Online arsenic removal device and detection method

Abstract

The invention discloses an online arsenic removal device and a detection method.The online arsenic removal device comprises a recovery tank and a weighing device, filter cloth is arranged in the recovery tank, a nano-metal adsorbent is arranged in the filter cloth, a feeding port and an exhaust port are formed in the top of the recovery tank, and a discharging port is formed in the bottom of the recovery tank; a nitrogen inlet and a material changing opening are formed in the side wall. The online arsenic removal device has the advantages of being novel in structural design, low in production cost, flexible and simple in operation, efficient in arsenide separation and the like, can improve the efficiency of the device and reduce the cost in the field of chemical production, and has important guiding significance for operation, recovery and development of chemical production devices and technical services of the production devices.

Description

Technical Field

[0001] This invention belongs to the field of chemical wastewater treatment and resource utilization, specifically relating to an industrial online arsenic removal device and detection method, applicable to the field of waste gas and liquid recovery in the petroleum processing and refining industry. Background Technology

[0002] Arsenic, a carcinogen toxic to humans and other organisms, is often found in nature alongside non-ferrous metal ores and enters non-ferrous smelters along with the concentrates. During the processing of arsenic-containing materials in non-ferrous smelters, especially in hydrometallurgical processes such as leaching, purification, and electrolysis, arsenic oxide and arsenic hydrogenate, substances far more toxic than arsenic trioxide, are produced. Among the various arsenic compounds, arsenic hydrogenate is the most toxic; it is a potent hemolytic agent, and poisoning can lead to the accumulation of hydrogen peroxide and damage to cell membranes. Therefore, the management of arsenic-containing gases and liquids must be extremely cautious, strictly preventing contact with water and humid air. Currently, there are no suitable methods for the treatment of arsenic compounds in China, and the environmental problems caused by arsenic compounds have long plagued metallurgical workers. Some factories rely solely on plant ventilation and simple absorption and purification methods. Therefore, it is essential to establish an online arsenic removal device and method for industrial applications to monitor the arsenic content in products and raw materials in a timely manner, adjust process methods and parameters promptly, reduce the concentration of arsenic in the reaction solution, reduce catalyst deactivation, extend catalyst lifespan, and improve economic efficiency.

[0003] Because arsenic has strong reducing properties, early removal of arsine generally employed chemical absorption, using a strongly oxidizing aqueous solution to oxidize arsenic, converting it into trivalent or pentavalent arsenic. Taking potassium permanganate as an example, using it alone as an absorbent to purify arsenic produces potassium sulfate, potassium arsenate, and manganese dioxide, causing secondary pollution. These problems limited the application of chemical absorption. However, connecting other equipment in series to treat arsenic significantly improves the effect. Currently, the research and application of modified adsorbents for purifying arsenic oxide and arsenic hydride are the most widespread. Modification involves loading single metals, metal oxides, composite metal oxides, or sulfides onto activated carbon, alumina, carbon nanotubes, and molecular sieves, allowing the removal of arsenic oxide and arsenic hydride through adsorption and catalytic oxidation. Modified adsorbents are widely used due to their simple preparation, selective adsorption, and lack of secondary pollution. Activated carbon, in particular, as an adsorbent carrier, has advantages such as low cost, wide availability, acid and alkali resistance, good adsorption performance, large specific surface area, and non-toxicity, and is widely used in various adsorption fields, including arsenic removal research. Physical activation, chemical physical activation, catalytic activation, and template methods are all commonly used methods for preparing modified activated carbon adsorbents. Currently, arsenic removal is mainly achieved by loading single-metal compounds or bimetallic oxides such as copper-based, lead-based, zinc-based, and palladium-based compounds.

[0004] Arsenic compounds have a wide range of sources, and waste gases and liquids generated during industrial production processes are a major source of arsine, including those in the phosphorus chemical, coal chemical, non-ferrous metal smelting, and petroleum refining industries. Waste gas and liquid recovery and treatment is an essential step in laboratory and industrial polymerization experiments, primarily to reduce the content of toxic substances in raw materials and prevent these substances from polluting the atmosphere, rivers, lakes, and soil through diffusion. Therefore, reducing the arsenic content in waste gases and liquids not only meets production requirements but also avoids adverse effects on the polymerization reaction.

[0005] Research reports on the removal of organic arsenic are limited both domestically and internationally, mainly focusing on adsorption using multi-walled nanotubes and iron-aluminum oxides, as well as catalytic oxidation using nano-TiO2. Furthermore, the adsorption of organic arsenic is more difficult than that of inorganic arsenic. In addition, traditional adsorption methods generate highly alkaline regeneration wastewater, the treatment and disposal of which remains an unsolved problem. Indeed, in practical production, many projects have failed to properly dispose of regeneration wastewater or arsenic-containing waste residue, leading to widespread secondary arsenic pollution. If arsenic could be efficiently separated and recovered, it could potentially solve these problems fundamentally. However, to date, key technologies and system solutions for the treatment and disposal of arsenic wastewater and the control of secondary pollution are still lacking both domestically and internationally.

[0006] Chinese patent CN202311109235.X discloses a method for treating high-concentration organic arsenic wastewater and recovering arsenic resources. Addressing the challenge of treating high-concentration organic arsenic wastewater, it proposes a method based on "conversion of organic arsenic to inorganic arsenic—inorganic arsenic adsorption—inorganic arsenic separation and recovery." Specifically, it utilizes a two-stage catalytic chemical oxidation method to convert organic arsenic to inorganic arsenic, then uses nano-ferric hydroxide to complete the adsorption of inorganic arsenic in a fully mixed-flow reactor, and finally recovers arsenic using acid dissolution and ion exchange methods. However, a single metal adsorbent structure is not stable enough and is easily oxidized and decomposed.

[0007] Chinese patent CN201620367717.4 discloses an arsenic removal device for arsenic-containing materials, including a mixing tank and a heating kiln. The mixing tank includes a feed port, a discharge port, and an exhaust channel. The feed port is located at the top of the mixing tank, and the discharge port is located at the bottom of the mixing tank. The mixing tank is located inside the heating kiln. Multiple horizontal baffles are arranged axially along the mixing tank, dividing the inner cavity of the mixing tank into multiple spaces to form multiple buffer chambers. Several through holes are also provided on the horizontal baffles, and a shaft hole is provided at the center of the horizontal baffles. An axially arranged stirring shaft is also provided in the mixing tank, and the stirring shaft passes through the multiple horizontal baffles through the shaft hole. Scrapers are provided on the stirring shaft corresponding to the position of each buffer chamber, and the scrapers are attached to the horizontal baffles. The exhaust channel is axially arranged on the outer wall of the mixing tank. The side walls of the multiple buffer chambers corresponding to the exhaust channel have openings connected to the exhaust channel, and guide vanes are provided in the openings. However, this method removes arsenic by heating, and cannot recover arsenic from the liquid, and the overall structure is complex.

[0008] Chinese patent CN201821261940.6 discloses an arsenic removal device for petrochemical processes, belonging to the field of chemical equipment technology. This arsenic removal device includes a main body, an inlet, support rings, a stirring mechanism, and a circulation mechanism. The main body includes a reaction section and a settling section. The inlet is located on the reaction section. Two support rings are located at the top and bottom of the reaction section, respectively. Arsenic removal agent is placed on the support ring at the bottom of the reaction section. The stirring mechanism is located inside the reaction section. The circulation mechanism is external to the main body and connects the reaction section and the settling section. A heating component is installed inside the settling section. In the reaction section, the raw material and the arsenic removal agent are thoroughly mixed under the action of the stirring mechanism. Then, the reacted raw material is transferred to the settling section. The heating component causes the hydrogen sulfide in the raw material to volatilize. The circulation device then discharges the hydrogen sulfide back into the reaction section. However, this preparation method is overly cumbersome and complex, and the recovery device has a complex structure, making operation inconvenient. Furthermore, it is difficult to determine the consumption of the adsorbent material and the recovery effect, making it unsuitable for industrial applications.

[0009] Chinese patent CN112755957 A discloses a highly efficient arsenic removal agent and its preparation method, belonging to the field of arsenic removal and purification technology. This arsenic removal agent is composed of 13x molecular sieve and TS1 titanium-silicon molecular sieve as carriers I, group IVB elements as carriers II, group VIII fourth-period elements as main agent I, group VIII fifth and sixth-period elements as main agents II, and lanthanide elements as auxiliary agents. However, this method cannot remove and adsorb arsenic from liquids.

[0010] Chinese patent CN201811162149.4 discloses an arsenic removal agent, its preparation method, and its uses. The arsenic removal agent of this invention includes a carrier and an active component loaded on the carrier. The carrier is a mixture of activated carbon and alumina, and the active component is a NiCuMoCo system active component. Specifically, based on the mass of the carrier (100%), the mass percentage of Ni is 10-20%, the mass percentage of Cu is 5-10%, the mass percentage of Mo is 1-5%, and the mass percentage of Co is 1-3%. However, this preparation method is overly cumbersome and complex, and has high costs. Summary of the Invention

[0011] The purpose of this invention is to address the shortcomings of the existing technologies by providing an online arsenic removal device and detection method for industrial applications. This method utilizes a recovery and processing device to chemically react the raw material slurry with an adsorbent to remove arsenic compounds from the raw material slurry, and can detect the arsenic content online.

[0012] To achieve the above objectives, the present invention provides an online arsenic removal device, which includes a recovery tank and a weighing device. The recovery tank is equipped with a filter cloth inside, and the filter cloth is equipped with a nano-metal adsorbent. The top of the recovery tank is equipped with a feed inlet and an exhaust outlet, the bottom is equipped with a discharge outlet, and the side wall is equipped with a nitrogen inlet and a material exchange outlet.

[0013] Preferably, the weighing device of the present invention is an explosion-proof electronic platform scale with a weighing range of 100g to 200kg and a readability of 1g to 0.1mg, preferably 0.1mg, but the present invention is not limited thereto.

[0014] This invention also provides an online arsenic removal detection method, which includes: firstly, weighing the nano-metal adsorbent and filter cloth; loading the weighed nano-metal adsorbent and filter cloth into a recovery tank and weighing the recovery tank filled with nano-metal adsorbent and filter cloth; purging the recovery tank with nitrogen; inputting the raw material slurry from the inlet of the recovery tank; the raw material slurry undergoes chemical and physical adsorption with the nano-metal adsorbent inside the filter cloth, and the raw material slurry completes the arsenic removal and recovery treatment; the treated waste liquid is discharged from the outlet for further treatment; after the waste liquid treatment is completed, rinsing the nano-metal adsorbent and filter cloth and measuring the arsenic content; purging with nitrogen; and weighing the recovery tank.

[0015] In one embodiment, the recycling tank is a cylindrical, closed tank with a volume of 1000ml to 10000ml, a pressure resistance of 0.1 to 10MPa, an internal pressure of 0.1 to 5MPa, a temperature of 5 to 90°C, and a feed rate of 0.5 to 200cm³. 3 / min; preferably, the pressure inside the recovery tank is 1.5–5 MPa, the temperature is 5–50°C, and the feed rate is 0.5–100 cm³. 3 / min; the bottom of the recovery tank is also equipped with a connecting pipe, and the top is also equipped with a flexible hose, which can be adjusted according to the actual situation. The detachable installation pipe is flexible and convenient to disassemble, effectively avoiding damage and increasing the service life of the reactor. It can be used in different application scenarios, improving the applicability of the device.

[0016] In some embodiments, the bottom of the recycling tank is equipped with three support legs, and a fixing frame is installed between the support legs.

[0017] In some embodiments, the vent is connected to a venting line via a flanged stainless steel pipeline, and a safety valve is provided before the vent to maintain a constant pressure inside the recovery tank.

[0018] In some embodiments, the filter cloth is embedded in the groove of the filter frame.

[0019] In some embodiments, the filter cloth is provided with a single layer or multiple layers depending on the processing volume, preferably multiple layers; the pore size of the filter cloth is 100-300 mesh, preferably 100 mesh.

[0020] In some embodiments, the nano-metal adsorbent comprises the reaction product of the following components: metal compound, nano-adsorbent carrier, and polydopamine;

[0021] The nano-adsorbent carrier is mainly selected from at least one of activated carbon, graphene oxide, carbon nanotubes, clay minerals, zeolite, montmorillonite, modified alumina, and molecular sieves.

[0022] In some embodiments, the rinsing of the nano-metal adsorbent and filter cloth uses an alkyl liquid compound that does not react with the nano-metal, preferably at least one of hexane, isopentane and isobutane.

[0023] In some embodiments, the online arsenic removal detection method judges the recovery effect and the remaining amount of nano-metal adsorbent by the weight change before and after recovery. If the weight increases before and after weighing, it means that the nano-metal adsorbent has undergone a chemical reaction with the arsenic compounds in the raw material slurry. If the weight does not change, it is considered that the nano-metal adsorbent has been completely consumed and needs to be replaced and replenished in time.

[0024] In some embodiments, the raw material slurry is a recycled organic solvent, which may include one or more of aliphatic hydrocarbon solvents, alcohol solvents, fatty acid ester solvents, ketone solvents, haloalkyl solvents, and benzene solvents.

[0025] Preferably, the aliphatic hydrocarbon solvent is one or more selected from n-pentane, isopentane, methylcyclopentane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, n-hexane, cyclohexane, n-heptane, and n-octane;

[0026] Preferably, the alcohol solvent may be selected from one or more of methanol, ethanol, isopropanol, and n-butanol;

[0027] Preferably, the fatty acid ester solvent may be selected from one or more of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate;

[0028] Preferably, the ketone solvent may be selected from one or more of acetone, butanone, methyl ethyl ketone, cyclohexanone, isoacetone, methyl butanone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methyl pentanone, and cyclohexanone;

[0029] Preferably, the haloalkyl solvent may be selected from one or more of dichloromethane, n-hexane, and 1,2-dichloroethane;

[0030] Preferably, the benzene solvent may be selected from one or more of benzene, toluene, and xylene.

[0031] The purpose of this invention is to remove arsenic from raw material slurry, which can be used as waste gas and liquid from chemical industrial plants. Through recycling and treatment, it can achieve good arsenic removal effect, provide technical support for the recycling and operation of waste gas and liquid from chemical industrial plants, and solve the shortcomings of the prior art.

[0032] This invention provides an online arsenic removal device and detection method. The method uses a nano-metal adsorbent as the recovery agent. The online arsenic removal device chemically reacts the raw material slurry with the nano-metal adsorbent to remove arsenic compounds, bringing the slurry to the required experimental specifications. This solves the operational hazards caused by the high toxicity of arsenic compounds. It ensures that the arsenic content in chemical wastewater meets the specified standards before subsequent treatment, thereby improving product quality. This method is particularly suitable for waste gas and liquid recovery in the petroleum processing and refining industry. The advantage of this arsenic removal method lies in determining the recovery effect and the remaining amount of nano-metal adsorbent through a quality difference method. It eliminates the need for expensive specialized equipment, simplifies the storage and replacement of expensive nano-metal adsorbents, avoids the risk of combustion and explosion, and allows for online detection of arsenic compound content.

[0033] Compared with existing recovery and separation technologies, the online arsenic removal device of this invention significantly shortens the time for separating arsenic compounds from raw material slurry, and is safe and environmentally friendly. The online arsenic removal device of this invention has advantages such as novel structural design, low production cost, flexible and simple operation, and high-efficiency arsenic compound separation. It can improve the efficiency of equipment and reduce costs in the chemical production field, and has important guiding significance for the operation of chemical production equipment, recovery development, and technical services for production equipment. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This is a schematic diagram of the online arsenic removal device of the present invention.

[0036] In the attached figures, the following labels are used:

[0037] Recycling tank 1

[0038] Inlet 2

[0039] Discharge port 3

[0040] Nano metal adsorbent 4

[0041] Filter cloth 5

[0042] Exhaust port 6

[0043] Nitrogen inlet 7

[0044] Material change port 8 Detailed Implementation

[0045] The technical solution of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments to further understand the purpose, solution and effect of the present invention, but it is not intended to limit the scope of protection of the appended claims.

[0046] This specification uses certain terms to refer to specific components or parts. Those skilled in the art will understand that users or manufacturers may use different names or terms to refer to the same component or part. This specification does not distinguish components or parts by differences in name, but rather by differences in function. The terms "comprising" and "including" used in this specification are open-ended and should be interpreted as "including but not limited to." Furthermore, the term "connection" here includes any direct and indirect electrical connection means. Indirect electrical connection means include connections through other means.

[0047] It should be noted that in the description of this invention, the terms "lateral", "longitudinal", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and "about", or "approximately", "substantially", "left and right", etc., indicating the orientation or positional relationship or parameters, are all based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, a specific size, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0048] The technical solution of the present invention will be further described with reference to the accompanying drawings. An online arsenic removal device and method are provided, wherein the steps for removing arsenic compounds from industrial wastewater using the online arsenic removal device are as follows:

[0049] like Figure 1 As shown, the present invention provides an online arsenic removal device and detection method, which utilizes the online arsenic removal device to chemically react with a nano-metal adsorbent to remove arsenic compounds from the raw material slurry.

[0050] Example 1:

[0051] use Figure 1 The online arsenic removal device shown includes a recovery tank 1 and a weighing device. The bottom of the recovery tank 1 is equipped with three support legs, and a fixing frame is installed between the support legs. A connecting pipe is installed at the bottom of the recovery tank 1, and a flexible hose is installed at the top. Inside the recovery tank 1, there is a filter cloth 5 embedded in a filter mesh frame groove. Nano-metal adsorbent 4 is placed inside the filter cloth 5. The top of the recovery tank 1 has a feed inlet 2 and an exhaust port 6, and the bottom has an outlet 3. The side wall has a nitrogen inlet 7 and a material exchange port 8. The exhaust port 6 is connected to a venting pipeline via a flanged stainless steel pipeline. A safety valve is installed before the exhaust port 6 to maintain a constant pressure inside the recovery tank 1.

[0052] The online arsenic removal detection method includes the following steps:

[0053] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, activated carbon and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 1000ml and a pressure of 0.1MPa.

[0054] Step 2: Before performing the arsenic removal operation, purge the recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open the exhaust port 6 manual valve and the nitrogen inlet port 7 manual valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 0.1 MPa and the temperature at 5°C. Then, close the nitrogen inlet port 7 manual valve. The exhaust port 6 manual valve will be fully open during the following operations.

[0055] Step 3: Open the slurry inlet valve 2 of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is fed at a speed of 200 cm. 3 The chemical and physical adsorption of arsenic compounds and nano-metal adsorbents 4 are carried out by a single-layer 100-mesh filter cloth 5 at a linear velocity of / min, and the arsenic compounds are separated by dearsenic removal on the filter cloth.

[0056] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0057] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recovery tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with hexane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recovery tank 1, and the online arsenic removal process is complete.

[0058] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after adjusting the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content is 0.8μg / Kg, and the recovery rate is above 99%.

[0059] Example 2:

[0060] The online arsenic removal device is the same as in Example 1.

[0061] The online arsenic removal detection method includes the following steps:

[0062] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, graphene oxide and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 10000ml and a pressure of 10MPa.

[0063] Step 2: Before performing arsenic removal operations, purge recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open exhaust port 6 manual valve and nitrogen inlet port 7 manual valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 5 MPa and the temperature at 90°C. Then close nitrogen inlet port 7 manual valve. Exhaust port 6 manual valve remains fully open during the following operations.

[0064] Step 3: Open the manual valve 2 at the slurry inlet of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is introduced at a speed of 0.5 cm. 3 The linear velocity is / min. The chemical and physical adsorption of arsenic compounds and nano-metal adsorbent 4 are carried out by the double-layer 100-mesh filter cloth 5, and the arsenic compounds are separated on the filter cloth.

[0065] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0066] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recycling tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with isopentane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recycling tank 1, and the online arsenic removal process is complete.

[0067] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after adjusting the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content is 2.3μg / Kg, and the recovery rate is above 99%.

[0068] Example 3:

[0069] The online arsenic removal device is the same as in Example 1.

[0070] The online arsenic removal detection method includes the following steps:

[0071] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, carbon nanotube and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 5000ml and a pressure of 2.5MPa.

[0072] Step 2: Before performing arsenic removal operations, purge recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open exhaust port 6 manual valve and nitrogen inlet port 7 manual valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 1 MPa and the temperature at 20°C. Then close nitrogen inlet port 7 manual valve. Exhaust port 6 manual valve remains fully open during the following operations.

[0073] Step 3: Open the slurry inlet valve 2 of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is fed at a speed of 150 cm. 3 The linear velocity is 0.5 min. The chemical and physical adsorption of arsenic compounds and nano-metal adsorbent 4 are carried out by the three-layer 100-mesh filter cloth 5, and the arsenic compounds are separated on the filter cloth.

[0074] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0075] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recycling tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with isobutane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recycling tank 1, and the online arsenic removal process is complete.

[0076] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after adjusting the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content is 3.6μg / Kg, and the recovery rate is above 99%.

[0077] Example 4

[0078] The online arsenic removal device is the same as in Example 1.

[0079] The online arsenic removal detection method includes the following steps:

[0080] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, montmorillonite and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 1000ml and a pressure of 2MPa.

[0081] Step 2: Before performing the arsenic removal operation, purge the recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open the exhaust port 6 hand valve and the nitrogen inlet port 7 hand valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 1.5 MPa and the temperature at 50°C. Then close the nitrogen inlet port 7 hand valve. The exhaust port 6 hand valve will be fully open during the following operations.

[0082] Step 3: Open the slurry inlet valve 2 of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is introduced at a speed of 50 cm. 3 The linear velocity is 0.5 min. Arsenic and nano-metal adsorbent 4 are chemically and physically adsorbed by a four-layer 100-mesh filter cloth 5, and arsenic is removed and separated on the filter cloth.

[0083] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0084] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recovery tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with hexane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recovery tank 1, and the online arsenic removal process is complete.

[0085] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after adjusting the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content is 8.4μg / Kg, and the recovery rate is above 99%.

[0086] Example 5:

[0087] The online arsenic removal device is the same as in Example 1.

[0088] The online arsenic removal detection method includes the following steps:

[0089] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, molecular sieve and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 3000ml and a pressure of 3.5MPa.

[0090] Step 2: Before performing arsenic removal operations, purge recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open exhaust port 6 manual valve and nitrogen inlet port 7 manual valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 2 MPa and the temperature at 20°C. Then close nitrogen inlet port 7 manual valve. Exhaust port 6 manual valve remains fully open during the following operations.

[0091] Step 3: Open the manual valve 2 at the slurry inlet of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is introduced at a speed of 0.5 cm. 3 The linear velocity is 0.5 min. Arsenic and nano-metal adsorbent 4 are chemically and physically adsorbed by a four-layer 100-mesh filter cloth 5, and arsenic is removed and separated on the filter cloth.

[0092] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0093] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recovery tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with hexane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recovery tank 1, and the online arsenic removal process is complete.

[0094] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after adjusting the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content is 51.6μg / Kg, and the recovery rate is above 99%.

[0095] Example 6:

[0096] The online arsenic removal device is the same as in Example 1.

[0097] The online arsenic removal detection method includes the following steps:

[0098] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, activated carbon and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 7000ml and a pressure of 4MPa.

[0099] Step 2: Before performing arsenic removal operations, purge recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open exhaust port 6 manual valve and nitrogen inlet port 7 manual valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 3.5 MPa and the temperature at 20°C. Then close nitrogen inlet port 7 manual valve. Exhaust port 6 manual valve remains fully open during the following operations.

[0100] Step 3: Open the manual valve 2 at the slurry inlet of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is introduced at a speed of 0.5 cm. 3 The linear velocity is / min. The chemical and physical adsorption of arsenic compounds and nano-metal adsorbent 4 are carried out by the double-layer 200-mesh filter cloth 5, and the arsenic compounds are separated on the filter cloth.

[0101] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0102] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recovery tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with hexane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recovery tank 1, and the online arsenic removal process is complete.

[0103] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after making up the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content was 101.4μg / Kg, and the recovery rate was over 99%.

[0104] Example 7:

[0105] The online arsenic removal device is the same as in Example 1.

[0106] The online arsenic removal detection method includes the following steps:

[0107] Step 1: First, weigh the filled nano-metal adsorbent 4 and filter cloth 5. The nano-metal adsorbent 4 includes the reaction products of the following components: metal compound, graphene oxide and polydopamine. Put the weighed nano-metal adsorbent 4 and filter cloth 5 into the recovery tank 1 through the material exchange port 8 and weigh the recovery tank 1 filled with nano-metal adsorbent 4 and filter cloth 5. The recovery tank 1 is a cylindrical closed tank with a volume of 1000ml and a pressure of 2MPa.

[0108] Step 2: Before performing the arsenic removal operation, purge the recovery tank 1 with nitrogen to ensure a nitrogen environment within the online arsenic removal unit. Specifically, open the exhaust port 6 manual valve and the nitrogen inlet port 7 manual valve to purge with nitrogen, maintaining the pressure of the online arsenic removal unit at 0.2 MPa and the temperature at 20°C. Then, close the nitrogen inlet port 7 manual valve. The exhaust port 6 manual valve will be fully open during the following operations.

[0109] Step 3: Open the slurry inlet valve 2 of the online arsenic removal unit. The raw material slurry is pressurized into the recovery unit by nitrogen gas at 0.7 MPa. The raw material slurry entering the online arsenic removal unit is introduced at a speed of 100 cm. 3 The linear velocity is / min. The chemical and physical adsorption of arsenic and nano metal adsorbent 4 is carried out by the double-layer 300-mesh filter cloth 5, and the arsenic is removed and separated on the filter cloth.

[0110] Step 4: After the raw material slurry has completed the arsenic removal and recovery treatment, open the manual valve at outlet 3 and discharge the treated raw material from outlet 3 for further reaction;

[0111] Step 5: After multiple rounds of recycling and refining, once there is no significant weight change in the recovery tank 1, rinse the nano-metal adsorbent 4 and filter cloth 5 with hexane, open the exhaust port 6 to exhaust the gas; open the nitrogen inlet valve 7 and use nitrogen to purge the entire tank, weigh the recovery tank 1, and the online arsenic removal process is complete.

[0112] Take 5g of adsorbent material, dissolve it in 5% hydrochloric acid, and after adjusting the volume, determine the arsenic content in the acid solution by atomic fluorescence hydride generation. The arsenic content is 15.72μg / Kg, and the recovery rate is above 99%.

[0113] Table 1. Adsorption results of arsenic compounds at different mass concentrations

[0114]

[0115] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments for application in other fields. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. An online arsenic removal device, characterized in that, include: The recycling tank (1) and the weighing device are provided. The filter cloth (5) is provided inside the recycling tank (1). The filter cloth (5) is provided with nano metal adsorbent (4). The top of the recycling tank (1) is provided with a feed inlet (2) and an exhaust port (6). The bottom is provided with a discharge port (3). The side wall is provided with a nitrogen inlet (7) and a material replacement port (8).

2. An online arsenic removal detection method, characterized in that, include: First, the nano-metal adsorbent (4) and filter cloth (5) are weighed. The weighed nano-metal adsorbent (4) and filter cloth (5) are loaded into the recovery tank (1). The recovery tank (1) filled with nano-metal adsorbent (4) and filter cloth (5) is weighed. The recovery tank (1) is purged with nitrogen. The raw material slurry is fed into the inlet (2) of the recovery tank (1). The raw material slurry undergoes chemical and physical adsorption with the nano-metal adsorbent (4) inside the filter cloth (5). The raw material slurry completes the arsenic removal and recovery treatment. The treated waste liquid is discharged from the outlet (3) for further treatment. After the waste liquid treatment is completed, the nano-metal adsorbent (4) and filter cloth (5) are rinsed and the arsenic content is measured. The recovery tank (1) is purged with nitrogen and weighed.

3. The online arsenic removal device according to claim 1 or the online arsenic removal detection method according to claim 2, characterized in that, The recycling tank (1) is a cylindrical closed tank with a volume of 1000ml to 10000ml and a pressure of 0.1 to 10MPa. The pressure inside the recycling tank (1) is 0.1 to 5MPa, the temperature is 5 to 90℃, and the feed rate is 0.5 to 200cm³. 3 / min; the bottom of the recycling tank (1) is also equipped with a connecting pipe, and the top is also equipped with a hose.

4. The online arsenic removal device according to claim 1 or the online arsenic removal detection method according to claim 2, characterized in that, The bottom of the recycling tank (1) is equipped with three support legs, and a fixing frame is installed between the support legs.

5. The online arsenic removal device according to claim 1 or the online arsenic removal detection method according to claim 2, characterized in that, The exhaust port (6) is connected to the venting pipeline via a stainless steel pipeline with a flange. A safety valve is provided in front of the exhaust port (6) to maintain a constant pressure inside the recovery tank (1).

6. The online arsenic removal device according to claim 1 or the online arsenic removal detection method according to claim 2, characterized in that, The filter cloth (5) is embedded in the groove of the filter frame.

7. The online arsenic removal device according to claim 1 or the online arsenic removal detection method according to claim 2, characterized in that, The filter cloth (5) may be single-layered or multi-layered depending on the processing volume; the pore size of the filter cloth (5) is 100-300 mesh.

8. The online arsenic removal device according to claim 1 or the online arsenic removal detection method according to claim 2, characterized in that, The nano metal adsorbent (4) comprises the reaction product of the following components: metal compound, nano adsorbent carrier and polydopamine; The nano-adsorbent carrier is mainly selected from at least one of activated carbon, graphene oxide, carbon nanotubes, clay minerals, zeolite, montmorillonite, modified alumina, and molecular sieves.

9. The method according to claim 2, characterized in that, The rinsing nano-metal adsorbent (4) and filter cloth (5) use at least one of hexane, isopentane and isobutane.

10. The online arsenic removal detection method according to claim 2, characterized in that, The online arsenic removal detection method judges the recovery effect and the remaining amount of nano metal adsorbent (4) by the weight change before and after recovery. If the weight increases before and after weighing, the nano metal adsorbent (4) reacts chemically with the arsenic in the raw material slurry. If the weight does not change, it is considered that the nano metal adsorbent (4) is completely consumed and needs to be replaced and replenished in time. The raw material slurry is a recycled organic solvent, which includes one or more of the following: aliphatic hydrocarbon solvents, alcohol solvents, fatty acid ester solvents, ketone solvents, haloalkyl solvents, and benzene solvents; The aliphatic hydrocarbon solvent is one or more selected from n-pentane, isopentane, methylcyclopentane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2,2-dimethylbutane, n-hexane, cyclohexane, n-heptane, and n-octane. The alcohol solvent is selected from one or more of methanol, ethanol, isopropanol, and n-butanol; The fatty acid ester solvent is selected from one or more of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; The ketone solvent may be selected from one or more of acetone, butanone, methyl ethyl ketone, cyclohexanone, isopropanone, methyl butanone, methyl isobutyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, methyl ethyl ketone, methyl pentanone, and cyclohexanone; The haloalkyl solvent is selected from one or more of dichloromethane, n-hexane, and 1,2-dichloroethane; The benzene-based solvent is selected from one or more of benzene, toluene, and xylene.

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