CN115889422A - Method for treating solid waste containing heavy metals - Google Patents
Method for treating solid waste containing heavy metals Download PDFInfo
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- CN115889422A CN115889422A CN202111154760.4A CN202111154760A CN115889422A CN 115889422 A CN115889422 A CN 115889422A CN 202111154760 A CN202111154760 A CN 202111154760A CN 115889422 A CN115889422 A CN 115889422A
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- bioleaching
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- solid waste
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of solid waste disposal, and discloses a method for treating heavy metal-containing solid waste, which comprises the following steps: performing bioleaching treatment on the heavy metal-containing solid waste by using bioleaching bacteria in a bioleaching reactor; the bioleaching reactor comprises a tank body, a first stirring device positioned at the bottom of the tank body and a second stirring device which is positioned above the first stirring device and has an aeration function; the top of the tank body is provided with an openable top cover, and the second stirring device is connected with the tank body through the top cover. This bioleaching reactor simple structure, first agitating unit can effectively solve the deposit of powdered solid waste (for example FCC spent catalyst), and second agitating unit has stirring and aeration function concurrently, and the bubble can be dispersed better under the stirring effect, effectively improves bioleaching efficiency, can also avoid aerating device's jam, is applicable to the bioleaching that contains heavy metal solid waste.
Description
Technical Field
The invention relates to the field of solid waste disposal, and discloses a method for treating heavy metal-containing solid waste.
Background
The hazardous solid wastes rich in heavy metals, such as smelting tailings, fly ash, waste batteries, waste circuit boards, municipal sludge, waste catalysts and the like, have higher environmental hazard. However, some of the heavy metal components contained in the solid wastes have extremely high value, such as gold, silver, palladium, platinum, indium, gallium, cobalt, nickel, copper, zinc, manganese, lanthanum, cerium and the like, and the recovery of the valuable metals is a win-win strategy and a development direction of the treatment process while the solid wastes containing the heavy metals are treated by adopting a proper process method.
At present, the main processes for treating solid waste containing heavy metals and recovering valuable metals are a pyrogenic process and a wet process. Pyrometallurgy is a process for extracting metals from solid phase by using high temperature, generally the temperature can reach more than 2500 ℃, the energy consumption is very high, the pollution is serious, the material requirement is very high, the operation condition is harsh, the cost is also high, and the treatment cost of each ton of solid wastes is nearly 3000 yuan. Hydrometallurgy utilizes acid solution to extract target metal from solid waste, and separation and purification are carried out through electrolysis, adsorption and extraction. The hydrometallurgy has strong selectivity and high recovery efficiency, but the hydrometallurgy needs large-scale practical strong acid and has extremely high cost. And the wet method has high requirements on equipment materials, harsh operating conditions and higher safety risk.
Bioleaching is a technique based on the metabolic activity of various bacteria to remove metals. Compared with the traditional wet and fire process, the bioleaching method has the advantages of environmental protection, low cost, simple operation and maintenance, mild required treatment conditions, no discharge of hazardous wastes and the like. The bioleaching technology can effectively remove heavy metals in solid waste, is a solid waste heavy metal treatment and recovery technology with wide application prospect, and has important significance for safe treatment and resource utilization of the heavy metal-containing solid waste. Most of the existing solid waste bioleaching treatment processes have the problems of long treatment period, insufficient stirring, complex process and the like. In addition, the disposal of powdery solid waste such as fly ash and waste catalyst has problems of easy sedimentation, difficult stirring, uneven mixing, and poor solid-liquid contact effect.
CN105859074A provides a sludge heavy metal resource extraction system and an extraction method thereof, designs a flow method of bioleaching treatment, covers multiple links of bacterial liquid preparation, reaction, metal recovery and the like, and does not introduce the used reactor in detail. And the method is only suitable for bioleaching treatment of sludge and is not suitable for treating powdery solid waste such as waste catalyst, fly ash and the like.
CN102091710B discloses a method and a device for removing heavy metal pollutants in fly ash, which is a chemical method. Heavy metals and compounds thereof in the fly ash are subjected to oxidation-reduction reaction under the action of an electric field gradient formed by direct current inserted into an electrode in a fly ash/liquid phase system, are migrated and concentrated in a cathode region, form a pH sudden-crossing region in a meeting region, change the pH value of the cathode region, empty the pH sudden-crossing region and inject an acidic solution to change the pH value, and the acidic solution circularly flows by using a peristaltic pump, so that heavy metal pollutants in the fly ash are effectively removed; and intermediate circulation washing or bioleaching and electrode conversion are adopted, and a cation exchange membrane is additionally arranged, so that the effect of removing heavy metal pollutants in the fly ash is improved.
In order to improve the treatment efficiency, enhance the bioleaching leaching efficiency and effectively promote the engineering application of the bioleaching technology in the solid waste treatment, the bioleaching technology needs to be further improved.
Disclosure of Invention
The invention aims to solve the problems of low treatment efficiency and the like of a bioleaching process for treating solid waste containing heavy metal.
In order to achieve the above object, the present invention provides a method for treating heavy metal-containing solid waste, comprising: performing bioleaching treatment on the heavy metal-containing solid waste by using bioleaching bacteria in a bioleaching reactor;
the bioleaching reactor comprises a tank body, a first stirring device positioned at the bottom of the tank body and a second stirring device which is positioned above the first stirring device and has an aeration function;
the top of the tank body is provided with an openable top cover, and the second stirring device is connected with the tank body through the top cover.
Preferably, the biological leacheate comprises chemoautotrophic aerobic bacteria, preferably sulfur bacteria and/or iron bacteria.
Preferably, the bioleaching strain comprises at least one of thiobacillus oxysulphide (thiobacillus thiooxidans), thiobacillus ferrooxidans (thiobacillus ferrooxidans), thiobacillus caldus (acithiobacillus caldus) and leptospirillum ferriphilum (leptium ferrophilum).
Preferably, the Acidithiobacillus caldus is at least one selected from the group consisting of the Acidithiobacillus caldus with the preservation number of CCTCC No: M2021708, CCTCC No: M2021709 and CCTCC No: M2021710.
The bioleaching reactor provided by the method has a simple structure, the second stirring device has stirring and aeration functions, and bubbles can be better dispersed under the stirring action; the first agitating unit of bottom can effectively solve the bottom deposit of powdered solid waste (for example FCC spent catalyst), does not basically have the mixing dead angle, still is favorable to the contact of waste and fungus liquid, effectively improves bioleaching efficiency.
The second stirring device provided by the method of the invention has the functions of aeration and stirring, and can also avoid the problem that the aeration device positioned at the bottom of the reactor in the traditional reactor is easy to block.
The bioleaching reactor and the bioleaching system can be used for bioleaching heavy metal-containing solid waste (such as fly ash, activated sludge, waste catalyst and other dangerous solid waste rich in heavy metals), especially for bioleaching powdery solid waste, removing and recycling heavy metals, implementing harmless and recycling treatment, and are beneficial to realizing the recycling of the heavy metal-containing solid waste and low in energy consumption.
In addition, the bioleaching strain used in the bioleaching process often has the problems of slow growth and low leaching efficiency, and particularly has poor tolerance to heavy metal-containing solid waste (such as FCC waste catalyst) with high toxicity and poor bioleaching effect. The preferred bacterial strain (especially at least one thermophilic thiobacillus with the preservation number of CCTCC No: M2021708, CCTCC No: M2021709 and CCTCC No: M2021710) related in the invention has high tolerance to the FCC waste catalyst and good bioleaching effect, and is especially suitable for recycling the FCC waste catalyst.
Drawings
FIG. 1 is a schematic view of a bioleaching reactor according to the invention.
Description of the reference numerals
1. A tank body; 2. a first stirring device; 3. a second stirring device; 4. a temperature control device.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a method for treating solid waste containing heavy metals, which comprises the following steps: performing bioleaching treatment on the heavy metal-containing solid waste by using bioleaching bacteria in a bioleaching reactor;
the bioleaching reactor comprises a tank body, a first stirring device positioned at the bottom of the tank body and a second stirring device which is positioned above the first stirring device and has an aeration function;
the top of the tank body is provided with an openable top cover, and the second stirring device is connected with the tank body through the top cover.
The bioleaching reactor is used for treating solid waste containing heavy metals, and is particularly suitable for bioleaching for treating powdery solid waste (such as FCC waste catalyst).
According to the present invention, preferably, the can is cylindrical.
According to the present invention, preferably, the height-diameter ratio of the tank is 2 to 3:1, for example, it can be 2:1, 2.2, 1, 2.4.
The material of the tank is not particularly limited, and may be a material conventionally used in the art as a tank of a bioleaching reactor, and may be, for example, SUS316 stainless steel, SUS316L stainless steel, or the like.
The shape of the top cover is not particularly limited, and may be an arc surface or a plane surface.
Typically, the lid is sealingly connected to the can, for example by a rubber ring or the like filling the connection between the lid and the can.
Preferably, the top cover of the tank body is provided with an exhaust port. The size of the vent can be determined by one skilled in the art based on the size of the reactor.
The top cover of the tank body can also comprise other devices, such as a feeding port for feeding or supplementing materials, a sensor connecting port for monitoring parameters (such as temperature, dissolved oxygen, pH and the like) of the bioleaching process, and the like.
Preferably, the bottom of the tank body is horizontal. The bottom plate at the bottom of the tank body can be fixedly connected to the tank body, and the discharge is controlled by the switch of a discharge port on the bottom plate; the discharging device can also be movably connected to the tank body, or at least part of the bottom plate (for example, a half bottom plate) is movably connected to the tank body, and the discharging is controlled by opening and closing at least part of the bottom plate. The movable connection may be, for example, a hinge.
Preferably, the bottom of the tank body is provided with a discharge opening. The discharge opening may be an aperture of any shape located at the bottom of the can body or may be formed by at least partially opening the bottom plate of the can bottom.
It will be appreciated that in the unopened condition of the discharge opening, the bottom of the tank is closed, i.e. does not leak liquid or material.
According to the invention, said first stirring means can be connected to the floor of the tank in a manner conventional in the art, for example by being fixed by bearings.
Preferably, the first stirring device is a disc stirrer, a paddle stirrer, a propeller stirrer or a turbine stirrer.
It should be understood that in order to ensure the proper operation of the first stirring device, it is provided with a drive shaft, a drive motor and the like.
The material of the first stirring device is not particularly limited, and may be, for example, stainless steel, high-strength plastic, alloy, or the like.
Preferably, the outer diameter of the first stirring device is 3/5 to 3/4 of the diameter of the tank body.
Preferably, the height of the inner part of the first stirring device in the tank body is not more than 1/10 of the height of the tank body.
The person skilled in the art can select the first stirring device with a suitable height according to the size of the tank.
According to the invention, the second stirring device is positioned above the first stirring device to perform the functions of aeration and stirring.
Preferably, the second stirring device comprises a hollow stirring rod connected with the top cover and at least one stirring paddle arranged on the stirring rod.
The stirring rod may be attached to the top cover in a manner conventional in the art, such as by being fixed by bearings.
Preferably, capillary pores with the diameter of 0.5-1.5mm are distributed on the surface of the stirring rod for aeration.
The capillary holes can be uniformly distributed on the surface of the stirring rod, and preferably, the capillary holes are uniformly distributed on the part of the lower end of the stirring rod, the length of which is 1/6 to 1/3 of the height of the tank body.
It should be understood that the number of capillary openings should not affect the strength of the stir bar, allowing the stir bar to function properly without being susceptible to damage. Preferably, the total area of the capillary holes is 20 to 30% of the surface area of the portion of the stirring rod having the capillary holes.
Preferably, one end of the stirring rod, which is positioned outside the tank body, is connected with a gas supply device, and is used for aerating gas provided by the gas supply device through capillary holes.
Preferably, the number of paddles is at least one, more preferably at least two.
Preferably, the stirring paddle is selected from at least one of a turbine stirring paddle, a cross-shaped stirring paddle, a paddle stirring paddle, a propeller stirring paddle and an anchor stirring paddle.
Preferably, the diameter of the outer periphery of the stirring paddle is 3/5 to 3/4 of the diameter of the tank body. That is, the maximum diameter of the paddle is 3/5 to 3/4 of the diameter.
The height of the single stirring paddle can be selected according to the size of the tank body, and preferably, the height of the stirring paddle is 1/15 to 1/8 of the height of the tank body.
If the number of the stirring paddles is at least two, the interval between the two stirring paddles is preferably 1/8 to 1/5 of the height of the tank. The interval refers to the distance between the installation nodes of the two stirring paddles.
Preferably, the shortest distance between the stirring paddle and the bottom of the tank body is 1/3 to 1/6 of the height of the tank body, and more preferably 1/4 to 1/6.
The second stirring device may further comprise, for example, a drive device (e.g., a motor) for powering the second stirring device.
It will be appreciated that the first and second agitating means are in concentric circular relationship with the tank.
Preferably, the outer wall or the inner wall of the tank body is detachably or fixedly connected with a temperature control device.
The temperature control device can be, for example, a coil, a jacket, an additional heating jacket, and the like, and can be, for example, a detachable cast aluminum heating jacket. It will be appreciated that the reactor will be provided with a relatively low level water inlet and a relatively high level water outlet.
Preferably, the bioleaching reactor further comprises monitoring means, which may be, for example, a pH meter, a solvent oxygen electrode, an oxidation-reduction potentiometer, a temperature sensor, etc., for monitoring changes in the corresponding parameters during the bioleaching process.
Preferably, the bioleaching reactor further comprises a control system for controlling the operation of the first stirring device, the second stirring device and the temperature control device.
Through control system can control the switch of first agitating unit and second agitating unit, stirring rotational speed and air output, thereby can also control temperature control device's operation and realize the purpose of regulation and control temperature.
The control system can also control feeding, discharging, feeding and the like.
The control system may be one conventionally used in the art and may for example comprise a controller, which may for example be a PLC controller, and a display device, which may for example be a touch screen.
According to the invention, the strain can be directly expanded in the bioleaching reactor, or exogenous bioleaching strains can be provided, i.e. the strain can be expanded outside the bioleaching reactor, for example, by using a fermentation tank.
Preferably, the bioleaching bacteria comprise chemoautotrophic aerobic bacteria. The chemoautotrophic aerobic bacteria can oxidize certain inorganic substances and utilize the generated chemical energy to reduce carbon dioxide and generate organic carbon compounds.
Preferably, the bioleaching bacteria comprise sulphur and/or iron bacteria.
Preferably, the bioleaching strain comprises at least one of thiobacillus oxysulphide (thiobacillus thiooxidans), thiobacillus ferrooxidans (thiobacillus ferrooxidans), acidovorax brucei (acidianus brierrlyi), sulfolobus metallothioneius (sulfolobus), thiobacillus caldarius (acidianhiobacillus caldus) and leptospirillum ferriphilum (leptospirillum).
Preferably, the Acidithiobacillus caldus is at least one selected from the group consisting of the Acidithiobacillus caldus with the preservation number of CCTCC No: M2021708, CCTCC No: M2021709 and CCTCC No: M2021710.
The Acidithiobacillus caldus (Acidithiobacillus caldus) CCTCC No. M2021708, CCTCC No. M2021709 and CCTCC No. M2021710 are preserved in the China center for type culture Collection (address: wuhan city, wuhan university, postal code: 430072) in 2021, 6 and 9 days (the preservation unit is abbreviated as CCTCC).
In the present invention, the concentration of the bioleaching bacteria in the bioleaching system is not particularly limited, and may be specifically selected according to specific conditions, for example, the viable count of the bioleaching bacteria may be 10 8 More than cfu/mL.
The bioleaching strain provided by the invention can be in different dosage forms (such as liquid or solid), and different components can be added according to actual conditions. The specific choices are well known to those skilled in the art and the present invention will not be described in detail herein.
The biological leacheate is preferably in the form of a liquid inoculum, such as a culture solution.
The preparation method of the liquid microbial inoculum can be a preparation method which is conventional in the field, for example, the preparation method of the liquid microbial inoculum can comprise the following steps: inoculating the biological leaching bacteria into an expanding culture medium for expanding culture to obtain a liquid microbial inoculum.
In the present invention, the expanding medium may be a medium conventionally used in the art, such as when the microorganism to be cultured is a sulfur bacterium, preferably, the expanding medium comprises: (NH) 4 ) 2 SO 4 1.5-4g/L，KH 2 PO 4 0.1-3g/L，MgSO 4 ·7H 2 O 0.3-0.7g/L，CaCl 2 0.1-0.3g/L，FeSO 4 0.005-0.02g/L, and 8-15g/L of sulfur powder; the pH of the bioleaching culture medium is 2-5. Concentrated sulfuric acid can be used, for example, in the preparation processThe pH is adjusted. The skilled person will be able to select a suitable medium depending on the particular microorganism species used and will not be described in detail here.
It should be understood that the conditions for propagation may also vary from one bioleaching species to another, for example, when the bioleaching species is Acidithiobacillus caldus, the conditions for propagation include: the temperature is 40-45 ℃ and the time is 48-96h; in the case of thiobacillus thiooxidans, the temperature may be between 32 ℃ and 38 ℃.
When the propagation is carried out in a shake flask, the rotation speed may be controlled to be 100-150rpm, preferably 120-135rpm.
It should be understood that the scale of the propagation may be determined by those skilled in the art according to the production scale, and may be at least one stage of propagation, for example.
Preferably, the number of viable bacteria in the culture solution is 1 × 10 8 More than cfu/mL.
In order to shorten the bioleaching cycle, the culture broth can be transferred in its entirety to the bioleaching reactor for bioleaching without a longer incubation time again. Preferably, the inoculation amount is such that the number of living bacteria of bioleaching bacteria in the bioleaching system is 10 8 cfu/mL or more.
When the number of the biological leaching bacteria is two or more, the biological leaching bacteria can be inoculated after being cultured independently or after being cultured in a mixed way. Inoculum size of the broth was based on total broth volume. The addition of various biological leachates can be adjusted by those skilled in the art according to actual conditions.
Preferably, the bioleaching treatment is carried out in the presence of a bioleaching medium.
Preferably, the bioleaching media comprises an energy source substrate and an inorganic salt.
Preferably, the energy source substrate comprises a ferrous salt (which may be ferrous sulphate, for example) and/or sulphur. For example, when the strain is Acidithiobacillus caldus, the energy substrate may be sulfur powder.
In a preferred embodiment of the invention, the bioleaching medium comprises 1-2.5g/L of a nitrogen source, 0.5-0.8g/L of a magnesium source, 0.05-0.25g/L of CaCl 2 、0.25-1g/L KH 2 PO 4 5-20g/L of a sulfur source and/or a ferrous salt; wherein the nitrogen source is selected from KNO 3 、(NH 4 ) 2 SO 4 And urea; the magnesium source is MgSO 4 And/or MgCl 2 (ii) a The sulfur source is sulfur powder; the ferrous salt is FeSO 4 And/or FeCl 2 . Preferably, the content of the ferrous salt is 0.001-0.1g/L. Preferably, the content of sulfur is 8-15g/L.
Preferably, the bioleaching media has a pH of from 2 to 5. The person skilled in the art can adjust the pH by means of the addition of an acid.
The conditions of bioleaching can be adjusted by those skilled in the art according to the type of bioleaching bacteria, and preferably include: the temperature is 30-48 ℃.
It should be understood that the bioleaching process can be continuous or intermittent, and the mode and time can be adjusted by one skilled in the art according to the actual condition of bioleaching. For example, after the concentration of the target metal in the solid waste containing heavy metal in the bioleaching reactor meets the requirement, the material is discharged from the discharge port, a new batch of solid waste and fresh bacterial liquid to be treated is supplemented, a new round of bioleaching treatment is carried out, the solid waste is continuously treated and discharged by the circulation until the leaching strain growth is obviously inhibited due to too high metal ions. Preferably, the conditions of the bioleaching process include: the time is 24-96h.
Oxygen-containing gas (such as air or mixed gas containing oxygen with different concentrations) can also be introduced in the bioleaching process, and the ventilation quantity can be selected in a wide range, and is preferably 0.05-0.2vvm.
The solid waste containing heavy metal can be the solid waste containing heavy metal in the prior art, such as smelting tailings, fly ash, waste batteries, waste circuit boards, municipal sludge, waste catalysts and the like, and preferably at least one of fly ash, activated sludge and waste catalysts.
Preferably, the addition amount of the solid waste containing heavy metals is 100-250g/L based on the total volume of the bioleaching system.
In a preferred embodiment of the present invention, the heavy metal-containing solid waste is FCC waste catalyst. In the preferred case, the biological gonococci comprise Acidithiobacillus caldus (Acidithiobacillus caldus) selected from at least one species of Acidithiobacillus caldus with a collection number of CCTCC No: M2021708, CCTCC No: M2021709 and CCTCC No: M2021710. Preferably, the conditions of the bioleaching process include: the temperature is 40-48 ℃ and the time is 24-96h.
The present invention will be described in detail below by way of examples.
In the following examples, the reagents and materials used were all commercially available unless otherwise specified.
The selection is made in a manner conventional in the art without specific mention.
The Acidithiobacillus caldus CCTCC No. M2021708, the CCTCC No. M2021709 and the CCTCC No. M2021710 are preserved in China center for type culture collection (address: wuhan university, wuhan mountain, the postal code 430072) in 2021 and 6 months and 9 days (the abbreviation of the preservation unit is CCTCC).
The preparation method of the bioleaching culture medium comprises the following steps: 2g (NH) per 1000mL of distilled water 4 ) 2 SO 4 、3gKH 2 PO 4 、0.5g MgSO 4 ·7H 2 O、0.01g FeSO 4 ·7H 2 O、0.25g CaCl 2 ·2H 2 O, with 2 mol. L -1 Adjusting pH to 3.0 with sulfuric acid solution, autoclaving at 115 deg.C for 30min, and adding 10g sulfur powder sterilized by steaming under normal pressure for 2 hr.
The FCC spent catalyst was obtained from the chinese petrochemical Qingdao refinery, where the contents of heavy metals (Ni, V, sb, la and Ce) are shown in table 1.
The content of heavy metals before and after bioleaching was measured according to the method for measuring 22 metal elements in solid waste by inductively coupled plasma emission spectrometry (HJ 781-2016).
Preparation example 1
This preparation example is intended to explain the method for preparing a bacterial solution of biological gonococci.
Performing first-stage amplification culture on Acidithiobacillus caldus CCTCC No. M2021708 in a 500mL triangular flask at 45 ℃ and with shaking culture at 135rpm, wherein the culture volume is 200mL.
Culturing until the cell density of the strain reaches 1 × 10 8 At cfu/mL, the seed solution was transferred to a fermentor (effective volume 100L) for secondary propagation at a stirring speed of 60rpm with an aeration rate of 10L/min at 45 ℃. After 96h of culture, the density of bacteria in the fermentation tank reaches 5 multiplied by 10 9 cfu/mL。
Wherein, the culture solution of the first-stage amplification culture and the culture solution of the second-stage amplification culture are both bioleaching culture mediums.
And conveying the prepared bacterial liquid to a bioleaching reactor through a pipeline for bioleaching. And (4) transferring the bacterial liquid to the bioleaching reactor, and repeating the steps to prepare the bacterial liquid.
Example 1
This example illustrates the method of the present invention for treating solid waste containing heavy metals.
(1) Bioleaching reactor
As shown in fig. 1, the bioleaching reactor comprises a tank body 1, a first stirring device 2 positioned at the bottom of the tank body, a second stirring device 3 positioned above the first stirring device 2 and having an aeration function, a temperature control device 4 (a cast aluminum heating body) wrapped outside the tank body 1, and a control system.
The tank body 1 is cylindrical, 105cm in height, 40cm in bottom surface diameter, 2.65 in height-diameter ratio and made of SUS316L. An openable top cover is arranged at the top of the tank body 1, and an exhaust hole is formed in the top cover; and the stirring rod of the second stirring device 3 is fixed on the top cover by a bearing and is connected with the tank body 1. The top cover of the tank body 1 is provided with an air outlet, 1/3 of the bottom plate of the tank body 1 part is movably connected to the bottom plate of the other part fixedly connected with the tank body 1 through a hinge, and the material is discharged through the opening and closing of the bottom plate of the movable part. The first stirring device 2 comprises a disc type stirrer (the diameter of the periphery is 25cm, the height of a disc is 5 cm), the disc type stirrer is fixed at the center of the bottom of the tank body 1, and the height in the tank body is 8cm. The second stirring device 3 comprises a hollow stirring rod and two cross-shaped stirring paddles arranged on the stirring rod, and the top end of the second stirring device is connected with an air pump and used for aeration. The distance between the lower frame type stirring paddle and the bottom of the tank body is 20cm, and the distance between the two stirring paddles is 15cm. The stirring paddle has a peripheral diameter of 25cm and a height of 8cm. Capillary holes (accounting for 25 percent of the surface area of the part) with the diameter of 1mm for aeration are uniformly distributed in the length range of 20cm at the lower end of the stirring rod; the first stirring device and the second stirring device are driven to stir by a driving motor, and the control system controls the switch and the stirring speed.
The bioleaching reactor is connected with the fermentation tank in the preparation example 1 through a pipeline, and a water pump is arranged on the pipeline and used for conveying the bacterial liquid of the fermentation tank to the bioleaching reactor.
(2) Bioleaching
20kg of FCC spent catalyst was added to the bioleaching reactor, and the bacterial solution prepared in preparation example 1 was added in an inoculum size of 2 vol%, and the culture medium was supplemented until the working volume was 100L. Starting the reactor to carry out bioleaching treatment on the waste catalyst, wherein the working conditions comprise: the temperature is 45 ℃; aeration rate 0.1vvm; the rotating speed of the stirring rod is 10rpm; the disk stirrer was turned on at 60rpm for 10s per minute.
After reacting for 24 hours in the bioleaching reactor, stopping stirring, standing for a moment, and discharging the treated waste catalyst from a discharge port. And continuously adding a new batch of waste catalyst, supplementing fresh bacterial liquid from the fermentation tank to the liquid level of the working volume, and starting a new round of bioleaching.
After 3 times of operation, the metal concentration in the leachate reaches a higher level, and the spent catalyst and the leachate are all discharged. The treated waste catalyst is dewatered by a plate-and-frame filter press to meet the relevant standard requirements. And removing bacteria and heavy metals in the leachate by adopting a multi-stage membrane method.
And after all the materials in the bioleaching reactor are discharged, continuously adding a new batch of waste catalyst, pumping fresh bacterial liquid from the fermentation tank, and continuing the reaction.
The method can treat 20kg of waste catalyst in one batch, the treatment time of each batch is 24h, more than three batches of waste catalyst can be continuously treated, and the average generation amount of biological leachate of each batch is 30.5L.
The heavy metal content in the treated FCC spent catalyst was sampled and measured, and the metal removal rate was calculated, and the results are shown in table 1.
Example 2
This example illustrates the method for treating solid waste containing heavy metals according to the present invention.
The treatment of FCC spent catalyst was carried out as described in example 1, except that the bioleaching reactor was different and in particular, the structure of the bioleaching reactor was as follows:
the tank body 1 is cylindrical, the height is 110cm, the bottom surface diameter is 37cm, the height-diameter ratio is 2.97. An openable top cover is arranged at the top of the tank body 1, and an exhaust hole is formed in the top cover; and the stirring rod of the second stirring device 3 is fixed on the top cover by a bearing and is connected with the tank body 1. The top cover of the tank body 1 is provided with an air outlet, 1/3 of the bottom plate of the tank body 1 part is movably connected to the bottom plate of the other part fixedly connected with the tank body 1 through a hinge, and the material is discharged through the opening and closing of the bottom plate of the movable part. The first stirring device 2 comprises a propeller type stirrer (the diameter of the periphery is 25cm, the height of the stirrer is 6 cm), and the propeller type stirrer is fixed at the center of the bottom of the tank body 1, and the height in the tank body is 8cm. The second stirring device 3 comprises a hollow stirring rod and a turbine type stirring paddle arranged on the stirring rod, and the top end of the second stirring device is connected with an air pump for aeration. The distance between the lower turbine type stirring blade pitch and the bottom of the tank body is 30cm. The turbine type stirring paddle has a peripheral diameter of 25cm and a height of 6cm. Capillary holes (20 percent of the surface area of the part) with the diameter of 1mm for aeration are uniformly distributed in the length range of 15cm at the lower end of the stirring rod; the first stirring device and the second stirring device are driven to stir by a driving motor, and the control system controls the switch and the stirring speed.
The heavy metal content in the treated FCC spent catalyst was measured by sampling and the metal removal rate was calculated, and the results are shown in table 1.
Example 3
This example illustrates the method for treating solid waste containing heavy metals according to the present invention.
The procedure was followed as described in preparation example 1 and example 1, except that Thiobacillus caldus CCTCC No: M2021709 was used in place of Thiobacillus caldus CCTCC No: M2021708.
The heavy metal content in the treated FCC spent catalyst was sampled and measured, and the metal removal rate was calculated, and the results are shown in table 1.
Example 4
This example illustrates the method for treating solid waste containing heavy metals according to the present invention.
The procedure was followed as described in preparation example 1 and example 1, except that Thiobacillus caldus CCTCC No: M2021710 was used in place of Thiobacillus caldus CCTCC No: M2021708.
The heavy metal content in the treated FCC spent catalyst was sampled and measured, and the metal removal rate was calculated, and the results are shown in table 1.
Example 5
This example illustrates the method for treating solid waste containing heavy metals according to the present invention.
The procedure was followed as described in preparation example 1 and example 1, except that Thiobacillus caldus CICC 24169, obtained from the China center for Industrial culture of microorganisms, was used in place of Thiobacillus caldus CCTCC No: M2021708.
The heavy metal content in the treated FCC spent catalyst was sampled and measured, and the metal removal rate was calculated, and the results are shown in table 1.
Comparative example 1
This comparative example is used to illustrate a reference process for treating solid waste containing heavy metals.
Bioleaching is carried out according to the bioleaching reactor described in the embodiment 1, except that the bioleaching reactor does not comprise a first stirring device, a stirring rod (without capillary holes) of a second stirring device penetrates through a tank body, 3 frame type stirring paddles are arranged on the stirring rod, the lowest stirring paddle is positioned at the bottom of the tank body, and the interval between the stirring paddles is 10cm; the bottom of the tank body is also provided with a gas distributor which is connected with an external source gas supply device.
In the process, the air distributor is blocked, the bottom of the reactor is provided with a dead angle, and a large amount of waste catalyst samples are difficult to be fully mixed with the bioleaching liquid due to long-time accumulation. And partial thalli are also accumulated at the dead angle part of the reactor, anaerobic fermentation occurs, and the metal leaching rate in the waste catalyst is greatly reduced.
The heavy metal content in the treated FCC spent catalyst was sampled and measured, and the metal removal rate was calculated, and the results are shown in table 1.
TABLE 1
| Metal content (mg. G) -1 ) | Ni | V | Sb | La | Ce |
| Content in FCC spent catalyst | 3.57 | 6.19 | 2.15 | 11.87 | 6.11 |
| Example 1 | 1.64(54％) | 2.72(56％) | 0.71(67％) | 4.15(65％) | 2.69(56％) |
| Example 2 | 1.86(48％) | 2.85(54％) | 0.77(64％) | 4.51(62％) | 2.87(53％) |
| Example 3 | 1.72(52％) | 3.10(50％) | 0.67(69％) | 3.92(67％) | 2.51(59％) |
| Example 4 | 1.89(47％) | 2.85(54％) | 0.62(71％) | 4.75(60％) | 2.87(53％) |
| Example 5 | 2.32(35％) | 3.65(41％) | 1.23(43％) | 7.36(38％) | 3.91(36％) |
| Comparative example 1 | 2.61(27％) | 4.21(32％) | 1.53(29％) | 8.78(26％) | 4.46(27％) |
Note: the parenthesis indicates the metal removal rate.
From the above results, it can be seen that when the bioleaching reactor of the present invention and the preferred microorganism strain of the present invention are used for bioleaching FCC waste catalyst, the bioleaching effect is better.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1. A method for treating solid waste containing heavy metals is characterized by comprising the following steps: performing bioleaching treatment on the heavy metal-containing solid waste by using bioleaching bacteria in a bioleaching reactor;
the bioleaching reactor comprises a tank body, a first stirring device positioned at the bottom of the tank body and a second stirring device which is positioned above the first stirring device and has an aeration function;
the top of the tank body is provided with an openable top cover, and the second stirring device is connected with the tank body through the top cover.
2. The method of claim 1 wherein the can body is cylindrical with an aspect ratio of 2 to 3:1;
the top cap of the jar body is provided with the gas vent, jar body bottom is provided with the bin outlet.
3. The method of claim 1, wherein the first stirring device is a disc stirrer, a paddle stirrer, a propeller stirrer, or a turbine stirrer;
preferably, the outer diameter of the first stirring device is 3/5 to 3/4 of the diameter of the tank body;
preferably, the height of the inner part of the first stirring device in the tank body is not more than 1/10 of the height of the tank body.
4. The method of claim 1, wherein the second stirring device comprises a hollow stirring rod connected with the top cover and at least one stirring paddle mounted on the stirring rod; capillary holes with the diameter of 0.5-1.5mm for aeration are distributed on the surface of the stirring rod;
preferably, one end of the stirring rod, which is positioned outside the tank body, is connected with the gas supply device and is used for aerating the gas provided by the gas supply device through capillary holes.
5. The method of claim 4, wherein the paddle is selected from at least one of a gate paddle, a turbine paddle, a cross paddle, a paddle, a propeller paddle, and an anchor paddle;
preferably, the shortest distance between the stirring paddle and the bottom of the tank body is 1/3 to 1/6 of the height of the tank body;
preferably, the diameter of the outer periphery of the stirring paddle is 3/5 to 3/4 of the diameter of the tank body.
6. The method according to claim 1, wherein the outer wall or the inner wall of the tank body is detachably or fixedly connected with a temperature control device; and/or
The bioleaching reactor also comprises a control system which is used for controlling the operation of the first stirring device, the second stirring device and the temperature control device.
7. The method according to claim 1, wherein the biological leacheate comprises chemoautotrophic aerobic bacteria, preferably sulfur bacteria and/or iron bacteria;
preferably, the bioleaching strain comprises at least one of thiobacillus oxysulphide (thiobacillus thiooxidans), thiobacillus ferrooxidans (thiobacillus ferrooxidans), acidovorax brucei (acidianus brierrlyi), sulfolobus metallothioneius (sulfolobus), thiobacillus caldarius (acidianhiobacillus caldus) and leptospirillum ferriphilum (leptospirillum ferrophilum);
preferably, the Acidithiobacillus caldus is at least one selected from the group consisting of the Acidithiobacillus caldus with the preservation number of CCTCC No: M2021708, CCTCC No: M2021709 and CCTCC No: M2021710.
8. A process as claimed in claim 1, wherein the bioleaching system has a viable count of 10 for bioleaching bacteria 8 cfu/mL or more.
9. The method of claim 1, wherein the bioleaching treatment is carried out in the presence of a bioleaching medium;
the bioleaching medium comprises an energy substrate and inorganic salts;
preferably, the energy source substrate comprises a ferrous salt and/or sulphur.
10. The method of claim 9, wherein the bioleaching media comprises 1-2.5g/L nitrogen source, 0.5-0.8g/L magnesium source, 0.05-0.25g/L CaCl 2 、0.25-1g/L KH 2 PO 4 5-20g/L of sulfur source and/or ferrous salt; the pH value is 2.5-3.5;
wherein the nitrogen source is selected from KNO 3 、(NH 4 ) 2 SO 4 And urea;
the magnesium source is MgSO 4 And/or MgCl 2 ；
The sulfur source is sulfur powder;
the ferrous salt is FeSO 4 And/or FeCl 2 。
11. The method according to claim 1, wherein the addition amount of the solid waste containing heavy metals is 100-250g/L based on the total volume of the bioleaching system.
12. The method according to claim 1, wherein the heavy metal-containing solid waste is at least one of fly ash, activated sludge and spent catalyst;
preferably, the heavy metal-containing solid waste is FCC spent catalyst.
13. The method of claim 1, wherein the conditions of the bioleaching process include: the temperature is 30-48 ℃ and the time is 24-96h.
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| CN210394342U (en) * | 2019-05-27 | 2020-04-24 | 东营职业学院 | Stirrer for biological fermentation |
| CN210560140U (en) * | 2019-08-19 | 2020-05-19 | 启迪桑德(宁波)环境资源有限公司 | Intelligent control sludge composting device |
| CN212954915U (en) * | 2020-08-20 | 2021-04-13 | 江西龙驰生物工程有限公司 | Can retrieve ecological fertilizer fermenting installation who purifies to gas |
| CN113083884A (en) * | 2021-03-30 | 2021-07-09 | 上海市环境科学研究院 | Method for repairing heavy metal contaminated soil by using rice straw biogas residue-based soil repairing agent |
| CN215998037U (en) * | 2021-09-29 | 2022-03-11 | 中国石油化工股份有限公司 | Bioleaching reactor and bioleaching system |
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