Background technology
Usually contain platinum (Pt), rhodium (Rh), three kinds of noble metals of palladium (Pd) in the automobile catalyst of scrapping, platinum group metal content more than 0.15% (w/w), is the highest platinum group metal secondary resource of content generally.Conventional with chloroazotic acid high-temperature process automobile catalyst, the recovery rate of platinum and rhodium is respectively less than 60% and 45%.Mainly use in the world at present plasma high-temperature stove (1800 ℃) with the catalyst carrier cordierite fusing slag making of load platinum group metal, from alloy phase, the platinum group metal of enrichment is extracted with aqua regia dissolution.The noble metal recovery rate of this process is at 90-95%, but energy consumption is large, and step is many, and equipment requirement is high.At the chloridizing unit that is used for extracting useful metal, also use chlorine under middle temperature (25-1100 ℃) condition, to process solid mineral.Adopt chlorine about 600 ℃, to process the automobile catalyst powder in the laboratory, the powder after processing with the watery hydrochloric acid leaching again, platinum, rhodium, palladium recovery rate are all more than 98% in the catalyst.Therefore extract in the abandoned car catalyst with chloridising, reaction temperature is lower about 1200 ℃ than pyrogenic process, but recovery rate is higher than pyrogenic process, and step is simple.Whole chlorination reaction can be carried out in the system of complete closed, can not make chlorine leakage in environment, and environment is not polluted.But pending raw material is to be seated in advance in the reaction tube in the use for laboratory chloridising, changes raw material after the processing again and carries out the next group processing, can not carry out continuously, and inefficiency is unfavorable for commercial Application.Similar approach also is used for the chlorination of refractory gold gold to be extracted, and the chlorination of packet header steel plant tailing dam rare earth elements is extracted, and the chlorination of titanium is extracted in the steel climbing high slag, and the chlorination of the rare precious metals such as the V in the difficult mineral, Ga, Mo, W is extracted.Therefore, it is very wide that chloridising is used, and extracting with chloridising has the valency rare precious metal to have the characteristics of low temperature, efficient, environmental protection in the difficult mineral, meet the development trend of low-carbon economy.
But as mentioned above, the chloridising industrialization is difficult to generally realize that main because chlorination reaction device is difficult to design, chlorination furnace in the past almost all adopts the fluidized bed type chlorination furnace.Such fluidized bed type chlorination furnace has several like this problems: (1) stove shape has determined that some parts of stove must be made by metal, so that machine-shaping, but metal at high temperature is difficult to resist the corrosion of chlorine, cause the fluid bed parts short service life, so how the fluidized bed type chlorination furnace prevent that the high-temperature chlorine gas corrosion from just having become a very thorny difficult problem; (2) many metal chloride fusing points and boiling point are more much lower than corresponding metal oxide, therefore form the chloride of easy bonding when chlorination, and this causes the defluidization phenomenon of fluidized-bed reactor so that the gas distribution grid eyelet of fluid bed easily stops up; (3) fluidized-bed reactor has strict requirement to the mineral solids diameter of particle scope of processing, and diameter of particle often requires to concentrate on a narrow scope, but after the actual mineral fragmentation, particle size distribution range is very wide, causes the waste of many valuable breezes.Be industrialization and the special the present invention of proposition of above three difficult problems of solution who realizes chloridising.
Summary of the invention
The invention provides a kind of continuous chlorination horizontal pipe type device, it not only can carry out under middle temperature (25-1100 ℃) condition, can realize environmental friendliness, and withstand corrosion, can carry out continuously, can realize large-scale continuous industry production, avoid some intrinsic weakness of fluidized bed chlorination reactor: (1) parts are easily by chlorine corrosion, and service life is short; (2) the gas distribution grid eyelet of fluid bed easily stops up; (3) can not process the mineral powder that some density are too small or excessive or granularity is inhomogeneous.This device has kept making that the fluidized bed chlorination reactor has breeze has been kicked up in reactor, the advantage of " boiling " simultaneously, and this is so that this device is also very high to chlorine utilization.This device also can be used for small-scale laboratory research.
Continuous chlorination horizontal pipe type device of the present invention comprises following structure: source of the gas, raw material injector, reaction tube, tube furnace, seal nipple, rotation traction traction device, liftable brace table and product-collecting device, wherein reaction tube is arranged in tube furnace, source of the gas, raw material injector and product-collecting device are communicated with reaction tube is mobile by the seal nipple at reaction tube two ends, be flexible connection between seal nipple and the reaction tube, the rotation traction traction device arranges to make reaction tube to rotate around the axle center and material is kicked up, and the liftable brace table arranges to make reaction tube feed end liftable.
In one embodiment of the invention, the raw material injector can be the spiral injector.
In embodiments of the present invention, continuous chlorination horizontal pipe type device can also comprise following one or more parts: the cooler that is positioned at the reaction tube lower, outer perimeter; Be arranged in the dust filter unit in product-collecting device and/or product-collecting device downstream; Be positioned at the negative pressure generating device in product-collecting device downstream; Be positioned at the exhaust gas processing device in product-collecting device downstream; Control the electric meter controller of each operation of components; Be positioned at reaction tube tail end De lookout mouth; And anti-leak protection cover.
Negative pressure generating device can comprise gas diverter and air exhauster in one embodiment of the invention.
The inside of reaction tube can have and promotes that when reaction tube rotates material is wherein further kicked up, the structure of " boiling " in another embodiment of the invention.
In one embodiment of the invention, the outside of seal nipple can be equipped with around the protective cover of the anti-chlorine leakage of seal nipple.
Below in conjunction with accompanying drawing, describe a kind of specific embodiment of continuous chlorination horizontal pipe type device of the present invention in detail, but this only is for the purpose of illustrating the invention rather than limits the scope of the invention.Those skilled in the art understand after having read this specification easily, and the present invention can have other specific embodiment or its equivalent embodiments, and these are all in the protection domain of the application's claim.
The specific embodiment
As shown in Figure 1, a kind of specific embodiment of continuous chlorination horizontal pipe type device of the present invention comprises following structure: the pipeline 17 of source of the gas 1, spiral injector 2, reaction tube 3, tube furnace 4, cooler 5, seal nipple 6, rotation traction traction device 7, liftable brace table 8, product-collecting device 9, dust filter unit 10, gas diverter 11, air exhauster 12, exhaust gas processing device 13, electric meter controller 14, Bo Li lookout mouth 15, anti-chlorine leakage protective cover 16, ventilation.
Source of the gas 1 can comprise in chlorine and the following gas one or more: nitrogen, oxygen, hydrogen, carbon monoxide etc.Concrete source of the gas composition depends primarily on material component to be processed, and those skilled in the art select easily according to known chemical reaction knowledge and actual conditions.The effect of source of the gas is to process to reaction tube 3 interior supplies to use gas.
The Rotatable circular mast that the charging hopper and that spiral injector 2 is the contracting taper by a bottom is carved with spiral groove forms.The charging hopper outer surface is equipped with an automatically controlled vibrator.Hopper and cylindrical bar material are 20-100 ℃ of ability chlorine corrosion.The effect of spiral injector is that raw material such as breeze are inputted reaction tube inside continuously, preferably arrives conversion zone.It also can use the injector of other types, as long as can input raw material reaction tube inside.
The effect of reaction tube 3 provides the space of warm chlorination reaction during object element and chlorine occur in raw material such as the breeze.The circular pipe type reactor material is at 25-1100 ℃ of energy resistance to chlorine or chlorine adds simple substance carbon or chlorine adds the carbon monoxide corrosion.Reaction tube for example can be made greater than 99% graphite (C) greater than 99% carborundum (SiC), purity by purity.Certain shape or structure can be made in circular pipe type reaction tube interior section zone, so that raw material such as breeze in the pipe when rotation pipe can further be kicked up under external force, are " boiling " state.This interior shape or structure can be rough inwalls for example, or other forms.The wall thickness of pipe is 2 millimeters at least.
The effect of tube furnace 4 is by heating reaction tube outer surface portion subregion, so that pipe inside, the zone of heating reaches needed chlorination reaction temperature.Tube furnace can be openable up and down, also can be closed type or other types, as long as can hold reaction tube 3.For simplicity, tube furnace is openable up and down but preferably.The tube furnace furnace temperature is the highest to rise to 1400 ℃.
The effect of cooler 5 is by cooling reaction tube outer surface, so that pipe inside, the zone of cooling off reaches needed low temperature.The cooling medium of cooler 5 can be the wind that the fan around tube outer surface blows, and can be the cooling liquid in the cooling tube of tube outer surface, also can be cooling liquid or the gas that is sprayed at tube outer surface, etc.In other embodiments, for example during the reaction tube long enough cooler 5 optional.Cooler 5 can comprise one or more when using.
The effect of seal nipple 6 is that reaction tube and other components bonding part are not leaked, and avoids causing environmental pollution.The material of seal nipple is at 25-300 ℃ of energy resistance to chlorine or chlorine adds simple substance carbon or chlorine adds the carbon monoxide corrosion.Be equipped with around the protective cover of the anti-chlorine leakage of seal nipple the outside of seal nipple 6.
The effect of rotation traction traction device 7 is to make the reaction tube can be along the rotation of the axle center of pipe, also can make reaction tube that downward slippage not occur during horizontal by certain angle at reaction tube.Wherein material rolls, kicks up when reaction tube rotates.Under the effect of rotation traction traction device, the reaction tube rotating speed can be regulated and control continuously, and maximum (top) speed can reach 20 rev/mins.The concrete form of rotation traction traction device 7 can add for rotating band the form of bearing, and those skilled in the art understand other rotation traction traction device forms that can make the reaction tube rotation easily.The number of rotation traction traction device 7 is unrestricted, for example is in the present embodiment 3, but in other embodiments can be for being less than or more than 3.
The effect of liftable brace table 8 is that reaction tube can be tilted upward near an end of spiral injector, can put down again the free lifting of realization response Guan Yiduan after sticking up.The reaction tube feed end is usury entering in raw material slightly.The angle of liftable brace table can be regulated and control continuously, and inclination maximum can reach 15 °.
The effect of product-collecting device 9 is breezes of collecting after chlorination is processed.The use of can connecting of several product-collecting devices.Product-collecting device inner-wall material is 20-150 ℃ of ability chlorine corrosion.
The effect of dust filter unit 10 is only to allow gas pass through, and does not allow dust pass through.The dust filter unit material is 20-150 ℃ of ability chlorine corrosion.It is inner that dust filter unit can be contained in the product-collecting device, and it is outside also can be contained in the product-collecting device, but also two parts all fill, as shown in Figure 1.
The effect of gas diverter 11 is that gas is shunted, make the part chlorine in the tail gas cycle through reaction tube inside, improve the chlorine utilization rate, and drain partial tail gas and make it to enter chlorine gas absorption tower, and make and be negative pressure state in the reaction tube, do not make chlorine leakage in the pipe.The gas diverter material is 20-150 ℃ of ability chlorine corrosion.Gas diverter 11 can have a plurality of.
The effect of air exhauster 12 is that gas is taken away, helps the formation of negative pressure state in the reaction tube.The air exhauster internal material is 20-50 ℃ of ability chlorine corrosion.The protective cover of anti-chlorine leakage can be equipped with in air exhauster 12 outside some position.
The effect of exhaust gas processing device 13 is that the chlorine in absorption and the processing tail gas makes it not to be discharged in the external environment condition.Exhaust gas processing device can be made by plastics alkaline-resisting under the normal temperature, the resistance to chlorine corrosion.Many bigger serface spheres are equipped with in exhaust gas processing device inside, and chlorine and top-down aqueous slkali abundant haptoreaction on sphere in the tail gas from bottom to top is so that chlorine is removed by complete reaction.Exhaust gas processing device can be installed in inside aqueous slkali pH and ORP (oxidation-reduction potential) controller, and it can replenish fresh aqueous slkali automatically according to inner aqueous slkali pH and ORP detected value to inside, remove efficient to guarantee chlorine.And when the researcher can know the inner old alkali absorbent solution of this replacing according to controller pH and ORP detected value.
The effect of electric meter controller 14 is the rotary speed of control spiral sample feeding rod and the vibration frequency of hopper, with the control blanking velocity; The flow velocity of control gas, the amount of the gas that metering process consumes is for cost accounting provides foundation; Control fresh soda solution adds speed, and the aqueous slkali volume that metering process consumes is for cost accounting provides foundation; Control reaction tube inclination angle and reaction tube rotary speed; Control tube furnace heating-up temperature; Detection system each several part temperature and pressure; The electric weight that metering process consumes is for cost accounting provides foundation.
The effect of Bo Li lookout mouthfuls 15 be can observation tube under the cooperation of projector light in other situation in material movement situation and the pipe.Lookout mouth 15 also can be made with other transparent materials.
The almost totally enclosed anti-chlorine leakage protective cover 16 of top with exhausting also has been installed in the specific embodiment of apparatus of the present invention shown in Figure 1, and it all covers on parts shown in Figure 1 wherein.The effect of anti-chlorine leakage protective cover 16 is just in case chlorine is arranged from these cover inner parts to external leakage; also can in time be taken away and be entered chlorine gas absorption tower; thereby can not pollute surrounding environment, in any case so that whole factory can not produce staff's intoxication accident yet yet.
The pipeline 17 of all ventilations is all by making at the material that adds simple substance carbon or chlorine less than 100 ℃ of energy resistance to chlorine or chlorine and add the carbon monoxide corrosion.
As mentioned above, this paper illustrates the present invention with a specific embodiment of apparatus of the present invention shown in Figure 1, but is not limited to this embodiment.For example, the position that source of the gas enters reaction tube can not be to enter from feed end, its flow direction even can be opposite with feedstock direction; Whole system also can be under the certain pressure; Etc..
Embodiment
The following examples are used for the use of this device of explanation.
With pack into the hopper of spiral injector 2 of 120kg breeze, the hopper lid is simply buckled sealing.Open computer control 14 programs, open two air exhausters 12 from computer control screen dialog interface, by certain distribution ratio adjustments of gas part flow arrangement 11, so that be negative pressure state in the reaction tube 3, pass into the nitrogen (N of 10L/min in the reaction tube
2), reaction tube is rotated by 1 rev/min speed, give diamond heating, after reaching 620 ℃, tube furnace 4 temperature are incubated again 1 hour, make the interior constant temperature zone of pipe reach 600 ℃, reaction tube one end perk is 3 ° of inclination angles, the reaction tube rotating speed is brought up to 6 rev/mins, turn off nitrogen, pass into the chlorine (Cl of 100L/min in the reaction tube
2), by the feed hopper blanking, the vibration frequency that the rotary speed of spiral sample feeding rod is controlled at rank 7 and hopper is controlled at moderate strength behind the 30min.At this moment can Cong Bo Li lookout mouthful 15 projector lights of injecting, see that breeze is violent " boiling " state in the kermesinus thermal treatment zone.1.6 after hour, material all adds, and turns off spiral injector operation, stops reaction tube and rotates, and turns off chlorine, passes into the nitrogen of 100L/min in the reaction tube, after half an hour, opens the hopper lid, inwardly adds the 120kg breeze; Meanwhile, open first product-collecting device 9 outside two spirals, change rapidly a new product-collecting device, turn off nitrogen after this, pass into the chlorine (Cl of 100L/min in the reaction tube
2), behind the 30min, the reaction tube rotating speed is brought up to 6 rev/mins, open again the operation of spiral injector, by the feed hopper blanking, following steps are the same.Way can be processed one ton of sample ore in one day (24 hours meters) like this.
As stopping whole process, can wait all mineral aggregates to enter the product-collecting device after, the reaction tube rotating speed is dropped to 1 rev/min.At this moment the tube furnace stopped heating is turned off chlorine, passes into the nitrogen of 20L/min in the reaction tube.Treat that the tube furnace temperature drops to about 150 ℃, stop reaction tube and rotate, the reaction tube inclination angle is down to 0 °.Open the sample divider lid, take out the breeze after chlorination is processed, treat that the tube furnace temperature drops to about 50 ℃, close two air exhausters, finish.
This is tested used reaction tube and is made by high purity graphite, and 10 meters of pipe overall lengths are spliced by two 5 meters appearance pipe together, and the pipe inside diameter is 40cm, and the pipe outer dia is 50cm.