Device and method for regenerating powdery iron oxyhydroxide desulfurizer and purifying sulfur

Abstract

The invention discloses a device and a method for regenerating a powdery iron oxyhydroxide desulfurizer and purifying sulfur, and the device and the method are characterized in that invalid iron oxyhydroxide is completely reduced into a ferrous oxide and ferrous sulfide after sulfide is added, the reaction of an iron compound is enhanced through ultrasound and stirring, and the separation of the iron compound and the sulfur is promoted. Further fully aerating to fully oxidize the ferrous iron to generate new iron oxyhydroxide; at the moment, the iron oxyhydroxide is in a completely dispersed state, the single particle size is not higher than 1 micron, and small flocs with the particle size of 0-5 microns are formed in laminar water; the surface of the sulfur has hydrophobicity, and the sulfur is gathered to generate hydrophobic self-flocculation, so that large flocs with the particle size of 30-300 microns are formed in the laminar water; the mixture is flushed by water flows with different flow speeds, the iron oxyhydroxide with small particle size is flushed out at a certain flow speed, and the sulfur with large particle size is suspended in the grading pipe, so that the regeneration of the iron oxyhydroxide desulfurizer and the purification of the sulfur are realized.

Description

Technical Field

[0001] The invention belongs to the field of treatment of hydrogen sulfide-containing gas or sulfide-containing water, and particularly relates to the regeneration of a powdered iron oxyhydroxide desulfurizer for treating sulfur-containing wastewater or waste gas and the separation and purification of sulfur. Background Art

[0002] Hydrogen sulfide gas is commonly found in oil and natural gas, biogas, and industrial odors. Its emission can lead to a range of serious environmental and safety issues, making desulfurization essential. Wet desulfurization is a common hydrogen sulfide desulfurization technology, with iron-based desulfurization methods using iron oxyhydroxide as a desulfurizer being widely used, as described in Chinese Patent CN101766946B.

[0003] The treatment of sulfide-containing wastewater is present in the pulp and paper industry (Wani et al., 1999; Janssen et al., 2009), food processing, animal husbandry (Chung et al., 2001), tanneries, rubber processing, and acid mine drainage (AMD). The method of treating sulfide-containing wastewater using iron oxyhydroxide as an iron-based desulfurizer has been widely used due to its high efficiency and separability, such as Chinese patent CN117466360A, (Levent et al., 2008 ).

[0004] During the application of iron-based desulfurizers, which are primarily iron oxyhydroxide, the generation and accumulation of sulfur will inevitably reduce the desulfurization effect of the iron-based desulfurizer or even make it ineffective. Therefore, to solve the problem of regeneration of iron-based desulfurizers, sulfur must be efficiently separated from the iron-based desulfurizer. Otherwise, the ineffective iron-based desulfurizer will mix with the sulfur and become hazardous waste. The generated sulfur must also be separated to a high purity before it can be recycled.

[0005] Currently, the most common method for regenerating iron-based desulfurizers involves dissolving sulfur in an organic solvent to separate it from the ferric oxyhydroxide. High-temperature distillation is then used to evaporate the sulfur and organic solvent to produce a more purified ferric oxyhydroxide (e.g., CN111686473A, CN111661822A, and CN111686473A). Direct distillation and permeation steam methods also involve heating to melt or vaporize the sulfur, thereby separating it from the iron-based desulfurizer.

[0006] Although the above method is relatively efficient for separating the two, the cost of chemical reagents required for the separation process and the high-temperature heating is high. Secondly, the toxicity of the chemical reagents themselves can cause secondary environmental pollution. In addition, even a very small amount of chemical reagent residue may cause the iron-based desulfurizer to contain harmful substances and cannot be reused. The input of chemical reagents is extremely undesirable, especially for sulfide-containing wastewater. Therefore, the separation process of the above method cannot meet the current market demand for iron-based desulfurizer to recover sulfur, and also causes this type of mixture to be unable to be recycled and become hazardous waste. Summary of the Invention

[0007] In order to overcome the above problems, the inventors conducted intensive research and designed a device and method for regenerating a powdered ferric oxyhydroxide desulfurizer and purifying sulfur. The device and method completely reduce the ineffective ferric oxyhydroxide to divalent iron oxide and ferrous sulfide by adding sulfide, enhance the reaction of the iron compound through ultrasound and stirring, and promote the separation of the iron compound and sulfur. After further sufficient aeration, the divalent iron is fully oxidized to generate new ferric oxyhydroxide, which exists in one or more forms of lepidocrocite, ferrihydrite or goethite. At this time, the ferric oxyhydroxide is in a completely dispersed state, with a single particle size of no more than 1 micron, forming small flocs with a particle size of 0-5 microns in laminar water. The sulfur on the surface of the ferric oxyhydroxide and the sulfur generated by oxidation of the added sulfide are uniformly distributed in the water. The sulfur surface is hydrophobic, and the sulfur aggregates to undergo hydrophobic self-flocculation, thereby forming large flocs with a particle size of 30-300 microns in the laminar water. The mixture is then flushed with water at different flow rates, and the small-sized ferric oxyhydroxide particles are flushed out at a certain flow rate, while the large-sized sulfur particles are suspended in the grading pipe, thereby completing the present invention.

[0008] Specifically, the object of the present invention is to provide a powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device, comprising a first ultrasonic system 1, a regeneration system 2 and a hydraulic separation system 3;

[0009] The first ultrasonic system 1 is used to break up and separate the ferric oxyhydroxide and the sulfur, so that the ferric oxyhydroxide and the sulfide fully react to obtain divalent iron oxide and ferrous sulfide.

[0010] The regeneration system 2 is used to fully oxidize the divalent iron and generate ferric oxyhydroxide;

[0011] The iron oxyhydroxide and sulfur are separated by the hydraulic separation system 3 .

[0012] The first ultrasonic system 1 includes a container in which a stirring mechanism and an ultrasonic generator are provided, and the iron-based desulfurizer to be purified and the sulfide-containing water are contained in the container;

[0013] The regeneration system 2 is connected to the first ultrasonic system 1 and is used to hold the mixture treated by the first ultrasonic system 1; a stirring mechanism is provided in the regeneration system 2; the bottom of the regeneration system 2 is connected to the aeration device 4, and air is introduced into the regeneration system 2 through the aeration device 4;

[0014] The hydraulic separation system 3 is connected to the regeneration system 2 and is used to hold the mixture treated by the regeneration system 2; the hydraulic separation system 3 includes a vertically arranged tubular classification pipe 31, which uses the characteristic that the particle size of iron oxyhydroxide flocs is smaller than the particle size of sulfur flocs to separate iron oxyhydroxide and sulfur.

[0015] The hydraulic separation system 3 includes more than one grading pipe 31, wherein the first grading pipe is connected to the regeneration system 2, and the bottom of the first grading pipe is connected to the water inlet system 5;

[0016] An overflow port is provided at the top of each classification pipe 31, and the overflow port is connected to the bottom of the next classification pipe. The overflow port on the last separation pipe is connected to the iron oxyhydroxide recovery device 6;

[0017] The bottom of each of the classification pipes 31 is connected to the sulfur recovery device 7 .

[0018] The inner diameters of the plurality of grading tubes 31 are different. Preferably, among the plurality of grading tubes 31 , the inner diameter of the preceding grading tube 31 is smaller than the inner diameter of the following grading tube 31 .

[0019] Preferably, there are five or more grading pipes 31 , and more preferably, there are seven grading pipes 31 .

[0020] Among them, a constant speed flow meter 8 is provided between the water inlet system 5 and the separation system 3, and the flow rate of water entering the separation system 3 is controlled by the constant speed flow meter 8; preferably, the flow rate in the grading pipe 31 is set between 0.1-5m / h by the constant speed flow meter 8.

[0021] The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device further includes a second ultrasonic system 9, which is used to break up the sulfur in the sulfur recovery device 7;

[0022] Preferably, the second ultrasonic system 9 is connected to the sulfur recovery device 7 and the separation system 3, and the sulfur with insufficient purity in the sulfur recovery device 7 is broken up by the second ultrasonic system 9 and sent to the separation system 3 for further separation and purification.

[0023] The present invention also provides a method for regenerating a powdered ferric oxyhydroxide desulfurizer and purifying sulfur, which is carried out using the powdered ferric oxyhydroxide desulfurizer regeneration and sulfur purification device described above.

[0024] The method comprises the following steps:

[0025] Step 1: adding the iron-based desulfurizing agent to be purified into the container of the first ultrasonic system 1, and then adding water containing sulfide of corresponding concentration;

[0026] Step 2: Turn on the ultrasonic generator and stirring mechanism of the first ultrasonic system 1. Preferably, the ultrasonic intensity of the ultrasonic generator is not less than 30 kHz, and the working time of the ultrasonic generator is not less than 10 minutes.

[0027] Step 3: After the first ultrasonic system 1 is completed, all the ferrosulfur mixture in the first ultrasonic system 1 is pumped into the regeneration system 2, the aeration device 4 is turned on, and the stirring mechanism is started until all the ferrous iron in the ferrosulfur mixture is completely oxidized. Preferably, the regeneration system 2 continues to work for more than 1.5 hours;

[0028] Step 4: pumping the mixed ferrosulphur mixture in the regeneration system 2 into the classification system 3; preferably, only pumping into the first classification pipe 31;

[0029] Step 5, the water inlet system 5 pumps water into the first classification pipe 31 through the constant speed flow meter 8;

[0030] Step 6, precipitating the liquid in the iron oxyhydroxide recovery device 6, recycling the upper water to the water inlet system 5, collecting the bottom mud, and drying it to obtain a powdered iron oxyhydroxide desulfurizer;

[0031] Step 7, precipitating the liquid in the hydraulic separation system 3, and recovering the precipitate at the bottom of the classification pipe 31 to the sulfur recovery device 7;

[0032] In step 8, the sulfur in the sulfur recovery device 7 is filtered and dried to obtain finished sulfur.

[0033] In step 5, the flow rate is controlled by the constant speed flow meter 8 so that the flow rate in each classification pipe 31 is between 0.1-5 m / h;

[0034] Preferably, the water inlet time is not less than 5 minutes; further preferably, the water inlet time should be not less than 20 minutes.

[0035] After executing step 7, when the sulfur purity in the sulfur recovery device 7 is insufficient, the precipitate in the sulfur recovery device 7 is pumped into the second ultrasonic system 9, and after ultrasonic treatment, is directly pumped into the classification system 3, and steps 5, 6 and 7 are executed again.

[0036] The beneficial effects of the present invention include:

[0037] (1) The present invention provides a device and method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur. The device and method utilize a sulfurization aeration regeneration plus hydraulic classification to effectively separate sulfur and iron oxyhydroxide, allowing sulfur to be sold or reused at a purity exceeding 95%, thereby regenerating the ineffective iron oxyhydroxide caused by excessive sulfur accumulation.

[0038] (2) The powdered oxyhydroxide desulfurizer regeneration and sulfur purification device and method provided by the present invention are relatively milder in operation than traditional distillation and other methods, do not require heating, and are simple and easy to operate. Compared with traditional chemical extraction or leaching methods, the advantage is that the input of chemical reagents does not bring about the addition of additional elements, thus eliminating the secondary toxic effects. The regenerated oxyhydroxide becomes less crystalline or amorphous, which is conducive to the reuse of the regenerated oxyhydroxide. Similarly, the purified sulfur does not contain toxic components and plays a vital role in the utilization of industries such as food, fertilizer, and sewage treatment.

[0039] (3) The present invention provides a device and method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur. The cost required for the device and method is first the input of sulfide-containing water. The sulfide in this water will be oxidized to form sulfur after the regeneration reaction and finally mixed with the purified sulfur, so there is no additional cost. The other cost is the water used for hydraulic classification, and this part of water can be reused after precipitation and separation by the iron oxyhydroxide and sulfur recovery device. Therefore, the operating cost of the device and method is extremely low, which has a great economic cost advantage over traditional methods.

[0040] (4) The present invention provides a device and method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur. The device and method are capable of waste recycling. Existing methods for removing hydrogen sulfide or sulfide using iron-based desulfurizers fail after long-term sulfur accumulation. Due to the relatively low sulfur purity at this time, the separation and regeneration costs are high, even exceeding the cost of newly purchased iron oxyhydroxide, resulting in the two being mixed and unable to be separated and becoming solid waste. The device and method can regenerate the iron oxyhydroxide desulfurizer through an extremely low cost advantage, greatly reducing the cost of the desulfurization process, while completing the initial purification of sulfur and improving the marketability of the sulfur products produced by the desulfurization process. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a schematic diagram of the overall structure of the powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device provided by the present invention;

[0042] Figure 2 Graph showing sulfur purity and sulfur recovery under various hydraulic conditions for Example 1 of the present invention;

[0043] Figure 3Graph showing the change in sulfur purity before and after separation in Examples 2, 3, and 4 of the present invention;

[0044] Figure 4 Graph showing the purity change of the iron-based desulfurizer before and after separation in Examples 2, 3, and 4 of the present invention.

[0045] Description of Figure Numbers:

[0046] 1-First Ultrasound System

[0047] 2-Regeneration system

[0048] 3-Hydraulic separation system

[0049] 31-Grading tube

[0050] 4-Aeration device

[0051] 5-Water inlet system

[0052] 6-Ferric Hydroxide Recovery Unit

[0053] 7-Sulfur recovery unit

[0054] 8-Constant speed flow meter

[0055] 9-Second Ultrasound System DETAILED DESCRIPTION

[0056] The present invention will be further described in detail below by way of the accompanying drawings and examples. Through these descriptions, the features and advantages of the present invention will become more clearly understood. Wherein, although various aspects of the embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless otherwise noted.

[0057] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected," and "connected" should be understood in a broad sense. For example, they can refer to fixed, detachable, or integral connections; mechanical or electrical connections; direct or indirect connections through an intermediate medium; and internal communication between two components. Those skilled in the art will understand the specific meanings of the above terms in the present invention in specific contexts.

[0058] The present invention provides a powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device, such as Figure 1 As described, it includes a first ultrasonic system 1, a regeneration system 2 and a hydraulic separation system 3;

[0059] The first ultrasonic system 1 is used to break up and separate the ferric oxyhydroxide and the sulfur, so that the ferric oxyhydroxide and the sulfide fully react to obtain divalent iron oxide and ferrous sulfide.

[0060] The regeneration system 2 is used to fully oxidize the divalent iron and generate ferric oxyhydroxide;

[0061] The iron oxyhydroxide and sulfur are separated by the hydraulic separation system 3 .

[0062] Preferably, the first ultrasonic system 1 includes a container in which a stirring mechanism and an ultrasonic generating device are provided, and the iron-based desulfurizer to be purified and sulfide-containing water are contained in the container; the sulfide in the sulfide-containing water is one or more of sodium sulfide, potassium sulfide, zinc sulfide, ferrous sulfide, calcium sulfide, mercaptan, and sulfide, preferably sodium sulfide.

[0063] The regeneration system 2 is connected to the first ultrasonic system 1, mainly through a pump and a pipe. The regeneration system 2 is used to hold the mixture treated by the first ultrasonic system 1. The regeneration system 2 is provided with a stirring mechanism. The bottom of the regeneration system 2 is connected to the aeration device 4, and air is introduced into the regeneration system 2 through the aeration device 4. The introduced air is used to oxidize the divalent iron therein to obtain the desired ferric oxyhydroxide in the form of one or more of lepidocrocite, ferrihydrite or goethite.

[0064] The hydraulic separation system 3 is connected to the regeneration system 2, primarily via a pump and pipeline. It is used to hold the mixture processed by the regeneration system 2. The hydraulic separation system 3 includes a vertically arranged tubular grading pipe 31. This grading pipe 31 utilizes the smaller particle size of ferric oxyhydroxide flocs than that of sulfur flocs to separate ferric oxyhydroxide from sulfur. Preferably, the grading pipe 31 has a constant diameter and is a uniformly long straight pipe or cylinder.

[0065] Preferably, the hydraulic separation system 3 includes more than one grading pipe 31, wherein the first grading pipe is connected to the regeneration system 2, and the bottom of the first grading pipe is connected to the water inlet system 5; the water inlet system 5 includes a water storage tank and a water supply pump.

[0066] An overflow port is provided at the top of each grading pipe 31, which is connected to the bottom of the next grading pipe. The connections in the hydraulic separation system 3 can be solely pipeline-connected, and a power pump system may not be provided. The overflow port on the last separation pipe is connected to the iron oxyhydroxide recovery device 6 to recover the iron oxyhydroxide desulfurizer. The connection between the grading pipes 31 is such that the multiple grading pipes are connected in series, so that most of the materials entering the hydraulic separation system 3 pass through the multiple grading pipes in sequence.

[0067] The bottom of each of the classification pipes 31 is connected to the sulfur recovery device 7 so as to recover sulfur.

[0068] In a preferred embodiment, the inner diameters of the plurality of grading pipes 31 are different. Preferably, among the plurality of grading pipes 31, the inner diameter of the preceding grading pipe 31 is smaller than the inner diameter of the succeeding grading pipe 31, that is, the inner diameters of the grading pipes 31 are getting larger and larger. The front and back mentioned in this application are determined based on the liquid flow path. The grading pipe through which the liquid passes first is the front grading pipe, and the grading pipe through which the liquid passes later is the succeeding grading pipe. For example, the grading pipe connected to the water inlet system 5 is set as the first grading pipe, the grading pipe connected to the overflow port of the first grading pipe is the second grading pipe, the grading pipe connected to the overflow port of the second grading pipe is the third grading pipe, and so on. The inner diameter of the second grading pipe is larger than the inner diameter of the first grading pipe, the inner diameter of the third grading pipe is larger than the inner diameter of the second grading pipe, and so on.

[0069] Preferably, there are five or more grading pipes 31 , and more preferably, there are seven grading pipes 31 .

[0070] Preferably, a constant-speed flowmeter 8 is provided between the water inlet system 5 and the separation system 3 to control the flow rate of water entering the separation system 3. Preferably, the flow rate in each grading pipe 31 is set between 0.1 and 5 m / h by the constant-speed flowmeter 8. More preferably, when seven grading pipes are provided, the flow rates in each grading pipe are 0.08, 0.25, 0.42, 0.59, 0.76, 0.93, and 1.1 m / h, respectively.

[0071] Preferably, the water inlet system 5 is connected to the iron oxyhydroxide recovery device 6 and the sulfur recovery device 7 to recycle water in the iron oxyhydroxide recovery device 6 and the sulfur recovery device 7.

[0072] Preferably, the powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device also includes a second ultrasonic system 9, which is used to break up the sulfur in the sulfur recovery device 7; preferably, the second ultrasonic system 9 is connected to the sulfur recovery device 7 and the separation system 3, and the sulfur with insufficient purity in the sulfur recovery device 7 is broken up by the second ultrasonic system 9 and sent to the separation system 3 for further separation and purification.

[0073] The present invention also provides a method for regenerating a powdered ferric oxyhydroxide desulfurizer and purifying sulfur, which is carried out using the powdered ferric oxyhydroxide desulfurizer regeneration and sulfur purification device described above.

[0074] The method comprises the following steps:

[0075] Step 1: Add the iron-based desulfurizer to be purified into the container of the first ultrasonic system 1, and then add sulfide-containing water of corresponding concentration; control the concentration and amount of sulfur in the sulfide-containing water so that the trivalent iron in the iron-based desulfurizer to be purified can be fully utilized and converted into divalent iron; the sulfide in the sulfide-containing water in the present application is one or more of sodium sulfide, potassium sulfide, zinc sulfide, ferrous sulfide, calcium sulfide, mercaptan, and thioether, preferably sodium sulfide;

[0076] Step 2: Turn on the ultrasonic generator and stirring mechanism of the first ultrasonic system 1. Preferably, the ultrasonic intensity emitted by the ultrasonic generator is not less than 30 kHz, and the ultrasonic generator operates for not less than 10 minutes, so as to fully disperse the sulfur and ferric oxyhydroxide, so that the ferric oxyhydroxide can fully participate in the chemical reaction and be reduced to divalent iron oxide and ferrous sulfide.

[0077] Step 3: After the first ultrasonic system 1 is completed, all the ferrosulfur mixture in the first ultrasonic system 1 is pumped into the regeneration system 2, the aeration device 4 is turned on, and the stirring mechanism is started until all the ferrous iron in the ferrosulfur mixture is completely oxidized. Preferably, the regeneration system 2 continues to operate for more than 1.5 hours to ensure sufficient oxidation;

[0078] Step 4: pumping the mixed ferrosulphur mixture in the regeneration system 2 into the classification system 3; preferably, only pumping into the first classification pipe 31;

[0079] Step 5: The water inlet system 5 pumps water into the first classification pipe 31 through the constant speed flow meter 8; preferably, the flow rate is controlled by the constant speed flow meter 8 so that the flow rate in each classification pipe 31 is between 0.1-5 m / h;

[0080] Preferably, the water inlet time is not less than 5 minutes; further preferably, the water inlet time should be not less than 20 minutes.

[0081] Step 6, precipitate the liquid in the iron oxyhydroxide recovery device 6, generally for at least 5 hours, recover the upper water to the water inlet system 5, collect the bottom mud, and dry it to obtain the powdered iron oxyhydroxide desulfurizer;

[0082] Step 7, settling the liquid in the hydraulic separation system 3, generally for at least 5 hours, and recovering the precipitate at the bottom of the classification pipe 31 to the sulfur recovery unit 7;

[0083] In step 8, the sulfur in the sulfur recovery device 7 is filtered and dried to obtain finished sulfur.

[0084] After executing step 7, when the sulfur purity in the sulfur recovery device 7 is insufficient, all the precipitates in the sulfur recovery device 7 are pumped into the second ultrasonic system 9, and after ultrasonic treatment, are directly pumped into the classification system 3, preferably, only pumped into the first classification pipe 31, and steps 5, 6, and 7 are performed again.

[0085] Example 1:

[0086] Setting up something like Figure 1 The powdered ferric oxyhydroxide desulfurizer regeneration and sulfur purification device shown in the figure includes a first ultrasonic system 1, a regeneration system 2, a hydraulic separation system 3, an aeration device 4, a water inlet system 5, a ferric oxyhydroxide recovery device 6, a sulfur recovery device 7, a constant-speed flowmeter 8 and a second ultrasonic system 9; wherein, only one grading pipe is provided in the hydraulic separation system 3, the overflow port at the top of the grading pipe is connected to the ferric oxyhydroxide recovery device 6, and the bottom is connected to the sulfur recovery device 7. The grading pipe is also connected to the regeneration system 2 and the constant-speed flowmeter 8.

[0087] The device is used to separate and treat the iron-based desulfurizer to be purified, wherein the iron-based desulfurizer to be purified is a mixture of iron oxyhydroxide and sulfur produced after treating sulfide-containing wastewater, wherein the mass ratio of sulfur to iron oxyhydroxide is 70:30;

[0088] The specific operation process is as follows:

[0089] Step 1: pumping the iron-based desulfurizer to be purified into a first ultrasonic system, and then adding water containing sodium sulfide so that the molar ratio of iron to sodium sulfide in the resulting mixture is 1:1;

[0090] Step 2: Turn on the ultrasonic generator and stirring mechanism of the first ultrasonic system 1 for 30 minutes, wherein the ultrasonic intensity is 40 kHz;

[0091] Step 3: discharge the entire mixture in the first ultrasonic system 1 into the regeneration system 2, open the aeration device 4, start the stirring mechanism, and continue aeration for 2 hours;

[0092] Step 4, pumping the mixture in the regeneration system 2 into the classification pipe of the classification system 3;

[0093] Step 5: Use the water inlet system 5 and the constant flowmeter 8 to control the flow rate of water injected into the classification pipe so that the flow rate of the liquid rising in the classification pipe is 0 m / h, which lasts for 30 minutes. Take the sediment at the bottom of the classification pipe, measure the purity of sulfur in the sediment, and calculate the sulfur recovery rate.

[0094] Step 6: Repeat steps 1 to 5 seven more times. Each time the steps are repeated, the rising flow rate of the liquid in the grading tube in step 5 is different, namely 0.08m / h, 0.25m / h, 0.42m / h, 0.59m / h, 0.76m / h, 0.93m / h, and 1.1m / h.

[0095] Example 2:

[0096] Set as Figure 1 The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device shown includes a first ultrasonic system 1, a regeneration system 2, a hydraulic separation system 3, an aeration device 4, a water inlet system 5, an iron oxyhydroxide recovery device 6, a sulfur recovery device 7, a constant-speed flowmeter 8 and a second ultrasonic system 9; wherein, the hydraulic separation system 3 is provided with 7 grading pipes connected in series, each of which has an inner diameter of 1 cm, 3 cm, 5 cm, 7 cm, 9 cm, 11 cm, and 13 cm, and a height of 1.5 m.

[0097] The device is used to separate and treat the iron-based desulfurizer to be purified, wherein the iron-based desulfurizer to be purified is a mixture of iron oxyhydroxide and sulfur produced after treating sulfide-containing wastewater, wherein the mass ratio of sulfur to iron oxyhydroxide is 70:30;

[0098] The specific operation process is as follows:

[0099] Step 1: pumping the iron-based desulfurizer to be purified into a first ultrasonic system, and then adding water containing sodium sulfide so that the molar ratio of iron to sodium sulfide in the resulting mixture is 1:1;

[0100] Step 2: Turn on the ultrasonic generator and stirring mechanism of the first ultrasonic system 1 for 30 minutes, wherein the ultrasonic intensity is 40 kHz;

[0101] Step 3: discharge the entire mixture in the first ultrasonic system 1 into the regeneration system 2, open the aeration device 4, start the stirring mechanism, and continue aeration for 2 hours;

[0102] Step 4: pump the mixture in the regeneration system 2 into the first classification pipe of the classification system 3 at a pumping rate of 1000 ml / min for 30 minutes;

[0103] Step 6, precipitating the liquid in the iron oxyhydroxide recovery device 6 for 5 hours, collecting the bottom sludge, and drying it to obtain a powdered iron oxyhydroxide desulfurizer;

[0104] Step 7, settling the liquid in the hydraulic separation system 3 for 5 hours, and recovering all the sediment at the bottom of the classification pipe 31 to the sulfur recovery device 7;

[0105] In step 8, the sulfur in the sulfur recovery device 7 is filtered and dried to obtain finished sulfur.

[0106] Example 3:

[0107] The sulfur recovered after the eight separation operations in Example 1 was collected and added to the second ultrasonic system 9, ultrasonicated at an intensity of 60 kHz for 5 minutes while stirring, and then directly pumped into the classification system 3 of Example 1. The water inlet system 5 and the constant flowmeter 8 were used to control the flow rate of water injected into the classification tube so that the liquid in the classification tube rose at a flow rate of 1.1 m / h. The flow rate was continued for 30 minutes. The sedimentation was carried out for 5 hours. The sediment at the bottom of the classification tube was taken, the purity of the sulfur in the sediment was measured, and the sulfur recovery rate was calculated. The sediment after 5 hours of sedimentation in the iron oxyhydroxide recovery device 6 was taken, and the purity of the iron oxyhydroxide desulfurizer therein was measured.

[0108] Example 4:

[0109] The same as Example 2, except that the iron-based desulfurizer to be purified in Example 4 is different from that in Example 2. The iron-based desulfurizer to be purified in Example 4 is a mixture of iron oxyhydroxide and sulfur produced after treating hydrogen sulfide-containing waste gas, wherein the mass ratio of sulfur to iron oxyhydroxide is 70:30;

[0110] like Figure 2 As shown in Example 1, when hydraulic flushing was performed at different flow rates, the sulfur purity gradually increased with increasing flow rate, while the sulfur recovery rate gradually decreased. At a flow rate of 1.1 m / h, the maximum sulfur purity reached 96.7%, and the sulfur recovery rate was 94% under this condition.

[0111] like Figure 3 As shown, in Example 2, for the separation of a mixture of iron oxyhydroxide and sulfur for treating sulfur-containing wastewater, the sulfur purity increased directly from 70% before separation to 97.6%, demonstrating the effectiveness of the process of the present invention for separating and purifying such mixtures. In Example 3, through ultrasound and secondary hydraulic classification, the sulfur purity was increased to 99%, meeting the purity requirements of the primary market. In Example 4, for the separation of a mixture of iron oxyhydroxide and sulfur for treating hydrogen sulfide gas, the sulfur purity increased from 70% to 96.7%, demonstrating the effectiveness of the powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification apparatus and method provided by the present invention for separating and purifying such mixtures.

[0112] like Figure 4 As shown, after separation in Example 2, the purity of the iron oxyhydroxide increased to 83.7%, while after further separation in Example 3, the purity decreased to 80.9%. This demonstrates the effectiveness of the process of the present invention in regenerating iron oxyhydroxide from such sulfur-containing wastewater. After separation in Example 4, the purity of the iron oxyhydroxide increased to 84.2%, demonstrating the effectiveness of the process of the present invention in regenerating iron oxyhydroxide from such hydrogen sulfide-containing waste gas.

[0113] The present invention has been described above with reference to preferred embodiments, but these embodiments are merely exemplary and serve only as illustrations. On this basis, various replacements and improvements can be made to the present invention, all of which fall within the scope of protection of the present invention.

Claims

1. A powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device, characterized in that: It comprises a first ultrasonic system (1), a regeneration system (2) and a hydraulic separation system (3); wherein the first ultrasonic system (1) is used to break up and separate the ferric oxyhydroxide and the sulfur, so that the ferric oxyhydroxide and the sulfide fully react to obtain a divalent iron oxide compound and ferrous sulfide, The divalent iron is fully oxidized by the regeneration system (2) to generate iron oxyhydroxide; The iron oxyhydroxide and sulfur are separated by the hydraulic separation system (3).

2. The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device according to claim 1, characterized in that: The first ultrasonic system (1) comprises a container in which a stirring mechanism and an ultrasonic generating device are arranged, and the iron-based desulfurizing agent to be purified and sulfide-containing water are contained in the container; The regeneration system (2) is connected to the first ultrasonic system (1) and is used to contain the mixture treated by the first ultrasonic system (1); a stirring mechanism is provided in the regeneration system (2); the bottom of the regeneration system (2) is connected to the aeration device (4), and air is introduced into the regeneration system (2) through the aeration device (4); The hydraulic separation system (3) is connected to the regeneration system (2) and is used to hold the mixture treated by the regeneration system (2); the hydraulic separation system (3) includes a vertically arranged tubular classification pipe (31), and the classification pipe (31) uses the characteristic that the particle size of the ferric oxyhydroxide flocs is smaller than the particle size of the sulfur flocs to separate the ferric oxyhydroxide and the sulfur.

3. The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device according to claim 2, characterized in that: The hydraulic separation system (3) includes one or more grading pipes (31), wherein the first grading pipe is connected to the regeneration system (2) and the bottom of the first grading pipe is connected to the water inlet system (5); An overflow port is provided at the top of each grading pipe (31), the overflow port being connected to the bottom of the next grading pipe, and the overflow port on the last separation pipe being connected to the iron oxyhydroxide recovery device (6); The bottom of each of the classification pipes (31) is connected to the sulfur recovery device (7).

4. The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device according to claim 3, characterized in that: The inner diameters of the plurality of grading tubes (31) are different. Preferably, among the plurality of grading tubes (31), the inner diameter of the preceding grading tube (31) is smaller than the inner diameter of the succeeding grading tube (31); Preferably, the number of the grading tubes (31) is more than 5, and more preferably, the number of the grading tubes (31) is 7.

5. The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device according to claim 3, characterized in that: A constant-speed flowmeter (8) is provided between the water inlet system (5) and the separation system (3), and the flow rate of water entering the separation system (3) is controlled by the constant-speed flowmeter (8); preferably, the flow rate in the grading pipe (31) is set between 0.1 and 5 m / h by the constant-speed flowmeter (8).

6. The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device according to claim 3, characterized in that: The powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device further comprises a second ultrasonic system (9), wherein the second ultrasonic system (9) is used to break up the sulfur in the sulfur recovery device (7); Preferably, the second ultrasonic system (9) is connected to the sulfur recovery device (7) and the separation system (3), and the sulfur with insufficient purity in the sulfur recovery device (7) is broken up by the second ultrasonic system (9) and sent to the separation system (3) for further separation and purification.

7. A method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur, characterized in that: The method is carried out by using the powdered iron oxyhydroxide desulfurizer regeneration and sulfur purification device according to any one of claims 1 to 6.

8. The method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur according to claim 7, characterized in that: The method comprises the following steps: Step 1, adding the iron-based desulfurizing agent to be purified into the container of the first ultrasonic system (1), and then adding water containing sulfide of corresponding concentration; Step 2, turning on the ultrasonic generator and stirring mechanism of the first ultrasonic system (1), preferably, the ultrasonic intensity emitted by the ultrasonic generator is not less than 30KHz, and the working time of the ultrasonic generator is not less than 10 minutes; Step 3, after the first ultrasonic system (1) is completed, all the ferrosulphur mixture in the first ultrasonic system (1) is pumped into the regeneration system (2), the aeration device (4) is turned on, and the stirring mechanism is started until all the ferrous iron in the ferrosulphur mixture is completely oxidized. Preferably, the regeneration system (2) continues to work for more than 1.5 hours; Step 4, pumping the mixed ferrosulphur mixture in the regeneration system (2) into the classification system (3); preferably, pumping it only into the first classification pipe (31); Step 5, the water inlet system (5) pumps water into the first classification pipe (31) through the constant speed flow meter (8); Step 6, precipitating the liquid in the iron oxyhydroxide recovery device (6), recovering the upper water to the water inlet system (5), collecting the bottom mud, and drying it to obtain a powdered iron oxyhydroxide desulfurizer; Step 7, precipitating the liquid in the hydraulic separation system (3), and recovering the precipitate at the bottom of the classification pipe (31) to the sulfur recovery device (7); Step 8: The sulfur in the sulfur recovery device (7) is filtered and dried to obtain finished sulfur.

9. The method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur according to claim 8, wherein: In step 5, the flow rate is controlled by a constant speed flow meter (8) so that the flow rate in each classification pipe (31) is between 0.1-5 m / h; Preferably, the water inlet time is not less than 5 minutes; further preferably, the water inlet time should be not less than 20 minutes.

10. The method for regenerating a powdered iron oxyhydroxide desulfurizer and purifying sulfur according to claim 8, characterized in that: After executing step 7, when the sulfur purity in the sulfur recovery device (7) is insufficient, all the precipitates in the sulfur recovery device (7) are pumped into the second ultrasonic system (9), and after ultrasonic treatment, are directly pumped into the classification system (3), and steps 5, 6 and 7 are executed again.

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