed through to mitigate weight that pipeline itself brings and material Caused impulse force is weighed the influence brought to equipment；Within the precision ± 0.5kg of the weighing spring of installation, dissolving stirring produces Vibration spring is weighed no influence, and weighing spring is installed need to be evenly distributed on device bottom.Under being installed in dissolution kettle The on-line densimeter of portion side is used to measure solution density and the density data signal measured is sent to the stream on hot water piping Adjustable valve and solution density when being adjusted to the aperture of regulating valve (open big or turn down) and controlling the water to dissolve；More preferably, Flushing pipe is installed, the rich product of salt particle meeting is made on pipeline or densitometer when being used for a long time with prevention on on-line densimeter It is inaccurate into blocking or measuring.
In other preferred embodiments, the mixed salt evaporating kettle 13 in the crude salt dry component 1 also includes evaporation regulation Device, the adjusting means is by Trunk Line switch valve, by-pass regulating valve, liquid level gauge, upper steam valve and lower steam valve Composition；The evaporation adjusting means is used to be controlled the evaporation rate and evaporation capacity of mixed salt evaporating kettle：By controlling mixed salt Liquid level and enter the steam flow of evaporating kettle to control the evaporation rate of evaporating kettle and evaporation capacity in evaporating kettle feed rate, kettle. Steam pipe coil inside mixed salt evaporating kettle is divided into two sections, and epimere coil pipe is more than the middle part of evaporation kettle barrel, using interior The form of outer two layers of distribution, its spacing are the outer tube clear distance 50mm of two layers of coil pipe；Hypomere coil pipe is located at the middle and lower part of cylinder, and upper The distribution form in portion is consistent.The mixed salt solution preheated by the steam gone out by evaporating kettle adds evaporating kettle by Trunk Line, Mixed salt solution to be added in evaporating kettle to evaporating kettle capacity 60-70% liquid levels when, close mixed salt solution supervisor wiretap Valve, while by-pass regulating valve is opened, liquid level data signal is sent to pair by liquid level gauge (preferably double flange differential pressure levelmeters) in time Flow control valve on line mixed salt solution pipeline, so as to which the aperture to regulating valve and switch are controlled with size；When being evaporated to When solution level is less than 50%, the steam on evaporating kettle top is closed, only opens the steam of bottom；It can so meet needed for evaporation Heating surface (area) (HS, and can save steam consumption quantity when amount of solution is few.
Sodium sulfocyanate evaporating kettle 24 in the sodium sulfocyanate separation and purification component 2 also includes evaporation adjusting means, described Adjusting means is made up of Trunk Line switch valve, by-pass regulating valve, liquid level gauge, upper steam valve and lower steam valve, described Evaporation adjusting means is used to be controlled the evaporation rate and evaporation capacity of sulphur cyanogen evaporating kettle；By controlling sodium sulfocyanate evaporating kettle Liquid level and enter the steam flow of evaporating kettle to control the evaporation rate of evaporating kettle and evaporation capacity in feed rate, kettle.Mixed salt steams Steam pipe coil inside hair kettle is divided into two sections, and epimere coil pipe is more than the middle part of evaporation kettle barrel, using inside and outside two layers The form of distribution, its spacing are the outer tube clear distance 50mm of two layers of coil pipe；Hypomere coil pipe is located at the middle and lower part of cylinder, point with top Cloth form is consistent.Be stripped of sodium thiosulfate, sodium sulphate sodium sulfocyanate methanol solution by Trunk Line add evaporating kettle in, it is to be added Enter mixed salt solution into evaporating kettle to evaporating kettle capacity 60-70% liquid levels when, close mixed salt solution Trunk Line switch valve, together When open by-pass regulating valve, liquid level data signal is sent to by-pass mixed salt by liquid level gauge (preferably double flange differential pressure levelmeters) in time Flow control valve on solution pipeline, so as to which the aperture to regulating valve and switch are controlled with size；When being evaporated to solution liquid When position is less than 50%, the steam on evaporating kettle top is closed, only opens the steam of bottom；It can so meet to evaporate required heating surface Product, and can save steam consumption quantity when amount of solution is few.
A kind of method that refined salt is extracted from waste liquid caused by wet method ISS-J desulfurization, this method comprise the following steps：
The step that S11 crude salts are dried：
Desulfurization waste liquor caused by the sulfur removal technology of wet method ISS-J types desulphurization catalyst catalysis is transferred in desulfurization waste liquor tank, Add activated carbon, stirring 6 hours to carry out decolorization, it is preferred that bleaching agent activated carbon dosage be 2 ‰ -2%, during thing Expect that temperature control at 35~40 DEG C, filters after decolouring, filter residue returns to coal works (delivering to coke oven) and filtrate exchanges heat via crude salt It is pumped into after device preheating in crude salt evaporating kettle, crude salt evaporating kettle has agitating device and inner coil pipe, and low-pressure steam is passed through to inner coil pipe To be evaporated to filtrate, the concentrate after evaporation is flowed into crude salt crystallization kettle by potential difference, and crude salt crystallization kettle has agitating device And external jacket, recirculated cooling water is passed through into external jacket to carry out crystallisation by cooling, 50 DEG C or so of crude salt after crystallization to concentrate Suspension is centrifuged by potential difference into crude salt centrifuge, and the crude salt after having centrifuged expects to be conveyed by crude salt conveying worm admittedly Into crude salt dissolution kettle；
The step of S12 sodium sulfocyanate separation and purifications：
Crude salt dissolution kettle arranges that container bottom is provided with heating steam pipe coil, and stirring dress is provided with container for semi-underground type Put, by crude salt drier Lai crude salt and by qualified methanol pump Lai qualified methanol be stirred dissolving 4h (utilize sodium sulfocyanate It is dissolved in methanol, and the physical characteristic of sodium thiosulfate and sodium sulphate insoluble in methanol), the quantity of methyl alcohol of addition is controlled to ensure solution Density keeps solution temperature at 40~60 DEG C or so in 1030~1050kg/m3, the sodium sulfocyanate methanol solution dissolved by Crude salt solution transfer pump delivers to crude salt filter-pressing cauldron and carries out separation of solid and liquid, is press-filtered out the sodium thiosulfate come and solid sodium sulfate enters Thio dissolution kettle.Sodium sulfocyanate methanol solution enters sulphur cyanogen evaporating kettle, is evaporated by evaporation time 6h, 120 DEG C of evaporating temperature Processing, the methanol gas of evaporated on top return to unqualified methanol after over cure cyanogen evaporating heat exchanger and the condensation of sulphur cyanogen condenser Recycled that (the qualified methanol being steamed out is recycled, and unqualified methanol carries out methanol in tank or qualified methanol tank Rectifying Posterior circle use).Sodium sulfocyanate methanol concentrate after evaporation enters sulphur cyanogen crystallization kettle and carries out crystallisation by cooling, crystallization time 50 DEG C or so of 1.5h, crystallization temperature, the sodium sulfocyanate methanol slurry after crystallization carry out centrifugation point by potential difference into sulphur cyanogen centrifuge From the clear liquid being centrifuged out returns to desulfurization waste liquor tank as supplement water, and the sodium sulfocyanate centrifuged expects to enter sulphur cyanogen drying machine admittedly Dry, sodium sulfocyanate purity more than 98%, methanol content ＜ 0.2% sodium sulfocyanate product are obtained after drying, into sulphur cyanogen bag Installation carries out packaging and storage.
More preferably, the clear liquid after the centrifugation in the step of S12 sodium sulfocyanates separation and purification does not return directly de- Sulphur waste liquid tank but returned again to after processing in desulfurization waste liquor tank through the first separation and double evaporation-cooling the step of；The first separation Step includes：Mother liquor of sulphur cyanogen after centrifugation enters in mother liquor tank of sulphur cyanogen, and mother liquor tank of sulphur cyanogen is with heating steam Coil pipe and agitating device, activated carbon is added to adsorb the impurity of mother liquor of sulphur cyanogen, stirring and adsorbing 4h to mother liquor of sulphur cyanogen Absorption is completed afterwards and mother liquor of sulphur cyanogen and Mixture of Activated Carbon are delivered to sulphur cyanogen activity through mother liquor delivery pump of sulphur cyanogen Enter after carbon filter removal activity charcoal in decolouring Clear liquid tank, decolouring clear liquid pump is defeated by mother liquor of sulphur cyanogen in decolouring Clear liquid tank Mother liquid evaporation kettle of sulphur cyanogen is delivered to, processing, the methanol of evaporated on top are evaporated by evaporation time 6h, 120 DEG C of evaporating temperature Gas returns to unqualified methanol tank after the mother liquor condenser condensation of over cure cyanogen or qualified methanol tank reclaims.The sulphur being evaporated Cyanogen methanol concentrate enters mother liquor crystallization kettle of sulphur cyanogen and carries out crystallisation by cooling, 50 DEG C or so of crystallization time 1.5h, crystallization temperature, Sulphur cyanogen methanol slurry after crystallization is centrifuged by potential difference into mother liquor centrifuge of sulphur cyanogen, by mother liquor of sulphur cyanogen from The sulphur cyanogen secondary mother liquid that scheming is centrifuged out is transferred in sulphur cyanogen secondary mother liquid tank, and the sodium sulfocyanate that centrifugation is obtained expects to enter admittedly Sulphur cyanogen drying machine is dried, dried sodium sulfocyanate ＜ containing methanol 0.2%, and packaging and storage is carried out into sulphur cyanogen packing machine.
The step of double evaporation-cooling, includes：It is secondary that sulphur cyanogen secondary mother liquid through sulphur cyanogen secondary mother liquid delivery pump is delivered to sulphur cyanogen Mother liquid evaporation kettle, evaporating temperature control are evaporated processing at 120 DEG C, and the methanol gas of evaporated on top is through over cure cyanogen secondary mother liquid Unqualified methanol tank is returned to after condenser condensation.The sodium sulfocyanate supplying process water being evaporated forms suspension and enters doctor solution Underground tank, then deliver to desulfurization waste liquor tank through doctor solution submerged pump.
In addition, the sodium sulfocyanate in the step of S12 sodium sulfocyanates separation and purification is expected dry step and once divided admittedly From the step of in sodium sulfocyanate expect dry step using same sulphur cyanogen drier or using respective sulphur cyanogen respectively admittedly Drier；I.e. S12 sodium sulfocyanates separation and purification the step of can there is a sulphur cyanogen drier to be used in conjunction with for two steps, also may be used To be used respectively for two steps provided with two sulphur cyanogen driers, the latter is considered more preferably.
The step of S13 sodium thiosulfate separation and purifications：
The condensate liquid (such as water) for adding 95 DEG C in thio dissolution kettle enters to sodium thiosulfate and solid sodium sulfate mixture Row stirring and dissolving (utilizes the dissolubility difference of sodium thiosulfate and sodium sulphate in water), control solution density 1600kg/m3, temperature 80 DEG C of degree is stirred dissolving, and the solidliquid mixture dissolved is delivered to thio filter-pressing cauldron by thio delivery pump and carries out solid-liquid point From, it is press-filtered out the filter residue (solid sodium sulfate) come and enters sodium sulphate dissolution kettle, and filtrate (sodium thiosulfate solution) enters sulphur For Clear liquid tank, activated carbon is added to the impurity of thio Clear liquid tank absorption sodium thiosulfate solution, filtered subsequently into activated carbon Enter thio filtrate tank after device removal activity charcoal, then sodium thiosulfate solution is delivered to thio knot through thio filtrate delivery pump Brilliant kettle, the inner coil pipe that recirculated cooling water is passed through to thio crystallization kettle carry out decrease temperature crystalline, and decrease temperature crystalline 24h is thio after crystallization Sodium sulphate suspension is centrifuged into thio centrifuge, and the clear liquid being centrifuged out returns to doctor solution system as supplement water System, the sodium thiosulfate that centrifugation obtains water content ＜ 2% are expected admittedly, and packaging and storage is carried out into thio packing machine.Add thio molten Solution kettle in water be by the water tank in water circulation component and come, its pass through the pre-heat treatment and be heated to 95 DEG C.
The step of S14 sodium sulphate separation and purifications：
The concentrated sulfuric acid is added drop-wise in sodium sulphate dissolution kettle by sulfuric acid high position tank by proportioning, controls the pH value 6-7 of solution, with A small amount of sodium thiosulfate in sodium sulphate dissolution kettle is set to be oxidized to sodium sulphate, sodium sulphate delivery pump will aoxidize in sodium sulphate dissolution kettle The metabisulfite solution of completion enters sodium sulphate Clear liquid tank after having filtered particulate matter by filtered over sodium sulfate device, then through sodium sulphate clear liquid pump Metabisulfite solution is delivered into sodium sulphate evaporating kettle to be evaporated, evaporating temperature is controlled at 120 DEG C, the sodium sulphate concentrate being evaporated It is centrifuged by potential difference into sodium sulphate centrifuge, the sodium sulphate centrifuged expects that entering sodium sulphate drying machine dries, and does admittedly Water content ＜ 0.2% sodium sulphate is obtained after dry, packaging and storage is carried out into sodium sulphate packing machine.
The step of S15 solvent recovery cycles：
Recovery circulation and the recovery of water of the step of solvent recovery cycle including methanol circulate, the recovery circulation of methanol Comprise the following steps：By the methanol gas evaporated, (sulphur cyanogen evaporating kettle, mother liquid evaporation kettle of sulphur cyanogen, sulphur cyanogen secondary mother liquid steam Send out kettle etc.) after condenser condenses, it is transferred in qualified methanol tank and stores.And inorganization row caused by each equipment operation breathing Methanol gas may also be contained in deflation body, it is delivered into absorption tower through air-introduced machine is absorbed, and air-introduced machine is transported to The bottom of towe on absorption tower, two sections of fillers are set, the gas containing methanol is entered by bottom of towe, the fresh water sprayed into tower top in absorption tower Reverse contact is absorbed, and fresh water circulated sprinkling to absorption tower, circulating pump are set side line to convey methanol solution by circulating pump Into unqualified methanol tank；The methanol of low concentration is pumped to methanol fractionation system by unqualified methanol, and the complete methanol of rectifying is again Deliver to standby in qualified methanol tank.
The step of Water Sproading circulation, includes：Vapor caused by being evaporated from crude salt evaporating kettle is imported in condenser, It is condensed into aqueous water, be then transferred in condensate drum store it is standby；Pumped out when needing to use, will by heat exchanger It is heated to 95 DEG C subsequently into being used in thio dissolution kettle.
In certain embodiments, the step of also including expansion drying in the step that the S11 crude salts are dried；After centrifugation Crude salt expect to contain a small amount of water admittedly, therefore the crude salt after centrifugation is expected that being delivered to crude salt drier by crude salt conveying worm is carried out admittedly Expansion drying processing, to improve follow-up sodium sulfocyanate product quality.Crude salt after centrifugation is expected admittedly defeated by crude salt conveying worm Deliver to crude salt drier and carry out expansion drying, water content in crude salt is reduced to less than 1%, most preferably, crude salt is aqueous after drying Rate ＜ 0.5%；Crude salt after expansion drying is sent into standby in crude salt dissolution kettle by potential difference.
In further embodiments, the step of S12 sodium sulfocyanates separation and purification also includes the step of sedimentation separation, will The methanol solution of sodium sulfocyanate after press filtration carries out sedimentation separation processing first before sulphur cyanogen evaporating kettle is transferred to, by sodium sulfocyanate Methanol solution be pumped into subsider progress solid-liquid sedimentation separation, settle after 24h by the sulphur cyanogen methanol solution through sedimentation separation by Sedimentation clear liquid is pumped into sulphur cyanogen evaporating kettle, and solid is then transferred in thio dissolution kettle and carries out subsequent treatment.
In some preferred embodiments, methods described also includes：
The step of methanol solution density is controlled when in the step of S12 sodium sulfocyanates separation and purification to dissolving： The density of sodium sulfocyanate methanol solution is strict controlled in by 1.03-1.05kg/ by weight method and the method for online density measuring Cm3, more preferably, temperature control during dissolving is kept at 40~60 DEG C or so；The mixed salt that the step dried through crude salt is dried to obtain (i.e. crude salt is expected admittedly) weighs when being delivered to dissolution kettle to mixed salt, while the sodium sulfocyanate content in mixed salt needs to be examined (under conditions of desulfurization material gas and desulphurization catalyst are stable, the measure of sodium sulfocyanate content only need to be in initial measure once for survey ), weighing is completed by the weighing spring installed in dissolution kettle bottom, and its pipeline being connected with equipment dissolution kettle is adopted Connected with flexible pipe and flow through impulse force caused by pipeline to mitigate weight that pipeline itself brings and material and that brings is weighed to equipment Influence；Within the precision ± 0.5kg of the weighing spring of installation, no influence of being weighed on spring is vibrated caused by dissolving stirring, and The weighing spring of installation need to be evenly distributed on device bottom.Mixed salt quality and combination measurement in the dissolution kettle for weighing to obtain Sodium sulfocyanate content meter in the mixed salt gone out calculates required quantity of methyl alcohol, then toward adding methanol in dissolution kettle and be stirred Dissolving, solution density is measured by being installed on the on-line densimeter of dissolution kettle middle and lower part side in stirring and dissolving and will be measured Flow control valve that density data signal is sent in methanol line and the aperture (open big or turn down) of regulating valve is adjusted And methanol solution density when controlling dissolving.More preferably, flushing pipe is installed, when being used for a long time with prevention on on-line densimeter Salt particle can be rich long-pending inaccurate in resulting in blockage or measuring on pipeline or densitometer.Most preferably, by strict in above-mentioned steps Methanol usage is controlled, and control solution density is controlled at 40~60 DEG C or so (most in 1030~1050kg/m3, solution temperature Good is 50 DEG C or so), while the methanol of volatilization is subjected to tail gas recycle to reduce methanol consumption, it is produced into so as to reduce This.
In some preferred embodiments, methods described also includes：
The step that solution density when being dissolved in the step of S13 sodium thiosulfate separation and purification to water is controlled Suddenly：The density of hypo solution is controlled to take off in 1.6-1.65kg/cm3 by weight method and the method for online density measuring Need to weigh to the mixed salt for adding dissolution kettle except the mixed salt of sodium sulfocyanate is delivered to when in dissolution kettle, it is to pass through peace to weigh What the weighing spring mounted in dissolution kettle bottom was completed, its pipeline being connected with equipment dissolution kettle is connected using flexible pipe, to mitigate The weight and material that pipeline itself is brought flow through impulse force caused by pipeline and equipment weighed the influence brought；The bullet of weighing of installation Within the precision ± 0.5kg of spring, dissolve and no influence of being weighed on spring is vibrated caused by stirring, and weighing spring is installed to need uniformly It is distributed in device bottom.Sodium thiosulfate in the mixed salt measured is combined according to the quality of mixed salt in the dissolution kettle for weighing to obtain Content meter, which calculates, needs hot water amount, is then stirred dissolving toward addition hot water in dissolution kettle, passes through installation in stirring and dissolving On-line densimeter in dissolution kettle middle and lower part side measures solution density and the density data signal measured is sent into hot-water line Flow control valve on line and solution density when being adjusted to the aperture (open big or turn down) of regulating valve and controlling the water to dissolve； More preferably, flushing pipe is installed, the rich product of salt particle meeting is in pipeline or density when being used for a long time with prevention on on-line densimeter Result in blockage or measure on meter and be inaccurate.
In some preferred embodiments, methods described also includes：
The step being controlled in the step that the S11 crude salts are dried to the evaporation rate and evaporation capacity of mixed salt evaporating kettle Suddenly：Liquid level and enter the steam flow of evaporating kettle to control the steaming of evaporating kettle by controlling mixed salt evaporating kettle feed rate, in kettle Send out speed and evaporation capacity：Mixed saltSteam pipe coil inside evaporating kettle is divided into two sections, and epimere coil pipe is positioned at evaporation kettle barrel More than middle part, using the form of inside and outside two layers distribution, its spacing is the outer tube clear distance 50mm of two layers of coil pipe；Hypomere coil pipe is located at cylinder The middle and lower part of body, it is consistent with the distribution form on top.The mixed salt solution preheated by the steam gone out by evaporating kettle is by leading Pipeline adds evaporating kettle, during the 60-70% liquid levels of the mixed salt solution to be added in evaporating kettle to evaporating kettle capacity, closing mixed salt Solution Trunk Line switch valve, while by-pass regulating valve is opened, liquid level gauge (preferably double flange differential pressure levelmeters) is in time by liquid level number It is believed that the flow control valve on by-pass mixed salt solution pipeline number is sent to, so as to the aperture to regulating valve and switch and size progress Control；When being evaporated to solution level less than 50%, the steam on evaporating kettle top is closed, only opens the steam of bottom；So both Heating surface (area) (HS needed for evaporation can be met, and can saves steam consumption quantity when amount of solution is few.
In some preferred embodiments, methods described also includes：
The evaporation rate and evaporation capacity of sulphur cyanogen evaporating kettle are controlled in the step of S12 sodium sulfocyanates separation and purification The step of processed：Liquid level and enter the steam flow of evaporating kettle to control by controlling sodium sulfocyanate evaporating kettle feed rate, in kettle The evaporation rate and evaporation capacity of evaporating kettle,Mixed saltSteam pipe coil inside evaporating kettle is divided into two sections, and epimere coil pipe is positioned at steaming More than the middle part for sending out kettle barrel, using the form of inside and outside two layers distribution, its spacing is the outer tube clear distance 50mm of two layers of coil pipe；Hypomere Coil pipe is located at the middle and lower part of cylinder, consistent with the distribution form on top.It is stripped of the sodium sulfocyanate first of sodium thiosulfate, sodium sulphate Alcoholic solution is added in evaporating kettle by Trunk Line, 60-70% liquid of the mixed salt solution to be added in evaporating kettle to evaporating kettle capacity During position, mixed salt solution Trunk Line switch valve is closed, while opens by-pass regulating valve, liquid level gauge (preferably double flange differential pressure levelmeters) Liquid level data signal is sent to the flow control valve on by-pass mixed salt solution pipeline in time, so as to the aperture to regulating valve and opened Pass is controlled with size；When being evaporated to solution level less than 50%, the steam on evaporating kettle top is closed, only opens bottom Steam；It can so meet to evaporate required heating surface (area) (HS, and can saves steam consumption quantity when amount of solution is few.
Most domestic coke-oven plant is live by the individual of operator to waste treatment process caused by ISS-J desulfurization at present Experience and field observation are operated, so that the quantity of solvent that is added during dissolving it is more or less, time for being concentrated by evaporation it is long or It is short can not accurate judgement, cause the refined salt product purity that extracts not enough or the comparatively high consumption in operating process；Above-mentioned control Step (i.e. control method) solves the difficulty artificially judged in live actual mechanical process or error, reaches energy-conservation and improves production The purpose of product quality, it has very useful directive significance to execute-in-place.

Claims (9)

1. it is a kind of from waste liquid caused by wet method ISS-J desulfurization extract refined salt device, described device include crude salt dry component, Sodium sulfocyanate separation and purification component, sodium thiosulfate separation and purification component and sodium sulphate separation and purification component, in addition to solvent return Receive recirculation assembly；
Characterized in that,
The crude salt dry component includes desulfurization waste liquor tank, crude salt heat exchanger, crude salt evaporating kettle, crude salt crystallization kettle and crude salt centrifugation Machine, desulfurization waste liquor tank are connected to desulphurization system；
The sodium sulfocyanate separation and purification component include crude salt dissolution kettle, crude salt filter-pressing cauldron, sulphur cyanogen evaporating kettle, sulphur cyanogen crystallization kettle, Sulphur cyanogen centrifuge, sulphur cyanogen drying machine and sodium sulfocyanate packing machine；Crude salt dissolution kettle is connected with the solid material outlet of crude salt centrifuge, slightly The solid material outlet of salt filter-pressing cauldron is connected to thio dissolution kettle, filtrate (liquid is connected to sulphur cyanogen evaporating kettle；The solid material of sulphur cyanogen centrifuge Outlet is connected to sulphur cyanogen drying machine and purified liquor outlet is connected to desulfurization waste liquor tank；
The sodium thiosulfate separation and purification component include thio dissolution kettle, condensate drum, thio filter-pressing cauldron, thio crystallization kettle, Thio centrifuge and sodium thiosulfate packing machine；The solid material outlet of thio filter-pressing cauldron is connected to sodium sulphate dissolution kettle and filtrate (liquid It is connected to thio crystallization kettle；
The sodium sulphate separation and purification component include sodium sulphate dissolution kettle, concentrated sulfuric acid head tank, sodium sulphate evaporating kettle, sodium sulphate from Scheming, sodium sulphate drying machine and sodium sulphate packing machine, concentrated sulfuric acid head tank are connected to sodium sulphate dissolution kettle；
The solvent recovery cycle component includes Methanol Recovery cycling element and Water Sproading cycling element；The Methanol Recovery circulation Unit includes：Condenser, qualified methanol tank, air-introduced machine, absorption tower, circulating pump, unqualified methanol tank and methanol fractionation system, inhale Receive and two sections of fillers are set in tower；The Water Sproading cycling element includes：Condenser, condensate drum and heat exchanger.
2. device according to claim 1, it is characterised in that the crude salt dry component also includes crude salt drier, institute Crude salt drier entrance is stated to be connected to crude salt centrifuge and export and be connected to crude salt dissolution kettle.
3. device according to claim 1, it is characterised in that the sodium sulfocyanate separation and purification component also includes sedimentation Groove, the entrance of the subsider are connected to the filtrate (liquid of crude salt filter-pressing cauldron, and outlet is connected to sulphur cyanogen evaporating kettle.
4. device according to claim 1, it is characterised in that the sodium sulfocyanate separation and purification component also includes sulphur cyanogen one Secondary separation assembly and sulphur cyanogen secondary separation component；The sulphur cyanogen first separation component includes mother liquid evaporation kettle of sulphur cyanogen, sulphur cyanogen Mother liquor crystallization kettle, mother liquor centrifuge of sulphur cyanogen, sulphur cyanogen drying machine and sodium sulfocyanate packing machine；The sulphur cyanogen secondary separation Component includes sulphur cyanogen secondary mother liquid evaporating kettle, and the concentrated solution outlet of sulphur cyanogen secondary mother liquid evaporating kettle is connected to desulfurization waste liquor tank；Sulphur Mother liquid evaporation kettle entrance of cyanogen is connected to the purified liquor outlet of sulphur cyanogen centrifuge, and the solid material outlet of mother liquor centrifuge of sulphur cyanogen connects It is connected to sulphur cyanogen drying machine and purified liquor outlet is connected to sulphur cyanogen secondary mother liquid evaporating kettle.
5. device according to claim 1, it is characterised in that dissolution kettle in the sodium sulfocyanate separation and purification component and Dissolution kettle in sodium thiosulfate separation and purification component has an identical structure, evaporating kettle bottom be provided with precision ± 0.5kg with Interior weighing spring, the weighing spring is evenly distributed on dissolution kettle bottom and it uses flexible pipe to be connected to dissolution kettle；Dissolving Kettle middle and lower part side is provided with on-line densimeter, and on-line densimeter electrically connects with the flow control valve in methanol line.
6. device according to claim 5, it is characterised in that be provided with flushing pipe on the on-line densimeter.
7. device according to claim 5, it is characterised in that dissolution kettle in the sodium sulfocyanate separation and purification component Flow control valve is by weighing spring and on-line densimeter by the density domination of sodium sulfocyanate methanol solution in 1.03-1.05kg/ cm3。
8. device according to claim 5, it is characterised in that the dissolution kettle in the sodium thiosulfate separation and purification component Flow control valve by weighing spring and on-line densimeter by the density domination of hypo solution in 1.6-1.65kg/ cm3。
9. device according to claim 1, it is characterised in that mixed salt evaporating kettle and sulphur cyanogen in the crude salt dry component Sodium sulfocyanate evaporating kettle in sour sodium separation and purification component also includes evaporation adjusting means, and the adjusting means is opened by Trunk Line Close valve, by-pass regulating valve, liquid level gauge, upper steam valve and lower steam valve composition.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109626400A (en) * 2019-01-09 2019-04-16 申恒杰 A kind of heavy alkali production technology

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109626400A (en) * 2019-01-09 2019-04-16 申恒杰 A kind of heavy alkali production technology
CN109626400B (en) * 2019-01-09 2021-09-17 合肥龙之韵医药技术有限公司 Heavy alkali production process

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