CN109173956A

CN109173956A - The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water

Info

Publication number: CN109173956A
Application number: CN201810172037.0A
Authority: CN
Inventors: 陈春茂; 刘植昌; 易忠进; 张睿; 梁家豪; 孟祥海; 刘海燕; 徐春明; 王庆宏
Original assignee: China University of Petroleum Beijing
Current assignee: China University of Petroleum Beijing
Priority date: 2018-03-01
Filing date: 2018-03-01
Publication date: 2019-01-11
Anticipated expiration: 2038-03-01
Also published as: CN109173956B

Abstract

The present invention provides a kind of system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water.The system includes hydrolysis reactor, neutralization reactor, flocculation sedimentation system, mechanical dehydration device and desiccation apparatus；Hydrolysis reactor, which is used to mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, carries out hydrolysis；Neutralization reactor is connect with hydrolysis reactor, and the acidic hydrolysis liquid for generating hydrolysis is mixed with the lye comprising alkaline waste water carries out neutralization reaction；Flocculation sedimentation system is connect with neutralization reactor, and the neutralizer for generating neutralization reaction and flocculant are sufficiently mixed and implement sedimentation separation；Mechanical dehydration device is connect with flocculation sedimentation system, for being carried out dehydrating to the concentration wadding body formed through sedimentation separation；Desiccation apparatus is connect with mechanical dehydration device, for the wet solid slag formed through dehydration to be dried.Above system can leniently eliminate the activity of dead catalyst, and the stability of operation and safety are good.

Description

The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water

Technical field

The invention belongs to technical field of petrochemical industry, and in particular to a kind of processing chlorine aluminium acidic ionic liquids dead catalyst and The system of alkaline waste water.

Background technique

Enter the acceleration propulsion phase as national clear gusoline upgrades strategy, it is high as ideal clean gasoline blend component The demand of octane number alkylate oil has welcome the growth of explosion type.It is the master for producing alkylate oil by catalytic material alkylation of C4 Technique is wanted, existing alkylation process mostly uses greatly two conventional processing routes of hydrogen fluoride and sulfuric acid process.However, above-mentioned tradition Process route, as catalyst, it is hidden not only to cause huge safety to technique, equipment and personnel using hydrofluoric acid and sulfuric acid Suffer from, a large amount of " acid sludges " and great environment hidden danger is also constituted containing alkali waste water that furthermore technical process is discharged.Even if being thrown with height Enter and regeneration treatment, flue gas SO are carried out to " acid sludge "₂、NO_xEnvironmental protection standard can not be met with sulphuric acid mist content.Therefore, alkylate oil Production be badly in need of the advanced technologies of safer environmental protection.

Using ionic liquid as the catalyst of alkylated reaction, in product transformation efficiency, process safety and environment friend To be much better than traditional hydrogen fluoride and sulfuric acid process in good property.Compared with hydrogen fluoride and sulfuric acid process, chlorine aluminium acidic ionic liquids Alkylation process whole competitiveness is stronger, and the alkylate oil process units created at present uses.However, chlorine aluminic acid class Ionic liquid allcylation technique still can generate a small amount of dead catalyst and alkaline waste water (i.e. alkali-wash waste water), wherein alkyl per ton Carburetion by-product dead catalyst 3kg or so, alkali-wash waste water 20-30kg, yield are respectively the 5% and 3% of sulfuric acid process.Chlorine aluminic acid class from The component of dead catalyst and raw catelyst that sub- liquefied alkyl technique generates is essentially identical, and only activity slightly reduces, and Containing acid-soluble hydrocarbon, therefore there are the characteristics such as high activity, peracidity and high oil-containing, innoxious and disposal of resources is carried out to it It is extremely necessary.

The patent of invention of 105457973 A of Publication No. CN discloses a kind of pair of chlorine aluminium acidic ionic liquids dead catalyst The method and system handled, first clear up by dead catalyst and aqueous slkali-neutralization reaction is to eliminate dead catalyst Activity with it is acid, then again in dead catalyst metal and oils resource recycle.The above method and system can be Harmless treatment is carried out to chlorine aluminium acidic ionic liquids dead catalyst to a certain extent and realizes that Metals from Spent Catalysts and acid are molten The recycling of oil, however the present inventor has found through numerous studies, there are still following defects for the above method and system: 1) anti-in resolution Answering in device directly adds alkali clear up-neutralize to dead catalyst, and reaction process is very violent, the stability and peace of technique and system Full property is relatively poor；2) the molten oil of acid in dead catalyst easily causes carbonization, the recycling of the molten oil of acid during resolution-neutralization reaction Rate is lower than 70%, and the moisture content for the molten oil of acid that furthermore recycling obtains is high (moisture content is 7% or so), and there are particle carbon impurities (content of particle carbon impurity is 5% or so), the inferior quality of oil product；3) it is to what dead catalyst clear up-neutralize The three-phase mixture being made of the molten oily phase/wadding body of water phase/acid needs to carry out oil emulsion demulsification in the molten oil of recovery acid and receives oil, It is unfavorable for subsequent processing；4) metal and the molten oil of acid in dead catalyst, technique are recycled using flocculation and twice dehydration mode twice Relative complex, operating cost is higher.

In addition, carrying out alkali cleaning to alkylate oil product is to ensure oil quality in the technique of chlorine aluminic acid class ionic liquid allcylation The important measures of amount usually contain sodium hydroxide, sodium metaaluminate, sodium chloride and a small amount of petroleum in the alkali-wash waste water discharged Pollutant.It is handled currently, the alkali-wash waste water is usually discharged to sewage disposal system, not only needs to add a large amount of external source Acids neutralizes it, and can increase a large amount of aluminium hydroxide materialized mud newly after neutralizing, the salt load of waste water after neutralization It is higher with organic loading, serious impact is constituted to the stable operation of sewage disposal system.

It is useless for dead catalyst and alkali cleaning since chlorine aluminic acid class ionic liquid allcylation is the new process of petrochemical industry The processing mode of these two types of novel pollution sources of water is still among continuous explore.Therefore, how useless to chlorine aluminium acidic ionic liquids Catalyst and alkali-wash waste water these two types pollution sources carry out innoxious, recycling processing and utilization, thus realize chlorine aluminic acid class from The green upgrading of sub- liquefied alkyl technique, is the significant problem that petrochemical industry faces.

Summary of the invention

The present invention provides a kind of system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, which can Overcome the problems of the above-mentioned prior art, can not only leniently eliminate the activity of dead catalyst, the stability of system operatio Good with safety, furthermore the molten oil of acid in dead catalyst is not easy to be carbonized, and the rate of recovery of the molten oil of acid is high, in the molten oil of the acid recycled The content of water and impurity is low, and the quality of oil product is high.

The present invention provides a kind of system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, including hydrolysis is instead Answer device, neutralization reactor, flocculation sedimentation system, mechanical dehydration device and desiccation apparatus；

The hydrolysis reactor, which is used to mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, carries out hydrolysis；

The neutralization reactor is connect with the hydrolysis reactor, the acidic hydrolysis liquid for generating the hydrolysis It is mixed with the lye comprising alkaline waste water and carries out neutralization reaction；

The flocculation sedimentation system is connect with the neutralization reactor, the neutralizer for generating the neutralization reaction with Flocculant is sufficiently mixed and implements sedimentation separation；

The mechanical dehydration device is connect with the flocculation sedimentation system, for the concentration to being formed through the sedimentation separation Wadding body is carried out dehydrating；

The desiccation apparatus is connect with the mechanical dehydration device, for the wet solid slag formed through the dehydration into Row is dried.

System of the invention is used for chlorine aluminium acidic ionic liquids dead catalyst (hereinafter referred to as dead catalyst) and alkalinity Waste water is handled；Chlorine aluminium acidic ionic liquids dead catalyst to be processed and alkaline waste water are not limited strictly, catalysis of giving up Agent can be that the ionic liquid-catalyzed carbon four of chlorine aluminic acid class is utilized to produce the dead catalyst that alkylate oil generates, the chlorine aluminium acidic ionic The viscosity of liquid dead catalyst reaches 600-800mPas, and active component is mainly aluminium chloride, copper chloride etc., and other components are main For acid-soluble hydrocarbon (i.e. sour molten oil)；Alkaline waste water can produce to produce alkylate oil using the ionic liquid-catalyzed carbon four of chlorine aluminic acid class Raw alkali-wash waste water, sodium hydrate content are 10-15wt% or so.

The present inventor it has been investigated that, the above-mentioned prior art directly adds alkali to disappear dead catalyst using resolution reactor Solution-neutralization, which will lead to resolution reactor in reaction process it is very violent, reason may is that chlorine aluminic acid class from The main active component of sub- liquid dead catalyst is aluminium chloride, and hydrolysis reaction is higher, after contact with water can rapid water Solution generates hydrogen chloride and makes hydrolyzate in highly acid；Meanwhile hydrolysis heat release increases Hydrolysis rate constant, further Improve the hydrolysis reaction of aluminium chloride.In particular, being directly added into highly basic, highly basic and hydrogen chloride in aluminium chloride hydrolytic process Neutralization reaction can discharge a large amount of heat, further increase the hydrolysis reaction of aluminium chloride；It cannot such as radiate in time, instantaneously Violent heat release will form localized hyperthermia, to cause the carbonization of the molten oil of acid and the generation of oil smoke, hydrogen chloride acid mist, additionally There are the risks of explosion.

Therefore, system of the invention sets gradually hydrolysis reactor and neutralization reactor, thus being urged using lye useless Before agent carries out neutralization reaction, first chlorine aluminium acidic ionic liquids dead catalyst and strong brine are mixed into hydrolysis reactor Row hydrolysis；The study found that the heat that a large amount of strong brine can generate hydrolysis in the hydrolytic process of dead catalyst Rapid dispersion, so that the autoacceleration mechanism of hydrolysis be interrupted；Meanwhile the chloride ion of strong brine middle and high concentration increases hydrolysis The concentration of product has certain inhibiting effect to hydrolysis.Aforesaid way can not only leniently eliminate dead catalyst Activity, while neutralization reaction heat can be eliminated to the facilitation of hydrolysis reaction, the operating process of whole system is more steady Fixed and safety.

Further, the present inventor it has been investigated that, the prior art carries out clearing up-neutralization reaction using complete mixing flow reactor The molten oil carbonization of acid be will lead to which the rate of recovery is lower, reason may is that the viscosity of dead catalyst is higher, in strong brine In the form of drop occur, in the hydrolysis reaction of dead catalyst, the mass transfer between active component and moisture be control because Element；Since hydrocarbon acid-soluble in dead catalyst is to the cladding of active component, so that the mass transfer between active component and moisture is weakened, Its mild progress for being conducive to hydrolysis.However, if making between dead catalyst drop and water body with the progress of complete mixing flow state Contact, can accelerate the separation of acid-soluble hydrocarbon and active component, and the mass transfer between active component and water body is reinforced, hydrolysis speed Rate is enhanced, and hydrolysis reaction can more acutely；Meanwhile the molten oil of acid of generation can also be swept along into reaction system, both be held Carbonization is easily caused, the rate of recovery of the molten oil of acid is furthermore reduced.

Therefore, hydrolysis reactor is set plug flow packed bed reactor by the present invention, to heat hydrolysis more (i.e. realization mild hydrolysis)；At this point, dead catalyst is contacted with strong brine in hydrolysis reactor with flat-pushing stream mode, object The back-mixing degree of material is low, small to the disturbance of dead catalyst drop, and the mass transfer between active component and moisture is weakened, and not only reduces The intensity of hydrolysis, and be conducive to the separation and recycling of the molten oil of acid.

Density in view of dead catalyst is about 1.36kg/L, and the density of acidic hydrolysis liquid and strong brine is about 1.2kg/L；This When, sinking speed of the dead catalyst drop in strong brine is very fast, is unfavorable for the complete hydrolysis of dead catalyst.Therefore, of the invention Structured packing is filled in plug flow packed bed reactor, which fully utilizes the high viscosity characteristic of dead catalyst, filling out Crown_interception of the behavior of boundary layer and filler on material surface to catalyst；Since the viscosity of dead catalyst is high, inlet amount is small, It is in membranaceous Laminar Flow on structured packing surface, and forms thicker laminar boundary layer, biggish stickiness power makes dead catalyst The rate of settling be effectively controlled.Further, since the presence of inner layer of boundary layer laminar sublayer, the resistance to mass tranfer of storeroom increases, because Mass-transfer efficiency between this dead catalyst and strong brine is also effectively controlled.Relative to random packing, the material stream of structured packing Through-hole road is uniform, is less prone to channeling.

In particular, the present invention can provide unobstructed flow path, and protect substantially using high-throughput structured packing for strong brine Laminar condition is held, while the mass transfer between dead catalyst can be weakened.When reaction is hydrolyzed, dead catalyst is in structured packing Hole in be uniformly distributed, the numerous elementary reaction environment of forming quantity, when contact of the strong brine of the big scale of construction with dead catalyst Between it is long, to ensure that the thorough hydrolysis to dead catalyst.

Research is found: the porosity and specific surface area of structured packing are affected to hydrolysis；Porosity it is too low or When specific surface area is excessive, there is the risk of the molten oil of acid and impurity blocking filler duct；When porosity is excessively high or specific surface area is too small, The crown_interception of dead catalyst is weakened, there are the incomplete risks of hydrolysis.In the present invention, the porosity of structured packing For 0.95-0.97m³/m³(i.e. every m³The pore volume of structured packing is 0.95-0.97m³), specific surface area 300-500m²/m³ (i.e. every m³The specific surface area of structured packing is 300-500m²)；Under above range, the rate control of hydrolysis is preferable, neither Duct is easily caused to block, while hydrolysis easily carries out completely.

Further, structured packing can be oleophobic property filler and can have inclined plate structure；The structured packing can also Enough coarses promoted to the molten oil droplet of acid make bulky grain oil droplet be easier to float, to be conducive to the recycling of the molten oil of acid.The present invention Specific structure and material to structured packing do not limit strictly；Structured packing for example can be the orifice plate structured packing of Y type ripple Deng the inclination angle of ripple and axis can be 45 ° or so, so that the rejection effect to dead catalyst drop is good.In addition, regular fill out The material of material can be polyethylene (PE), polyvinyl chloride (PVC) or Kynoar (PVDF), with oleophobic property and acidproof resistance to Chlorine corrosion is conducive to the coarse of the molten oil of acid, consequently facilitating the molten oil recycling of acid.

Further, the air speed of above-mentioned plug flow packed bed reactor can be 0.25-0.5h^-1.Wherein, when air speed is 0.5h^-1When, dead catalyst is able to complete hydrolysis, and pH value can be stablized in 2.5-2.8；When air speed is 0.25h^-1When, acidic hydrolysis The oil content of liquid is minimum, and the molten oil of the acid recycled is at most.

The present invention does not limit the specific structure of hydrolysis reactor strictly, can use the hydrolysis of this field routine Device.In concrete scheme of the invention, hydrolysis reactor includes shell, is successively arranged ring from top to bottom on the top of the shell Shape collection tank, the water distributor for being distributed strong brine and the distributing device for being distributed chlorine aluminium acidic ionic liquids dead catalyst, The lower part of the shell is equipped with the filler support bracket for supporting filler, exhaust outlet is equipped at the top of the shell, described The side wall of shell is equipped with oil discharge outlet, water inlet and feed inlet, and the oil discharge outlet is connected to the annular collection tank, the water inlet It is connected to the water distributor, the feed inlet is connected to the distributing device, is equipped with liquid outlet in the bottom of the shell.

It is extremely strong in view of the acidity of dead catalyst, and viscosity is up to 600-800mPas, and has containing a small amount of machinery Impurity, to prevent blocking and corrosion, it is preferred to use the Machinery Diaphragm Pump of fluoroplastics material conveys it；In addition, strong brine In sodium chloride content be up to 15-22wt%, corrosivity is strong, it is preferred to use the centrifugal pump of stainless steel material conveys it.

In above-mentioned hydrolysis reactor, dead catalyst is mixed with strong brine carries out hydrolysis, and the acid in dead catalyst is molten Property hydrocarbon separated with active component, the molten oil of acid of formation floats up to liquid level, after the collection of annular collection tank, then through oil discharge outlet and its pipe Road is from sump oil storage tank is flowed into case freshening.In particular, water inlet and water distributor are separately positioned in above-mentioned hydrolysis reactor The top of feed inlet and distributing device not only contributes to dispersion of the strong brine to dead catalyst, and can make dead catalyst The region of hydrolysis avoids influence of the hydrolysis localized heat release to acid molten oil quality and the rate of recovery far from the molten oil reservoir of acid.

In addition, the active component contained in dead catalyst and acid-soluble hydrocarbon can generate the organic dirt of volatility in hydrolytic process Object (VOCs) and hydrogen chloride are contaminated, is enriched at the top of hydrolysis reactor, in order to avoid being polluted to air, can hydrolyze Exhaust outlet is arranged in the top of reactor, and gas is led to the water seal mouth of strong brine storage tank, and the strong brine in strong brine storage tank was both These gaseous pollutants can be absorbed, while also can use liquid level and carrying out water seal；Water seal can also provide just for hydrolysis reactor Pressure, promotes acidic hydrolysis liquid to the re-absorption of these pollutants.

In the present invention, the structure of the water distributor of hydrolysis reactor is not limited strictly, as long as it can make strong brine It is uniformly distributed in hydrolysis reactor.

In concrete scheme of the invention, the water distributor includes cloth supply mains, is distinguished in the two sides of the cloth supply mains Equipped with multiple parallel and spaced set water distribution branch pipes, multiple water distributing pores, water distribution is distributed in the bottom of each water distribution branch pipe The total open area in hole accounts for 1% or more of the hydrolysis reactor sectional area.At this point, water distributor is fishbone type；Wherein, adjacent cloth Spacing between water branch pipe can be set to 5cm or more, to avoid the floating for influencing the molten oil of acid and collect；In addition, to water distribution The set-up mode of water distributing pore on branch pipe does not limit strictly, and multiple water distributing pores can be with spaced set, and can will be multiple The aperture of water distributing pore is set as identical.

Water distributor perforated area with above structure is big, the number of openings is more, consequently facilitating promoting uniformly dividing for strong brine Cloth；Further, since the flow velocity that portals of water distributing pore is small, back-mixing is low, Laminar Flow is formed in hydrolysis reactor, is reduced and is urged with useless Mass transfer between agent, and it is smaller to the molten oil reservoir disturbance of acid on hydrolysis liquid level, it is more advantageous to the recycling of the molten oil of acid.

In the present invention, the structure of the distributing device of hydrolysis reactor is not limited strictly, as long as it can make useless catalysis Agent is uniformly distributed in hydrolysis reactor.

In concrete scheme of the invention, the distributing device includes cloth general pipeline, is distinguished in the two sides of the cloth general pipeline Equipped with multiple concentric and spaced set semicircle cloth branch pipes, it is distributed in the bottom of each semicircle cloth branch pipe multiple Cloth hole, the total open area in cloth hole account for 2% or more of the hydrolysis reactor sectional area.At this point, distributing device is ring-like；Its In, the spacing between adjacent cloth branch pipe can be set to 5cm or more, to avoid the floating for influencing the molten oil of acid and collect；This Outside, the set-up mode in the cloth hole on cloth branch pipe is not limited strictly, multiple cloth holes can be with spaced set, and can To set identical for the aperture in multiple cloth holes, the internal diameter in cloth hole for example can be set to 3-5mm.

Distributing device perforated area with above structure is big, cloth hole number is more, consequently facilitating dead catalyst cloth is uniform； Further, since the internal diameter of cloth material mouth is small, dead catalyst is extruded with droplet, is more advantageous to its dispersion in strong brine.

In the present invention, neutralization reactor be used for the acidic hydrolysis liquid that generates the hydrolysis with comprising alkaline waste water Lye mixing carry out neutralization reaction；The specific structure of neutralization reactor is not limited strictly, it can be conventional using this field Neutralization reactor.

In concrete scheme of the invention, the neutralization reactor is complete mixing flow reactor；The neutralization reactor includes Shell is successively arranged the water distributor for being distributed lye and the cloth for being distributed neutralizer on the top of the shell from top to bottom Glassware, is equipped with side-feeding mixer at the middle part of the shell, exhaust outlet is equipped at the top of the shell, in the shell Side wall is equipped with alkali inlet and inlet, and the alkali inlet is connected to the water distributor, and the inlet is connected to the distributing device, Liquid outlet is equipped in the bottom of the shell.

The present inventor's studies have shown that be separately positioned on inlet and cloth for the alkali inlet of neutralization reactor and water distributor The position of the top of device, the metal hydroxides wadding body that neutralization reaction can be made to generate is lower, to be not easy to plug water distributor.It is special It is not using side-feeding mixer, to accelerate the mass transfer between acidic hydrolysis liquid and lye and neutralization reaction, while can also prevent Wadding body premature precipitation is to block liquid outlet and its pipeline.

Preferably, acidic hydrolysis liquid of the centrifugal pump of fluoroplastics material to height containing chlorine can be used to convey；Alkali cleaning is useless Water and external source lye height contain chlorine, are high containing alkali, and need accurately to be matched with acidic hydrolysis liquid to reach neutralization, therefore preferably use The metering pump of fluoroplastics material conveys alkali-wash waste water and external source lye.Further, since acidic hydrolysis liquid and alkali-wash waste water In carry a small amount of oil, N-process will cause enrichment of the VOCs at the top of neutralization reactor；It, can be with to prevent air pollution Exhaust outlet is set at the top of neutralization reactor, and gas is led to the water seal mouth of strong brine storage tank, it is dense in strong brine storage tank These gaseous pollutants had both can be absorbed in salt water, also can use liquid level and carried out water seal；Water seal can also provide for neutralization reactor Positive pressure, to promote neutralizer to the re-absorption of these pollutants.

The structure of water distributor and distributing device to neutralization reactor does not limit strictly, as long as can make lye and acidity Hydrolyzate is uniformly distributed in neutralization reactor, can use and structure identical in hydrolysis reactor；At this point, in water distributor The total open area of water distributing pore accounts for 1% or more of neutralization reactor sectional area, during the total open area in cloth hole accounts in distributing device With 2% or more of reactor cross section product.Alkali-wash waste water merge with external source lye after through by above-mentioned fishbone type water distributor in and Water distribution in reactor, since the perforated area of water distributor is big, the number of openings is more, promote alkali-wash waste water and external source lye in and Being uniformly distributed in reactor；In addition, acidic hydrolysis liquid matches liquid, the cloth via above-mentioned ring-like distributing device in neutralization reactor The perforated area of glassware is small, the quantity of cloth material mouth is few, internal diameter is small, forms local turbulence after liquid out, facilitate acidic hydrolysis liquid with Mass transfer and neutralization reaction between lye.

In the present invention, flocculation sedimentation system is for the neutralizer that the neutralization reaction generates to be sufficiently mixed with flocculant And implement sedimentation separation；The specific structure of flocculation sedimentation system is not limited strictly, the structure of this field routine can be used.

In concrete scheme of the invention, the flocculation sedimentation system includes that the pipe-line mixer set gradually and flocculation are heavy Shallow lake device, the flocculation deposition apparatus include seal casinghousing, be equipped with inside the seal casinghousing annular overflow weir, central tube and The inside of the central tube is arranged in cloth tube, the cloth tube, umbellate form baffle is equipped in the bottom of the central tube, described The top of seal casinghousing be equipped with exhaust outlet, the seal casinghousing side wall be equipped with water outlet and feed inlet, the water outlet with The annular overflow weir connection, the feed inlet are connected to the cloth tube, are equipped with slag notch in the bottom of the seal casinghousing.

It is understood that the liquid outlet of neutralization reactor is connect with the import of pipe-line mixer by the road, it is in and anti- It answers device liquid outlet and the connecting line of pipe-line mixer import is equipped with plus agent mouth, flocculating agent formulation tank goes out agent mouth through stainless steel The metering pump and pipeline of material are connect with agent mouth is added.In the present invention, pipe-line mixer be easy to implement neutralizer and flocculant it Between come into full contact with；In addition, carrying out adding agent using the metering pump of stainless steel material, convenient for matching flocculant accurately with neutralizer With the flocculating effect being optimal.

In the present invention, the flocculation deposition apparatus with above structure is the vertical sedimentation basin form of sealing；Contain wadding The neutralizer and flocculant of body are sufficiently mixed through pipe-line mixer, carry out precipitating point into above-mentioned flocculation deposition apparatus through gravity flow From the moisture content that wadding body is concentrated reduces, and alleviates the processing load of subsequent mechanical dehydration device, while the strong brine of Precipitation Hydrolysis reactor can be back to.Since the material in flocculation deposition apparatus is possible to evolution gaseous pollutant, using sealing Form, while exhaust outlet is set at the top of it, gas is led into the progress water seal of strong brine storage tank.In particular, based on separation equipment Maturity and operational simplicity carry out strong brine and wadding body using the flocculation deposition apparatus of above-mentioned vertical sedimentation basin form Separation；Neutralizer through feed inlet enters flocculation deposition apparatus after mixing with flocculant, during cloth tube squeezes into downwards neutralizer Heart pipe, through umbellate form baffle baffling, metal hydroxides wadding body is concentrated to the bottom precipitation of flocculation deposition apparatus；Meanwhile strong brine Enter strong brine storage tank to the top lift of flocculation deposition apparatus, and through annular overflow weir and water outlet gravity flow.It is certain when reaching Sedimentation time, the interface being concentrated between wadding body and strong brine is clear, and strong brine is carried secretly almost without wadding body.

The present inventor's studies have shown that being carried out dehydrating using mechanical dehydration device to concentration wadding body can be significantly reduced Solid slag amount.Solid content in view of concentration wadding body is about 2-3wt%, and contains strong brine, therefore can select stainless steel material Screw pump conveyed.In addition, the moisture in concentration wadding body is based on Free water, thus using conventional plate and frame filter press or Centrifugal dehydrator can get good dehydrating effect.In view of plate and frame filter press is big with land occupation, the processing time is long, cannot be continuous The disadvantages of operation, therefore mechanical dehydration device is preferably centrifugal dehydrator, separation factor can be 3000 or so, at this time can Wadding body will be concentrated and be prepared into the wet solid slag that moisture content is 60-70%.

It can continue to reduce solid slag yield since wet solid slag is dried, and be more advantageous to reuse, therefore this hair Desiccation apparatus is arranged so that the wet solid slag formed through the mechanical dehydration device is dried in bright system.In the present invention In, wet solid slag can be conveyed using screw conveyor；The mode of movement is cleaner, avoids the scaling-off of belt transmission Phenomena such as.

The present inventor's studies have shown that the moisture in above-mentioned wet solid slag is mainly capillary water, no matter using plate and frame filter press Or centrifugal dehydrator is difficult to continue to reduce its moisture content and solid slag yield, and it is more suitable to carry out dehumidifying desiccation using drying mode It closes.Therefore, the desiccation apparatus can use thin layer desiccation machine or low temperature dehumidification desiccation machine, and it is aqueous for capable of drying wet solid slag The solid slag of rate 10-20%.

Thin layer desiccation machine has coupled conduction and radiant drying principle, hot fluid indirect heating manner is generally used, to wet The vaporization rate of moisture is fast in solid slag, however energy consumption and equipment investment are higher；Low temperature dehumidification desiccation machine is former based on convective drying Reason generally directly heats mode using electricity, and the speed for dehumidifying of gasifying is slower than thin layer drying, however equipment investment is low, technique behaviour Make simple.In the case where can use there are waste heat medium (such as steam), it is preferred to use thin layer desiccation machine.Due in solid slag Moisture be mainly the crystallization water, continue to reduce moisture content not only low efficiency and uneconomical.

In addition, the moisture in wet solid slag can be converted into water vapour during removal moisture drying, recycles vapour latent heat and return It uses drying process and is more advantageous to reduction energy consumption.Therefore, system of the invention can also include heat reclaim unit (i.e. condensed water Storage tank), it is used to recycle the condensed water that above-mentioned desiccation apparatus generates；Since the pollutional load for recycling obtained condensed water is low, because This can be back to the preparation of external source lye and flocculant.

It is understood that system of the invention is other than including aforementioned body component, it can also include other mating Component, for example, it is dead catalyst storage tank, strong brine storage tank, alkali-wash waste water storage tank, external source Alkali liquid compounding tank, flocculating agent formulation tank, solidifying Storage tank, sump oil storage tank and various for conveying pump and conveyer of material etc. are born water, the routine of this field can be used Device or component, and can be configured in a usual manner.

In the present invention, dead catalyst storage tank includes tank body, side-feeding mixer is equipped in tank interior, in tank wall Lower end is equipped with inlet port and outlet port, is equipped with evacuation port in tank base, is equipped with gas feed in top of the tank；Wherein, side into Formula blender is used to carry out the dead catalyst from different periods homogeneous average, and gas feed is used for dead catalyst storage tank Tank deck inflated with nitrogen is protected, and to avoid the contact with moisture in dead catalyst and air, prevents hydrolysis from exploding.

In the present invention, strong brine storage tank includes tank body and water sealing (sealing water) pipe, water inlet is equipped in tank wall upper end, in tank body Side wall lower ends are equipped with water outlet, are equipped with evacuation port in tank base, are equipped with water seal mouth in top of the tank, water sealing (sealing water) pipe and water seal mouth connect It connects.Strong brine storage tank is set and not only provided space for the storage of intermediate product strong brine, but also provides raw material for hydrolysis, is The key node that whole system intermediate product recycles；Meanwhile hydrolysis reactor, neutralization reaction can also be controlled by water seal The evolution of gaseous pollutant, avoids air pollution in device and flocculation deposition apparatus.

In the present invention, alkali-wash waste water storage tank includes tank body, side-feeding mixer is equipped in tank interior, in tank wall Lower end is equipped with water inlet and water outlet, is equipped with evacuation port in tank base；Wherein, when side-feeding mixer is used for coming from different The alkali-wash waste water of section carries out homogeneous average.

In the present invention, condensation water storage tank includes tank body, water inlet is equipped in tank wall upper end, in tank wall lower end Equipped with condensation water out, evacuation port is equipped in tank base.The storage that condensation water storage tank had both been intermediate product condensed water is arranged to mention For space, and the preparation for external source lye and flocculant provides water source, and it is important to be that whole system intermediate product recycles Node.

Further, system of the invention includes Machinery Diaphragm Pump and centrifugal pump, and the dead catalyst storage tank passes through described Machinery Diaphragm Pump is connect with the feed inlet of the hydrolysis reactor, and the strong brine storage tank passes through the centrifugal pump and the hydrolysis The water inlet of reactor connects, and the oil discharge outlet of the hydrolysis reactor is connect with sump oil storage tank.

Further, system of the invention includes centrifugal pump and metering pump, and the liquid outlet of the hydrolysis reactor passes through institute It states centrifugal pump to connect with the inlet of the neutralization reactor, the alkali-wash waste water storage tank and external source Alkali liquid compounding tank pass through respectively The metering pump is connect with the alkali inlet of the neutralization reactor, the liquid outlet of the neutralization reactor and the pipe-line mixer Connection.

Further, system of the invention includes metering pump, and the condensation water storage tank passes through the metering pump and outer respectively The water inlet connection of the water inlet and flocculating agent formulation tank of source Alkali liquid compounding tank.Condensed water is conveyed using metering pump, convenient for external The concentration of source lye and flocculant is accurately controlled.

In particular, the exhaust outlet of the exhaust outlet of the hydrolysis reactor, the neutralization reactor, the flocculation sedimentation system Water outlet and exhaust outlet pass through pipeline respectively and connect with the water seal mouth of strong brine storage tank.

In addition, the flocculation sedimentation system and mechanical dehydration device have brine outlet, the brine outlet and institute The connection of strong brine storage tank is stated, consequently facilitating carrying out reuse to strong brine.

Using above system of the invention to being handled chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water Method may include steps of:

1) chlorine aluminium acidic ionic liquids dead catalyst is mixed in above-mentioned hydrolysis reactor with strong brine and is hydrolyzed instead It answers, until the residual activity of chlorine aluminium acidic ionic liquids dead catalyst completely eliminates, hydrolysis product is separated, respectively To acidic hydrolysis liquid and the molten oil of acid；

2) the acidic hydrolysis liquid is mixed with the lye comprising alkaline waste water in above-mentioned neutralization reactor in progress and Reaction obtains the neutralizer containing metal hydroxides wadding body until reaction system is alkalescent；

3) neutralizer and flocculant are sufficiently mixed and implement sedimentation separation in above-mentioned flocculation sedimentation system, collected The strong brine on upper layer is back to the hydrolysis, while collecting the concentration wadding body of lower layer；

4) the concentration wadding body is carried out dehydrating using above-mentioned mechanical dehydration device, collects wet solid slag, and will abjection Strong brine be back to the hydrolysis；

5) the wet solid slag is dried using above-mentioned desiccation apparatus, obtains desiccation solid slag.

In step 1), hydrolysis is mainly used for completely disappearing the residual activity of chlorine aluminium acidic ionic liquids dead catalyst It removes；Specifically, when residual activity completely eliminates, for the pH stable of acidic hydrolysis liquid in 2.5-2.8, as hydrolysis is whole Point.In particular, the content of sodium chloride can be 15-22wt% in the strong brine；In addition, the chlorine aluminium acidic ionic liquids are useless The input material volume ratio of catalyst and strong brine can be 1:(50-60).

Research is found: the input material volume ratio of strong brine and dead catalyst is bigger, and the hydrolysis of dead catalyst is milder；When When the input material volume ratio of strong brine and dead catalyst is lower than 50:1, the temperature rise of hydrolysis reaction system becomes obviously, and has hydrogen chloride Acid mist evolution；When the volume ratio that feeds intake of strong brine and dead catalyst is lower than 10:1, starts the carbonization for the molten oil of acid occur and have oil Cigarette generates.In view of strong brine and dead catalyst input material volume ratio it is excessive when required reactor volume it is excessive, therefore can will The input material volume ratio of chlorine aluminium acidic ionic liquids dead catalyst and strong brine is set as 1:(50-60).

In addition, the mass content of sodium chloride is higher in strong brine, the hydrolysis of dead catalyst is milder；However, when dense When the content of sodium chloride is higher than 22wt% in salt water, the excessive concentration of chloride ion in hydrolyzate can be made so as to cause sodium chloride crystallization It is precipitated；When the content of sodium chloride in strong brine is lower than 15wt%, the temperature rise of hydrolysis reaction system becomes obvious.It therefore, can be with 15-22wt% is set by the content of sodium chloride in the strong brine.

Under the above conditions, the heating of entire hydrolysis reaction system is unobvious, and does not occur the molten oil carbon of acid and bright Aobvious acid mist escapes phenomenon, and hydrolysis is more mild.

In step 2), when carrying out neutralization reaction, the concentration of lye is not limited strictly, concentration of lye can be in It carries out being suitable for adjusting with the concentration of sodium chloride in liquid；When alkaline waste water is insufficient for neutralization reaction necessary requirement, can mend External source lye is filled, alkaline waste water and external source alkalinity collectively form the lye that neutralization reaction is carried out to acidic hydrolysis liquid at this time.

Specifically, when the concentration of sodium chloride in neutralizer is lower than 15wt%, the concentration of lye can be increased；Work as neutralizer When the concentration of middle sodium chloride is higher than 22wt%, the concentration of lye can be reduced.The compound concentration of external source lye is not limited strictly It makes, the content of sodium hydroxide can be 25-35wt% in external source lye.

In particular, the air speed of complete mixing flow reactor can be 1-2h^-1；Wherein, when the air speed of complete mixing flow reactor reaches 2h^-1When, acidic hydrolysis liquid complete neutralization, the pH stable of neutralizer is in 8.0-8.5, as neutralization reaction terminal；When air speed increases To 1h^-1When, the yield highest of the metal hydroxides wadding body in neutralizer, the content of metal hydroxides wadding body reaches 2.5- 3wt%.

In step 3), flocculant can use anion-polyacrylamide flocculant, more suitable for metal hydrogen-oxygen The flocculation of compound wadding body.Specifically, the relative molecular weight of anion-polyacrylamide flocculant may range from 600-1800 Ten thousand, it is further 1200-1800 ten thousand；Charge density may range from 10-40%, be further 10-30%.

Further, research is found: when the above-mentioned flocculant of 20g or more being added in neutralizer per ton, the wadding body of formation Coarse closely knit, settling property is good；When the additional amount of flocculant in neutralizer per ton is more than 30g, settling of floccus performance is mentioned It rises less, and uneconomical in cost.Therefore, the dosage of above-mentioned flocculant can be set to neutralizer per ton and flocculation is added Agent 20-30g.

In addition, when the sedimentation separation time reaching 2h, the boundary between wadding body and strong brine is concentrated when implementing sedimentation separation Face is clear, and strong brine is carried secretly almost without wadding body, and concentration wadding body layer accounts for 25% or so of neutralizer volume；The sedimentation separation time is in 3h When above, concentration wadding body layer precipitating is very thorough, only accounts for the 20% of neutralizer volume, and it is dense for reducing to continue growing the sedimentation time Contracting wadding body layer volume is not contributed.Therefore, the time of sedimentation separation can be set to 2-3 hours.

After above-mentioned sedimentation separation, the content of strong brine is about 85-90wt%, metal hydroxide in the concentration wadding body of formation The solid content of object is about 10-15wt%.In addition, a small amount of oil in neutralizer is concentrated in strong brine phase, therefore it is concentrated The oil content of wadding body is very low, more cleans, and is convenient for its subsequent recycling.

In step 4), when being dehydrated using plate compression mode, operating pressure can be 0.45MPa or so；Using When centrifugation is dehydrated, the separation factor of centrifugal dehydration can be 3000 or so.It is formed through above-mentioned dehydration wet solid Slag (i.e. metal hydroxides concentration wadding body) moisture content is 60-70wt% or so.

In step 5), wet solid slag is dried using thin layer drying or low temperature dehumidification drying mode；Through above-mentioned Being dried the desiccation solid slag moisture content formed is 10-20wt%.

System of the invention be for chlorine aluminium acidic ionic liquids dead catalyst and with the characteristic of alkali-wash waste water and propose, Its innoxious and oils resource reclaim that dead catalyst and alkali-wash waste water are realized using hydrolysis reactor and neutralization reactor, and And the minimizing and recycling of metal solid slag are realized using flocculation sedimentation system, mechanical dehydration device and desiccation apparatus；In addition, Recycling for intermediate product is realized using strong brine storage tank and condensation water storage tank.The operational process of whole system is mild, behaviour Make process safety, no new pollution source is high to the rate of recovery of resource, especially recycles containing for the obtained molten W/O of acid and impurity Measure low, the quality height of oil product.

Detailed description of the invention

Fig. 1 is the processing chlorine aluminium acidic ionic liquids dead catalyst of an embodiment of the present invention and the system of alkaline waste water Structural schematic diagram；

Fig. 2 is the structural schematic diagram of the hydrolysis reactor of an embodiment of the present invention；

Fig. 3 is the Section A-A schematic diagram of Fig. 2；

Fig. 4 is the structural schematic diagram of the annular collection tank of the hydrolysis reactor of an embodiment of the present invention；

Fig. 5 is the structural schematic diagram of the water distributor of an embodiment of the present invention；

Fig. 6 is the structural schematic diagram of the distributing device of an embodiment of the present invention；

Fig. 7 is the section B-B schematic diagram of Fig. 6；

Fig. 8 is the structural schematic diagram of the neutralization reactor of an embodiment of the present invention；

Fig. 9 is the structural schematic diagram of the flocculation deposition apparatus of an embodiment of the present invention.

Description of symbols:

1: hydrolysis reactor；11: shell；12: annular collection tank；13: water distributor；14: distributing device；15: filler support bracket； 16: exhaust outlet；17: oil discharge outlet；18: water inlet；19: feed inlet；110: liquid outlet；111: overflow weir；112: packing layer；

2: neutralization reactor；21: shell；22: water distributor；23: distributing device；24: side-feeding mixer；25: exhaust outlet； 26: alkali inlet；27: inlet；28: liquid outlet；

3: flocculation deposition apparatus；31: seal casinghousing；32: annular overflow weir；33: central tube；34: cloth tube；35: umbellate form Baffle；36: exhaust outlet；37: water outlet；38: feed inlet；39: slag notch；

4: mechanical dehydration device；5: desiccation apparatus；

61: dead catalyst storage tank；611: gas feed；62: strong brine storage tank；63: alkali-wash waste water storage tank；64: external source alkali Liquid preparing tank；65: flocculating agent formulation tank；66: condensation water storage tank；67: sump oil storage tank；

71: Machinery Diaphragm Pump；72,77: centrifugal pump；73,74,75,76: metering pump；78: screw pump；

8: pipe-line mixer；9: screw conveyor；10: feed bin；

101: cloth supply mains；102: water distribution branch pipe；

201: cloth general pipeline；202: cloth branch pipe；203: cloth hole.

Specific embodiment

To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing of the invention and implementation Example, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.

In conjunction with shown in Fig. 1 to Fig. 9, processing chlorine aluminium acidic ionic liquids dead catalyst of the invention and alkaline waste water are System, including hydrolysis reactor 1, neutralization reactor 2, flocculation sedimentation system, mechanical dehydration device 4 and desiccation apparatus 5；Hydrolysis Device 1, which is used to mix chlorine aluminium acidic ionic liquids dead catalyst with strong brine, carries out hydrolysis；Neutralization reactor 2 and hydrolysis are anti- Device 1 is answered to connect, the acidic hydrolysis liquid for generating hydrolysis is mixed with the lye comprising alkaline waste water carries out neutralization reaction； Flocculation sedimentation system is connect with neutralization reactor 2, and the neutralizer for generating neutralization reaction and flocculant are sufficiently mixed simultaneously in fact Apply sedimentation separation；Mechanical dehydration device 4 is connect with flocculation sedimentation system, for carrying out to the concentration wadding body formed through sedimentation separation Dehydration；Desiccation apparatus 5 is connect with mechanical dehydration device 4, for place to be dried to the wet solid slag formed through dehydration Reason.

System of the invention is by being respectively set hydrolysis reactor 1 and neutralization reactor 2, thus being urged using lye useless Before agent carries out neutralization reaction, first chlorine aluminium acidic ionic liquids dead catalyst is mixed in hydrolysis reactor 1 with strong brine Reaction is hydrolyzed；In hydrolysis reactor 1, a large amount of strong brine can be by hydrolysis in the hydrolytic process of dead catalyst The hot rapid dispersion generated, so that the autoacceleration mechanism of hydrolysis be interrupted；Meanwhile the chloride ion of strong brine middle and high concentration increases The concentration for having added hydrolysate has certain inhibiting effect to hydrolysis.Aforesaid way can not only leniently be eliminated useless The activity of catalyst, while neutralization reaction heat can be eliminated to the facilitation of hydrolysis reaction, make the operation of whole system Process is more stable and safe.

The structure of each component of present system is described in detail below.

1, hydrolysis reactor

In one embodiment, hydrolysis reactor 1 is set as plug flow packed bed reactor, can make hydrolysis more Heating and, to realize mild hydrolysis；At this point, dead catalyst and strong brine are in hydrolysis reactor 1 with the progress of flat-pushing stream mode Contact, the back-mixing degree of material is low, and small to the disturbance of dead catalyst drop, the mass transfer between active component and moisture is weakened, The intensity of hydrolysis is not only reduced, and is conducive to the separation and recycling of the molten oil of acid.

Further, structured packing is filled in plug flow packed bed reactor, which fully utilizes dead catalyst High viscosity characteristic, filler surface behavior of boundary layer and filler to the crown_interception of catalyst；Due to dead catalyst Viscosity is high, inlet amount is small, is in membranaceous Laminar Flow on structured packing surface, and form thicker laminar boundary layer, larger Stickiness power so that the rate of settling of dead catalyst is effectively controlled.Further, since the presence of inner layer of boundary layer laminar sublayer, storeroom Resistance to mass tranfer increase, therefore the mass-transfer efficiency between dead catalyst and strong brine is also effectively controlled.Relative to random packing, The material flow passage of structured packing is uniform, is less prone to channeling.

In particular, unobstructed flow path, and basic retaining layer can be provided by using high-throughput structured packing for strong brine Stream mode, while the mass transfer between dead catalyst can be weakened.When reaction is hydrolyzed, dead catalyst is in the hole of structured packing It being uniformly distributed in gap, the numerous elementary reaction environment of forming quantity, the strong brine of the big scale of construction and the time of contact of dead catalyst are long, To ensure that the thorough hydrolysis to dead catalyst.Specifically, the porosity of structured packing is 0.95-0.97m³/m³, specific surface Product is in 300-500m²/m³；At this point, the rate control of hydrolysis is preferable, neither duct is easily caused to block, while hydrolysis is easy It carries out completely.

In particular, the air speed of above-mentioned plug flow packed bed reactor can be 0.25-0.5h^-1.Wherein, when air speed is 0.5h^-1When, dead catalyst is able to complete hydrolysis, and pH value can be stablized in 2.5-2.8；When air speed is 0.25h^-1When, acidic hydrolysis The oil content of liquid is minimum, and the molten oil of the acid recycled is at most.

In conjunction with shown in Fig. 2 to Fig. 4, hydrolysis reactor 1 includes shell 11, is successively arranged from top to bottom on the top of shell 11 Annular collection tank 12, the water distributor 13 for being distributed strong brine and the cloth for being distributed chlorine aluminium acidic ionic liquids dead catalyst Device 14, is equipped with the filler support bracket 15 for supporting filler in the lower part of shell 11, is equipped with exhaust outlet 16 at the top of shell 11, It is equipped with oil discharge outlet 17, water inlet 18 and feed inlet 19 in the side wall of shell 11, oil discharge outlet 17 is connected to annular collection tank 12, intakes Mouth 18 is connected to water distributor 13, and feed inlet 19 is connected to distributing device 14, is equipped with liquid outlet 110 in the bottom of shell 11.

It is understood that above-mentioned structured packing is seated on filler support bracket 15 (referring to Fig. 3), to form packing layer 112；Further, it is also possible to overflow weir 111 be arranged in the top of annular collection tank 12, to maintain oil reservoir and the molten oil of acid to be made uniformly to overflow Out.

Further, extremely strong in view of the acidity of dead catalyst, and viscosity is up to 600-800mPas, and have containing A small amount of mechanical admixture, to prevent blocking and corrosion, it is preferred to use the Machinery Diaphragm Pump 71 of fluoroplastics material conveys it； In addition, the sodium chloride content in strong brine is up to 15-22wt%, corrosivity is strong, it is preferred to use the centrifugal pump 72 of stainless steel material It is conveyed.

In above-mentioned hydrolysis reactor 1, dead catalyst is mixed with strong brine carries out hydrolysis, and the acid in dead catalyst is molten Property hydrocarbon separated with active component, the molten oil of acid of formation floats up to liquid level, after the collection of annular collection tank 12, then through oil discharge outlet 17 and Its pipeline is from sump oil storage tank 67 is flowed into case freshening (referring to fig. 4).In particular, in above-mentioned hydrolysis reactor 1, by water inlet 18 And water distributor 13 is separately positioned on the top of feed inlet 19 and distributing device 14, not only contributes to strong brine and divides dead catalyst It dissipates, and it is molten to acid to avoid hydrolysis localized heat release far from the molten oil reservoir of acid for the region that can make dead catalyst that hydrolysis occur The influence of oil quality and the rate of recovery.

In addition, the active component contained in dead catalyst and acid-soluble hydrocarbon can generate the organic dirt of volatility in hydrolytic process Object (VOCs) and hydrogen chloride are contaminated, is enriched at the top of hydrolysis reactor 1, it, can be in water in order to avoid being polluted to air Exhaust outlet 16 is arranged in the top for solving reactor 1, and gas is led to the water seal mouth of strong brine storage tank 62, in strong brine storage tank 62 These gaseous pollutants had both can be absorbed in strong brine, while also can use liquid level and carrying out water seal；Water seal can also be hydrolysis Device 1 provides positive pressure, promotes acidic hydrolysis liquid to the re-absorption of these pollutants.

In the present invention, the structure of the water distributor 13 of hydrolysis reactor 1 and distributing device 14 is not limited strictly, as long as its Strong brine and dead catalyst can be made to be uniformly distributed in hydrolysis reactor 1.

Specifically, as shown in figure 5, in one embodiment, water distributor 13 includes cloth supply mains 101, in cloth supply mains 101 Two sides be respectively equipped with multiple parallel and spaced set water distribution branch pipes 102, be distributed in the bottom of each water distribution branch pipe 102 Multiple water distributing pores (not shown), the total open area of water distributing pore account for 1% or more of 1 sectional area of hydrolysis reactor.At this point, water distributor 13 be fishbone type；Wherein, the spacing between adjacent water distribution branch pipe 102 can be set to 5cm or more, to avoid influencing the molten oil of acid Floating and collect；In addition, the set-up mode to the water distributing pore on water distribution branch pipe 102 does not limit strictly, multiple water distributing pores can With spaced set, and it can set identical for the aperture of multiple water distributing pores.

The perforated area of water distributor 13 with above structure is big, the number of openings is more, consequently facilitating promoting the equal of strong brine Even distribution；Further, since the flow velocity that portals of water distributing pore is small, back-mixing is low, Laminar Flow is formed in hydrolysis reactor 1, is reduced Mass transfer between dead catalyst, and it is smaller to the molten oil reservoir disturbance of acid on hydrolysis liquid level, it is more advantageous to the recycling of the molten oil of acid.

As shown in Figure 6 and Figure 7, in one embodiment, distributing device 14 includes cloth general pipeline 201, cloth general pipeline's 201 Two sides are respectively equipped with multiple concentric and spaced set semicircle cloth branch pipes 202, in each semicircle cloth branch pipe 202 Multiple cloth holes 203 (referring to Fig. 7) are distributed in bottom, and the total open area in cloth hole 203 accounts for 1 sectional area of hydrolysis reactor 2% or more.At this point, distributing device 14 is ring-like；Wherein, the spacing between adjacent cloth branch pipe 202 can be set to 5cm or more, To avoid the floating for influencing the molten oil of acid and collect；In addition, not making to the set-up mode in the cloth hole 203 on cloth branch pipe 202 Stringent limitation, multiple cloth holes 203 can be with spaced set, and can set identical for the aperture in multiple cloth holes 203, The internal diameter in cloth hole 203 for example can be set to 3-5mm.

The perforated area of distributing device 14 with above structure is big, cloth hole number is more, consequently facilitating dead catalyst cloth Uniformly；Further, since the internal diameter in cloth hole 203 is small, dead catalyst is extruded with droplet, is more advantageous to it in strong brine Dispersion.

2, neutralization reactor

Neutralization reactor 2 is used to the acidic hydrolysis liquid that hydrolysis generates mixing progress with the lye comprising alkaline waste water Neutralization reaction；The specific structure of neutralization reactor 2 is not limited strictly, the neutralization reactor of this field routine can be used.

Specifically, neutralization reactor 2 is set as complete mixing flow reactor；As shown in figure 8, neutralization reactor 2 includes shell 21, It is successively arranged the water distributor 22 for being distributed lye and the distributing device for being distributed neutralizer from top to bottom on the top of shell 21 23, it is equipped with side-feeding mixer 24 at the middle part of shell 21, exhaust outlet 25 is equipped at the top of shell 21, in the side wall of shell 21 Equipped with alkali inlet 26 and inlet 27, alkali inlet 26 is connected to water distributor 22, and inlet 27 is connected to distributing device 23, in shell 21 Bottom be equipped with liquid outlet 28.

The alkali inlet 26 of neutralization reactor 2 and water distributor 22 are arranged in the top of inlet 27 and distributing device 23, it can The position for the metal hydroxides wadding body for generating neutralization reaction is lower, to be not easy to plug water distributor 22.In particular, using side Feeding mixer 24 accelerates the mass transfer between acidic hydrolysis liquid and lye and neutralization reaction, while also wadding body can be prevented too early Precipitating is to block liquid outlet 28 and its pipeline.

Preferably, it can be conveyed using acidic hydrolysis liquid of the 77 pairs of height of centrifugal pump containing chlorine of fluoroplastics material；Alkali cleaning Waste water and external source lye height contain chlorine, are high containing alkali, and need accurately to be matched with acidic hydrolysis liquid to reach neutralization, therefore preferably adopt It is conveyed with 73,74 pairs of alkali-wash waste waters of metering pump and external source lye of fluoroplastics material.Further, since acidic hydrolysis liquid and alkali It washes and carries a small amount of oil in waste water, N-process will cause VOCs in the enrichment at 2 top of neutralization reactor；To prevent air dirty Dye can be arranged exhaust outlet 25 at the top of neutralization reactor 2, and gas is led to the water seal mouth of strong brine storage tank 62, dense salt These gaseous pollutants had both can be absorbed in strong brine in water storage tank 62, also can use liquid level and carried out water seal；Water seal can also be Neutralization reactor 2 provides positive pressure, to promote neutralizer to the re-absorption of these pollutants.

The structure of water distributor 22 and distributing device 23 to neutralization reactor 2 does not limit strictly, as long as can make lye It is uniformly distributed in neutralization reactor 2 with acidic hydrolysis liquid, can be used and identical structure in hydrolysis reactor 1.Alkali cleaning Waste water passes through the water distribution in neutralization reactor 2 of water distributor 22 by above-mentioned fishbone type after merging with external source lye, due to water distributor 22 Perforated area is big, the number of openings is more, promote alkali-wash waste water and external source lye being uniformly distributed in neutralization reactor 2；This Outside, acidic hydrolysis liquid matches liquid, the perforated area of the distributing device 23 via above-mentioned ring-like distributing device 23 in neutralization reactor 2 Small, cloth material mouth quantity is few, internal diameter is small, forms local turbulence after liquid out, facilitates the mass transfer between acidic hydrolysis liquid and lye And neutralization reaction.

3, flocculation sedimentation system

Flocculation sedimentation system is used to for neutralizer and flocculant that neutralization reaction generates being sufficiently mixed and implements sedimentation separation； The specific structure of flocculation sedimentation system is not limited strictly, the structure of this field routine can be used.

Specifically, flocculation sedimentation system includes the pipe-line mixer 8 and flocculation deposition apparatus 3 set gradually；Such as Fig. 9 institute Show, flocculation deposition apparatus 3 includes seal casinghousing 31, and annular overflow weir 32, central tube 33 and cloth are equipped with inside seal casinghousing 31 Expects pipe 34, the inside of the centrally disposed pipe 33 of cloth tube 34 are equipped with umbellate form baffle 35 in the bottom of central tube 33, in seal casinghousing 31 top is equipped with exhaust outlet 36, is equipped with water outlet 37 and feed inlet 38, water outlet 37 and annular in the side wall of seal casinghousing 31 Overflow weir 32 is connected to, and feed inlet 38 is connected to cloth tube 34, is equipped with slag notch 39 in the bottom of seal casinghousing 31.

It is understood that the liquid outlet 28 of neutralization reactor 2 is connect with the import of pipe-line mixer 8 by the road, in It is equipped with the connecting line of 2 liquid outlet 28 of reactor and 8 import of pipe-line mixer plus agent mouth, flocculating agent formulation tank 65 goes out agent Metering pump 75 and pipeline of the mouth through stainless steel material are connect with agent mouth is added.In the present invention, pipe-line mixer 8 is easy to implement neutralization Coming into full contact between liquid and flocculant；In addition, carried out plus agent using the metering pump 75 of stainless steel material, convenient for make flocculant with The flocculating effect that neutralizer is accurately matched to be optimal.

Flocculation deposition apparatus 3 with above structure is the vertical sedimentation basin form of sealing；Neutralizer containing wadding body It is sufficiently mixed with flocculant through pipe-line mixer 8, enters above-mentioned flocculation deposition apparatus 3 through gravity flow and carry out precipitation and separation, concentration wadding The moisture content of body reduces, and alleviates the processing load of subsequent mechanical dehydration device 4, while the strong brine of Precipitation can be back to Hydrolysis reactor 1.Since the material in flocculation deposition apparatus 3 is possible to evolution gaseous pollutant, seal form is used, together Gas is led to strong brine storage tank 62 and carries out water seal by the exhaust outlet 36 being arranged at the top of Shi Qi.In particular, based on separation equipment Maturity and operational simplicity carry out strong brine and wadding using the flocculation deposition apparatus 3 of above-mentioned vertical sedimentation basin form The separation of body；Neutralizer through feed inlet 38 enters flocculation deposition apparatus 3 after mixing with flocculant, and cloth tube 34 is downward by neutralizer Central tube 33 is squeezed into, through 35 baffling of umbellate form baffle, metal hydroxides wadding body is concentrated to the bottom precipitation of flocculation deposition apparatus 3； Meanwhile strong brine enters strong brine to the top lift of flocculation deposition apparatus 3, and through annular overflow weir 32 and the gravity flow of water outlet 37 Storage tank 62.When reaching certain sedimentation time, the interface being concentrated between wadding body and strong brine is clear, and strong brine is pressed from both sides almost without wadding body Band.

4, mechanical dehydration device

Mechanical dehydration device 4 is used to be carried out dehydrating concentration wadding body, to significantly reduce solid slag amount；It wads a quilt with cotton in view of concentration The solid content of body is about 2-3wt%, and contains strong brine, therefore it is defeated that the screw pump 78 of stainless steel material can be selected to carry out It send.In addition, the moisture in concentration wadding body is based on Free water, therefore using conventional plate and frame filter press or centrifugal dehydrator Obtain good dehydrating effect.Have the shortcomings that land occupation is big, the processing time is long in view of plate and frame filter press, cannot operate continuously, because This mechanical dehydration device 4 is preferably centrifugal dehydrator, and separation factor can be 3000 or so, at this time can be by the wadding body system of concentration The standby wet solid slag for being 60-70% at moisture content.

5, desiccation apparatus

Desiccation apparatus 5 is for being dried the wet solid slag formed through mechanical dehydration processing, to continue to reduce solid Slag yield, and it is conducive to reuse.Wherein it is possible to be conveyed using screw conveyor 9 to wet solid slag；The mode of movement is more clear It is clean, avoid belt transmission it is scaling-off phenomena such as.

Moisture in above-mentioned wet solid slag is mainly capillary water, no matter is difficult to using plate compression or centrifugal dehydration mode Continue to reduce its moisture content and solid slag yield, carries out dehumidifying desiccation using drying mode and be more suitable for.Therefore, desiccation apparatus 5 can To use thin layer desiccation machine or low temperature dehumidification desiccation machine, wet solid slag can be dried to the solid slag for moisture content 10-20%.

In addition, the moisture in wet solid slag can be converted into water vapour during removal moisture drying, recycles vapour latent heat and return It uses drying process and is more advantageous to reduction energy consumption.Therefore, system of the invention can also include heat reclaim unit (i.e. condensed water Storage tank 6666), it is used to recycle the condensed water that above-mentioned desiccation apparatus 5 generates；Due to recycling the pollutional load of obtained condensed water It is low, therefore the preparation of external source lye and flocculant can be back to.

6, other matching components

It is understood that system of the invention is other than including aforementioned body component, it further include other matching components, Match including dead catalyst storage tank 61, strong brine storage tank 62, alkali-wash waste water storage tank 63, external source Alkali liquid compounding tank 64, flocculant Tank 65 processed, condensation water storage tank 66, sump oil storage tank 67 and it is above-mentioned refer to it is various for conveying pump and conveyer of material etc., Can the conventional equipment or component of this field be used, and can be configured in a usual manner.

Specifically, dead catalyst storage tank 61 includes tank body, side-feeding mixer is equipped in tank interior, under tank wall End is equipped with inlet port and outlet port, is equipped with evacuation port in tank base, is equipped with gas feed 611 in top of the tank；Wherein, side into Formula blender is used to carry out the dead catalyst from different periods homogeneous average, and gas feed 611 is used to store up dead catalyst The tank deck inflated with nitrogen of tank 61 is protected, and to avoid the contact with moisture in dead catalyst and air, prevents hydrolysis from exploding.

Strong brine storage tank 62 includes tank body and water sealing (sealing water) pipe, water inlet is equipped in tank wall upper end, in tank wall lower end Equipped with water outlet, it is equipped with evacuation port in tank base, is equipped with water seal mouth in top of the tank, water sealing (sealing water) pipe is connect with water seal mouth.Setting Strong brine storage tank 62 not only provided space for the storage of intermediate product strong brine, but also provided raw material for hydrolysis, was entire The key node that system intermediate product recycles；Meanwhile by water seal can also control hydrolysis reactor, neutralization reactor with And in flocculation deposition apparatus gaseous pollutant evolution, avoid air pollution.

Alkali-wash waste water storage tank 63 includes tank body, is equipped with side-feeding mixer in tank interior, is equipped in tank wall lower end Water inlet and water outlet are equipped with evacuation port in tank base；Wherein, side-feeding mixer is used for the alkali cleaning from different periods Waste water carries out homogeneous average.

Condensing water storage tank 66 includes tank body, is equipped with water inlet in tank wall upper end, is equipped with condensation in tank wall lower end Water out is equipped with evacuation port in tank base.Storage of the condensation water storage tank 66 both for intermediate product condensed water is set, space is provided, The preparation for external source lye and flocculant provides water source again, is the important node that whole system intermediate product recycles.

Further, dead catalyst storage tank 61 is connect by Machinery Diaphragm Pump 71 with the feed inlet 19 of hydrolysis reactor 1, dense Brine reservoir 62 is connect by centrifugal pump 72 with the water inlet 18 of hydrolysis reactor 1, the oil discharge outlet 17 and sump oil of hydrolysis reactor 1 Storage tank 67 connects.

Further, the liquid outlet 110 of hydrolysis reactor 1 is connected by the inlet 27 of centrifugal pump 77 and neutralization reactor 2 It connects, alkali-wash waste water storage tank 63 and external source Alkali liquid compounding tank 64 pass through the alkali inlet 26 of metering pump 73,74 and neutralization reactor 2 respectively Connection, the liquid outlet 28 of neutralization reactor 2 are connect with the import of pipe-line mixer 8.

Further, the outlet of pipe-line mixer 8 is connect with the feed inlet 38 of flocculation deposition apparatus 3, flocculation deposition apparatus 3 Slag notch 39 connect with the import of mechanical dehydration device 4 by screw pump 78.

Further, the slag-drip opening of mechanical dehydration device 4 is connect with feed bin 10；Feed bin 10 is by screw conveyor 9 and does 5 import connection is set in makeup；In addition, condensation water storage tank 66 is connect with desiccation apparatus 5 to recycle condensed water.Condense water storage tank 66 also It is connect by metering pump 76 with the water inlet of the water inlet of external source Alkali liquid compounding tank 64 and flocculating agent formulation tank 65.

In particular, the water outlet of the exhaust outlet 25, flocculation deposition apparatus of the exhaust outlet 16 of hydrolysis reactor 1, neutralization reactor 2 Mouth 37 and exhaust outlet 36 are connect by pipeline with the water seal mouth of strong brine storage tank 62 respectively.

In addition, flocculation deposition apparatus 3 and mechanical dehydration device 4 have brine outlet, brine outlet and strong brine are stored up Tank 62 connects, consequently facilitating carrying out reuse to strong brine.

Below to the method handled using above system chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water It is described in detail.

By taking yield is 300,000 tons/year of chlorine aluminic acid class compound ion liquid alkyl plant as an example, which was being produced The amount that journey discharges dead catalyst is 2140 tons/year, and it is stand-by that dead catalyst comes together in the storage of dead catalyst storage tank；Meanwhile the device It is 6340 tons/year in the amount of production process discharge alkali-wash waste water.Wherein, the viscosity of chlorine aluminium acidic ionic liquids dead catalyst is about 740mPas, active component are mainly aluminium chloride and copper chloride, and total content accounts for about 85wt%, and other components are acid-soluble hydrocarbon, are contained Amount accounts for about 15wt%；Naoh concentration in alkali-wash waste water is about 12wt%.

One, reagent preparation

Compound concentration is the sodium chloride solution (i.e. strong brine) of 15wt% or so in strong brine storage tank 62, is stored for future use.

Compound concentration is the sodium hydroxide solution (i.e. external source lye) of 30wt% or so, storage in external source Alkali liquid compounding tank 64 It deposits spare.

Compound concentration is the flocculant solution of 0.5wt% or so in flocculating agent formulation tank 65, is stored for future use；Wherein, it wads a quilt with cotton Solidifying agent is anionic polyacrylamide, and relative molecular weight is 15,000,000, charge density 20%.

Mentioned reagent is all made of fresh water (such as tap water) before going into operation and is prepared；After operation, lye and flocculation The preparation of agent uses the condensed water from desiccation apparatus 5, and the preparation of strong brine, which uses, comes from flocculation deposition apparatus 3 and mechanical dehydration The strong brine of device 4.

Two, hydrolysis

The dead catalyst of 255kg/h is promoted through the Machinery Diaphragm Pump 71 of fluoroplastics material, and the strong brine of 12457kg/h is not through The centrifugal pump 72 for steel material of becoming rusty is promoted, and dead catalyst and strong brine respectively enter hydrolysis with by the input material volume ratio of 1:50 Reaction is hydrolyzed in device 1.Hydrolysis carries out in plug flow packed bed reactor, fills in plug flow packed bed reactor There is structured packing, dead catalyst is hydrolyzed with the fluidised form of plug flow in packing layer 112 with strong brine to react；Wherein, regular to fill out Material selects the Y type ripple orifice plate structured packing of polyvinyl chloride material, specific surface area 350m²/m³, porosity 0.95m³/ m³, the air speed control of 1 packing layer 112 of hydrolysis reactor is in 0.25h^-1.PH stable to hydrolysis product 2.6 or so, The residual activity of dead catalyst is completely eliminated.

Sedimentation separation is carried out to hydrolysis product, respectively obtains acidic hydrolysis liquid and the molten oil of acid；Wherein, acidic hydrolysis liquid PH value be 2.6 or so, oil content is about 120mg/L；Meanwhile the molten oil of acid of 40kg/h or so enters sump oil by gravity flow recycling It is stored in storage tank 67.The composition of the molten oil of acid is cyclopentadiene compound, can periodically be sent to delayed coking unit work For raw material recycling.

Three, neutralization reaction

The acidic hydrolysis liquid of 12672kg/h through fluoroplastics material 77 centrifugal pumps promoted, 754kg/h alkali-wash waste water and 251kg/h external source lye is promoted through the metering pump 73,74 of fluoroplastics material, and acidic hydrolysis liquid, alkali-wash waste water and external source lye are pressed The input material volume ratio of 50:3:1, which respectively enters, carries out neutralization reaction in neutralization reactor 2.Neutralization reaction is in complete mixing flow reactor It carries out, acidic hydrolysis liquid, alkali-wash waste water and external source lye carry out quick neutralization reaction with the fluidised form of complete mixing flow；Wherein, it neutralizes The air speed of reactor 2 is controlled in 1h^-1, when the pH value of neutralizer reaches 8.5 or so, acidic hydrolysis liquid complete neutralization neutralizes at this time The oil content of liquid is about 120mg/L, and sodium chloride content is about 20wt%, and aluminium hydroxide/Kocide SD wadding body content is about 2.8wt%.

Four, it flocculates

The flocculant solution of 0.5wt% is added into neutralizer, the mass ratio for controlling neutralizer and flocculant solution is 230:1 (i.e. flocculant dosage is that flocculant 22g or so is added in neutralizer per ton), after being sufficiently mixed in pipe-line mixer 8, Gravity flow, which enters in flocculation deposition apparatus 3, carries out sedimentation separation.

After implementing sedimentation separation 2 hours, concentration wadding body layer volume accounts for 25% left side of volume of material in flocculation deposition apparatus 3 The right side, the strong brine content that wadding body is concentrated is about 90wt%.The 75wt% of volume of material is strong brine, stone in flocculation deposition apparatus 3 Oil content is about 150mg/L, and strong brine is back to hydrolysis reactor 1 from strong brine storage tank 62 is flowed into.

Five, dehydration

Concentration wadding body delivers into centrifugal dehydrator (i.e. mechanical dehydration device 4) through the screw pump 78 of stainless steel material and carries out Dehydration, wherein the separation factor of centrifugal dehydrator is 3000 or so；The moisture content that dehydration generates is the wet of 70wt% or so Solid slag self-unloading enters feed bin 10, and the strong brine oil content isolated from concentration wadding body is 100mg/L, and strong brine flows into dense salt certainly Water storage tank 62 is back to hydrolysis reactor 1.

Six, it is dried

Wet solid slag in feed bin 10 is sent into thin layer desiccation machine (i.e. desiccation apparatus 5) through the screw conveyor 9 of stainless steel material, The moisture content for generating 454kg/h is the solid slag of 15wt%.The content of sodium chloride is about 54.7wt%, hydroxide in the solid slag The content of aluminium is about 22.5wt%, and the content of Kocide SD is about 6.7wt%, and oil content is less than 1wt%, be can be used as general solid Useless factory is utilized as metallurgical raw material.

The condensed water CODcr that thin layer desiccation machine drying process generates is about 500mg/L, hardly oil-containing and salt, gravity flow Into condensation water storage tank 66, it is back to the preparation of lye and flocculant solution.

After above-mentioned processing, the rate of recovery of the molten oil of acid reaches 90% or so in dead catalyst；In addition, being recycled through detecting The moisture content of the molten oil of acid arrived is 1wt% or so, and carbon particle impurity is not detected, and the quality for recycling oil product is high.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims

1. a kind of system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water, which is characterized in that anti-including hydrolyzing Answer device, neutralization reactor, flocculation sedimentation system, mechanical dehydration device and desiccation apparatus；

The neutralization reactor is connect with the hydrolysis reactor, the acidic hydrolysis liquid for generating the hydrolysis and packet Lye mixing containing alkaline waste water carries out neutralization reaction；

The flocculation sedimentation system is connect with the neutralization reactor, neutralizer and flocculation for generating the neutralization reaction Agent is sufficiently mixed and implements sedimentation separation；

The mechanical dehydration device is connect with the flocculation sedimentation system, for the concentration wadding body formed through the sedimentation separation It is carried out dehydrating；

The desiccation apparatus is connect with the mechanical dehydration device, for doing to the wet solid slag formed through the dehydration Dry processing.

2. system according to claim 1, which is characterized in that the hydrolysis reactor is plug flow packed bed reactor, Structured packing is filled in the plug flow packed bed reactor, the porosity of the structured packing is 0.95-0.97m³/m³, Specific surface area is 300-500m²/m³。

3. system according to claim 1, which is characterized in that the hydrolysis reactor includes shell, in the shell Top is successively arranged annular collection tank, the water distributor for being distributed strong brine and from top to bottom for being distributed chlorine aluminic acid class ionic liquid The distributing device of body dead catalyst is equipped with the filler support bracket for supporting filler in the lower part of the shell, in the shell Top is equipped with exhaust outlet, is equipped with oil discharge outlet, water inlet and feed inlet, the oil discharge outlet and the annular in the side wall of the shell Collection tank connection, the water inlet are connected to the water distributor, and the feed inlet is connected to the distributing device, in the shell Bottom is equipped with liquid outlet.

4. system according to claim 1, which is characterized in that the neutralization reactor is complete mixing flow reactor；In described Include shell with reactor, is successively arranged the water distributor for being distributed lye from top to bottom on the top of the shell and is used to divide The distributing device of cloth neutralizer, is equipped with side-feeding mixer at the middle part of the shell, is equipped with exhaust outlet at the top of the shell, It is equipped with alkali inlet and inlet in the side wall of the shell, the alkali inlet is connected to the water distributor, the inlet and institute Distributing device connection is stated, is equipped with liquid outlet in the bottom of the shell.

5. system according to claim 3 or 4, which is characterized in that the water distributor includes cloth supply mains, in the water distribution The two sides of general pipeline are respectively equipped with multiple parallel and spaced set water distribution branch pipes, are distributed in the bottom of each water distribution branch pipe more A water distributing pore, the total open area of water distributing pore account for 1% or more of reactor cross section product.

6. system according to claim 3 or 4, which is characterized in that the distributing device includes cloth general pipeline, in the cloth The two sides of general pipeline are respectively equipped with multiple concentric and spaced set semicircle cloth branch pipes, in each semicircle cloth branch pipe Multiple cloth holes are distributed in bottom, and the total open area in cloth hole accounts for 2% or more of reactor cross section product.

7. system according to claim 1, which is characterized in that the flocculation sedimentation system includes that the pipeline set gradually mixes Clutch and flocculation deposition apparatus, the flocculation deposition apparatus include seal casinghousing, and annular is equipped with inside the seal casinghousing and is overflow The inside of the central tube is arranged in stream weir, central tube and cloth tube, the cloth tube, is equipped with umbrella in the bottom of the central tube Type baffle is equipped with exhaust outlet at the top of the seal casinghousing, is equipped with water outlet and feed inlet in the side wall of the seal casinghousing, The water outlet is connected to the annular overflow weir, and the feed inlet is connected to the cloth tube, at the bottom of the seal casinghousing Portion is equipped with slag notch.

8. according to system described in claim 3,4 or 7, which is characterized in that further include strong brine storage tank, stored up in the strong brine The top of tank is equipped with water seal mouth, and the exhaust outlet is connect by pipeline with the water seal mouth of the strong brine storage tank.

9. system according to claim 1, which is characterized in that the desiccation apparatus is that thin layer desiccation machine or low temperature dehumidification are dry Change machine.

10. system according to claim 8, which is characterized in that the flocculation sedimentation system and mechanical dehydration device have Brine outlet, the brine outlet are connect with the strong brine storage tank.