CN1053413A - Handle the method and apparatus of salt solution and contaminated inorganic salt or its mixture - Google Patents

Abstract

The present invention relates to a kind of device that is used to handle method and this method of enforcement of salt solution and contaminated inorganic salt or its mixture.Method comprises that (a) separates organic constituent from mixture; (b) resulting mixture is carried out vacuum-evaporation; (c) at high temperature heat treatment section exsiccant inorganic salt or its mixture, pure dry inorganic salt or its mixture; (d) condensation makes this steam carry out reverse osmosis by the steam that the vacuum-evaporation step obtains; (e) obtain pure water from reverse osmosis step.Device comprises the organic component equipment of separation, vacuum-evaporation appts, Equipment for Heating Processing, condenser and the equipment that is used for the phlegma reverse-osmosis treated, and the transfer equipment between each parts of this device.

Description

Handle the method and apparatus of salt solution and contaminated inorganic salt or its mixture

The present invention relates to be used to handle the method and apparatus of salt solution and contaminated inorganic salt or its mixture.Specifically, the present invention relates to a kind of method and apparatus, adopt this method and apparatus to remove pollutent from supersaturated brine or contaminated inorganic salt or its mixture, this pollution is before leather is made, use inorganic salt, particularly cause when sodium-chlor preparation and slaking animal hides.For example, this pollutent can be animal excreta and urine, residual blood, skin and meat and hair.

From the animal skin that animal body peels, i.e. so-called " green hide ", seldom tanning immediately after butchering must be delivered to tannery and be processed into leather.Usually to spend several weeks or time several months,, by weight and quality classification, break into bag to collect large quantities of green hides, more respectively from the slaughterhouse or the place of preparation deliver to tannery.Yet because its protein structure, the rawhide of slaking and not tanning still is not in natural hygrometric state, usually can make to cause rotten bacterium and spread, and warm weather is the top condition of bacteriological aftergrowth.For avoiding causing rotten bacterium in green hide vertical spread and regeneration, must be with its slaking.

Though consider from ecology, other ageing method has been proposed, in fact have only with the sodium-chlor slaking to have obtained success.And up to now, have only with the sodium-chlor slaking and can satisfy two required primary conditions of slaking: the first, slaking must reach lasting antibacterial effect, in order to avoid cause rotten bacterium at the green hide vertical spread.The second, must after slaking and standing storage, again green hide be processed into perfect leather, that is, can restore to the original state fully after the slaking.Satisfy this two requirements best with the sodium-chlor slaking.

In detail, method with sodium-chlor slaking green hide is as follows: hide surface is carried out pre-clean processes, spray in the above then and contain common denaturing agent, as naphthalene or similar organic solid sodium chloride, be immersed in green hide saturated or supersaturated brine in reach 24 hours.When rawhide is piled up or build up bag, or solid salt is from partly peeling off with salt, and perhaps saturated or supersaturated brine drips from rawhide.Past usually directly enters limbers passage with the solid that obtains or dissolved salt or enters in the environment, and this can cause the sodium-chlor severe contamination lake and the river of high density.

In addition, respectively with before the rawhide tanning or being processed into leather, ripening salt is dissolved in the water that soaks rawhide.The water that this step stays contains the salt of high density, also enters in the limbers passage or flows directly in the river, and this also can make, and salt concn increases greatly in the natural water.

Its another shortcoming of traditional treatment method that rawhide slaking meeting obtains a large amount of salt is that the sodium-chlor price is more and more expensive, can not recycle.Therefore, the expense of purchase inorganic salt all is added on the price of ripe animal skin.Among the similar Deutsches Reichs-Patent application P3835418.7 that on October 17th, 1988 submitted to a kind of method and apparatus has been described respectively, to be used to handle contaminated inorganic salt or its mixture.Be described in this patent application in the heatable container, contaminated inorganic salt or its mixture of handling be heated to more than 350 ℃ continuously or intermittently, at least for 4 minutes.The gas and the steam that produce in the heat-processed are entered atmosphere.This container is preferably an axial cylindrical tube, makes whole length reach the technological temperature of wanting by the heating spiral tube.The described method of this application or install its critical defect and be, can only be substantially free of solid pollutant through pretreated inorganic salt.The organic component that produces in this technology can not separate.And, use this device that certain danger is arranged, because sedimentary salt deposit thickens day by day on the Heated container inwall, so that heat passage more and more difficult.Along with the increase of salt layer thickness, can hinder and final the prevention in gas and the salt penetration container.Other known method of the prior art carries out under low treatment temp, and resulting salt still contains the bacterium that produces owing to low temperature.

The present invention seeks to overcome respectively the shortcoming of said apparatus or method.New device of the present invention provides can be avoided because of deposition causes the equipment that blocks, and can avoid salt solution and inorganic salt circulation and purification process equipment continue or periodical operation in the efficient reduction.

For reducing environmental pollution and reducing cost, it would also be desirable to provide a kind of method and apparatus, it can not only make the water desalination that obtains in the rawhide treating processes, and can handle salt solution and inorganic salt or its mixture that contains pollutent, to remove pollutent, be used further to curing process.

Another object of the present invention provides particle diameter and is suitable for the pourable granulated salt that the user needs.

Another object of the present invention is to handle contaminated inorganic salt, makes the product salt that obtains not have bacterium.

At last, a further object of the present invention provides a kind of method that is used to handle salt solution and contaminated inorganic salt or its mixture, and energy-conservation, the simplicity of design of this method can be carried out continuously or intermittently.The product of this method is not only the salt that quality meets customer requirements, and is purity.May be the highest water, it can be introduced in process water or the tap water circulation once more.Present method purpose is the whole handicraft products of high-quality recovery, and can economic these products of repeated use.

Have now found that above-mentioned technical problem can solve with described method of claim 1 (being a kind of method of handling salt solution and contaminated inorganic salt and composition thereof) and the described device of claim 13 (promptly being used to handle the device of salt solution and contaminated inorganic salt and composition thereof).The preferred embodiments of the invention and further develop and derive from independent claim.

The present invention relates to be used to handle the method for salt solution and contaminated inorganic salt and composition thereof, this method comprises the steps:

(a) from process mixture, separate organic component basically,

(b) resulting mixture is carried out the vacuum-evaporation step,

(c) at high temperature heat treatment section exsiccant inorganic salt or its mixture, thus pure exsiccant inorganic salt or its mixture obtained,

(d) condensation is carried out reverse osmosis step from the steam that straight empty evaporation step obtains with said steam, and

(e) obtain pure water from reverse osmosis step.

In addition, the present invention relates to be used to handle the device of salt solution or contaminated inorganic salt or its mixture, this device comprises:

(a) equipment (1) is used for separating organic constituent from process mixture,

(b) equipment (4) is used for vacuum-evaporation, with the dry inorganic salt of part or its mixture,

(c) equipment (5) is used for the dry inorganic salt of the part that obtained by equipment (4) vacuum-evaporation or its mixture is heat-treated.

(d) condenser (7) is used for the damp steam that condensing equipment (4) vacuum-evaporation obtains, and

(e) equipment (9) is used for the resulting phlegma of step (d) is carried out reverse-osmosis treated, and

(f) transfer equipment (12,71,93) the said equipment (1) that is used to separate organic component that is linked in sequence, the equipment (4) that is used for vacuum-evaporation, condenser (7) and the equipment (9) that is used for reverse-osmosis treated, and transfer equipment (41) is connected said vacuum-evaporation appts (4) with the equipment (5) that is used for said salt is heat-treated.

The salt solution that the inventive method is handled is the aqueous solution that contains mineral salt, mainly is sodium-chlor, and it derives from the result of green hide maturation process or the preceding slaking animal skin immersion of tanning.The salts contg of these aqueous solution is lower than the saturation point of this solution under the application conditions.But, also may handle supersaturated brine solution by the inventive method.In view of the object of the invention, inorganic salt can be regarded as the compound of all containing metal positively charged ions and mineral acid acid group.The present invention also comprises the mixture of these class inorganic salt.Best, " inorganic salt " this term is interpreted as the salt that comprises that the green hide maturation process is used.Particularly sodium-chlor belongs to a kind of of those salt; But the present invention is not limited to handle sodium-chlor, or the salt solution of salt mixture or sodium chloride-containing.Though be illustrated with this particularly preferred embodiment.

Be used to handle the method for salt solution, contaminated inorganic salt and composition thereof by the present invention, its first step is separated organic component basically from process mixture.This organic component mainly is the animal residue that stays from slaughtering process, as the residue and the hair of animal excreta and urine, meat and skin.This first step operation is based on said residue, and part contains callable component, its objective is planned reusing, as makes feed.The simplest and economic separation is at heterogeneous system from salt solution or inorganic salt or its mixture respectively, as carrying out in flotation, filtration, decant and the centrifugal system.Method for floating is best suited for this purpose.In the method, salt solution that will be polluted by organic component or inorganic salt or its mixture add in the aqueous flotation system respectively, and with suitable flotation agent, its operating method itself is a known prior art.Flotation agent is FeCL preferably ₃Or diatomite.Temperature is generally 5-25 ℃, and room temperature is best.Because the result that flotation agent works, organic component swims in the surface, and available ordinary method is skimmed it.What stay is oversaturated salts solution sometimes, and it contains undissolved salt part, as the bottom of can not the buoyant solid staying solution.By other preferred embodiment of the present invention, except that with the floating method, also available filtration, decant and centrifugal method.

In the preferred embodiment of present method, contain the slip utilization again more capable of circulation of floating organic component, as make feed.If necessary, can wash to remove flotation agent.Use the known method drying then, and pulverize, be used as fodder additives again.

By second step of the inventive method is will separate the aqueous mixture that stays behind the organic constituent (wherein containing undissolved inorganic salt does can not the buoyant solid to stay the bottom) to deliver to the vacuum-evaporation step, for this reason, preferably this mixture is sent into an encloses container, in autoclave or similar containers, use ordinary method again, be removed as stirring.

In a preferred embodiment of the invention, the vacuum-evaporation of the aqueous solution or mixture is handled and is carried out in pressurized vessel, this container can bear the pressure of this operation, alternative (preferably) controlled with thermostat, said pressurized vessel is cylindrical, there is the gradually bypass of point of taper its lower end, or cone point down.By suitable charge line (being preferably nozzle) aqueous solution or mixture are sent in the container, this moment, its temperature raise and the pressure reduction.By the operation of the outer thermal source of container, liquid fuel or fuel gas are flowed, in the outer cover of automatic temperature regulator so that the pressurized vessel outer wall heats up.This vessel top termination one pipe makes pressurized vessel link to each other with the conventional vacuum pump, to cause vacuum.

Separate the salt that obtains in the vacuum-evaporation process and slowly flow in the container, can be removed off and on or continuously, optionally adopt lock chamber, directly send into subsequent processing.But vacuum-evaporation appts operate continuously under the constant vacuum condition, and salt still continues to discharge, and this shows that the lock chamber that is used for desalination has specific advantage.By the present invention, preferably can obtain bigger salt crystallization, for example its particle diameter is 0.2-0.3mm, the salt crystallization can not taken away with steam flow like this, thereby the liquid phase treatment step of back is had problems.In a particularly preferred embodiment of the inventive method, by the pipeline on the ring nozzle in the container aqueous solution or mixture to be sent in the container, the number of ring nozzle is optional in the container, as is preferably 6-8, and each nozzle is sprayed solution or mixture respectively.This makes water-soluble liquid phase uniform distribution in the container, thereby but consecutive evaporation, this method not only produces the successive vapour stream under the constant vacuum condition, and can form uniform salt crystallization.In certain limit, grain size can be respectively controlled by temperature etc. in jet velocity or spraying pressure, jet size, the container.

The pipeline that the steam that is obtained by evaporation step is drawn by the pressurized vessel top is discharged, and this pipe is connected with vacuum pump or other pump respectively.Cool off this pipe by the cooling system that links to each other with cooling apparatus (be preferably the reinforcement that is contained in the container in the spiral type mode and cool off system).In the ingress (with respect to the pipe lower end of flow of vapor direction), the temperature of cooling system is 8-12 ℃, and in the exit (with respect to the pipe upper end of flow of vapor direction), the temperature of cooling system is 14-32 ℃.Therefore, preferably cool off by adverse current.Owing to strengthen cooling system, be placed in the steam escape pipe to save the spatial mode, steam can reach total condensation.

In another preferred embodiment of the present invention, one or more steam traps are arranged in the outer steam escape pipe of pressure vessel outlet, are preferably in certain distance at turning in the pipe, as inserting in the steam pipeline as simple obstacle.First obstacle is established in the steam escape pipe exit that is preferably in pressurized vessel immediately.Separate the salt crystallization of taking out of herein, fall again to entering pressurized vessel, thereby a large amount of salt that the phlegma of back is not taken out of pollutes by steam.And this steam trap can stop pressure significantly to descend, and like this, it is stable that operation pressure can keep.

In steam escape pipe lower end, phlegma flows in the holder, removes continuously or off and on then.

In a preferred embodiment of the inventive method, at 0.5-10 ^-3Bar is preferably in 10 ^-1-10 ^-2Under the pressure of bar, carry out the vacuum-evaporation step.Technological temperature is 20-50 ℃, and 42-50 ℃ better.With known method, compare as in the container of heating, handling, advantage with the concentrated aqueous mixture of vacuum-evaporation appts is, use the inventive method, on the one hand, can obtain saliniferous steam hardly by energy-saving manner, on the other hand, the water-content of inorganic salt or its mixture obviously reduces, and the highest water-content is 40%, is preferably 25-35%.This equipment or its each parts do not have the danger of obstruction, can not hinder heat passage loss of energy because of salt deposit yet.

In another preferred embodiment of present method, the aqueous mixture of sending into the vacuum-evaporation step carries out preheating with the used heat that these technology other places produce.For example,, make aqueous mixture be heated to 20-50 ℃, be preferably 42-50 ℃, in the vacuum-evaporation process, keep this temperature, necessary vaporization heat promptly is provided with the warm air that salt thermal treatment as described below obtains.The energy-conservation benefit that increases this method.

Under the best circumstances, the dry inorganic salt of the part that obtains or its mixture can be respectively as the products of vacuum-evaporation step, and it almost only contains sodium-chlor, also contains water certainly.But said sodium-chlor can mix mutually with the pollutent that produces in other salt and a small amount of natural or operation, for example, and the muriate of other metal, bromide, sulfonated bodies, carbonate, supercarbonate, phosphoric acid salt, vitriol or other salt.In the next step of the inventive method, at high temperature respectively inorganic salt or its mixture are heat-treated.The high water content of the inorganic salt of heat-treating or its mixture is 40%, is preferably 25-35%.Available common equipment such as travelling belt or screw spreader carry out this step.In a preferred embodiment of the inventive method, use the filler transfer equipment, inorganic salt to be heated or its mixture are sent into rotary tube furnace.For example, this equipment is made of right cylinder, feed nozzle or feeding container are equipped with in its side, filler can be therein manually or machinery move a segment distance (on the flow direction of confession salt), from the side feed nozzle front a bit move to feed nozzle back, said side a bit.Because filler moves in right cylinder, and the feed nozzle is when closing, and a certain amount of salt transmits along the direction of swivel pipe, is added in the pipe that is connected with the filler transfer equipment, and the opening end of this pipe extends to the charging opening of swivel pipe.Then, remove filler.Appropriate device in the pipe as, awl point can prevent the refluence of salt respectively towards the cone of inorganic salt or its mix flow direction.When filler is got back to zero position, open the feed nozzle, thereby can supply with other salt, in case the feed nozzle is closed again, available filler is sent salt into swivel pipe.Transmit if must interrupt for a certain reason, inorganic salt in the transfer equipment or its mixture absorb moisture respectively, when long-term placement can bond together when spending the night, but the advantage of this filler transfer equipment is that the salt that transmits on the tube furnace direction can not stop up charging opening.Even filler transfer equipment of the present invention also can be delivered to swivel pipe with inorganic salt or its mixture without a doubt again after the long-time placement of salt.

In a specific embodiment of present method, the inorganic salt or its mixture that are obtained by the vacuum-evaporation step can mix with other salt of similar consistency, and be promptly so-called from the abraum salt in the operation.The high water content of this abraum salt is 40%, and does not contain unprocessed organic pollutant, as residual excrement or urine, blood, meat, skin and analogue.For example, salt can be added in the storage vessel separately, mix with the salt face that obtains from the vacuum-evaporation step again, send to thermal treatment then, perhaps separate, send to thermal treatment immediately with inorganic salt or its mixture.

By the present invention, the known any method of those of ordinary skills is heat-treated inorganic salt or its mixture respectively in the available prior art, as long as can reach the object of the invention, i.e. and the abacterial inorganic salt of production high purity.And it is consistent with the selection process method of heat-treating in the rotary tube furnace.The Design and Features that it plants rotary tube furnace is known prior art for those of ordinary skills.Advanced thereby be that its diameter of preferred rotary tube furnace is equal to or greater than 450mm, length is equal to or greater than 1500mm.

The speed of rotation of this stove is preferably variable, can adapt with relevant processing condition, for example, the water-content of the inorganic salt of being supplied with, or the feed speed of inorganic salt and the speed of from stove, discharging salt.Preferably 5-20 rev/min of the variation range of speed of rotation.Another preferred embodiment of present method is that the inorganic salt of above-mentioned vacuum drying step or its mixture are supplied with rotary tube furnace, and this stove is downward-sloping along the flow direction of salt, and its inclination angle (α) is 2-10 °, is preferably 3-5 °.So just can control handled salt and flow to the Rotary pipe type outlet of still, this stove adopts the associated process conditions relevant with speed, and expensive device needn't be provided in stove more for this purpose.

By the present invention, also the most handy hot gas charges into rotary tube furnace, to produce higher temperature.These are the gas of oxygen-free gas, by the suitable technique device, as coil for heating or thermal converter, they are heated to required technological temperature, and can mix mutually with oxygen or oxygen containing gaseous mixture.And the used device of the inventive method is filled with combustion gases, preferably is filled with the combustion gases from gas combustion chamber, wherein combustion gases and oxygen or oxygen mixture, and particularly air mixes mutually.By the present invention, the heat treated special optimum condition of the dry inorganic salt of part or its mixture is that the combustion gases from suitable big or small gas burner are charged in the rotary tube furnace, its quantity combusted and this operation adapt, the air capacity of sneaking in the air-flow is for the required amount of oxygen of organic component perfect combustion residual in the inorganic salt, excessive 100-300%, best excessive 200%.By measuring the concentration of oxygen in the waste gas, those of ordinary skills are easy to determine the amount that is applicable to that associated process conditions is required.This just guarantees to remove fully all contained in inorganic salt or its mixture organic components under treatment condition, particularly as the microorganism of bacterium and spore and so on, can not stay residue again, and burning becomes the gas of environmental sound.Therefore, can be owing to incomplete combustion generates coal smoke or toxic gas.

By the present invention, the thermal treatment of inorganic salt or its mixture is at high temperature carried out.Treatment temp is 140-500 ℃, is preferably 300-400 ℃.Usually hottest point can reach this temperature in the vertical stove of gas burner framework, also records this temperature by this place.In preferred temperature range, heat-treat, can guarantee to remain in the organic component perfect combustion in salt or its mixture, can not contain any microorganism again, can not damage green hide during after this again with this salt.In this respect, obviously the method than prior art is good for the inventive method.In addition, resulting salt is tasteless, and non-variegation, promptly is white.

As mentioned above, the hot waste gas of this operation is sent into Equipment for Heating Processing or rotary tube furnace, not only can be respectively applied for preheating inorganic salt or its mixture, and can be used for the used material of other operation of preheating present method.For example, salt solution or inorganic salt or its mixture used of preheating vacuum-evaporation.This is not waste heat can be used for non-technology boundary purpose yet.This can further increase the benefit of the inventive method, especially when cost of energy is high.

When thermal treatment finishes or after this in another preferred embodiment of the inventive method,, respectively inorganic salt or its mixture are worn into the desired particle diameter of user.In the preferred embodiment of present method, particle diameter is＜0.1mm to 0.6mm, is preferably 0.2-0.5mm.Though it is possible that the masher below being arranged in separates levigate,, is preferably in grinding of the place ahead of rotary tube furnace inner salt outlet and grinds salt in the chamber by the present invention.This grinds abrading-ball is housed in the chamber, and those of ordinary skills can select abrading-ball according to processing condition and desired particle diameter.And the sieve that is positioned at outlet the place ahead can prevent that the salt particle or the salt block that leave rotary tube furnace from exceeding the size of wanting.The salt that obtains like this is pourable, can be reused for the slaking green hide without a doubt.

When being substantially devoid of the process mixture of machine component by the vacuum-evaporation step process, except that obtaining inorganic salt or its mixture, also obtain steam, condenser is sent in this steam expansion.At least in present method less preferred embodiments, can not avoid a spot of salt to take out of with steam fully, thereby find this salt in phlegma, this situation is present method inherent.Usually, salts contg is every liter of phlegma 0.1-5 gram, and preferably every liter of phlegma is the 0.5-2 gram.For obtaining in fact pure no salt solution-resulting opposite, in subsequent handling, make phlegma carry out reverse osmosis with prior art.

Preferably control speed, the pressure and temperature of vacuum-evaporation step, so that phlegma can carry out reverse osmosis continuously.But also available another kind of method imports storage vessel with the phlegma of vacuum-evaporation step and the phlegma of subsequent condensation step earlier, then this phlegma is delivered to reverse osmosis step.The third method preferably provides above-mentioned two kinds of steps, and if only because the condensing liquid quantity that obtains is too big, because the cause of capacity can not immediately it be delivered to reverse osmosis step the time, can be put into storage vessel with phlegma.Another advantage of the third method is, but the equipment that is used for reverse osmosis also the short period of time close, for example clean or change film, and can not interrupt whole operation.

Carrying out reverse osmosis step under processing condition, itself is known technology, for example, adds 1-30 crust, preferably 5-20 bar pressure in film one side.The flow velocity that makes phlegma then be the 500-5000 liter/hour, be preferably the 100-1000 liter/hour, its result is favourable in all cases, the pure water that promptly obtains is the thing that sees through of reverse osmosis step.Usually, temperature is 0-30 ℃, is preferably 5-20 ℃.Polymkeric substance semipermeable partition commonly used as, polymeric amide and polysulfones or cellulose acetate matrix material are preferably polymeric amide/polysulfones matrix material, its aperture is 0.5-1nm, is preferably 0.5-0.8nm.

Needn't remove the residue that reverse osmosis step obtains, because it still contains salt, be useful matter therefore.In the preferred embodiment of present method, residue is at high temperature heat-treated, this can carry out in specific operation under specially suitable condition.But, preferably the residue of reverse osmosis step and the heat treated part exsiccant salt face that is used for from the vacuum-evaporation step are merged, two kinds of components are particularly heat-treated in rotary tube furnace together.For this reason, the residue from reverse osmosis step is directly mixed, or send into storage vessel with said salt face, mix, send into Equipment for Heating Processing again with salt face in the container.In another preferred embodiment of present method, make the residue of reverse osmosis step repeat the vacuum-evaporation step.For this reason, this residue is mixed mutually with the process mixture that is substantially devoid of the machine component through flotation, the two is all sent in the vacuum-evaporation appts.

As a result, the salt-free pure water that obtains can be used as the thing that sees through of reverse osmosis step.Perhaps water is used as process water again, perhaps sends into the tap water circulation.By prior art, can not from problematic salt solution, obtain complete salt-free water.

As mentioned above, the inventive method can be carried out continuously or intermittently.Be preferably the successive operation.

Below, with reference to the accompanying drawings, device of the present invention is described in more detail.

Fig. 1 is the schema of the inventive method, simultaneously, also is the peculiar device location figure of device that the present invention is used to handle salt solution, contaminated inorganic salt or its mixture.

Fig. 2 is the longitdinal cross-section diagram of rotary tube furnace 53, the preferred embodiment of its equipment 5 that thermal treatment is used as the part dry salt.

Fig. 3 is the cross-sectional view of rotary tube furnace 53, represents point with " 3 " among Fig. 2.

Fig. 4 is the top view of the flange 54 of rotary tube furnace 53.

Fig. 5 is the cross-sectional view of the preferred vacuum-evaporation appts of the present invention.

Fig. 6 is the cross-sectional view of filler transfer equipment, and this equipment is preferably used in the reinforced of rotary tube furnace.

The device that is used for handling salt solution or contaminated inorganic salt or its mixture comprises: the equipment 1 that is used for separating from process mixture organic component.This equipment is preferably floatation equipment.But it also can comprise strainer, decanting vessel or whizzer.The advantage of floatation equipment is in fact with simple but effective method, need not just can separate organic component from process mixture with complex apparatus.Whizzer also can effectively separate organic component.

In a preferred embodiment, below the equipment 1 that is used to separate organic component, equipment 2 is housed, to be used for dry and to pulverize isolating organic component.Two kinds of equipment (1 and 2) are connected by transfer equipment 12, this transfer equipment can be as, travelling belt, pipeline or analogue.The product that obtains at the drying and the pulverising step of equipment 2 or take out immediately and sell, or become packaged form or as bulk product, or it is sent into hold-up vessel 3 by vent pipe 21 or analogue.

The vacuum-evaporation appts 4 that is used for the dry inorganic salt of part or its mixture is positioned at the below of equipment 1 (separating organic component by managing 13).The pressure vessel that equipment 4 is preferably common, autoclave for example, it comprises movably device, for example stir the device of content, be used to supply with and discharge the device of contained component, device that is used to exert pressure or the like, these devices are essential to reaching this operation purpose.Be used for condensation and be positioned at the below of said vacuum-evaporation appts 4 from the condenser 7 of the expansion steam of equipment 4, the two links to each other by pipeline 71.Condenser commonly known in the art and water cooler all can be used as condenser 7.

In a preferred embodiment of apparatus of the present invention, vacuum-evaporation appts is the pressurized vessel that can keep this operation pressure, and optionally (preferably) this container is cylindrical with thermostat control, there is the gradually sharp bypass of taper its lower end, and perhaps the cone tip down.The aqueous solution or mixture as by nozzle, preferably pass through ring nozzle by suitable charge line, and the suitable charge line outside container is sent into.Thermal source in external container operation is preferably liquid fuel or fuel gas, flows in the automatic temperature regulator outer cover, available it heat this container to technological temperature.The pipe that this container head picks out makes the conventional vacuum pump be connected with this pressurized vessel, thereby cause vacuum in container.

In a preferred embodiment, the gradually nose part of cone lower end or container links to each other with the lock chamber that is used to discharge salt, this lock chamber be used to store the storage vessel of salt or be used to carry the transfer equipment of salt to link to each other.Under constant vacuum condition, vacuum-evaporation appts can operate continuously, and salt still continues to discharge, and Here it is is used to discharge the certain benefits of the lock chamber of salt.

In a particularly preferred embodiment of apparatus of the present invention, by pipeline the aqueous solution or mixture are sent into container one end of ring nozzle in the container, this ring nozzle number is optional, is preferably 6-8, and each nozzle sprays into solution or mixture in the container respectively.Thereby make water-soluble liquid phase uniform distribution in the container, to evaporate continuously, under constant vacuum condition, this can not only produce steam flow continuously, and can also form uniform salt crystallization.

Connect a pipe on the pressurized vessel top, this pipe is connected with one or more vacuum pumps respectively, and this pipe also can be used for discharging the steam that the vacuum-evaporation step is generated.This pipe is equipped with and cools off the cooling system that unit is connected, and in a particularly preferred embodiment, this system preferably strengthens cooling system, and it is with spiral fashion running in pipe.This cooling system ingress (with respect to the pipe lower end of flow of vapor direction) temperature is 8-12 ℃, and its exit (with respect to the pipe upper end of flow of vapor direction) temperature is 14-32 ℃.Therefore, preferably cool off by adverse current.Place in the steam escape pipe to save the spatial mode owing to strengthen cooling system, can make the steam total condensation, and save energy.

In another preferred embodiment of the present invention, one or more steam traps are positioned at the outer steam escape pipe of pressure vessel outlet, are preferably in certain distance at turning in the pipe, as inserting in the steam pipeline as simple obstacle.Be preferably in outer first obstacle of establishing immediately of steam escape pipe outlet of pressurized vessel.Separate the salt crystallization of taking out of herein, fall into pressurized vessel again, thereby a large amount of salt that the phlegma of back is not taken out of pollutes by steam.And this steam trap can stop pressure significantly to descend, and like this, it is stable that technological temperature can keep.

By apparatus of the present invention, the holder of another lock chamber form is housed in steam escape pipe lower end, phlegma flows into this holder, intermittently or continuously discharges then.The advantage of this embodiment is that pressure can keep constant more or less in the vacuum-evaporation appts.Discharge phlegma by lock chamber, can avoid break vacuum condensation, if vacuum breaking can rebulid vacuum with pump owing to vacuum breaking.

The primary element of apparatus of the present invention also comprises equipment 5, to be used for the part dry salt of thermal treatment from vacuum-evaporation appts 4.Though also available miscellaneous equipment commonly known in the art, the equipment 5 that the present invention is used for the heat treatment section dry salt is rotary tube furnace 53 preferably.Fact proved that the most handy diameter is equal to or greater than 450mm, the long rotary tube furnace that is equal to or greater than 1500mm.For example, the diameter of this rotary tube furnace is 450-1200mm, and length is 2000-4000mm.But also available other size.The rotating speed of this rotary tube furnace 53 is preferably 5-20 rev/min.

In a preferred embodiment, the position of rotary tube furnace 53 is downward-sloping, and the flow horizontal plane angle (α) of direction of it and salt is 2-10 °, is preferably 3-5 °, and this makes in the rotary tube furnace needn't just can effectively promote this salt with the device of costliness.But, allow salt along with gravity is sent into the high-temperature zone continuously, arrive outlet through said zone again.

In a further advantageous embodiment, rotary tube furnace 53 is heatable.Use hot gas, the most handy combustion gases heat.For this reason, selected equipment provides a combustion chamber 541, is preferably gas combustion chamber, on the correct position of rotary tube furnace 53, for example on flange 54, the size of the heating efficiency of this combustion chamber and relevant requirements such as stove, to add the flow or the water content of inorganic salt consistent.

At a correct position, for example in flange 54, rotary tube furnace comprises opening or nozzle 542, and gas is passed through.It is oxygen by this gas that the size of this opening or nozzle preferably can make gas, is preferably air, and its amount should excessive 100-300% the required oxygen amount of all residual organic component perfect combustions in inorganic salt, preferably excessive 200%.By measuring the oxygen concn in the waste gas, those of ordinary skills are easy to determine to be adapted to the necessary amount of relevant processing condition.Then, corresponding adjustments of gas feeds the size of mouth 542.Must be noted that in the case, can only produce light gas stream in rotary tube furnace 53, this air-flow provides enough oxygen being used for burning, and discharges contained moisture and waste gas in the salt.But this air-flow can not taken away lighter salt crystallization again.

From the special preferred embodiment of Fig. 2, can know and find out that this rotary tube furnace 53 mainly comprises:

(a) a fixed flange (54), it comprises a combustion unit 541, and a plurality of opening or nozzles 542 that are used for air feed, bearing 543 comprise the sealing-ring 544 of pressure-stabilisation and the chamber 545 that is used to grind and sieve said salt, and this chamber is positioned at the bottom of flange 54;

(b) fixed bottom 56, it is equipped with a plurality of deflated openings 561 that are used for, and also comprises the bearing 562 that pressure sealing circle 563 is housed.

(c) can be around the right cylinder (55) of longitudinal axis rotation, the side 551 of this right cylinder (55) is supported by the bearing 543 of flange 54 and the bearing 562 of this bottom 56, a plurality of actuator blades 552 are fixed in the longitudinal direction, parallel with the longitudinal axis of right cylinder 55, with respect to the side 551 of this right cylinder 55 basically at an angle of 90, the length of sieve grid 553 is consistent with the chamber 545 that is used to grind and sieve salt.

Above-mentioned sealing-ring 544,563 in the bearing 543,562 of rotary tube furnace flange 54 and bottom 56 can be used for the known sealing-ring of this purpose from prior art selects arbitrarily, as long as can protect bearing that salt is passed through.In apparatus of the present invention, the most handy so-called " labyrinth packing circle ".

As mentioned above, rotary tube furnace 53 of the present invention is equipped with chamber 545, by the groove in the flange 54, can be used for grinding and sieving.Grind and sieve exsiccant crystallization in chamber 545 in such a way, the result makes resulting inorganic salt particle diameter can satisfy user's requirement.For this reason, the chamber 545 that is used to grind and sieve preferably includes the equipment that grinds coarse crystallization, and good especially is abrading-ball.The advantage of abrading-ball is, in the rotatablely moving of rotary tube furnace 53, it moves automatically in the chamber 545 that is used for grinding and sieving, thereby can grind coarse crystallization or the broken crystallization that bonds together.Therefore, do not need to grind separately inorganic salt.Corresponding therewith, be used for by the opening of the sieve of levigated salt crystalline grid 553 preferably variablely, regulated by the desired salt particle diameter of user.Particle diameter can not be used the abrading-ball fragmentation again by the crystallization of adjustable opening, until can be by modulated sized opening.

By another preferred embodiment of the present invention, actuator blade 552 in the right cylinder 55 of rotary tube furnace 53, its shape is crooked, and it is 120-150 ° with the angle (γ) of the sense of rotation of relative right cylinder sieve grid 551 1 end rotary tube furnace right cylinders 55, is preferably 135 °.In the case, even preferred, neither be enforceable, actuator blade 552 is curved acute angle, as shown in Figure 3.

By transfer equipment 41, for example pipeline, screw spreader or analogue can directly be connected the equipment 4 that is used for vacuum-evaporation with the equipment 5 that is used for the dry inorganic salt of heat treatment section or its mixture.In a preferred embodiment of the invention, by filler transfer equipment 46 inorganic salt to be heated or its mixture are sent in the rotary tube furnace 53.This equipment 46 can be the right cylinder 461 that feed nozzle or feeding container 462 are equipped with in the side, in right cylinder 461, filler 463 can be manually or machinery move a segment distance (on the flow direction of confession salt), move to the back 1: 465 of this side feed nozzle 462 from the front 1: 464 of this side feed nozzle 462.Because this filler 463 moves in right cylinder 461, and feed nozzle 462 is closed, a certain amount of salt is sent into along the direction of swivel pipe 53.Like this, pending salt is sent in the pipe 47 that links to each other with filler transfer equipment 46, the opening end 472 of pipe 47 extends to the inlet of rotary oven 53.Suitable equipment is housed in the pipe, and as cone 471, its awl point is towards the flow direction of inorganic salt or its mixture, in order to avoid salt blows back into the filler moving area.The advantage of this filler transfer equipment is, the salt that transmits on tube furnace 53 directions can not stop up charging opening, if must interrupt transmit for a certain reason, the inorganic salt in the transfer equipment 46 or its mixture absorb moisture respectively, when long-term placement can bond together when spending the night.Even after the long-term placement of salt, also can again inorganic salt or its mixture be delivered to swivel pipe 53 without a doubt by filler transfer equipment of the present invention.

By another preferred embodiment of the present invention, also can with similar transfer equipment 43 said two equipment 4 be connected with 5 through holder 42.Its advantage is in the case, the salt of supply arrangement 5 also has the inorganic salt in other source except that from the vacuum-evaporation appts 4, as from the so-called abraum salt in the operation, or, add by feeder sleeve 92 and/or 44 from the salt of equipment 4 from the residue of reverse osmosis step.

Be used for heat treated inorganic salt product or discharge and sale by what equipment 5 obtained, or with packaged form or make bulk product, or by vent pipe 51 or analogue it is sent in the holder 6.

Device of the present invention also comprises equipment 9, is used for the reverse osmosis of the phlegma that obtained by condenser 7, can by pipe 71 or by pipe 72 with 82(if insertion holder 8) make equipment 9 directly be connected condenser 7.In addition, (its scope is the 1-30 crust in order apply the required operation pressure of reverse osmosis for equipment 9, be preferably 5-20 crust), optionally pressure pump 81 and 83 is placed the front or the back of said holder 8, when liquid level in this holder 8 reaches trigger pressure pump when the highest or minimum.

Common, commercially available parts or equipment comprise singlely, and the well-known components that independently obtains all can be used as the equipment 9 that reverse osmosis step is used as container, film, the web member that is used for reinforced and discharge etc.For ease of using, be convenient to clean and maintenance, and be convenient to regulate this equipment, this equipment preferably includes parts single, that independently obtain to be suitable for certain needs.

The high purity water that obtains by reverse osmosis equipment 9 can discharge immediately and the water tank of packing in, or send in the holder 10 through vent pipe 93 or analogue.Preferably do not remove residue, but this residue directly introduced vacuum-evaporation appts 4 again, or as mentioned above, be introduced in the holder 42, send into the equipment 5 that is used for the heat treatment section dry salt then by managing 92 by managing 91 from reverse osmosis equipment 9.

All parts of this equipment are made by the material of anti-inorganic salt and its solution corrosion, and for this reason, those of ordinary skills can select many materials, particularly preferably are stainless steel.

Below, by embodiment the present invention is described, but the present invention is not limited to the cycle applications field of the residual sodium-chlor of slaking green hide.

Embodiment

According to analysis, before carrying out the inventive method, the salt that scrapes on centrifugal drying process and the green hide and the sodium-chlor that obtains by slaking, it is composed as follows:

85.0% (weight) NaCL

0.4% (weight) naphthalene and

14.6% (weight) organic residue and moisture

This salt is dark red brown, gives out stench, the smell that excrement is the same.

After adding flotation agent diatomite, the residue of floating 200Kg in the 1000Kg salt solution, dry resulting residue under 60 ℃, and pulverizing then.The 120kg dry powder that obtains is used as feed.

800 liters of salt solution contain 15% sodium-chlor approximately, in vacuum-evaporation appts, at 40 ℃ and 10 ^-1The abraum salt of the severe contamination that bar pressure is obtained this salt solution by the green hide slaking with 426Kg is down handled, the dry sodium-chlor of part (containing 40% moisture) that obtains is like this delivered in the rotary tube furnace continuously, this furnace operating temperature is 350 ℃, (inclination alpha is 2 °, peripheral velocity is 10 rev/mins, diameter is 650mm, and long is 2500mm).Sodium-chlor is 60 minutes by the time of this stove.After the cooling, obtain the pourable white of 498kg, tasteless salt, this salt of analysis revealed is pure sodium chloride (＞99.5%).Its particle diameter is 0.3mm.

Steam expansion and condensation that vacuum-evaporation is obtained are chilled to room temperature with phlegma, and carry out reverse osmosis.With the film (aperture is 0.5nm) of polymeric amide/polysulfones matrix material, be 14 crust at pressure, temperature is 25 ℃, variable flow velocity is 100-1000 liter/hour carry out reverse osmosis.

Salts contg is a 2g NaCl/ liter, produces 60% pure water approximately, does not wherein have to find to have residual salt.

Another experimental result under conditions of similarity is, is 3g NaCl/l for salts contg, can obtain about 52% pure water.

Residue is delivered to the vacuum-evaporation step again.

Claims (23)

1, a kind of method that is used to handle salt solution and contaminated inorganic salt or its mixture, this method comprises the steps:

(a) from process mixture, separate organic component basically,

(b) mixture that obtains is carried out the vacuum-evaporation step,

(c) at high temperature heat treatment section exsiccant inorganic salt or its mixture, thus pure dry inorganic salt or its mixture obtained,

(d) steam that obtains from the vacuum-evaporation step of condensation carries out reverse osmosis step with said steam, and

(e) obtain pure water from reverse osmosis step.

2,, it is characterized by salt solution, inorganic salt and/or its mixture are carried out flotation, decant or centrifugation step to separate organic component, the optionally dry in addition and pulverizing of isolating organic component according to the method for claim 1.

3, according to the method for claim 1 or 2, it is characterized by the temperature of carrying out the vacuum-evaporation step is 20-50 ℃, is preferably 42-50 ℃, and/or pressure is 0.5-10 ^-3Crust is preferably 10 ^-1-10 ^-2Crust.

4,, it is characterized by in rotary tube furnace and heat-treat according to the method for claim 1-3.

5,, it is characterized by in rotating speed is 5-20 rev/min rotary tube furnace and heat-treat according to the method for claim 1-4.

6, according to the method for claim 1-5, it is characterized by in a downward-sloping rotary tube furnace and heat-treat, the flow direction of inorganic salt and the angle of horizontal plane (α) they are 2-10 °, are preferably 3-5 °.

7, according to the method for claim 1-6, it is characterized by and use the filler transfer equipment, inorganic salt or its mixture are sent in the rotary tube furnace.

8, according to the method for claim 4-7, it is characterized by rotary tube furnace and be filled with hot gas, the hot gas that is filled with the burning generation is better, preferably is filled with the hot gas that is produced by the gas burner burning.

9, according to the method for claim 4-8, it is characterized by and be filled with excess air in the rotary tube furnace, with the required air flow meter of residual organic component perfect combustion, air excess 100-300% in the air-flow, best excessive 200%.

10, according to the method for claim 1-9, it is characterized by at 140-500 ℃, be preferably under 300-400 ℃ the temperature and heat-treat.

11, according to the method for claim 1-10, it is characterized by and control the vacuum-evaporation step in such a way, promptly the phlegma that obtains from the vacuum-evaporation step is sent into reverse osmosis step serially or off and on, or sends into reverse osmosis step again by a holder.

12,, it is characterized by this method and undertaken by continuous mode according to the method for claim 1-11.

13, the device that is used to handle salt solution and contaminated inorganic salt and composition thereof comprises:

(a) equipment (1) is used for separating organic constituent from process mixture,

(b) equipment (4) is used for vacuum-evaporation, with the dry inorganic salt of part or its mixture,

(c) equipment (5) is used for the dry inorganic salt of part that equipment 4 vacuum-evaporation are obtained or its mixture is heat-treated,

(d) condenser (7) is used for the damp steam that condensing equipment 4 vacuum-evaporation obtain, and

(e) equipment (9) is used for the resulting phlegma of step (d) is carried out reverse-osmosis treated, and

(f) the be linked in sequence equipment (1) that is used to separate organic component, the equipment (4) that is used for vacuum-evaporation of transfer equipment (12,71,93), condenser (7) and the equipment (9) that is used for reverse-osmosis treated, and transfer equipment (41) is connected vacuum-evaporation appts (4) with the equipment (5) that is used for salt is heat-treated.

14, according to the device of claim 13, it is characterized by the equipment (1) that is used for from the organic component of process mixture separation is floatation equipment, decant machine or whizzer.

15,, comprise also that in addition equipment (2) is to be used for dry and to pulverize isolating organic component according to the device of claim 13 or 14.

16, device according to claim 13-15, it is characterized by vacuum-evaporation appts (4) and be used for the dry inorganic salt of part or its mixture, it comprises a cylindrical vessel (401), its lower end is connected with a cone (402) or reverse taper (402), optionally control the temperature of container (401) with thermostat, this container (401) comprises filling tube (4052), it is connected with ring-type nozzle (405), be used for ejecting container (401) aqueous solution contained inorganic salt or its mixture, one or more lock chamber (403) are arranged at the bottom of this container (401); Be used to remove part exsiccant inorganic salt or its mixture, pipeline (406) is used for removing water vapour from the top of container (401), it comprises one or more steam traps (4061) and refrigerating unit (407), be used for condensed steam, refrigerating unit (407) is connecting tube (406) preferably, one or more lock chamber (408) that are used to remove phlegma, and one or more vacuum pump (409).

17, according to the device of claim 13-16, it is characterized by the equipment (5) that is used for the part dry salt that thermal treatment obtains by the vacuum-evaporation step is a rotary tube furnace (53).

18, according to the device of claim 13-17, it is characterized by the equipment (5) that is used for the heat treatment section dry salt is a rotary tube furnace (53), it heats with hot gas, and is better with the hot gas that burning produces, the hot gas that burning produces in the most handy gas burner.

19,, it is characterized by rotary tube furnace (53) and mainly comprise according to the device of claim 13-18:

(a) a fixed flange (54), it comprises a combustion unit (541), a plurality of opening or nozzles (542) that are used for air feed, bearing (543) comprises the sealing-ring (544) of pressure-stabilisation and the chamber (545) that is used to grind and sieve this salt, this chamber is positioned at the bottom of flange (54);

(b) fixed bottom (56), it is equipped with and a plurality ofly is used for deflated opening (561), and comprises the bearing (562) of the sealing-ring (563) that pressure-stabilisation is housed;

(c) can be around the right cylinder (55) of longitudinal axis rotation, the side (551) of this right cylinder (55), supported by the bearing (543) of flange (54) and the bearing (562) of this bottom (56), a plurality of actuator blades (552) are fixing in the longitudinal direction, parallel with the longitudinal axis of right cylinder (55), be fixed on and at an angle of 90 position basically, the side (551) of this right cylinder (55).The length of sieve grid (553) is consistent with the chamber that is used to grind and sieve this salt (545).

20, according to the device of claim 13-19, also comprise the holder (42) in the pipeline (43) in addition, it is positioned between the equipment (5) of vacuum-evaporation appts (4) and heat treatment section dry salt.

21, according to the device of claim 13-29, also comprise feeder sleeve (44) in addition, be used for abraum salt is sent into other holder (42).

22,, also comprise the feeder sleeve (92) that is positioned between reverse osmosis equipment (9) and the other holder (42) in addition according to the device of claim 13-21.

23, according to the device of claim 13-22, also comprise one or more holders (3,6,10) in addition, be used to store isolating, drying and organic component of pulverizing, pure salt and/or pure water.

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