CN106498165A - Method for recovering nickel and vanadium from waste FCC catalyst through melting, chlorination and volatilization - Google Patents

Abstract

The invention discloses a method for recovering nickel and vanadium from waste FCC catalyst by melting chlorination and volatilization, comprising: adding chlorination agent, reducing agent and slagging agent to waste FCC catalyst, and mixing uniformly to obtain a mixed material to be smelted ; Use a smelting furnace to melt and chlorinate the mixed material to be smelted, the smelting temperature is 1250-1700 ° C, and the smelting time is 30-300 minutes, thereby obtaining flue gas containing nickel and vanadium chloride; The flue gas of the compound is passed into the flue gas washing system for flue gas washing and demisting, thereby obtaining a solution rich in nickel and vanadium; using solvent extraction method to separate the nickel and vanadium rich solution into nickel and vanadium, thereby obtaining Vanadium and Nickel Chloride. The invention can not only greatly improve the recovery rate of nickel and vanadium, but also has simple process, short flow process, flexible operation, high recycling rate, strong regional adaptability, non-toxic waste water, waste gas and slag, and little impact on the environment.

Description

A method for recovering nickel and vanadium from molten chlorination volatilization in waste FCC catalyst

technical field

The invention relates to the technical field of harmless treatment of waste FCC (Fluid Catalytic Cracking, fluidized catalytic cracking) catalysts in the petrochemical industry, in particular to a method for recovering nickel and vanadium from waste FCC catalysts by molten chlorination and volatilization.

Background technique

FCC catalyst is the most used catalyst in petroleum refining process, and its main component is zeolite molecular sieve. During the catalytic cracking process of crude oil containing metals, the metal compounds in the crude oil will be completely decomposed and accumulated on the FCC catalyst; with the continuous recycling of the FCC catalyst, the metals deposited on the FCC catalyst will gradually increase, which will affect the oil quality. Therefore, it is necessary to regularly and quantitatively discharge the FCC catalyst with excess metal deposits (that is, spent FCC catalyst) and replenish fresh FCC catalyst. These waste FCC catalysts contain heavy metals, which are difficult to handle and highly polluting, and pose a serious threat to the living environment of human beings. Therefore, these waste FCC catalysts have become dangerous solid wastes in the petrochemical industry, and their discharge into the natural environment has been expressly prohibited at home and abroad. These spent FCC catalysts.

Waste FCC catalysts generally contain nickel, vanadium, iron and other metal elements, the mass percentage of nickel is generally 0.3-6%, the mass percentage of V ₂ O ₅ is generally 0.1-2%, the mass percentage of Al ₂ O ₃ The percentage content is generally 40-55%, and these metals and metal oxidation are important strategic resources. If not handled properly, it will not only cause the loss and waste of these useful metals, but also cause environmental pollution. At present, the treatment method for waste FCC catalysts is mainly to use magnetic separation technology to separate and recover magnetic nickel, vanadium, and iron from waste FCC catalysts; and for waste FCC catalysts with high metal content, serious poisoning, poor activity and selectivity, mainly Focusing on building storage pools for centralized burial is not only a temporary solution but not the root cause, but also with the dwindling land resources, this centralized burying method is also greatly restricted.

In the prior art, the methods for recovering metals from spent FCC catalysts at home and abroad mainly include the following:

(1) Vulcanization-oxidation method: In this vulcanization-oxidation method, H ₂ S or sulfur is used as a vulcanizing agent to sulfide the metal on the spent FCC catalyst, and then O ₂ is used as an oxidant to oxidize. After the spent FCC catalyst is sulfided, the metal poisoning on the spent FCC catalyst exists in the form of sulfide and is enriched on the surface of the spent FCC catalyst; these metals in the form of sulfide are oxidized to become soluble sulfuric acid salt, and then use dilute acid for leaching, so that the leaching and recovery of nickel, vanadium and iron can be realized. The nickel removal rate of the vulcanization-oxidation method is about 80%, the iron removal rate is about 50%, and the vanadium removal rate is about 40%, that is to say, the nickel removal rate of the vulcanization-oxidation method is not high.

(2) Low-temperature chlorination-leaching method: This low-temperature chlorination-leaching method utilizes the difference in volatility and solubility of metal compounds to realize the purification of raw materials and products. First, use H ₂ S gas at 480-650°C to carry out sulfidation and roasting pretreatment on the spent FCC catalyst or use air to carry out oxidation roasting pretreatment on the spent FCC catalyst at 540-950°C, and then use chlorine or chlorine-containing mixed gas to pretreat the spent FCC catalyst. React with the pretreated spent FCC catalyst at 290-340°C, so that vanadium and iron form volatile chlorides, and nickel forms water-soluble chlorides, thereby realizing the separation of useful metals in spent FCC catalysts. Removal and recycling. The low-temperature chlorination-leaching method has relevant applications in the regeneration of spent FCC catalysts. The low-temperature chlorination-leaching method uses lower temperature for roasting, volatilizes vanadium and iron during the roasting process, converts nickel into nickel chloride and retains it in the calcined sand, and then leaches it with a low-acid solution.

(3) Mixed acid leaching method: the mixed acid leaching method uses a mixed acid mixed with _HNO3 and HCl in proportion to leach nickel, vanadium and iron in the spent FCC catalyst, thereby realizing separation from the matrix. The mixed acid leaching method has the problems of large acid consumption, high leaching rate of Al and Si, and difficulty in handling the obtained solution containing nickel, vanadium and iron.

In summary, the waste FCC catalyst contains nickel with a mass percentage of generally 0.3-6%, but part of the nickel in the waste FCC catalyst has been embedded in the molecular sieve lattice, and it is difficult to achieve low-cost, Efficient recycling without pollution.

Contents of the invention

In order to solve the technical problems in the above-mentioned prior art, the present invention provides a method for recovering nickel and vanadium from waste FCC catalysts by molten chlorination and volatilization, which can not only greatly improve the recovery rate of nickel and vanadium, but also has a simple process, The process is short, the operation is flexible, the recycling rate is high, and the regional adaptability is strong. The waste water, waste gas and slag produced are non-toxic and have little impact on the environment.

The purpose of the present invention is achieved through the following technical solutions:

A method for recovering nickel and vanadium from molten chlorination volatilization in waste FCC catalyst, comprising:

Step 1, adding a chlorinating agent, a reducing agent and a slagging agent to the spent FCC catalyst, and mixing them uniformly to obtain a mixed material to be smelted; wherein, the amount of the chlorinating agent is 2 to 50% of the total mass of the spent FCC catalyst, The amount of the reducing agent is 0.5-8% of the total mass of the spent FCC catalyst, and the amount of the slagging agent is 5-120% of the total mass of the spent FCC catalyst;

Step 2, using a smelting furnace to melt and chlorinate the mixed material to be smelted, the smelting temperature is 1250-1700°C, and the smelting time is 30-300 minutes, so as to obtain flue gas containing nickel and vanadium chlorides;

Step 3, passing the flue gas containing nickel and vanadium chloride into the flue gas scrubbing system for flue gas scrubbing and defogging, thereby obtaining a solution rich in nickel and vanadium;

Step 4, using a solvent extraction method to separate the solution rich in nickel and vanadium into nickel and vanadium, thereby obtaining vanadium pentoxide and nickel chloride.

Preferably, the spent FCC catalyst contains 0.3-6% by mass of nickel, _0.1-2 % by mass of _V2O5 , 40-55% by mass of _Al2O3 , and 40-55 _% by mass of _SiO2 . The percentage is 40-55%, and the spent FCC catalyst has been oxidized and roasted to remove tar and char, and the particle size is not larger than 1.47mm.

Preferably, the chlorination agent is at least one of calcium chloride, magnesium chloride, sodium chloride or ferric chloride; the reducing agent is at least one of coke, coke powder, anthracite or charcoal; the manufacturing The slag agent is at least one of lime, limestone, quartz sand or iron oxide.

Preferably, passing the flue gas containing nickel and vanadium chloride into the flue gas scrubbing system for flue gas scrubbing and defogging includes: the flue gas passing into the flue gas scrubbing system includes a flue gas scrubbing device and flue gas demisting device; wherein, the flue gas scrubbing device includes at least one of a spray tower, a bubble cap tower or a packed tower; the flue gas demisting device includes an electric demister, a baffle type demister, a swirling plate demister or At least one of flat-plate demisters; the flue gas containing nickel and vanadium chlorides is treated by multi-stage flue gas scrubbers and/or flue gas demisters, and nickel and vanadium chlorides enter the washing liquid to form The solution rich in nickel and vanadium, and the purified tail gas that reaches the standard is emptied.

Preferably, the separation of nickel and vanadium from the solution rich in nickel and vanadium by using solvent extraction method includes: adjusting the pH value of the solution rich in nickel and vanadium to 1-2, and performing extraction of vanadium-reverse Extraction-precipitation of vanadium to obtain vanadium pentoxide; and the remaining liquid after vanadium extraction is removed by P204 extractant, and then evaporated and crystallized to obtain nickel chloride.

Preferably, after the solution rich in nickel and vanadium is processed in step 4, a recovered raffinate mainly composed of sodium chloride is obtained; if the mass percentage of sodium chloride in the recovered raffinate is less than 10%, then the The recovered raffinate is reused in the flue gas washing system as a circulating liquid; if the mass percentage of sodium chloride in the recovered raffinate is 10-25%, the recovered raffinate is subjected to evaporation, concentration and crystallization treatment, thereby producing Sodium chloride was obtained as a solid.

Preferably, in step 2, the smelting furnace adopts a high-temperature smelting furnace with a heating temperature of 1250-1700°C; It is discharged from the top flue of the smelting furnace, while the remaining slag melt is continuously discharged from the side outlet of the smelting furnace through the chute, and the discharged slag melt is water-quenched and cooled by high-pressure water pump, and the amount of water pumped is slag melt 10 to 40 times the total mass, thus forming granular solid slag.

Preferably, in step 2, the mixed material to be smelted is fed into the silo of the smelting furnace through a conveyor, and the amount and speed of the material entering the smelting furnace are controlled through the feed valve of the silo.

Preferably, in Step 1, the spent FCC catalyst added with chlorinating agent, reducing agent and slagging agent is mixed with a drum mixer, a stirring mixer or a double screw mixer.

As can be seen from the technical solutions provided by the present invention above, the method for recovering nickel and vanadium from waste FCC catalysts by molten chlorination and volatilization provided by the embodiments of the present invention is to use Melt chlorination at 1250-1700°C for 30-300 minutes, so that the nickel and vanadium on the spent FCC catalyst can be volatilized into the flue gas in the form of chloride, thereby realizing the one-step removal and recovery of nickel and vanadium from the spent FCC catalyst resources, so the embodiment of the present invention can not only greatly increase the recovery rate of nickel and vanadium, but also has simple process, short process, flexible operation, high recycling rate, strong regional adaptability, and the generated waste water, waste gas and slag are non-toxic, Small impact on the environment.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the accompanying drawings that need to be used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For Those of ordinary skill in the art can also obtain other drawings based on these drawings on the premise of not paying creative work.

Fig. 1 is the flowchart of the method for recovering nickel and vanadium from molten chlorination volatilization in the embodiment of the present invention.

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

First of all, it should be explained that the method for recovering nickel and vanadium from spent FCC catalysts by reduction smelting provided by the present invention is aimed at containing 0.3-6% by mass of nickel, 0.1-2% by mass of V ₂ O ₅ , and 0.1-2% by mass of Al ₂ O ₃ mass percentage is 40-55%, SiO ₂ mass percentage is 40-55%, and the spent FCC catalyst has been oxidized and roasted to remove tar and charcoal, and the particle size is not greater than 1.47mm. In practical application, the waste FCC catalyst is best to use a waste FCC catalyst containing 0.5-3% by mass of nickel and _0.3-1 % by mass of _V2O5 , and the waste FCC catalyst with a particle size of less than 0.075mm is the best Accounting for more than 35% of the total spent FCC catalyst. The method for recovering nickel and vanadium from spent FCC catalysts by reduction smelting provided by the present invention will be described in detail below.

As shown in Figure 1, a kind of method that melts chlorination volatilization recovery nickel, vanadium from waste FCC catalyst, comprises:

Step 1: Add a chlorinating agent, a reducing agent and a slagging agent to the spent FCC catalyst, and mix them uniformly to obtain a mixed material to be smelted. Wherein, the chlorination agent is at least one of calcium chloride, magnesium chloride, sodium chloride or ferric chloride; the reducing agent is at least one of coke, coke powder, anthracite or charcoal; the slagging The agent is at least one of lime, limestone, quartz sand or iron oxide. The consumption of chlorinating agent is 2～50% (preferably 5～20%) of the total mass of waste FCC catalyst, and the consumption of reducing agent is 0.5～8% (preferably 0.8～3%) of the total mass of waste FCC catalyst, The dosage of the slagging agent is 5-120% (preferably 10-60%) of the total mass of the spent FCC catalyst. In practical application, it is better to mix the waste FCC catalyst added with chlorinating agent, reducing agent and slagging agent by using cylinder mixer, agitating mixer or twin-screw mixer in the prior art, so as to effectively ensure Uniformity of mixing.

Step 2: Melting and chlorinating the mixed material to be smelted in a smelting furnace, the smelting temperature is 1250-1700° C., and the smelting time is 30-300 minutes, so as to obtain flue gas containing nickel and vanadium chlorides. Wherein, the mixed material to be smelted can pass through a conveyor (for example: the conveyor can adopt a belt conveyor or a bucket elevator in the prior art, and can also select a conveyor that can transport powder in the prior art according to the terrain layout. machine) into the smelting furnace silo (that is, the feeding buffer silo at the top of the smelting furnace), and the silo feeding valve can control the feeding amount and Feeding speed. Specifically, during the process of melt chlorination of the mixed material to be smelted, the nickel and vanadium elements in the mixed material to be smelted will be volatilized and removed into the flue gas in the form of chloride, forming Chloride flue gas is discharged from the top flue of the smelting furnace and separated from the spent FCC catalyst substrate; while the remaining slag melt is continuously discharged from the side outlet of the smelting furnace through the chute, and the discharged slag melt High-pressure water pumps can be used to pump water for water quenching and cooling, and the pumping volume is 10 to 40 times the total mass of the slag melt, thereby forming granular solid slag; the granular solid slag can be used as raw materials for cement production, building materials, and road paving materials. The particle size and shape of the slag can be controlled by adjusting the amount of quenching water according to the actual use of the slag. In practical applications, the melting furnace is preferably a high-temperature melting furnace with a heating temperature of 1250-1700° C. in the prior art, such as electric arc furnace, submerged electric furnace, induction heating furnace, microwave heating furnace and other high-temperature melting furnaces.

Step 3, passing the flue gas containing nickel and vanadium chlorides into the flue gas washing system for flue gas washing and defogging, so as to obtain a solution rich in nickel and vanadium. Specifically, the flue gas passing into the flue gas scrubbing system may include a flue gas scrubbing device and a flue gas demisting device, and the circulating liquid in the flue gas scrubbing system may use clean water or dilute lye; the flue gas The scrubbing device can include at least one of a spray tower, a bubble cap tower or a packed tower; At least one of mist eliminator; the flue gas containing nickel and vanadium chloride is treated by multi-stage flue gas scrubber and/or flue gas demisting device, and nickel and vanadium chloride enter into the washing liquid to form rich The solution of nickel and vanadium, and the purified exhaust gas can be emptied after reaching the emission standard, which can effectively reduce the smoke out.

Step 4, using a solvent extraction method to separate nickel and vanadium from the solution rich in nickel and vanadium, so as to obtain vanadium pentoxide and nickel chloride. Specifically, the pH value of the solution rich in nickel and vanadium is adjusted to 1-2 by using Lix64 extractant, and the treatment of extracting vanadium-back extraction-precipitating vanadium is carried out, thereby obtaining vanadium pentoxide; and extracting vanadium The remaining liquid is removed by P204 extractant, and then evaporated and crystallized to obtain nickel chloride. In practical application, the solution rich in nickel and vanadium will obtain the recovery raffinate mainly based on sodium chloride after the treatment of step 4; if the mass percentage of sodium chloride in the recovery raffinate is less than 10% , then the recovered raffinate can be reused in the flue gas scrubbing system as circulating fluid; if the mass percentage of sodium chloride in the recovered raffinate is 10-25%, the recovered raffinate can be evaporated and concentrated Crystallization treatment to obtain solid sodium chloride.

Specifically, the principle of the method for recovering nickel and vanadium from waste FCC catalysts by molten chlorination and volatilization provided by the present invention is as follows: the nickel in the waste FCC catalysts is decomposed and deposited on the waste FCC catalysts by the metal decomposition in the crude oil catalytic cracking process. On the surface or in the molecular sieve lattice, it is in an oxidized state after oxidation and roasting. Under high temperature conditions, nickel and vanadium in spent FCC catalysts will form NiCl ₂ (boiling point 973°C) and VCl ₄ (boiling point 154°C) with lower boiling points under the action of chlorinating agent, and these two substances will form at high temperature Volatilize and enter the flue gas, so as to separate from the spent FCC catalyst matrix, and realize the removal and recovery of nickel and vanadium in the spent FCC catalyst; the following reactions mainly occur:

MCl _{n (solid)} +n/2H ₂ O _(gas) ＝MO _{n/2 (solid)} +nHCl _(gas)

2HCl _(gas) +NiO _(liquid) ＝NiCl _{2 (gas)} +H ₂ O _(gas)

4HCl _(gas) +VO _{2 (liquid)} ＝VCl _{4 (gas)} +2H ₂ O _(gas)

Compared with the prior art, the method provided by the present invention to recover nickel and vanadium from the spent FCC catalyst by melting chlorination volatilization has at least the following technical effects:

(1) The present invention utilizes the feature that chlorine salt forms easily volatile chlorides with nickel and vanadium in the waste FCC catalyst at high temperature, and realizes one-step removal and recovery of nickel and vanadium resources from the waste FCC catalyst, eliminating the need for wet methods The leaching process has a simple process and a short process.

(2) the chlorinating agent adopted in the present invention is easy to obtain, cheap chlorinated salts (for example: calcium chloride, magnesium chloride, sodium chloride, ferric chloride), has different chlorinating agent markets in different regions. Strong adaptability can effectively reduce the cost of raw materials.

(3) In the flue gas containing nickel and vanadium chloride obtained in step 2 of the present invention, the recovery rate of nickel is greater than 90%, and the recovery rate of vanadium can be made greater than 70% simultaneously, and nickel in the obtained slag melt The mass percentages of nickel and vanadium are not greater than 0.15%, so compared with the prior art, the invention can greatly improve the recovery rate of nickel and vanadium.

(4) The invention not only realizes the harmless treatment of the spent FCC catalyst, but also can effectively recover nickel and vanadium resources from the spent FCC catalyst.

(5) The present invention uses electric arc furnace heating for smelting, with less flue gas volume and a small flue gas absorption and treatment system.

In order to more clearly demonstrate the technical solutions provided by the present invention and the resulting technical effects, the method for recovering nickel and vanadium from molten chlorination and volatilization of spent FCC catalysts in the present invention will be described in detail below with specific examples.

Example 1

A method for recovering nickel and vanadium from molten chlorination and volatilization from waste FCC catalysts, using waste FCC catalysts discharged from a petroleum cracking plant in Shandong as raw material, the main elemental components of the waste FCC catalysts are shown in Table 1 below:

Table 1:

The method comprises: taking 100g of the spent FCC catalyst (wherein, the spent FCC catalyst with a particle size less than 0.075mm accounts for 40% of the total spent FCC catalyst), and adding 7g of anhydrous calcium chloride, 1g of anthracite, and 20g of calcium oxide, and mixing uniformly , so as to obtain the mixed material to be smelted. Put the mixed material to be smelted into the corundum crucible, cover the crucible lid, put the crucible containing the mixed material to be smelted into a closed tubular heating furnace, cover the sealing end cover of the tubular furnace tightly, and connect the air inlet and the gas outlet pipeline, turn on the heating system of the tube furnace, raise the melting temperature to 1450°C, and keep it warm for 60 minutes. The flue gas containing nickel and vanadium chloride is discharged from the closed tube heating furnace and passed into the flue gas washing system The two-stage base absorbs nickel and vanadium, thereby obtaining a solution rich in nickel and vanadium. The solution rich in nickel and vanadium is subjected to nickel and vanadium separation by using a solvent extraction method, so as to obtain vanadium pentoxide and nickel chloride.

Specifically, during the implementation of Example 1 of the present invention, the slag melt after the flue gas containing nickel and vanadium chloride was discharged was tested, and the result was: the mass fraction of nickel in the slag melt was 0.08%, and the slag melt The mass fraction of vanadium is 0.06%, the recovery rate of nickel is 92.31%, and the recovery rate of vanadium is 72.22%.

Example 2

A method for recovering nickel and vanadium by reducing smelting from waste FCC catalysts, using waste FCC catalysts discharged from a certain petroleum cracking plant in Hebei as raw material, the main elemental components of the waste FCC catalysts are shown in Table 2 below:

Table 2:

element Ni V Al ₂ O ₃ SiO ₂ Fe Sb Ca content/% 2.80 0.46 45.10 50.20 0.57 0.21 0.26

The method comprises: taking 100g of the spent FCC catalyst (wherein, the spent FCC catalyst with a particle size less than 0.075mm accounts for 45% of the spent FCC catalyst), and adding 10g of anhydrous magnesium chloride, 1g of coke powder, and 20g of quartz sand, and mixing evenly, Thus, the mixed material to be smelted is obtained. Put the mixed material to be smelted into the corundum crucible, cover the crucible lid, put the crucible containing the mixed material to be smelted into a closed tubular heating furnace, cover the sealing end cover of the tubular furnace tightly, and connect the air inlet and the gas outlet pipeline, turn on the heating system of the tube furnace, raise the melting temperature to 1500°C, and keep it warm for 90 minutes. The flue gas containing nickel and vanadium chloride is discharged from the closed tube heating furnace and passed into the flue gas washing system. The two-stage base absorbs nickel and vanadium, thereby obtaining a solution rich in nickel and vanadium. The solution rich in nickel and vanadium is subjected to nickel and vanadium separation by using a solvent extraction method, so as to obtain vanadium pentoxide and nickel chloride.

Specifically, during the implementation of Example 2 of the present invention, the slag melt after the flue gas containing nickel and vanadium chloride was discharged was tested, and the result was: the mass fraction of nickel in the slag melt was 0.10%, and the slag melt The mass fraction of vanadium is 0.08%, the recovery rate of nickel is 95.54%, and the recovery rate of vanadium is 78.26%.

Example 3

A method for recovering nickel and vanadium by reduction smelting from waste FCC catalysts, using waste FCC catalysts discharged from a certain petroleum cracking plant in Gansu as raw material, the main elemental components of the waste FCC catalysts are shown in Table 3 below:

table 3:

element Ni V Al ₂ O ₃ SiO ₂ Fe Sb Ca content/% 2.16 0.36 45.47 51.05 0.43 0.18 0.23

The method comprises: taking 100g of the spent FCC catalyst (wherein, the spent FCC catalyst with a particle size less than 0.075mm accounts for 50% of the spent FCC catalyst), and adding 9g of anhydrous calcium chloride, 1g of charcoal, and 25g of limestone, and mixing evenly, Thus, the mixed material to be smelted is obtained. Put the mixed material to be smelted into the corundum crucible, cover the crucible lid, put the crucible containing the mixed material to be smelted into a closed tubular heating furnace, cover the sealing end cover of the tubular furnace tightly, and connect the air inlet and the gas outlet pipeline, turn on the heating system of the tube furnace, raise the melting temperature to 1450°C, and keep it warm for 60 minutes. The flue gas containing nickel and vanadium chloride is discharged from the closed tube heating furnace and passed into the flue gas washing system The two-stage base absorbs nickel and vanadium, thereby obtaining a solution rich in nickel and vanadium. The solution rich in nickel and vanadium is subjected to nickel and vanadium separation by using a solvent extraction method, so as to obtain vanadium pentoxide and nickel chloride.

Specifically, in the implementation process of Example 3 of the present invention, the slag melt after the flue gas containing nickel and vanadium chloride was discharged was tested, and the result was: the mass fraction of nickel in the slag melt was 0.09%, and the slag melt The mass fraction of vanadium is 0.07%, the recovery rate of nickel is 94.79%, and the recovery rate of vanadium is 75.69%.

In summary, the embodiment of the present invention can not only greatly increase the recovery rate of nickel and vanadium, but also has simple process, short process, flexible operation, high recycling rate, strong regional adaptability, and the generated waste water, waste gas and slag are non-toxic , little impact on the environment.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.

Claims (9)

1. nickel, the method for vanadium are reclaimed in a kind of melting chloridizing volatilization from spent FCC catalyst, it is characterised in that included：

Step one, add chlorinating agent, reducing agent and slag former in spent FCC catalyst, and be well mixed, so as to obtain treating melting Mixed material；Wherein, urge for useless FCC in the consumption of chlorinating agent for spent FCC catalyst gross mass 2～50%, the consumption of reducing agent The 0.5～8% of agent gross mass, the consumption of slag former is the 5～120% of spent FCC catalyst gross mass；

Step 2, treat that melting mixed material carries out melting chlorination using smelting furnace to described, smelting temperature is 1250～1700 DEG C, Smelting time is 30～300 minutes, so as to obtain containing nickel, the muriatic flue gas of vanadium；

Step 3, will containing nickel, the muriatic flue gas of vanadium is passed through flue gas washing system carries out flue gas washing demisting, so as to obtain richness The solution of nickeliferous, vanadium；

Step 4, the solution rich in nickel, vanadium is entered using solvent extraction nickel vanadium separation, so as to obtain vanadic anhydride and Nickel chloride.

2. nickel, the method for vanadium are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1, and its feature exists In described spent FCC catalyst is that nickeliferous mass percent is 0.3～6%, contains V₂O₅Mass percent is 0.1～2%, contains Al₂O₃Mass percent is 40～55%, contains SiO₂Mass percent is 40～55%, and has carried out oxidizing roasting and go to devoke Oil and charcoal, and granularity is not more than the spent FCC catalyst of 1.47mm.

3. nickel, the method for vanadium, its feature are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1 and 2 It is, the chlorinating agent is at least one in calcium chloride, magnesium chloride, sodium chloride or iron chloride；The reducing agent is coke, Jiao At least one in powder, anthracite or charcoal；The slag former is at least in lime, lime stone, quartz sand or iron oxide Kind.

4. nickel, the method for vanadium, its feature are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1 and 2 Be, described will be passed through flue gas washing system containing nickel, the muriatic flue gas of vanadium and carry out flue gas washing demisting include：

Described flue gas is passed through flue gas washing system includes flue washing device and flue gas demister；Wherein, flue gas washing dress Put including at least one in spray column, bubble column or packed tower；Flue gas demister includes electrostatic precipitator, baffle plate type demisting At least one of device, spiral-flow plate-type demister or Flat defroster；

Described containing nickel, the muriatic flue gas of vanadium through multi-stage flue gas wash mill and/or flue gas demister process, nickel, vanadium Chloride is entered into, and the tail gas emptying up to standard after purifying.

5. nickel, the method for vanadium, its feature are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1 and 2 Be, described using solvent extraction the solution rich in nickel, vanadium is entered nickel vanadium separation include：By described rich in nickel, vanadium The pH value of solution is adjusted to 1～2, and carries out the process of extracting vanadium-back extraction-precipitation, so as to obtain vanadic anhydride；And extracting vanadium Extraction raffinate afterwards carries out removal of impurities using P204 extractants, then is evaporated crystallization, so as to obtain nickel chloride.

6. nickel, the method for vanadium are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 5, and its feature exists In the solution rich in nickel, vanadium after the process of step 4, is obtaining the recovery raffinate based on sodium chloride；If this time Receive raffinate in sodium chloride mass percent be less than 10%, then using the recovery residual liquid recycling in the flue gas washing system as Circulation fluid；If the mass percent of sodium chloride is 10～25% in the recovery raffinate, concentration is evaporated to the recovery raffinate Crystallization treatment, so that be obtained solid sodium chloride.

7. nickel, the method for vanadium, its feature are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1 and 2 It is, in step 2, the smelting furnace reaches 1250～1700 DEG C of high temperature melting furnace using heating-up temperature；Using smelting furnace To described when melting mixed material carries out melting chlorination, arranged by the top flue of smelting furnace containing nickel, the muriatic flue gas of vanadium Go out, and remaining slag melt is continuously discharged by chute from the side outlet of smelting furnace, and the slag melt after discharging Being drawn water using high-pressure hydraulic pump carries out water quenching cooling, and 10～40 times for slag melt gross mass of pump-out, so that form graininess Solid slag.

8. nickel, the method for vanadium, its feature are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1 and 2 Be, in step 2, described treat that melting mixed material is sent in the feed bin of smelting furnace by conveyer, and given by feed bin Feeding coal and delivery rate that material valve control is entered in smelting furnace.

9. nickel, the method for vanadium, its feature are reclaimed in melting chloridizing volatilization from spent FCC catalyst according to claim 1 and 2 It is, in step one, using trommel mixer, stirring mixer or double worm mixer to being added with chlorinating agent, reducing agent Mixed with the spent FCC catalyst of slag former.