CN109837395A - A kind of system and method for high-valued comprehensive utilization chromium type high vanadium slag - Google Patents

Abstract

The invention discloses a kind of system and methods of high-valued comprehensive utilization chromium type high vanadium slag.Corresponding gaseous chloride is converted by vanadium, chromium, the iron in chromium type high vanadium slag by recirculating fluidized bed selective chlorination, most of impurity such as manganese, titanium, silicon in vanadium slag is stayed in chloride residue, realizes the separation of valuable element and other impurities.Gaseous chloride, which is gathered dust by high temperature and separates thick chromium trichloride, medium temperature is gathered dust separates thick ferric trichloride, low temperature elution separates thick vanadium oxytrichloride.Thick chromium trichloride stirs to get its aqueous solution by dissolution and sends receipts chromic salts back to.Thick ferric trichloride and chloride residue obtain its oxidizing slag by pyrohydrolysis dechlorination and send ironmaking.Thick vanadium oxytrichloride obtains high purity vanadic anhydride powder by subsiding and purifying-rectification and purification-catalysis oxidation.The present invention realizes the high-valued comprehensive utilization of chromium type high vanadium slag, produces chromium chloride solution and high purity vanadic anhydride powder by an one-step chlorination-multistage recycling method.

Description

A system and method for high-value comprehensive utilization of high-chromium vanadium slag

technical field

The invention belongs to the fields of metallurgy and chemical industry, and particularly relates to a system and method for comprehensively utilizing high-chromium vanadium slag with high value.

Background technique

Vanadium pentoxide is an important metallurgical chemical material. It has been mainly used as an iron-based alloy additive to produce alloy steel. In recent years, with the rapid development of industrial technology, the application ratio of vanadium pentoxide in aviation alloys, energy storage materials, petrochemical catalysts and other fields has gradually increased. In particular, the rapid development of energy storage materials (all-vanadium flow battery electrolyte, lithium vanadate cathode material) and high-performance aviation alloys (vanadium-aluminum-based, vanadium-titanium-based alloys) industries have produced high-quality and high-purity vanadium pentoxide. huge demand. Chromium trichloride is also an important metallurgical chemical product and an important raw material for the synthesis of other chromium salts. It plays an important role in inorganic synthesis and organic synthesis. It is also commonly used as a mordant and catalyst in industry.

High-chromium vanadium slag contains important vanadium resources and chromium resources, which is of great significance for its high-value comprehensive utilization. Vanadium titanomagnetite is the main raw material for the production of vanadium pentoxide. At present, in the industry, vanadium-containing molten iron is obtained by reduction and smelting, and vanadium slag is obtained by further blowing; the vanadium slag is prepared by the process of "sodium roasting-leaching-vanadium precipitation-calcining decomposition" to prepare industrial-grade vanadium pentoxide; industrial-grade vanadium pentoxide Purity is further improved by repeatedly dissolving the precipitate to further remove impurities. But using this process to deal with high-chromium vanadium slag faces many outstanding problems. For example, the vanadium titanomagnetite in the Hongge area of Panzhihua has a higher chromium content, which is equivalent to vanadium. In the process of reducing and smelting Hongge vanadium titanomagnetite, chromium and vanadium enter molten iron together because of their similar properties, and are further blown to obtain high chromium vanadium slag. If the high chromium vanadium slag is treated by the process of "sodium roasting-leaching-vanadium precipitation-calcining decomposition", there are the following two main problems: (1) The recovery rate of vanadium is low. In high-chromium vanadium slag, chromium spinel and vanadium spinel are dissolved together, and chromium spinel is an ore that is more difficult to oxidize and decompose than vanadium spinel. Common vanadium slag extraction methods are used. , the recovery rate of vanadium is very low. (2) The vanadium-chromium liquids are mixed with each other, and the separation is difficult. In order to improve the recovery rate of vanadium, it is necessary to increase the amount of sodium salt during the sodium roasting process, and then leaching. Under such conditions, vanadium and chromium enter the liquid phase at the same time, which is difficult to separate effectively, and produces a large amount of chromium-containing wastewater, polluting the environment. And the sodium roasting process itself also has the following outstanding problems: (1) the process is lengthy, the energy consumption is high, and the production cost is high; (2) the recovery rate of vanadium is low, and the recovery rate from vanadium slag to vanadium oxide products is less than 80%; (3) ) The vanadium extraction residue is difficult to handle, and the sodium roasting introduces a large amount of sodium salts, which limits the direct return of the residue to blast furnace ironmaking; (4) environmental problems are prominent, and the leaching-vanadium precipitation process produces a large amount of Ammonia nitrogen wastewater has a serious impact on the ecological environment.

The vanadium extraction process by chlorination has attracted extensive attention due to its strong chlorination selectivity and easy rectification and purification. Some technicians began to use the chlorination process to treat vanadium slag, and applied for technical patents. For example, Chinese patent CN101709388B discloses a process for separating vanadium by chlorination roasting of vanadium slag. The vanadium slag oxidative roasting material, solid chlorinating agent and carbonaceous reducing agent are mixed in a certain proportion to form pellets, and then sent to a rotary kiln for roasting so that vanadium is chlorinated with chlorine. The form of compound volatilizes out, so as to achieve the purpose of separating and extracting vanadium. This process of using solid chlorinating agent combined with rotary kiln roasting has the problems of low efficiency and unfavorable large-scale operation. Moreover, the process does not involve the method for preparing vanadium pentoxide by vanadium oxychloride, and is not a complete technology for preparing vanadium pentoxide. Chinese patent CN101845552B discloses a method for recovering valuable elements by gradient chlorination of vanadium slag. The vanadium slag, solid salt, and elemental carbon are mixed uniformly, and chlorine gas is introduced into it at different temperatures to sequentially perform the chlorination of vanadium, iron, chromium and silicon. , in order to achieve the purpose of separating and enriching these elements. The process uses both solid chlorinating agent and gas chlorinating agent, and the process is complicated. The gradient chlorination method requires frequent temperature changes, which is not conducive to large-scale continuous production. The process does not involve a method for preparing vanadium pentoxide by vanadium oxychloride or vanadium tetrachloride, and is not a complete technology for preparing vanadium pentoxide. Although the separation of iron and vanadium has been achieved, the separation and high-value utilization of chromium chloride has not yet been achieved. Chinese patent CN103130279B discloses a method for preparing vanadium pentoxide by extracting vanadium pentoxide using vanadium slag and other vanadium-containing substances as raw materials, and chlorinating vanadium-containing substances with carbon (using solid chlorinating agent or gas chlorinating agent) , rectification and purification, liquid phase hydrolysis or ammonium salt precipitation, drying or calcination to prepare vanadium pentoxide. This process only provides a principle process flow of vanadium extraction by chlorination, and does not provide a technical solution with strong practicability for key issues such as selective chlorination of vanadium slag and efficient preparation of vanadium pentoxide from chloride. Moreover, this process of "carbon chlorination-purification-liquid-phase hydrolysis or ammonium salt precipitation-calcination" to prepare vanadium pentoxide was proposed by researchers at Iowa State University as early as the 1960s ( Journal of the Less-Common Metals, 1960, 2:29-35). Chinese patent CN105986126B discloses a system and method for high-efficiency chlorination and extraction of vanadium from vanadium slag. This process adopts the boiling chlorination technology, which presents a great technical advantage over the chlorination of solid chlorinating agents. Moreover, the gas phase hydrolysis process is used to prepare vanadium pentoxide from vanadium oxychloride. Compared with liquid phase hydrolysis or ammonium salt precipitation, the amount of waste water is greatly reduced, showing a significant technical advantage. However, this patent does not involve high-chromium vanadium slag, nor does it provide a separation method for ferrochrome vanadium. The chlorinated flue gas volatilized from the chlorination furnace is directly heat-exchanged without dedusting treatment, which will cause pipeline blockage and seriously affect production. The gas-phase hydrolysis process will generate a large amount of vanadium-containing hydrochloric acid, increasing the environmental protection cost. At the same time, the sensible heat of high temperature chlorinated flue gas is not well utilized.

To sum up, the existing technology for high-chromium vanadium slag still cannot achieve efficient treatment, and there is also a lack of process technology for high-value utilization of vanadium and chromium. Existing chlorination process presents significant technical superiority, but there are still some outstanding problems: (1) preparation of high-purity vanadium pentoxide by vanadium chloride (vanadium oxychloride) lacks efficient and clean technical route, Due to the high solubility of vanadium in hydrochloric acid solution, direct liquid-phase hydrolysis will cause the recovery rate of vanadium to be too low. Although the use of ammonium salt precipitation can improve the precipitation rate of vanadium, it will produce a large amount of ammonia nitrogen wastewater; the process of gas-phase hydrolysis Although it avoids the production of ammonia nitrogen and water separation, it will bring a large amount of vanadium-containing hydrochloric acid, and the environmental problems are prominent; (2) the existing chlorine extraction process of vanadium is mainly aimed at ordinary vanadium slag, and there is no efficient chlorination method for high-chromium type vanadium slag. The extraction technology can realize the high-value utilization of vanadium and chromium at the same time.

Therefore, it is of great significance to develop a new chlorination method for comprehensive utilization of high-chromium vanadium slag through technological innovation. Among them, the recovery and reuse of chlorinated dust, the comprehensive utilization of heat in the whole process, the realization of high-value utilization of vanadium resources and chromium resources, and the solution of the problem of efficiently preparing vanadium pentoxide from vanadium oxychloride are high-chromium vanadium slag chlorination methods. The key to the large-scale application of the process.

SUMMARY OF THE INVENTION

In view of the above problems, the present invention proposes a system and method for high-value comprehensive utilization of high-chromium vanadium slag, so as to realize the recovery and reuse of chlorinated dust, the comprehensive utilization of heat in the whole process, and the high-value utilization of vanadium resources and chromium resources. , Vanadium oxychloride efficiently prepares vanadium pentoxide. In order to achieve these objects, the present invention has adopted the following technical solutions:

The high-value comprehensive utilization system of high-chromium vanadium slag of the present invention is characterized in that it includes a mixing section 1, a chlorination and dust collection section 2, a leaching and sedimentation section 3, a refining section 4, a pulverizing section 5 and a chlorination section. Residue treatment section 6;

The mixing section 1 includes a high-chromium vanadium slag silo 1-1, a high-chromium vanadium slag screw feeder 1-2, a carbon source silo 1-3, a carbon source screw feeder 1-4, and a flow feeder 1-4. Chemical bed mixer 1-5;

The chlorination dust collecting section 2 includes a circulating fluidized bed main body 2-1, a circulating fluidized bed cyclone 2-2, a first-level dust collecting tower 2-3, a second-level dust collecting tower 2-4, and a dust collecting tower Heat exchanger 2-5 and chromium chloride dissolving kettle 2-6;

The rinsing and sedimentation section 3 includes a rinsing tower 3-1, a slurry pump 3-2, a rinsing tower heat exchanger 3-3, a drip catcher 3-4 and a rinsing slurry sedimentation tank 3-5;

The refining section 4 includes a reboiler 4-1, a reboiler heat exchanger 4-2, a rectification tower 4-3, a high-purity vanadium oxychloride condenser 4-4 and a high-purity vanadium oxychloride storage tank 4-5;

The pulverizing section 5 includes a pulverizing reactor 5-1, an ultrapure water vaporizer 5-2, a pulverizing heat exchanger 5-3, a pulverizing soft water storage tank 5-4, a pulverizing circulating water pump 5-5, a high Pure vanadium silo 5-6 and high-purity vanadium screw feeder 5-7;

The chlorinated residue treatment section 6 includes a process water vaporizer 6-1, a hydrolysis dechlorination fluidized bed 6-2, a cyclone separator 6-3 and a bag filter 6-4;

The discharge port of the high chromium type vanadium slag silo 1-1 is connected with the feed port of the high chromium type vanadium slag screw feeder 1-2; the high chromium type vanadium slag screw feeder 1 The discharge port of -2 is connected with the feed port of the fluidized bed mixer 1-5 through a pipeline; the discharge port of the carbon source silo 1-3 is connected with the carbon source screw feeder 1 -4 is connected to the feed port; the discharge port of the carbon source screw feeder 1-4 is connected with the feed port of the fluidized bed mixer 1-5 through a pipeline; the fluidized bed The fluidizing gas inlet of the mixer 1-5 is connected with the nitrogen main pipe; the discharge port of the fluidized bed mixer 1-5 and the feed port of the circulating fluidized bed main body 2-1 are connected through the pipeline. connect;

The air inlet of the circulating fluidized bed main body 2-1 is respectively connected with the nitrogen main pipe, the circulating chlorine gas main pipe and the chlorine gas main pipe; the chlorination flue gas outlet of the circulating fluidized bed main body 2-1 is connected with the circulating fluidized gas main pipe The inlet of the bed cyclone 2-2 is connected through a pipeline; the outlet of the chlorinated residue of the main body of the circulating fluidized bed 2-1 and the inlet of the hydrolysis and dechlorination fluidized bed 6-2 are connected through a pipeline. connection; the slurry inlet at the top of the circulating fluidized bed main body 2-1 is respectively connected with the underflow port of the rinsing slurry settling tank 3-5 and the underflow port of the reboiler 4-1 through pipes; The dust outlet of the circulating fluidized bed cyclone 2-2 is connected with the dust inlet on the side of the circulating fluidized bed main body 2-1 through a pipeline; the gas of the circulating fluidized bed cyclone 2-2 The outlet is connected with the gas inlet of the first-stage dust collecting tower 2-3 through a pipeline; the gas outlet of the first-stage dust collecting tower 2-3 is connected with the gas inlet of the second-stage dust collecting tower 2-4 through a pipeline. connection; the dust outlet of the first-stage dust collecting tower 2-3 is connected with the inlet of the chromium chloride dissolving kettle 2-6 through a pipeline; the process water inlet of the chromium chloride dissolving kettle 2-6 is connected to the The process water main pipe is connected; the solution outlet of the chromium chloride dissolving kettle 2-6 is connected with the solution inlet of the chromium salt recovery unit through pipes; the slurry inlet at the top of the first-stage dust collecting tower 2-3 is respectively connected with The bottom flow port of the leaching slurry sedimentation tank 3-5 and the bottom flow port of the reboiler 4-1 are connected by pipelines; the gas outlet of the secondary dust collecting tower 2-4 is connected to the rinsing tower 3 The gas inlets of -1 are connected through pipes; the discharge ports of the secondary dust collection tower 2-4 are connected with the feed ports of the hydrolysis and dechlorination fluidized bed 6-2 through pipes; the dust collection towers The heat exchanger 2-5 is arranged in the middle of the dust collecting tower 2-4; the hot fluid outlet of the dust collecting tower heat exchanger 2-5 and the heat flow inlet of the reboiler heat exchanger 4-2 pass through pipes The thermal fluid inlet of the dust collecting tower heat exchanger 2-5 is connected with the fluid outlet of the pulverizing circulating water pump 5-5 through a pipeline; the slurry pump 3-2 is arranged in the rinsing The bottom of the tower 3-1; the rinsing tower heat exchanger 3-3 is arranged on the top of the rinsing tower 3-1; the underflow outlet of the rinsing tower 3-1 settles with the rinsing slurry The inlet of groove 3-5 is connected by pipeline; The tail gas outlet of described rinsing tower 3-1 is connected with the gas inlet of described drop catcher 3-4 by pipeline; The gas outlet of described drop catcher 3-4 is connected with The gas inlet of the tail gas treatment system is connected through a pipeline; the liquid outlet of the drip catcher 3-4 is connected with the inlet of the leaching slurry settling tank 3-5 through a pipeline; the rinsing slurry settling tank 3 The supernatant liquid outlet of -5 is connected with the liquid inlet of described rectifying tower 4-3 by pipeline;

The reflux port of the rectification tower 4-3 is connected with the liquid inlet of the reboiler 4-1 through a pipeline; the gas outlet of the reboiler 4-1 is connected to the outlet of the rectification tower 4-3. The air inlets are connected by pipes; the reboiler heat exchanger 4-2 is arranged inside the reboiler 4-1; the hot fluid outlet of the reboiler heat exchanger 4-2 is connected to the The thermal fluid inlets of the powder heat exchanger 5-3 are connected by pipelines; the high-purity vanadium oxychloride gas outlet of the rectifying tower 4-3 and the gas inlet of the high-purity vanadium oxychloride condenser 4-4 Connected through pipelines; the liquid outlet of the high-purity vanadium oxychloride condenser 4-4 is connected with the liquid inlet of the high-purity vanadium oxychloride storage tank 4-5 through pipelines; The liquid outlet of the vanadium storage tank 4-5 is connected with the vanadium oxychloride inlet of the pulverizing reactor 5-1 through a pipeline; the pulverizing heat exchanger 5-3 is arranged in the pulverizing reactor 5 -1 Middle part; the thermal fluid outlet of the pulverizing heat exchanger 5-3 is connected with the thermal fluid inlet of the pulverizing soft water storage tank 5-4 through a pipeline; the thermal fluid of the pulverizing soft water storage tank 5-4 The fluid outlet is connected with the fluid inlet of the pulverizing circulating water pump 5-5 through a pipeline; the tail gas outlet of the pulverizing reactor 5-1 is connected with the chlorine circulation system inlet through a pipeline; the ultrapure water vaporizer 5- The feed port of 2 is respectively connected with the purification oxygen-enriched air main pipe and the ultrapure water main pipe; the air outlet of the ultrapure water vaporizer 5-2 is connected with the air inlet of the pulverizing reactor 5-1 through a pipeline; The discharge port of the pulverizing reactor 5-1 is connected with the feed port of the high-purity vanadium silo 5-6 through a pipeline; the discharge port of the high-purity vanadium silo 5-6 is connected to the The feed ports of the high-purity vanadium screw feeders 5-7 are connected by pipes;

The water inlet of the process water vaporizer 6-1 is connected with the process water main pipe; the air outlet of the process water vaporizer 6-1 is connected with the air inlet of the hydrolysis and dechlorination fluidized bed 6-2 through a pipeline; The air inlet of the hydrolysis and dechlorination fluidized bed 6-2 is connected with the air main pipe at the same time; the fuel inlet of the hydrolysis and dechlorination fluidized bed 6-2 is connected with the fuel main pipe; the hydrolysis and dechlorination fluidized bed is connected with the fuel main pipe; The middle part of 6-2 is provided with a disposal slag discharge port; the tail gas outlet of the hydrolysis and dechlorination fluidized bed 6-2 is connected with the air inlet of the cyclone separator 6-3 through a pipeline; the cyclone separator 6 The gas outlet of -3 is connected with the gas inlet of the bag filter 6-4 through a pipeline; the dust outlet of the cyclone 6-3 is connected with the feed port of the hydrolysis and dechlorination fluidized bed 6-2 Pipes are connected; the dust outlet of the bag filter 6-4 is connected with the air inlet of the cyclone 6-3 through pipes; the tail gas outlet of the bag filter 6-4 is connected to the inlet of the tail gas treatment system. The ports are connected by pipes.

The method for comprehensive utilization of high-chromium vanadium slag based on the high-valued system of the present invention, specifically comprises the following steps:

The high-chromium type vanadium slag in the high-chromium type vanadium slag silo 1-1 enters the fluidized bed mixer 1-5 through the high-chromium type vanadium slag screw feeder 1-2; The carbon source in the carbon source silo 1-3 enters the fluidized bed mixer 1-5 through the carbon source screw feeder 1-4; the carbon content is 5% of the mass of the high-chromium vanadium slag ~25%; under the action of fluidized nitrogen, it is evenly mixed with high-chromium vanadium slag into the main body 2-1 of the circulating fluidized bed; nitrogen from the nitrogen main pipe, chlorine in the circulating chlorine main pipe, chlorine in the chlorine main pipe Enter from the air inlet at the bottom of the main body 2-1 of the circulating fluidized bed; while maintaining the fluidization of the high-chromium type vanadium slag and the carbon source, a chlorination reaction occurs with them; the chlorination operating temperature is 500-1000 ° C; The chlorinated flue gas is recovered by the circulating fluidized bed cyclone 2-2 to recover the unchlorinated vanadium slag powder and then sent to the first-stage dust collector 2-3 for processing; the chlorinated tailings are sent to the hydrolysis dehydration The chlorine fluidized bed 6-2 is dechlorinated; the slurry from the rinsing slurry sedimentation tank 3-5 and the underflow of the reboiler 4-1 flow from the circulating fluidized bed main body 2-1. The top is sprayed to adjust the reaction temperature; the vanadium slag powder recovered by the circulating fluidized bed cyclone 2-2 is returned to the circulating fluidized bed main body 2-1 through the feed leg to continue the reaction; The slurry of the leaching slurry sedimentation tank 3-5 and the underflow of the reboiler 4-1 are sprayed from the top of the first-stage dust collector 2-3 to reduce the temperature of the chlorination flue gas; The gas outlet temperature of the first-stage dust collecting tower 2-3 is 400-700 °C; the chromium trichloride dust recovered by the first-stage dust collecting tower 2-3 is sent to the chromium chloride dissolving kettle 2-6 for configuration three. Chromium chloride solution is used to produce the raw material of chromium salt; the flue gas after separating chromium chloride in the first-level dust collecting tower 2-3 is sent to the second-level dust collecting tower 2-4 to separate the ferric chloride dust; The ferric chloride-rich dust in the secondary dust collector 2-4 is sent to the hydrolysis and dechlorination fluidized bed 6-2 for dechlorination; the dust collector heat exchanger 2-5 is removed from the dust collector The sensible heat of the high-temperature chlorinated flue gas is recovered in the tower 2-4, and heat is provided for the reboiler 4-1 and the pulverizing reactor 5-1 to realize energy saving and consumption reduction; the secondary dust collecting tower 2- The gas outlet temperature of 4 is 300-500°C; the flue gas after the ferric chloride dust is removed from the secondary dust collector 2-4 is sent to the leaching tower 3-1 for leaching;

The rinsing tail gas of the rinsing tower 3-1 is sent to the tail gas treatment system after the droplets are recovered by the drip catcher 3-4; the vanadium oxychloride slurry and the The vanadyl trichloride liquid recovered by the drop catcher 3-4 is sent to the rinsing slurry sedimentation tank 3-5 for sedimentation treatment; In the pulverizing reactor 5-1; the air from the purifying oxygen-enriched air main pipe and the ultrapure water from the ultrapure water main pipe are preheated and vaporized by the ultrapure water vaporizer 5-2 and then sent to the pulverizing reactor In 5-1, a catalytic oxidation reaction occurs with vanadium oxychloride to obtain chlorine-rich flue gas and high-purity vanadium pentoxide; the reaction temperature of the catalytic oxidation process is 120°C to 480°C; the chlorine-rich flue gas is sent to a chlorine gas circulation system; The high-purity vanadium pentoxide is sent to the high-purity vanadium silo 5-6; the process water from the process water main pipe is vaporized by the process water vaporizer 6-1 and sent to the said process water together with the air from the air main pipe. In the hydrolysis and dechlorination fluidized bed 6-2, the fluidization of the chlorinated residue is maintained, and a hydrolysis and dechlorination reaction occurs with it; the fuel from the fuel main pipe is removed from the fuel at the bottom of the hydrolysis and dechlorination fluidized bed 6-2 The inlet enters to provide heat for the reaction; the reaction temperature is 500 ° C ~ 900 ° C; the average residence time of the powder is 30 ~ 80 minutes; the chlorine content of the dechlorination tailings is within 2%; the dechlorination tailings are sent to iron making; The chlorine tail gas is sequentially removed from the dust by the cyclone separator 6-3 and the bag filter 6-4, and then sent to the tail gas treatment system; the dust recovered by the bag filter 6-4 is returned to the cyclone separator 6-3, Enter into the hydrolysis and dechlorination fluidized bed 6-2 together with the dust recovered by the cyclone separator 6-3 to continue the reaction.

Preferably, the mass fraction of vanadium pentoxide in the high chromium type vanadium slag is 8% to 28%, and the mass fraction of chromium oxide is 6% to 16%.

Preferably: the carbon source in the carbon source silos 1-3 refers to one or more of metallurgical coke, petroleum coke, coal powder and the like.

Preferably: in the main body 3-1 of the circulating fluidized bed, the operating gas velocity is 0.04m-4.00m/s, the mole fraction of chlorine in the chlorine-nitrogen mixture entering the air chamber is 15%-100%, and the pentoxide The chlorination rate of vanadium is above 95%, and the chlorination rate of chromium oxide is above 95%.

Preferably: the removal rate of chromium chloride in the first-stage dust collecting tower 2-3 is more than 95%, and the recovered chromium chloride is used as a raw material for producing chromium salt after being prepared with a solution.

Preferably: in the pulverizing reactor 5-1, the steam introduced into the powder is 0.05% to 12% of the mass of the vanadium oxychloride, and the volume fraction of the oxygen content in the clean oxygen-enriched air is 29% to 97%. %, the purity of high-purity vanadium pentoxide is above 99.5%.

The present invention converts vanadium, chromium and iron in high-chromium type vanadium slag into corresponding gaseous chlorides through selective chlorination in a circulating fluidized bed, and leaves most of the impurities such as manganese, titanium and silicon in the vanadium slag in the chlorination. In the residue, the separation of valuable elements and other impurities is achieved. The gaseous chloride is separated by high temperature dust collection to separate crude chromium trichloride, medium temperature dust collection to separate crude ferric chloride, and low temperature leaching to separate crude vanadium oxychloride. Crude chromium trichloride is dissolved and stirred to obtain its aqueous solution and sent to recover chromium salt. The crude ferric chloride and the chlorinated residue are subjected to high temperature hydrolysis and dechlorination to obtain the oxidized residue and sent to iron making. The crude vanadium oxychloride is purified by sedimentation, purified by rectification, and catalytically oxidized to obtain high-purity vanadium pentoxide powder.

Compared with the prior art, the present invention has the following outstanding advantages:

(1) the use of circulating fluidized bed can significantly reduce the overflow of unchlorinated vanadium slag fine powder, and then greatly improve the chlorination efficiency;

(2) The high-chromium vanadium slag and the carbon source are first fully mixed in the fluidized bed mixer according to a predetermined ratio, and then enter the chlorination furnace for reaction, which ensures the consistency of the ratio of the reaction raw materials and the uniformity of mixing, so as to ensure the Achieve efficient and stable chlorination;

(3) adopt the method of one-step chlorination-multi-stage recovery, produce and obtain chromium chloride solution and high-purity vanadium pentoxide powder, and simultaneously realize the recovery and utilization of vanadium resources and chromium resources;

(4) in the present invention, a dust collector heat exchanger is provided for recovering part of the sensible heat of the chlorinated flue gas, and provides heat for the reboiler and the pulverizing reactor, realizes energy saving and consumption reduction, and reduces production costs;

(5) the chlorinated residue in the present invention adopts the hydrolysis dechlorination fluidized bed dechlorination treatment, and the treated tailings can smelt ferrochromium, and realize the comprehensive utilization of tailings;

(6) In the present invention, the catalytic oxidation of vanadium oxychloride is realized by adding a small amount of water to oxygen-enriched air, obtaining high-purity vanadium pentoxide and chlorine-rich tail gas, realizing chlorine recirculation, and greatly reducing production and environmental protection costs.

The present invention utilizes high-chromium type vanadium slag to produce chromium chloride solution and high-purity vanadium pentoxide powder through one-step chlorination-multi-stage recovery process, realizes high-value utilization of vanadium resources and chromium resources, and simultaneously realizes chlorinated smoke Gas sensible heat recovery and chlorine gas recycling have the advantages of high efficiency, low energy consumption, and no pollution.

Description of drawings

Fig. 1 is the configuration schematic diagram of the high-value comprehensive utilization high-chromium type vanadium slag system of the present invention.

Reference number:

1 mixing section;

1-1 High chromium type vanadium slag silo 1-2 High chromium type vanadium slag screw feeder

1-3 Carbon source silo 1-5 Carbon source screw feeder

1-5 fluidized bed mixer;

2 chlorination dust collection section;

2-1 Main body of circulating fluidized bed 2-2 Cyclone separator of circulating fluidized bed

2-3 Level 1 Dust Collector 2-4 Level 2 Dust Collector

2-5 Dust collector heat exchanger 2-6 Chromium chloride dissolving kettle;

3 leaching and sedimentation section;

3-1 Elution tower 3-2 Slurry pump

3-3 Elution tower heat exchanger 3-4 Drop catcher

3-5 Rinse slurry settling tank;

4 Refining section;

4-1 Reboiler 4-2 Reboiler Heat Exchanger

4-3 Rectification tower 4-4 High purity vanadium oxychloride condenser

4-5 high-purity vanadium oxychloride storage tanks;

5 Milling section;

5-1 Pulverizing Reactor 5-2 Ultrapure Water Vaporizer

5-3 Pulverizing Heat Exchanger 5-4 Pulverizing Soft Water Storage Tank

5-5 Pulverizing circulating water pump 5-6 High-purity vanadium silo

5-7 High-purity vanadium screw feeder;

6. Chlorinated residue treatment section;

6-1 Process water vaporizer 6-2 Hydrolysis dechlorination fluidized bed

6-3 Cyclone separator 6-4 Bag filter.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Some, but not all, embodiments of the invention. It should be noted that the embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them. Fig. 1 is a kind of high-value comprehensive utilization system and method schematic diagram of high-chromium vanadium slag of the present invention.

Example 1

With reference to Fig. 1, a high-value comprehensive utilization system of high-chromium vanadium slag used in this embodiment includes a mixing section 1, a chlorination and dust collection section 2, a leaching and sedimentation section 3, a refining section 4, and a pulverizing section. Section 5 and chlorination residue treatment section 6;

The mixing section 1 includes a high-chromium vanadium slag silo 1-1, a high-chromium vanadium slag screw feeder 1-2, a carbon source silo 1-3, a carbon source screw feeder 1-4 and a fluidized bed Mixer 1-5;

The chlorination dust collection section 2 includes a circulating fluidized bed main body 2-1, a circulating fluidized bed cyclone 2-2, a primary dust collecting tower 2-3, a secondary dust collecting tower 2-4, and a dust collecting tower heat exchange device 2-5 and chromium chloride dissolving kettle 2-6;

The rinsing and sedimentation section 3 includes a rinsing tower 3-1, a slurry pump 3-2, a rinsing tower heat exchanger 3-3, a drip catcher 3-4 and a rinsing slurry sedimentation tank 3-5;

The refining section 4 includes a reboiler 4-1, a reboiler heat exchanger 4-2, a rectification tower 4-3, a high-purity vanadium oxychloride condenser 4-4 and a high-purity vanadium oxychloride storage tank 4- 5;

The pulverizing section 5 includes a pulverizing reactor 5-1, an ultrapure water vaporizer 5-2, a pulverizing heat exchanger 5-3, a pulverizing soft water storage tank 5-4, a pulverizing circulating water pump 5-5, a high-purity vanadium Silo 5-6 and high-purity vanadium screw feeder 5-7;

The chlorinated residue treatment section 6 includes a process water vaporizer 6-1, a hydrolysis dechlorination fluidized bed 6-2, a cyclone separator 6-3 and a bag filter 6-4;

The discharge port of the high chromium type vanadium slag silo 1-1 is connected with the feed port of the high chromium type vanadium slag screw feeder 1-2; the discharge port of the high chromium type vanadium slag screw feeder 1-2 It is connected with the feed port of the fluidized bed mixer 1-5 through a pipeline; the discharge port of the carbon source silo 1-3 is connected with the feed port of the carbon source screw feeder 1-4; the carbon source screw The discharge ports of the feeders 1-4 are connected with the feed ports of the fluidized bed mixers 1-5 through pipes; the fluidized gas inlets of the fluidized bed mixers 1-5 are connected with the nitrogen main pipe; The discharge port of the fluidized bed mixer 1-5 is connected with the feed port of the circulating fluidized bed main body 2-1 through a pipeline;

The air inlet of the circulating fluidized bed main body 2-1 is respectively connected with the nitrogen main pipe, the circulating chlorine gas main pipe and the chlorine gas main pipe; the chlorinated flue gas outlet of the circulating fluidized bed main body 2-1 is connected with the circulating fluidized bed cyclone separator 2- The air inlet of 2 is connected through a pipeline; the chlorinated residue outlet of the circulating fluidized bed main body 2-1 is connected with the feed port of the hydrolysis and dechlorination fluidized bed 6-2 through a pipeline; the circulating fluidized bed main body 2-1 The slurry inlet at the top is respectively connected with the bottom flow port of the leaching slurry sedimentation tank 3-5 and the bottom flow port of the reboiler 4-1 through pipes; the dust outlet of the circulating fluidized bed cyclone 2-2 is connected with the circulating flow The dust inlet on the side of the bed main body 2-1 is connected by a pipeline; the gas outlet of the circulating fluidized bed cyclone 2-2 is connected with the gas inlet of the primary dust collecting tower 2-3 by a pipeline; the primary dust collecting The gas outlet of the tower 2-3 is connected with the gas inlet of the secondary dust collecting tower 2-4 through a pipeline; the dust outlet of the primary dust collecting tower 2-3 is connected with the inlet of the chromium chloride dissolving kettle 2-6 through a pipeline ; The process water inlet of the chromium chloride dissolving kettle 2-6 is connected with the process water main pipe; the solution outlet of the chromium chloride dissolving kettle 2-6 is connected with the solution inlet of the chromium salt recovery unit through pipelines; the first-level dust collector 2 The slurry inlet at the top of -3 is respectively connected with the bottom flow port of the leaching slurry sedimentation tank 3-5 and the bottom flow port of the reboiler 4-1 through pipes; the gas outlet of the secondary dust collector 2-4 is connected to the rinsing The gas inlet of the tower 3-1 is connected through a pipeline; the discharge port of the secondary dust collecting tower 2-4 is connected with the feeding port of the hydrolysis and dechlorination fluidized bed 6-2 through a pipeline; the dust collector heat exchanger 2 -5 is arranged in the middle of the dust collection tower 2-4; the heat fluid outlet of the dust collection tower heat exchanger 2-5 is connected with the heat flow inlet of the reboiler heat exchanger 4-2 through a pipeline; the dust collection tower heat exchanger 2 The hot fluid inlet of -5 is connected with the fluid outlet of the pulverizing circulating water pump 5-5 through a pipeline; the slurry pump 3-2 is arranged at the bottom of the rinsing tower 3-1; the rinsing tower heat exchanger 3-3 is arranged in the The top of the rinsing tower 3-1; the bottom flow outlet of the rinsing tower 3-1 is connected with the inlet of the rinsing slurry sedimentation tank 3-5 through a pipeline; the tail gas outlet of the rinsing tower 3-1 is connected with the drop catcher 3-4 The gas inlet of the drip catcher 3-4 is connected with the gas inlet of the tail gas treatment system through the pipeline; the liquid outlet of the drip catcher 3-4 is connected with the inlet of the leaching slurry sedimentation tank 3-5 Connected through pipelines; the supernatant liquid outlet of the leaching slurry sedimentation tank 3-5 is connected with the liquid inlet of the rectification tower 4-3 through pipelines;

The reflux port of the rectification tower 4-3 is connected with the liquid inlet of the reboiler 4-1 through a pipeline; the air outlet of the reboiler 4-1 is connected with the air inlet of the rectification tower 4-3 through a pipeline; The reboiler heat exchanger 4-2 is arranged inside the reboiler 4-1; the hot fluid outlet of the reboiler heat exchanger 4-2 is connected with the hot fluid inlet of the pulverizing heat exchanger 5-3 through a pipeline; The high-purity vanadium oxychloride gas outlet of the rectifying tower 4-3 is connected with the gas inlet of the high-purity vanadium oxychloride condenser 4-4 through a pipeline; the liquid outlet of the high-purity vanadium oxychloride condenser 4-4 is connected to the The liquid inlet of the high-purity vanadium oxychloride storage tank 4-5 is connected through a pipeline; the liquid outlet of the high-purity vanadium oxychloride storage tank 4-5 and the vanadium oxychloride inlet of the pulverizing reactor 5-1 are connected through a pipeline The pulverizing heat exchanger 5-3 is arranged in the middle of the pulverizing reactor 5-1; the thermal fluid outlet of the pulverizing heat exchanger 5-3 is connected to the thermal fluid inlet of the pulverizing soft water storage tank 5-4 through a pipeline. connection; the hot fluid outlet of the pulverizing soft water storage tank 5-4 is connected with the fluid inlet of the pulverizing circulating water pump 5-5 through a pipeline; the tail gas outlet of the pulverizing reactor 5-1 is connected with the chlorine circulation system inlet through a pipeline; The feed port of the ultrapure water vaporizer 5-2 is respectively connected with the purified oxygen-enriched air main pipe and the ultrapure water main pipe; connection; the discharge port of the pulverizing reactor 5-1 is connected with the feed port of the high-purity vanadium silo 5-6 through a pipeline; the discharge port of the high-purity vanadium silo 5-6 is connected with the high-purity vanadium screw feeding The feed ports of machines 5-7 are connected by pipes;

The water inlet of the process water vaporizer 6-1 is connected with the process water main pipe; the gas outlet of the process water vaporizer 6-1 is connected with the air inlet of the hydrolysis and dechlorination fluidized bed 6-2 through a pipeline; the hydrolysis and dechlorination fluidized bed The air inlet of 6-2 is connected with the air main pipe at the same time; the fuel inlet of the hydrolysis and dechlorination fluidized bed 6-2 is connected with the fuel main pipe; the middle part of the hydrolysis and dechlorination fluidized bed 6-2 is provided with a disposal slag discharge port; The tail gas outlet of the hydrolysis dechlorination fluidized bed 6-2 is connected with the air inlet of the cyclone separator 6-3 through a pipeline; the gas outlet of the cyclone separator 6-3 is connected with the gas inlet of the bag filter 6-4 through a pipeline. Connection; the dust outlet of the cyclone 6-3 is connected with the feed port of the hydrolysis and dechlorination fluidized bed 6-2 through a pipeline; the dust outlet of the bag filter 6-4 is connected with the air inlet of the cyclone 6-3 Connected by pipes; the tail gas outlet of the bag filter 6-4 is connected with the air inlet of the tail gas treatment system by pipes.

Example 2

Using the system described in Embodiment 1, this embodiment provides a method for comprehensively utilizing high-chromium vanadium slag with high value, the method comprising the following steps:

The high-chromium type vanadium slag in the high-chromium type vanadium slag silo 1-1 enters the fluidized bed mixer 1-5 through the high-chromium type vanadium slag screw feeder 1-2; the carbon source silo 1-3 The carbon source is fed into the fluidized bed mixer 1-5 through the carbon source screw feeder 1-4; the carbon content is 5% to 25% of the mass of the high-chromium vanadium slag; The high-chromium vanadium slag is mixed evenly and enters into the main body 2-1 of the circulating fluidized bed; nitrogen from the nitrogen main pipe, chlorine gas in the circulating chlorine gas main pipe, and chlorine gas in the chlorine gas main pipe enter from the air inlet at the bottom of the main body 2-1 of the circulating fluidized bed ; While maintaining the fluidization of high-chromium vanadium slag and carbon source, a chlorination reaction occurs with them; the chlorination operating temperature is 500 ~ 1000 ° C; the chlorinated flue gas generated by the reaction is passed through the circulating fluidized bed cyclone separator 2-2 After recovering the unchlorinated vanadium slag powder, it is sent to the primary dust collector 2-3 for treatment; the chlorinated tailings are sent to the hydrolysis and dechlorination fluidized bed 6-2 for dechlorination; The bottom flow of the slurry and reboiler 4-1 is injected from the top of the circulating fluidized bed main body 2-1 to adjust the reaction temperature; the vanadium slag powder recovered by the circulating fluidized bed cyclone 2-2 passes through the feed leg Return to the main body 2-1 of the circulating fluidized bed to continue the reaction; the slurry from the rinsing slurry sedimentation tank 3-5 and the underflow of the reboiler 4-1 are injected from the top of the primary dust collection tower 2-3 , to reduce the temperature of the chlorinated flue gas; the gas outlet temperature of the primary dust collector 2-3 is 400-700 °C; the chromium trichloride dust recovered from the primary dust collector 2-3 is sent to the chromium chloride dissolving kettle 2-6 is equipped with chromium trichloride solution, which is used as the raw material for the production of chromium salts; the flue gas after the separation of chromium chloride in the primary dust collector 2-3 is sent to the secondary dust collector 2-4 to separate the ferric chloride dust ; The rich ferric chloride dust in the secondary dust collecting tower 2-4 is sent to the hydrolysis and dechlorination fluidized bed 6-2 for dechlorination treatment; the dust collecting tower heat exchanger 2-5 recovers high temperature chlorine from the dust collecting tower 2-4 The sensible heat of the flue gas is eliminated, and the heat is provided for the reboiler 4-1 and the pulverizing reactor 5-1 to achieve energy saving and consumption reduction; the gas outlet temperature of the secondary dust collector 2-4 is 300-500 °C; The flue gas after removing the ferric chloride dust from the dust collector 2-4 is sent to the leaching tower 3-1 for leaching;

The rinsing tail gas of the leaching tower 3-1 is sent to the tail gas treatment system after the droplets are recovered by the drip catcher 3-4; the vanadium oxychloride slurry obtained by the leaching of the leaching tower 3-1 and the drip catcher 3-4 are recovered The obtained vanadium oxychloride liquid is sent to the leaching slurry sedimentation tank 3-5 for sedimentation treatment; the obtained supernatant liquid is purified by the rectifying tower 4-3 and passed into the pulverizing reactor 5-1; The air in the air main pipe and the ultrapure water from the ultrapure water main pipe are preheated and vaporized by the ultrapure water vaporizer 5-2 and then sent to the pulverizing reactor 5-1 to undergo catalytic oxidation reaction with vanadium oxychloride to obtain chlorine-rich Flue gas and high-purity vanadium pentoxide; the reaction temperature of the catalytic oxidation process is 120℃～480℃; chlorine-rich flue gas is sent to chlorine gas circulation system; high-purity vanadium pentoxide is sent to high-purity vanadium silo 5-6; from The process water in the process water main pipe is vaporized by the process water vaporizer 6-1 and sent to the hydrolysis and dechlorination fluidized bed 6-2 together with the air from the air main pipe to maintain the fluidization of the chlorinated residue and generate Hydrolysis and dechlorination reaction; the fuel from the fuel main pipe enters from the fuel inlet at the bottom of the hydrolysis and dechlorination fluidized bed 6-2 to provide heat for the reaction; the reaction temperature is 500℃～900℃; the average residence time of the powder is 30～ 80 minutes; the chlorine content of the dechlorination tailings is within 2%; the dechlorination tailings are sent to iron making; the dechlorination tail gas is successively passed through the cyclone separator 6-3 and the bag filter 6-4 to remove dust and then sent to the tail gas treatment system; The dust recovered by the bag filter 6-4 is returned to the cyclone separator 6-3, and enters the hydrolysis and dechlorination fluidized bed 6-2 together with the dust recovered by the cyclone separator 6-3 to continue the reaction.

Example 3

In this embodiment, high-chromium vanadium slag is used as the raw material, wherein the mass fraction of vanadium pentoxide is 8%, and the mass fraction of chromium oxide is 6%. The processing capacity is 400kg/h, and the chromium chloride aqueous solution and high-purity vanadium pentoxide are prepared through processes such as mixing, chlorination in a circulating fluidized bed, grading dust collection, leaching and sedimentation, refining, and pulverizing, and the waste heat is utilized. , Residue treatment to achieve industrial waste energy utilization and residue dechlorination treatment.

In the fluidized bed mixer 1-5, the amount of metallurgical coke added is 5% of the mass of the high-chromium vanadium slag; the chlorination temperature of the circulating fluidized bed is 500°C, and the operating gas velocity of the circulating fluidized bed is 0.04m/ s, the mole fraction of chlorine in the chlorine-nitrogen mixture entering the air chamber is 15%, the chlorination rate of vanadium pentoxide is 95%, and the chlorination rate of chromium oxide is 95%; The removal rate is 95%; the flue gas outlet temperature of the primary dust collector is 400°C; the flue gas outlet temperature of the secondary dust collector is 300°C; in the pulverizing reactor, the water vapor introduced into the catalytic oxidation process is the quality of vanadium oxychloride. 0.05%, the reaction temperature is 120 ℃, the mass fraction of oxygen in the oxygen-enriched air introduced is 29%, the direct yield of vanadium reaches 94%, and the purity of the high-purity vanadium pentoxide product reaches 99.5wt% (2N5); In the hydrolysis and dechlorination fluidized bed, the reaction temperature is 500° C., the residence time of the powder is 30 minutes, and the chlorine content of the dechlorination tailings is 2%.

Example 4

In this example, high-chromium type vanadium slag is used as raw material, wherein the mass fraction of vanadium pentoxide is 28%, the mass fraction of chromium oxide is 16%, and the processing capacity is 500kg/h. After mixing, circulating fluidized bed chlorination , grading dust collection, leaching and sedimentation, refining, pulverizing and other processes to prepare chromium chloride aqueous solution and high-purity vanadium pentoxide, and realize industrial waste energy utilization and residue dechlorination through waste heat utilization and residue treatment.

In the fluidized bed mixer 1-5, the added amount of petroleum coke is 25% of the mass of the high-chromium vanadium slag; the chlorination temperature of the circulating fluidized bed is 1000℃, and the operating gas velocity of the circulating fluidized bed is 4m/s , the chlorination medium used is pure chlorine gas, the chlorination rate of vanadium pentoxide is 98%, the chlorination rate of chromium oxide is 98%; the removal rate of chromium chloride in the primary dust collector is 98%; The flue gas outlet temperature of the dust tower is 700°C; the flue gas outlet temperature of the secondary dust collector is 500°C; in the pulverizing reactor, the steam introduced into the catalytic oxidation process is 12% of the mass of vanadium oxychloride, and the reaction temperature is 480°C. The mass fraction of oxygen in the fed oxygen-enriched air is 97%, the direct yield of vanadium is 96%, and the purity of the high-purity vanadium pentoxide product is 99.95wt% (3N5); in the hydrolysis dechlorination fluidized bed, The reaction temperature was 900° C., the residence time of the powder was 80 minutes, and the chlorine content of the dechlorination tailings was 1%.

Example 5

In this example, high-chromium vanadium slag is used as the raw material, wherein the mass fraction of vanadium pentoxide is 20%, and the mass fraction of chromium oxide is 10%. Chromium chloride aqueous solution and high-purity vanadium pentoxide are prepared by sedimentation, refining, pulverizing and other processes, and industrial waste energy utilization and residue dechlorination treatment are realized through waste heat utilization and residue treatment.

In the fluidized bed mixer 1-5, the amount of pulverized coal added is 15% of the mass of the high-chromium vanadium slag; the chlorination temperature of the circulating fluidized bed is 800°C, and the operating gas velocity of the circulating fluidized bed is 2m/s , the mole fraction of chlorine in the chlorine-nitrogen mixture entering the air chamber is 50%, the chlorination rate of vanadium pentoxide is 97%, and the chlorination rate of chromium oxide is 97%; The removal rate is 97%; the flue gas outlet temperature of the primary dust collector is 600°C; the flue gas outlet temperature of the secondary dust collector is 450°C; in the pulverizing reactor, the water vapor introduced into the catalytic oxidation process is 3% of the mass of vanadium oxychloride. %, the reaction temperature is 400 ℃, the mass fraction of oxygen in the oxygen-enriched air introduced is 75%, the direct yield of vanadium reaches 95%, and the purity of the high-purity vanadium pentoxide product reaches 99.995wt% (4N5); In the hydrolysis and dechlorination fluidized bed, the reaction temperature is 700° C., the residence time of the powder is 50 min, and the chlorine content of the dechlorination tailings is 0.5%.

The parts of the present invention that are not described in detail belong to the well-known technology in the art.

Of course, the present invention can also have various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the disclosure of the present invention. The changes and deformations should belong to the protection scope of the claims of the present invention.

Claims (7)

1. a kind of system of high-valued comprehensive utilization chromium type high vanadium slag, which is characterized in that the system comprises mixing workshop section (1), Chloridized dust collection workshop section (2), elution sedimentation workshop section (3), refinement (4), Zhi Fen workshop section (5) and chloride residue processing section (6)；

The mixing workshop section (1) includes high-chromic vanadium slag charge storehouse (1-1), chromium type high vanadium slag screw feeder (1-2), carbon source feed bin (1-3), carbon source screw feeder (1-4) and fluidized bed blender (1-5)；

The chloridized dust collection workshop section (2) includes recirculating fluidized bed main body (2-1), recirculating fluidized bed whirlwind separator (2-2), level-one Tower (2-3), the second level of gathering dust are gathered dust tower (2-4), gather dust tower heat exchanger (2-5) and chromium chloride dissolution kettle (2-6)；

Elution sedimentation workshop section (3) includes eluting column (3-1), mashing pump (3-2), eluting column heat exchanger (3-3), drop catcher (3-4) and elution slurry subsider (3-5)；

The refinement (4) includes reboiler (4-1), reboiler heat exchanger (4-2), rectifying column (4-3), high-purity vanadium oxytrichloride Condenser (4-4) and high-purity vanadium oxytrichloride storage tank (4-5)；

The Zhi Fen workshop section (5) includes powder reactor (5-1) processed, ultrapure water vaporizer (5-2), powder heat exchanger processed (5-3), powder processed Soft water storage tank (5-4), powder water circulating pump processed (5-5), high purity vanadium feed bin (5-6) and high purity vanadium screw(-type) feeder (5-7)；

The chloride residue processing section (6) includes technique water vaporizer (6-1), hydrolysis dechlorination fluidized bed (6-2), cyclonic separation Device (6-3) and bag filter (6-4)；

The feed inlet phase of the discharge port in high-chromic vanadium slag charge storehouse (1-1) and the chromium type high vanadium slag screw feeder (1-2) Connection；The discharge port of the chromium type high vanadium slag screw feeder (1-2) and the feed inlet of the fluidized bed blender (1-5) pass through Pipeline is connected；The discharge port of the carbon source feed bin (1-3) is connected with the feed inlet of the carbon source screw feeder (1-4)； The discharge port of the carbon source screw feeder (1-4) is connected with the feed inlet of the fluidized bed blender (1-5) by pipeline； The fluidisation gas inlet of the fluidized bed blender (1-5) is connected with nitrogen header pipe；The fluidized bed blender (1-5) goes out Material mouth is connected with the feed inlet of the recirculating fluidized bed main body (2-1) by pipeline；

The air inlet of the recirculating fluidized bed main body (2-1) is connected with nitrogen header pipe, circulating chlorine gas general pipeline, chlorine general pipeline respectively It connects；The air inlet of the chlorination exhanst gas outlet of the recirculating fluidized bed main body (2-1) and the recirculating fluidized bed whirlwind separator (2-2) Mouth is connected by pipeline；Chloride residue outlet and the hydrolysis dechlorination fluidized bed (6- of the recirculating fluidized bed main body (2-1) 2) feed inlet is connected by pipeline；Slurry inlet at the top of the recirculating fluidized bed main body (2-1) respectively with the elution The underflow opening of slurry subsider (3-5) and the underflow opening of the reboiler (4-1) are connected by pipeline；The recirculating fluidized bed The dust outlet of cyclone separator (2-2) is connected with the dust inlet of recirculating fluidized bed main body (2-1) side by pipeline It connects；The gather dust gas access of tower (2-3) of the gas vent of the recirculating fluidized bed whirlwind separator (2-2) and the level-one passes through Pipeline is connected；The level-one gathers dust the gas vent of tower (2-3) and the second level is gathered dust, and the gas access of tower (2-4) passes through pipe Road is connected；The gather dust entrance of dust outlet and the chromium chloride dissolution kettle (2-6) of tower (2-3) of the level-one passes through pipeline phase Connection；The technique water inlet of the chromium chloride dissolution kettle (2-6) is connected with the technique supply mains；The chromium chloride dissolution kettle The taphole of (2-6) is connected with the solution inlet of chromic salts recovery unit by pipeline；The level-one is gathered dust at the top of tower (2-3) Slurry inlet pass through respectively with the underflow opening of elution slurry subsider (3-5) and the underflow opening of the reboiler (4-1) Pipeline is connected；The gather dust gas access of gas vent and the eluting column (3-1) of tower (2-4) of the second level passes through pipeline phase Connection；The gather dust discharge gate of tower (2-4) of the second level is connected with the feed inlet of the hydrolysis dechlorination fluidized bed (6-2) by pipeline It connects；The tower heat exchanger (2-5) that gathers dust is set to the middle part of tower (2-4) that gather dust；Described tower heat exchanger (2-5) hot-fluid that gathers dust Body outlet is connected with the hot inlet of the reboiler heat exchanger (4-2) by pipeline；The tower heat exchanger (2-5) that gathers dust Thermal fluid inlet is connected with the fluid outlet of the powder water circulating pump (5-5) processed by pipeline；Mashing pump (3-2) setting In the bottom of the eluting column (3-1)；The eluting column heat exchanger (3-3) is set to the top of the eluting column (3-1)；It is described The underflow outlet of eluting column (3-1) is connected with the entrance of elution slurry subsider (3-5) by pipeline；The eluting column (3-1) offgas outlet is connected with the gas access of the drop catcher (3-4) by pipeline；The gas of the drop catcher (3-4) Outlet is connected with the gas access of exhaust treatment system by pipeline；The liquid outlet of the drop catcher (3-4) and the leaching The entrance of pulp washing material subsider (3-5) is connected by pipeline；The supernatant outlet of elution slurry subsider (3-5) and institute The inlet for stating rectifying column (4-3) is connected by pipeline；

The refluxing opening of the rectifying column (4-3) is connected with the inlet of the reboiler (4-1) by pipeline；The reboiler The gas outlet of (4-1) is connected with the air inlet of the rectifying column (4-3) by pipeline；The reboiler heat exchanger (4-2) sets It is placed in the inside of the reboiler (4-1)；Reboiler heat exchanger (4-2) hot fluid outlet ports and the powder heat exchanger (5- processed 3) thermal fluid inlet is connected by pipeline；High-purity vanadium oxytrichloride gas vent of the rectifying column (4-3) with it is described high-purity The gas access of vanadium oxytrichloride condenser (4-4) is connected by pipeline；The liquid of high-purity vanadium oxytrichloride condenser (4-4) Outlet is connected with the liquid inlet of high-purity vanadium oxytrichloride storage tank (4-5) by pipeline；High-purity vanadium oxytrichloride storage tank The liquid outlet of (4-5) is connected with the vanadium oxytrichloride entrance of the powder reactor (5-1) processed by pipeline；The powder heat exchanger processed (5-3) is set in the middle part of the powder reactor (5-1) processed；The hot fluid outlet ports and the powder processed of the powder heat exchanger (5-3) processed The thermal fluid inlet of soft water storage tank (5-4) is connected by pipeline；The hot fluid outlet ports of the powder soft water storage tank (5-4) processed and institute The fluid inlet for stating powder water circulating pump (5-5) processed is connected by pipeline；The offgas outlet and chlorine of the powder reactor (5-1) processed Gas circulatory system entrance is connected by pipeline；The feed inlet of the ultrapure water vaporizer (5-2) respectively with purification oxygen-enriched air General pipeline, ultrapure supply mains are connected；The air inlet of the gas outlet of the ultrapure water vaporizer (5-2) and the powder reactor (5-1) processed Mouth is connected by pipeline；The discharge gate of the powder reactor (5-1) processed and the feed inlet of the high purity vanadium feed bin (5-6) pass through Pipeline is connected；The discharge gate of the high purity vanadium feed bin (5-6) and the feed inlet of the high purity vanadium screw(-type) feeder (5-7) pass through Pipeline is connected；

The water inlet of the technique water vaporizer (6-1) is connected with technique supply mains；The technique water vaporizer (6-1) goes out Port is connected with the air inlet of the hydrolysis dechlorination fluidized bed (6-2) by pipeline；The hydrolysis dechlorination fluidized bed (6-2) Air inlet is connected with air header simultaneously；The fuel inlet of the hydrolysis dechlorination fluidized bed (6-2) is connected with fuel manifold； Processing slag discharge gate is equipped in the middle part of the hydrolysis dechlorination fluidized bed (6-2)；The offgas outlet of the hydrolysis dechlorination fluidized bed (6-2) It is connected with the air inlet of the cyclone separator (6-3) by pipeline；The gas vent of the cyclone separator (6-3) and institute The gas access for stating bag filter (6-4) is connected by pipeline；The dust outlet of the cyclone separator (6-3) with it is described The feed inlet of hydrolysis dechlorination fluidized bed (6-2) is connected by pipeline；The dust outlet of the bag filter (6-4) with it is described The air inlet of cyclone separator (6-3) is connected by pipeline；The offgas outlet and vent gas treatment of the bag filter (6-4) The air inlet of system is connected by pipeline.

2. a kind of method of the high-valued comprehensive utilization chromium type high vanadium slag based on system described in claim 1, the method includes Following steps:

Chromium type high vanadium slag in high-chromic vanadium slag charge storehouse (1-1) by the chromium type high vanadium slag screw(-type) feeder (1-2) into Enter in the fluidized bed blender (1-5)；Carbon source in the carbon source feed bin (1-3) is through the carbon source screw feeder (1-4) Into in the fluidized bed blender (1-5)；Mixed carbon comtent is the 5%~25% of chromium type high vanadium slag quality；In the work of fluidisation nitrogen Entered in the recirculating fluidized bed main body (2-1) together with lower be uniformly mixed with chromium type high vanadium slag；From the nitrogen of nitrogen header pipe Gas, the chlorine of circulating chlorine gas general pipeline, chlorine general pipeline chlorine from the air inlet of recirculating fluidized bed main body (2-1) bottom into Enter；It maintains chromium type high vanadium slag and carbon source fluidised simultaneously, chlorination reaction occurs therewith；Chlorination operation temperature is 500~1000 ℃；The chlorination flue gas generated is reacted to send after the recirculating fluidized bed whirlwind separator (2-2) recycles the vanadium slag powder of non-chlorination The level-one gather dust tower (2-3) processing；Chlorination tailings send hydrolysis dechlorination fluidized bed (6-2) dechlorination to handle；From described The underflow of the slurry and the reboiler (4-1) of slurry subsider (3-5) is eluted from the top of the recirculating fluidized bed main body (2-1) Portion sprays into, to adjust reaction temperature；The vanadium slag powder of recirculating fluidized bed whirlwind separator (2-2) recycling is returned through dipleg To the reaction was continued in the recirculating fluidized bed main body (2-1)；From the elution slurry of slurry subsider (3-5) and described The underflow of reboiler (4-1) from the level-one gather dust tower (2-3) top spray into, to reduce the temperature of chlorination flue gas；It is described Level-one gather dust tower (2-3) gas outlet temperature be 400~700 DEG C；The level-one gather dust tower (2-3) recycling tri-chlorination chromium powder Dirt send chromium chloride dissolution kettle (2-6) the configuration chromium trichloride solution, for producing the raw material of chromic salts；The level-one is gathered dust tower Flue gas in (2-3) after Isolating chlorinated chromium send the second level gather dust tower (2-4) separation ferric trichloride dust；The second level is gathered dust Rich ferric trichloride dust in tower (2-4) send hydrolysis dechlorination fluidized bed (6-2) dechlorination to handle；The tower heat exchanger that gathers dust (2-5) recycles the sensible heat of high-temp chlorination flue gas from the tower that gathers dust (2-4), and reacts for the reboiler (4-1) and powder processed Device (5-1) provides heat, realizes energy-saving；The second level gather dust tower (2-4) gas outlet temperature be 300~500 DEG C；Institute State second level gather dust tower (2-4) removing ferric trichloride dust after flue gas send the eluting column (3-1) elute；

The elution tail gas of the eluting column (3-1) send exhaust treatment system after the drop catcher (3-4) recycles drop；The leaching The vanadium oxytrichloride liquid for washing the vanadium oxytrichloride slurry that tower (3-1) elution obtains and the drop catcher (3-4) recycling send the elution Slurry subsider (3-5) settlement treatment；Obtained supernatant is passed through the powder reaction processed after the rectifying column (4-3) purification In device (5-1)；Air from purification oxygen-enriched air general pipeline and the ultrapure water from ultrapure supply mains pass through described ultrapure It is sent in the powder reactor (5-1) processed after water vaporizer (5-2) preheating vaporization, catalytic oxidation occurs with vanadium oxytrichloride, obtains To rich chlorine flue gas and high purity vanadic anhydride；The reaction temperature of catalytic oxidation process is 120 DEG C~480 DEG C；Rich chlorine flue gas send chlorine The gas circulatory system；High purity vanadic anhydride send the high purity vanadium feed bin (5-6)；Described in process water warp from technique supply mains The hydrolysis dechlorination fluidized bed (6-2) is sent into together with from the air of air header after technique water vaporizer (6-1) gasification In, the fluidization of chloride residue is maintained, and hydrolysis dechlorination reaction occurs therewith；Fuel from fuel manifold is from the hydrolysis The fuel inlet of the bottom dechlorination fluidized bed (6-2) enters, and provides heat for reaction；Reaction temperature is 500 DEG C~900 DEG C；Powder Mean residence time be 30~80 minutes；Dechlorination tailings chlorinty is within 2%；Dechlorination tailings send ironmaking；Dechlorination tail gas according to It is secondary to send exhaust treatment system after the cyclone separator (6-3), bag filter (6-4) removing dust；The bag-type dust The dust of device (6-4) recycling returns in the cyclone separator (6-3), the dust one with the cyclone separator (6-3) recycling With entering in the hydrolysis dechlorination fluidized bed (6-2), the reaction was continued.

3. the method for high-valued comprehensive utilization chromium type high vanadium slag according to claim 2, which is characterized in that chromium type high vanadium slag The mass fraction of middle vanadic anhydride is 8%~28%, and the mass fraction of chromium oxide is 6%~16%.

4. the method for high-valued comprehensive utilization chromium type high vanadium slag according to claim 2, which is characterized in that the carbon source material Carbon source in storehouse (1-3) refers to one or more of metallurgical coke, petroleum coke and coal dust.

5. the method for high-valued comprehensive utilization chromium type high vanadium slag according to claim 2, which is characterized in that in the circulation In fluidized bed main body (3-1), operating gas velocity is 0.04m~4.00m/s, into chlorine in the indoor chlorine nitrogen mixture of wind Molar fraction is 15%~100%, and the chlorination rate of vanadic anhydride is 95% or more, and the chlorination rate of chromium oxide is 95% or more.

6. the method for high-valued comprehensive utilization chromium type high vanadium slag according to claim 2, which is characterized in that the level-one is received For the removal efficiency of chromium chloride 95% or more, the chromium chloride of recycling is used as the original for producing chromic salts after being configured solution in chimney (2-3) Material.

7. the method for high-valued comprehensive utilization chromium type high vanadium slag according to claim 2, which is characterized in that in the powder processed In reactor (5-1), being passed through vapor is be passed through vanadium oxytrichloride quality 0.05%~12%, is passed through in clean oxygen-enriched air and contains Oxygen amount volume fraction is 29%~97%, and the purity of high purity vanadic anhydride is 99.5% or more.