CN111321428A - Method for waste mercuric chloride catalyst molten salt electrolysis regeneration and mercury recovery - Google Patents
Method for waste mercuric chloride catalyst molten salt electrolysis regeneration and mercury recovery Download PDFInfo
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- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
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Abstract
The invention relates to the field of waste mercury catalyst recovery, and discloses a method for waste mercury chloride catalyst molten salt electrolysis regeneration and mercury recovery. The method comprises the following steps: s1, heating the molten salt to form a molten salt molten body; s2, mixing the waste mercuric chloride catalyst with the molten salt melt, and then electrolyzing to obtain electrolyte and mercury enriched on the cathode; s3, carrying out solid-liquid separation on the electrolyte to obtain activated carbon; wherein the melting temperature of the molten salt is not higher than 300 ℃. The method can recover mercury by electrochemical reduction, simultaneously realize activated recovery of activated carbon, has the melting temperature of the molten salt not higher than the sublimation temperature of mercury chloride, and can effectively avoid volatilization of mercury chloride.
Description
Technical Field
The invention relates to the field of waste mercury catalyst recovery, in particular to a method for waste mercury chloride catalyst molten salt electrolysis regeneration and mercury recovery.
Background
The mercury catalyst is an indispensable part for producing polyvinyl chloride by a calcium carbide method, and is used as a catalyst for synthesizing vinyl chloride by acetylene and hydrogen chloride gas in the process of not producing the polyvinyl chloride. The mercury catalyst is produced by taking activated carbon as a carrier and mercuric chloride as an active substance, and loading the mercuric chloride on the surface of the activated carbon. After the mercury catalyst is used for a certain period of time, the activity of the mercury catalyst is reduced and the mercury catalyst needs to be replaced, and the replaced waste mercury catalyst still contains 2-5% of mercuric chloride. Since mercuric chloride is extremely toxic, extremely volatile and easily soluble in water, if the replaced mercury catalyst is directly discarded or stacked, serious mercury pollution is caused and great potential safety hazards are caused.
According to the "treatment and disposal method for waste mercury catalyst" (GB/T36382-2008), distillation and oxygen-controlled dry distillation are mainly adopted for the harmless treatment of the waste mercury catalyst at present. The distillation method is to add quicklime, sodium hydroxide and the like to convert mercury in each valence state in the waste mercury catalyst into similar substances (most of which are mercury oxide) which are easy to decompose, volatilize and collect, the mercury oxide is heated and decomposed into elemental mercury and oxygen, and the elemental mercury vapor is quenched to realize the recovery of mercury in the waste mercury catalyst. However, the method does not realize the activation regeneration of the activated carbon, and due to the introduction of quicklime, sodium hydroxide and other substances in the pretreatment, a large amount of calcium carbonate, calcium oxide, sodium carbonate and other powders are attached to the surface of the waste mercury catalyst after the distillation process, so that the activated carbon is seriously inactivated, and the activated carbon is difficult to reuse. The oxygen-controlling dry distillation method is characterized in that mercury chloride is sublimated at high temperature, the coking temperature of the activated carbon is lower than the sublimation temperature of the mercury chloride, and the mercury chloride and the activated carbon can be simultaneously recovered under the inert gas atmosphere and negative pressure sealing conditions. However, the mixture of mercuric chloride vapor and mercury vapor is extremely corrosive, so that the existing metal/metal alloy material cannot be applied, and the industrial application of the metal/metal alloy material is limited.
In addition, the existing chemical method reactivates the activated carbon without separating the activated carbon from the mercuric chloride in the waste mercury catalyst, eliminates carbon deposit and catalyst poisoning, and realizes regeneration. For example, patent CN104138767A discloses a method for regenerating a waste mercuric chloride catalyst after three-stage activation, which comprises putting the waste mercuric chloride catalyst into a regeneration and regeneration activation furnace, carbonizing at low temperature of 100-. The method can effectively recycle the waste mercury catalyst, but has the problems of heating volatilization of mercury chloride, large consumption of chemical reagents and the like in the activation process.
Disclosure of Invention
The invention aims to solve the problems of high consumption of chemical reagents and volatile mercury chloride in the process of recovering a waste mercury chloride catalyst in the prior art, and provides a method for molten salt electrolysis regeneration and mercury recovery of the waste mercury chloride catalyst.
In order to achieve the above object, the present invention provides a method for waste mercury chloride catalyst molten salt electrolysis regeneration and mercury recovery, comprising:
s1, heating the molten salt to form a molten salt molten body;
s2, mixing the waste mercuric chloride catalyst with the molten salt melt, and then electrolyzing to obtain electrolyte and mercury enriched on the cathode;
s3, carrying out solid-liquid separation on the electrolyte to obtain activated carbon;
wherein the melting temperature of the molten salt is not higher than 300 ℃.
Preferably, the melting temperature of the molten salt is 100-.
Preferably, the molten salt comprises a base chloride salt and a conditioning chloride salt, the base chloride salt is sodium chloride and potassium chloride, and the conditioning chloride salt is one or more of aluminum chloride, lithium chloride and magnesium chloride.
Preferably, the mass ratio of the sodium chloride to the potassium chloride to the adjusting chlorine salt in the molten salt is (2-4): (0.3-2.5): 1.
preferably, the molten salt heating process in step S1 includes mixing the basic chlorine salt and the adjusted chlorine salt, grinding the mixture uniformly to obtain a molten salt, and then heating the molten salt.
Preferably, the mass ratio of the waste mercury chloride catalyst to the molten salt melt is 1: (5-10).
Preferably, the conditions of the electrolysis include: the reduction voltage is 0.3-0.6V and the current is 0.2-0.6A.
Through the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the waste mercury chloride catalyst is treated based on a molten salt system, on one hand, the waste mercury chloride catalyst can be heated through the temperature of a molten salt melt body, so that mercury chloride is separated from activated carbon and is melted in the molten salt, and mercury is recovered through electrochemical reduction; on the other hand, the fused salt adopts mixed chlorine salt, and the chlorine salt has certain activation effect on the activated carbon dispersed in the fused salt at high temperature, so that a rich pore structure is generated, and the activated recovery of the activated carbon is realized.
2. In the invention, when the waste mercuric chloride catalyst is regenerated and mercury is recycled, the composition of the fused salt is key, the melting temperature of the fused salt is not higher than the sublimation temperature of the mercuric chloride by regulating and controlling the mixing ratio of the sodium chloride, the potassium chloride and the chlorine salt, and the fused salt has good conductivity, and can effectively avoid the volatilization of the mercuric chloride while electrolyzing the mercuric chloride separated from the activated carbon.
3. According to the invention, after the activated carbon in the molten salt is separated, the molten salt melt can be recycled, and the consumption of chemical reagents is effectively reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a device for molten salt electrolysis regeneration and mercury recovery of a waste mercuric chloride catalyst in the invention;
FIG. 2 is a heating mechanism in the apparatus for molten salt electrolysis regeneration and mercury recovery of the waste mercury chloride catalyst shown in FIG. 1;
FIG. 3 is a telescopic structure of the device for the molten salt electrolysis regeneration and mercury recovery of the waste mercury chloride catalyst shown in FIG. 1.
Description of the reference numerals
1 Material storehouse 2 feed chamber
3 sealing structure 4 shaft lever
5 conveying pipe 6-shaft telescopic rod
7 power supply 8 computer
9 telescopic structure 10 weight measuring instrument
11 cylinder 12 conductive wire
13 electrode 14 motor
15 rotating blade 16 screw mechanism
17 heating mechanism 18 telescopic button
19 mechanical bar 20 control circuit
21 heat dissipation metal bar 22 electromagnetic coil
23 casing 24 metal pipe
25 temperature control feedback line 26 heater
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for waste mercuric chloride catalyst molten salt electrolysis regeneration and mercury recovery, which comprises the following steps:
s1, heating the molten salt to form a molten salt molten body;
s2, mixing the waste mercuric chloride catalyst with the molten salt melt, and then electrolyzing to obtain electrolyte and mercury enriched on the cathode;
s3, carrying out solid-liquid separation on the electrolyte to obtain activated carbon;
wherein the melting temperature of the molten salt is not higher than 300 ℃.
The heating, mixing and electrolyzing modes and apparatuses of the present invention are not particularly limited, and may be various conventional heating, mixing and electrolyzing modes and apparatuses in the art. The melting temperature of the molten salt in the present invention is limited to not higher than the sublimation temperature of mercury chloride, i.e., 300 ℃. And in S3, the electrolyte is subjected to solid-liquid separation to obtain the activated carbon, and at the moment, the molten salt melt can be recycled, so that the consumption of chemical reagents is effectively reduced.
Preferably, the melting temperature of the molten salt is 100-.
The composition of the molten salt is not particularly limited in the present invention, and preferably, the molten salt includes a base chlorine salt and a conditioning chlorine salt, the base chlorine salt is sodium chloride and potassium chloride, and the conditioning chlorine salt is one or more of aluminum chloride, lithium chloride and magnesium chloride.
Preferably, the mass ratio of the sodium chloride to the potassium chloride to the adjusting chlorine salt in the molten salt is (2-4): (0.3-2.5): 1.
preferably, the molten salt heating process in step S1 includes mixing the basic chlorine salt and the adjusted chlorine salt, grinding the mixture uniformly to obtain a molten salt, and then heating the molten salt.
The amount of the used mercury chloride catalyst and the molten salt melt is not particularly limited, and may be selected conventionally in the art, and preferably, the mass ratio of the used mercury chloride catalyst to the molten salt melt is 1: (5-10).
The conditions of the electrolytic treatment in the present invention are not particularly limited and may be conventionally selected in the art, and preferably, the conditions of the electrolysis include: the reduction voltage is 0.3-0.6V and the current is 0.2-0.6A.
According to a preferred embodiment of the invention, the device adopted by the method for waste mercury chloride catalyst molten salt electrolysis regeneration and mercury recovery is shown in fig. 1 to 3, and comprises a material bin 1, wherein the top end of the material bin 1 is sequentially provided with a feeding room 2 and a conveying pipe 5, the material bin 1 and the feeding room 2 are both communicated with the conveying pipe 5, and the feeding port of the feeding room 2 is provided with a sealing structure 3; the side wall of one side of the material bin 1 is detachably connected with the main body of the material bin 1 through a screw structure 16. The stirring mechanism comprises a motor 14 positioned outside the feeding room 2, a shaft lever 4 positioned in the feeding pipe 5, a shaft telescopic rod 6 sleeved outside the shaft lever 4 and a rotating blade 15 positioned at the bottom of the shaft telescopic rod 6; the heating mechanism 17 is positioned at the bottom of the inner cavity of the material bin 1, the heating mechanism 17 comprises a heating cavity, a sleeve 23 positioned in the heating cavity, a metal pipe 24 positioned in the sleeve 23 and an electromagnetic coil 22 wound on the metal pipe 24, a heat dissipation metal rod 21 is arranged outside the heating cavity, and a temperature control feedback circuit 25 is arranged between the heater 26 and the sleeve 23; the electrolysis mechanism comprises an electrode 13 positioned in the material bin 1, a conductive wire 12 connected with the electrode 13, a telescopic structure 9 for controlling the length of the conductive wire 12 and a power supply 7 connected with the conductive wire 12, the voltage and current frequency of the power supply 7 is controlled by a computer 8, a weight measuring instrument 10 is arranged on the conductive wire 12 connected with the cathode of the electrode 13, the weight measuring instrument 10 is positioned at the outer side of the material bin 1, a cylinder 11 for taking and placing the electrode 13 is arranged on the material bin 1, and the diameter of the electrode 13 is slightly smaller than that of the cylinder 11; the telescopic structure 9 comprises an adjusting chamber and a control circuit 20 installed in the side wall of the adjusting chamber, the electric conducting wire 12 is arranged in the adjusting chamber in a penetrating mode, the part, located in the adjusting chamber, of the electric conducting wire 12 is in a spiral shape, a mechanical rod 19 is arranged in the adjusting chamber, a telescopic button 18 is arranged on the outer side of the adjusting chamber, and the mechanical rod 19 is distributed on two sides of the electric conducting wire 12. The process for carrying out the waste mercury chloride catalyst molten salt electrolysis regeneration and mercury recovery by using the device can comprise the following steps:
1. adding the molten salt into the material bin 1 from the feeding room 2 through the conveying pipe 5, closing the sealing structure 3, and opening the heater 26 of the heating mechanism 17 to heat the molten salt to form a molten salt melt;
2. opening the sealing structure 3 to add the waste mercuric chloride catalyst into the material bin 1 from the feeding room 2, extending the shaft telescopic rod 6 to immerse the rotating blade 15 into the material, opening the motor 14 to drive the rotating blade 15 to rotate, fully and uniformly mixing the material in the material bin 1, closing the motor 14, and shortening the shaft telescopic rod 6 to lift the rotating blade 15 to the top of the material bin 1;
3. the length of the conductive wire 12 in the material bin 1 is adjusted through the telescopic button 18, so that the electrode 13 enters the material, the power supply 7 is turned on to adjust to proper voltage and current, the material is electrolyzed, and the electrolysis condition in the material bin 1 is observed through the weight measuring instrument 10;
4. and after the electrolysis is finished, the power supply 7 is turned off, the screw structure 16 is opened, the electrode 13 is taken out to collect mercury, the electrolyte is taken out to carry out solid-liquid separation to respectively obtain activated carbon, and the molten salt is recovered.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, iodine adsorption values and methylene blue adsorption values were determined in accordance with GB/T7702.7-2008 and GB/T7702.6-2008; the recovery rate of the activated carbon is the mass ratio of the recovered and separated activated carbon to the activated carbon in the waste mercury chloride catalyst raw material; the recovery rate of mercury is the mass ratio of the mercury recovered by electrolysis to the mercury in the waste mercury chloride catalyst raw material. The waste mercuric chloride catalyst comes from a certain polyvinyl chloride production enterprise, the mercury content of the waste mercuric chloride catalyst is 15 mu g/mg, the iodine adsorption value of the activated carbon is 9.4mg/g, the methylene blue adsorption value is 1.3mg/g, and the specific surface area is 432.9m2And/g, all other raw materials are commercial products.
The following examples use the above-described apparatus for molten salt electrolysis regeneration and mercury recovery of a spent mercury chloride catalyst.
Example 1
(1) Mixing aluminum chloride, lithium chloride and magnesium chloride according to a mass ratio of 1: 1: 1, mixing to form chlorine regulating salt, mixing sodium chloride, potassium chloride and chlorine regulating salt according to the mass ratio of 3:1.5:1, and fully grinding to be uniform to obtain molten salt;
(2) adding 7.5kg of the molten salt obtained in the step (1) into the material bin 1 from the feeding room 2, closing the sealing structure 3, and opening the heater 26 of the heating mechanism 17 to heat the molten salt to 200 ℃ to form a molten salt melt;
(3) opening the sealing structure 3 to add 1kg of waste mercuric chloride catalyst into the material bin 1 from the feeding room 2, extending the shaft telescopic rod 6 to immerse the rotating blade 15 into the material, opening the motor 14 to drive the rotating blade 15 to rotate, fully and uniformly mixing the material in the material bin 1, closing the motor 14, and shortening the shaft telescopic rod 6 to lift the rotating blade 15 to the top of the material bin 1;
(4) the length of the conductive wire 12 in the material bin 1 is adjusted through the telescopic button 18, so that the electrode 13 enters the material, the power supply 7 is turned on to adjust the reduction voltage to be 0.45V and the current to be 0.4A, the material is electrolyzed, and the weight of the cathode of the electrode 13 is observed through the weight measuring instrument 10 until the weight of the cathode is not increased any more;
(5) and after the electrolysis is finished, the power supply 7 is turned off, the screw structure 16 is opened, the electrode 13 is taken out to collect mercury, the electrolyte is taken out to carry out solid-liquid separation to respectively obtain activated carbon, and the molten salt is recovered.
The recovery amount of the activated carbon is 0.925kg, the recovery rate is 92.5 percent, the recovery amount of the mercury is 14.25g, the recovery rate of the mercury is 95 percent, the iodine adsorption value after the activated carbon is regenerated is 978mg/g, the methylene blue adsorption value is 189mg/g, and the specific surface area is 789.4m2/g。
Example 2
(1) Mixing aluminum chloride and lithium chloride according to a mass ratio of 2: 1, mixing to form a chlorine regulating salt, and mixing sodium chloride, potassium chloride and the chlorine regulating salt according to a mass ratio of 2: 0.3: 1, mixing, fully grinding to be uniform to obtain molten salt;
(2) adding 5kg of the molten salt obtained in the step (1) into the material bin 1 from the feeding room 2, closing the sealing structure 3, and opening the heater 26 of the heating mechanism 17 to heat the molten salt to 100 ℃ to form a molten salt melt;
(3) opening the sealing structure 3 to add 1kg of waste mercuric chloride catalyst into the material bin 1 from the feeding room 2, extending the shaft telescopic rod 6 to immerse the rotating blade 15 into the material, opening the motor 14 to drive the rotating blade 15 to rotate, fully and uniformly mixing the material in the material bin 1, closing the motor 14, and shortening the shaft telescopic rod 6 to lift the rotating blade 15 to the top of the material bin 1;
(4) the length of the conductive wire 12 in the material bin 1 is adjusted through the telescopic button 18, so that the electrode 13 enters the material, the power supply 7 is turned on to adjust the reduction voltage to be 0.3V and the current to be 0.2A, the material is electrolyzed, and the weight of the cathode of the electrode 13 is observed through the weight measuring instrument 10 until the weight of the cathode is not increased any more;
(5) and after the electrolysis is finished, the power supply 7 is turned off, the screw structure 16 is opened, the electrode 13 is taken out to collect mercury, the electrolyte is taken out to carry out solid-liquid separation to respectively obtain activated carbon, and the molten salt is recovered.
The recovery amount of the active carbon is determined to be 0.883kg, the recovery rate is 88.3 percent, the recovery amount of the mercury is 12.25g, the recovery rate of the mercury is 81.6 percent, the iodine adsorption value after the active carbon is regenerated is 908mg/g, and the methylene blue adsorption value is 908mg/g167mg/g, specific surface area 757.2m2/g。
Example 3
(1) Taking magnesium chloride as a chlorine regulating salt, and mixing sodium chloride, potassium chloride and the chlorine regulating salt according to a mass ratio of 4: 2.5: 1, mixing, fully grinding to be uniform to obtain molten salt;
(2) adding 10kg of the molten salt obtained in the step (1) into the material bin 1 from the feeding room 2, closing the sealing structure 3, and opening the heater 26 of the heating mechanism 17 to heat the molten salt to 300 ℃ to form a molten salt melt;
(3) opening the sealing structure 3 to add 1kg of waste mercuric chloride catalyst into the material bin 1 from the feeding room 2, extending the shaft telescopic rod 6 to immerse the rotating blade 15 into the material, opening the motor 14 to drive the rotating blade 15 to rotate, fully and uniformly mixing the material in the material bin 1, closing the motor 14, and shortening the shaft telescopic rod 6 to lift the rotating blade 15 to the top of the material bin 1;
(4) the length of the conductive wire 12 in the material bin 1 is adjusted through the telescopic button 18, so that the electrode 13 enters the material, the power supply 7 is turned on to adjust the reduction voltage to be 0.6V and the current to be 0.6A, the material is electrolyzed, and the weight of the cathode of the electrode 13 is observed through the weight measuring instrument 10 until the weight of the cathode is not increased any more;
(5) and after the electrolysis is finished, the power supply 7 is turned off, the screw structure 16 is opened, the electrode 13 is taken out to collect mercury, the electrolyte is taken out to carry out solid-liquid separation to respectively obtain activated carbon, and the molten salt is recovered.
The recovery amount of the activated carbon is determined to be 0.743kg, the recovery rate is 74.3 percent, the recovery amount of the mercury is 11.05g, the recovery rate of the mercury is 73.6 percent, the iodine adsorption value after the activated carbon is regenerated is 883mg/g, the methylene blue adsorption value is 143mg/g, and the specific surface area is 710m2/g。
Comparative example 1
(1)1kg useless mercuric chloride catalyst arranges stainless steel material groove in, with the whole electrolyte and to the cathode copper of getting into in first group stainless steel material groove on, give negative pole, positive pole circular telegram simultaneously, this stainless steel material groove is as the negative pole of electrolysis trough this moment, carries out the electroreduction to first group material, and the mercury that the electroreduction produced leaks to the tank bottom through material groove bottom mesh, and wherein, the composition of electrolyte is: the NaCl concentration is 30g/L,The HCl concentration is 75g/L and the thiourea concentration is 2 g/L; the electrolysis time is 50h, the circulation flow of the electrolyte is 12L/min, and the cathode current density is 1000A/m2；
(2) After the electro-reduction is finished, moving the first group of stainless steel material grooves to an ultrasonic oscillator station, cleaning and oscillating the un-leaked mercury by the ultrasonic oscillator for 10min, and leaking to the bottom of the material groove through meshes at the bottom of the material groove; meanwhile, the second group of stainless steel material grooves enter an electric reduction station for electric reduction, and the rest is done in the same way;
(3) the first group of stainless steel material grooves and the second group of stainless steel material grooves move out of the ultrasonic oscillator station, and after the materials are discharged to the funnel, the materials of the funnel enter an active carbon regeneration device to generate regenerated active carbon;
(4) and opening a mercury valve periodically, and discharging the cleaned mercury from the electrolytic cell.
The recovery amount of the activated carbon is 0.678kg, the recovery rate is 67.8 percent, the recovery amount of the mercury is 9.75g, the recovery rate of the mercury is 65 percent, the iodine adsorption value after the activated carbon is regenerated is 745mg/g, the methylene blue adsorption value is 126mg/g, and the specific surface area is 654.5m2/g。
As can be seen from the data of the examples 1-3 and the comparative example 1, the activated carbon and the mercury in the waste mercuric chloride catalyst are better recovered after the regeneration treatment by the molten salt electrolysis, and the adsorption capacity and the physical structural characteristics of the activated carbon are better regenerated.
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 (7)
1. A method for waste mercury chloride catalyst molten salt electrolysis regeneration and mercury recovery is characterized by comprising the following steps:
s1, heating the molten salt to form a molten salt molten body;
s2, mixing the waste mercuric chloride catalyst with the molten salt melt, and then electrolyzing to obtain electrolyte and mercury enriched on the cathode;
s3, carrying out solid-liquid separation on the electrolyte to obtain activated carbon;
wherein the melting temperature of the molten salt is not higher than 300 ℃.
2. The method according to claim 1, characterized in that the melting temperature of the molten salt is 100-300 ℃.
3. The method of claim 2, wherein the molten salt comprises a base chloride salt and a conditioning chloride salt, the base chloride salt being sodium chloride and potassium chloride, and the conditioning chloride salt being one or more of aluminum chloride, lithium chloride, and magnesium chloride.
4. The method according to claim 3, characterized in that the mass ratio of sodium chloride, potassium chloride and the adjusting chloride salt in the molten salt is (2-4): (0.3-2.5): 1.
5. the method of claim 3, wherein the molten salt heating process in step S1 comprises mixing the basic chlorine salt and the adjusted chlorine salt, grinding the mixture uniformly to obtain molten salt, and heating the molten salt.
6. The method according to any one of claims 1 to 5, wherein the mass ratio of the spent mercury chloride catalyst to the molten salt melt is 1: (5-10).
7. The method according to any one of claims 1 to 5, wherein the conditions of the electrolysis comprise: the reduction voltage is 0.3-0.6V and the current is 0.2-0.6A.
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| CN117619459A (en) * | 2024-01-23 | 2024-03-01 | 上海利元环保检测技术有限公司 | Automatic acid cylinder bivalent mercury removal device and method |
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| CN117619459B (en) * | 2024-01-23 | 2024-04-19 | 上海利元环保检测技术有限公司 | Automatic acid cylinder bivalent mercury removal device and method |
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