A renewable HgCl2 standard gas generator, its preparation method and application

Abstract

This invention provides a regenerable HgCl2 standard gas generator, its preparation method, and its application. The method includes the following steps: First, a transition metal chloride is dissolved in water to obtain a solution; second, a non-carbon-based carrier material is added to the solution and mixed to obtain a mixture; finally, the mixture is filtered and dried to obtain the HgCl2 generator. The HgCl2 standard gas generator prepared by this invention uses a transition metal chloride as the active component and a non-carbon-based material as both the active component and the dispersion carrier. Furthermore, it proposes that further modification with low-temperature plasma can enhance the content of the active component, and that low-temperature plasma treatment can restore the chemical activity of the HgCl2 standard gas generator, achieving regeneration. This HgCl2 standard gas generator can produce HgCl2 standard gas and be applied to online mercury monitoring systems for industrial mercury-containing flue gas. It provides key technical support for the quality and accuracy control of monitoring data in continuous online mercury monitoring systems and has broad application value.

Description

Technical Field

[0001] This invention belongs to the technical field of calibration systems for online mercury monitoring in mercury-containing flue gas generated from coal combustion or other industries. Specifically, it relates to a renewable HgCl2 standard gas generator and its preparation method, as well as its application in an online mercury monitoring system for mercury-containing flue gas. Further, this HgCl2 standard gas generator serves as a chlorine source, and elemental mercury (HgCl2) is used... 0 As a mercury source, HgCl2 standard gas is generated through a gas-solidification chemical reaction and used in the HgCl2 standard gas calibration module of the mercury online monitoring system. Background Technology

[0002] Mercury is highly toxic, non-degradable, and bioaccumulative, posing serious threats to human health and the natural environment. With the signing and implementation of the Minamata Convention on Mercury, various regions have introduced stricter mercury emission standards, making effective control and real-time monitoring of mercury emissions from coal-fired flue gas or other industrial sources an urgent need.

[0003] Currently, there are three main methods for detecting mercury in industrial mercury-containing flue gas: (1) wet chemical sampling (OHM), (2) adsorption tube offline sampling (EPA Method 30B), and (3) mercury online continuous monitoring system (Hg-CEMS). Among them, the mercury online continuous monitoring system is a complete set of equipment that integrates continuous acquisition and online monitoring of mercury emission concentration in flue gas. It is currently the fastest-developing and most technologically advanced method for monitoring mercury in flue gas. It includes a flue gas sampling pretreatment system, a mercury speciation separation and conversion system, a mercury analysis module, a calibration module, and a data acquisition and transmission module.

[0004] The Hg-CEMS standard gas calibration module system includes Hg 0 Standard gas generator and Hg 2+ The standard gas generator provides a stable supply of Hg to the flue gas pretreatment unit and the mercury detection module. 0 Standard gas and Hg 2+ Standard gas. Providing standard gas to the flue gas pretreatment module to test the reliability and stability of the mercury separation and conversion unit and the thermal dilution unit is called external standard; providing standard gas to the mercury detection module to test the stability and reliability of the mercury analysis optical path detection module is called internal standard. Therefore, the standard gas generator in the Hg-CEMS system becomes a key core technology for effectively ensuring the quality and accuracy control of monitoring data in the Hg-CEMS system.

[0005] Patent CN102500203B discloses a device for generating divalent mercury in simulated flue gas and its application. This device uses a peristaltic pump to evaporate a prepared HgCl2 solution of a certain concentration, which is then mixed with a dilution gas to obtain the desired HgCl2 standard gas. While this method can generate HgCl2 standard gas, it may pose hazards to operators during the preparation and use of the HgCl2 solution. Furthermore, the method is cumbersome, and the concentration of the HgCl2 standard gas is limited by the solution evaporation temperature, making it prone to instability. Patent CN105886796A discloses a device for generating mercury and divalent mercury standard gas based on the saturation principle. This device uses HgCl2 as the starting point for the divalent mercury standard gas. 0 Using mercury as the source and O2, HCl, Cl2, or H2O as the oxidant, Hg is discharged under plasma discharge conditions. 0 It is oxidized to HgCl2 or HgO. Although this invention can produce divalent mercury standard gas at a relatively low temperature, the HgCl2 standard gas contains a large number of impurity gases, which cannot yet meet the technical requirements of Hg-CEMS for HgCl2 standard gas.

[0006] Based on this, the present invention provides a high-purity, low-impurity, continuous and stable HgCl2 standard gas generator and its preparation method, which can meet the technical requirements and applications of HgCl2 standard gas in mercury online continuous monitoring (Hg-CEMS) systems. Summary of the Invention

[0007] One of the objectives of this invention is to provide a method for preparing a high-purity, low-impurity, and continuously stable HgCl2 standard gas generator.

[0008] The second objective of this invention is to provide a HgCl2 standard gas generator that can achieve high purity, low impurities, and continuous stability.

[0009] The third objective of this invention is to provide an application of HgCl2 standard gas generator in an online mercury monitoring system for mercury-containing flue gas.

[0010] One of the technical solutions adopted to achieve the objective of this invention is: to provide a method for preparing a solid HgCl2 generator, comprising the following steps:

[0011] S1. Dissolve the transition metal chloride in water to obtain a solution;

[0012] S2. Add the non-carbon-based carrier material to the solution and mix thoroughly to obtain a mixture;

[0013] S3. The mixture is subjected to filtration and drying processes to obtain HgCl2 generator;

[0014] S4. The expired HgCl2 standard gas generator will be regenerated by low-temperature plasma treatment.

[0015] In the above preparation method, firstly, an aqueous solution of transition metal chloride is prepared; secondly, a non-carbon-based support material is added to the solution to achieve loading of the transition metal chloride. The non-carbon-based support used in this invention has specific properties for loading Hg... 0 The generated HgCl2 is almost non-adsorbed, ensuring high purity and absence of impurities in the produced HgCl2 standard gas. Finally, considering the problem that some metal cations may be loaded in a low-valence form during impregnation, leading to poor oxidation efficiency, this invention modifies the prepared HgCl2 generator using low-temperature plasma under HCl or Cl2 conditions to enhance the efficiency and purity of HgCl2 conversion. During this modification process, low-valence metal cations are oxidized to high-valence metal cations under the action of high-energy electrons. Furthermore, the content of active Cl ions is increased, improving the oxidation effect of the HgCl2 generator.

[0016] Further, in step S1, the mass concentration of the transition metal chloride in the solution is 1 wt.% to 30 wt.%. Preferably, the mass concentration of the transition metal chloride in the solution is 5 to 20 wt.%.

[0017] Further, in step S1, the transition metal chloride is selected from one or more combinations of FeCl3, CuCl2, and MnCl2. Preferably, the transition metal chloride is CuCl2.

[0018] Further, in step S2, the non-carbon-based support material is selected from one or more combinations of porous Al2O3, mesoporous SiO2, TiO2, zeolite, and MCM-41 molecular sieve. Preferably, the non-carbon-based support material is γ-Al2O3 and / or MCM-41 molecular sieve, both of which are more favorable for Hg growth compared to other supports. 0 The mesoporous channels that diffuse with HgCl2 and the high specific surface area allow the active components to be highly dispersed on their surface. More preferably, the non-carbon-based support material is MCM-41 molecular sieve, which has an even higher specific surface area and a more uniform mesoporous channel structure.

[0019] Furthermore, in step S2, the mass-to-volume ratio of the non-carbon-based support material to the solution is 1:(5-20)g / mL. Under the above ratio conditions, it helps to improve the generation efficiency of HgCl2.

[0020] Preferably, in step S2, after the non-carbon-based carrier material is added to the solution, it is placed on a magnetic stirrer and stirred for 4 to 8 hours to fully load it and obtain a mixture.

[0021] Further, in step S3, excess water in the mixture is removed by vacuum filtration to obtain a semi-dry HgCl2 generator; further, the HgCl2 generator is dried at a temperature of 100-110°C for 2-24 hours to obtain a fully dried HgCl2 generator.

[0022] Furthermore, step S3 also includes: using HCl and / or Cl2 as modifying gases to perform low-temperature plasma modification on the HgCl2 generator.

[0023] Furthermore, the low-temperature plasma modification employs dielectric barrier discharge, with a modifying gas concentration of 10–10000 ppm, a modification time of 0.5–60 min, and a discharge power of 5–300 W. Preferably, the modifying gas concentration is 100–10000 ppm, the modification time is 5–30 min, and the discharge power is 30–200 W.

[0024] In this invention, low-temperature plasma is used to generate Cl radicals and active chlorine. Through charge exchange, the valence state of the metal cation is converted from low to high, while the generated active chlorine is loaded onto the support surface, giving it higher reactivity and promoting Hg reactivity. 0 The conversion to HgCl2.

[0025] Further, in step S4, the regeneration uses HCl and / or Cl2 as the regeneration gas, the concentration of the regeneration gas is 100-4000 ppm, the regeneration time is 5-60 min, and the discharge power is 60-400 W.

[0026] The second objective of this invention is achieved by providing a low-temperature plasma-modified HgCl2 generator, wherein the low-temperature plasma-modified HgCl2 generator is prepared by the preparation method described in one of the objectives of this invention.

[0027] The third objective of this invention is achieved by providing an application of a low-temperature plasma-modified HgCl2 generator, which includes applying the low-temperature plasma-modified HgCl2 generator to an online monitoring system for mercury in flue gas from coal combustion or other industries, thereby achieving stable generation of HgCl2 standard gas.

[0028] In some preferred embodiments, the aforementioned HgCl2 standard gas generator is used in the calibration module of the Hg-CEMS system. There are two methods for standard gas calibration of the Hg-CEMS system. The first is to perform internal standard calibration on the Hg-CEMS system, i.e., Hg... 0 The first method involves separately introducing carrier gas into the thermal dilution module and the mercury detection module; the second method involves external standard calibration of the Hg-CEMS system, i.e., Hg... 0The carrier gas undergoes an oxidation reaction with the HgCl2 generator of this invention, converting it into standard HgCl2 gas. The HgCl2 generator provided by this invention does not require the addition of other gases (such as Cl2, Cl2+HCl, HCl, etc.) as a chlorine source during use; HgCl2 can be generated under a pure N2 atmosphere. 0 It exhibits highly efficient oxidation. When used in the Hg-CEMS calibration system, it avoids the influence of additional HCl or Cl2 on the HgCl2 standard gas.

[0029] Furthermore, the HgCl2 generator provided by this invention is also suitable for the stable generation of HgCl2 standard gas in the laboratory.

[0030] Furthermore, the application of the low-temperature plasma-modified HgCl2 generator provided by this invention also includes regenerating the HgCl2 generator through low-temperature plasma treatment. By placing the used and degraded HgCl2 generator under HCl and / or Cl2 conditions and treating it with low-temperature plasma for a certain period of time, its oxidation efficiency can be improved back to the desired level.

[0031] Preferably, during the low-temperature plasma treatment and regeneration process, the concentration of HCl and / or Cl2 is 100–4000 ppm, the power is 60–400 W, and the ventilation time is 5–60 min.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] (1) This invention provides a method for preparing a HgCl2 generator, using transition metal chlorides as the active component and non-carbon-based substances as both the active component and the dispersion carrier, to prepare a HgCl2 standard gas generator. Low-temperature plasma modification can further enhance the content of the active component and improve the generation efficiency of the HgCl2 standard gas generator. The HgCl2 generator obtained by this invention can efficiently generate HgCl2 standard gas. 0 The chlorine is oxidized to HgCl2, achieving continuous and stable generation of high-purity, low-impurity HgCl2 standard gas. No additional gases (such as Cl2, Cl2+HCl, HCl, etc.) are required as a chlorine source; HgCl2 can be generated under a pure N2 atmosphere. 0 It exhibits highly efficient oxidation. When used in the Hg-CEMS calibration system, it avoids the influence of additional HCl or Cl2 on the HgCl2 standard gas. Compared with the solution evaporation method, it has advantages such as high safety, readily available materials, high stability, and high efficiency.

[0034] (2) The HgCl2 generator prepared by this invention can be applied to online mercury monitoring systems for mercury-containing flue gas from coal combustion or other industries to achieve stable generation of HgCl2 standard gas. It can also be used for stable generation of HgCl2 standard gas in the laboratory. Compared with conventional Cl2, Cl2+HCl, and HCl as chlorine sources for Hg oxidation... 0 Compared with plasma oxidation, the HgCl2 generator prepared in this invention has advantages such as high HgCl2 standard gas generation efficiency, high oxidation rate, and impurity-free standard gas. The preparation method is simple, stable, reliable, and produces high-purity and highly safe HgCl2 standard gas. It provides technical support for ensuring the quality and accuracy control of monitoring data in a continuous mercury online monitoring system (Hg-CEMS) and has broad application value. Attached Figure Description

[0035] Figure 1 A schematic flowchart illustrating a method for preparing a renewable HgCl2 standard gas generator according to an embodiment of the present invention;

[0036] Figure 2 The mercury oxidation rate (a) and mercury balance rate (b) of the HgCl2 generator prepared in Example 1 of the present invention at different temperatures are shown.

[0037] Figure 3 This is a comparison graph showing the mercury oxidation rate over time between the HgCl2 generator after low-temperature plasma modification in Example 2 and the HgCl2 generator without modification in Example 1.

[0038] Figure 4 This is a graph showing the change in mercury oxidation rate over time of the HgCl2 generator after low-temperature plasma modification treatment in Example 3 of the present invention.

[0039] Figure 5 The graph shows the change in mercury oxidation rate over time after plasma regeneration treatment of the HgCl2 standard gas generator prepared in Example 2 of this invention, which was used until it became ineffective. Detailed Implementation

[0040] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0041] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0042] The present invention will be further described below with reference to specific embodiments, but these are not intended to limit the scope of the invention.

[0043] The main parameters involved in the various embodiments and comparative examples of the present invention are shown in Table 1 below.

[0044] Table 1

[0045]

[0046] Example 1

[0047] A method for preparing a renewable HgCl2 standard gas generator includes the following steps:

[0048] Step 1: Weigh 5g of anhydrous CuCl2 and dissolve it in 45ml of deionized water to obtain a 10wt.% CuCl2 solution;

[0049] Step 2: Add 5g of γ-Al2O3 at a solid-liquid ratio of 1g:10ml; stir evenly, then place on a magnetic stirrer and stir for 5 hours to obtain a mixture;

[0050] Step 3: Filter the mixture using a vacuum filtration device to obtain semi-dry HgCl2 generator, and then place the semi-dry generator in an oven at 105°C for 12 hours to obtain HgCl2 generator.

[0051] Step 4: Regenerate the expired HgCl2 standard gas generator by low-temperature plasma treatment.

[0052] Example 2

[0053] A method for preparing a renewable HgCl2 standard gas generator includes the following steps:

[0054] Step 1: Weigh 5g of anhydrous CuCl2 and dissolve it in 45ml of deionized water to obtain a 10wt.% CuCl2 solution;

[0055] Step 2: Add 5g of γ-Al2O3 at a solid-liquid ratio of 1g:10ml; stir evenly, then place on a magnetic stirrer and stir for 5 hours to obtain a mixture;

[0056] Step 3: Filter the mixture using a vacuum filtration device to obtain semi-dry HgCl2 generator, and then place the semi-dry generator in an oven at 105°C for 12 hours to obtain HgCl2 generator.

[0057] Step 4: Place the dried HgCl2 generator in a low-temperature plasma modification device, use 2000ppm HCl as the modifying gas, discharge power of 30W, discharge time of 3min, and perform low-temperature plasma modification on the dried HgCl2 generator to obtain a low-temperature plasma modified HgCl2 generator.

[0058] Step 5: Regenerate the expired HgCl2 standard gas generator by low-temperature plasma treatment.

[0059] Example 3

[0060] A method for preparing a renewable HgCl2 standard gas generator includes the following steps:

[0061] Step 1: Weigh 5g of anhydrous CuCl2 and dissolve it in 45ml of deionized water to obtain a 10wt.% CuCl2 solution;

[0062] Step 2: Add 10g of mesoporous SiO2 at a solid-liquid ratio of 1g:5ml; stir evenly, then place on a magnetic stirrer and stir for 5 hours to obtain a mixture;

[0063] Step 3: Filter the mixture using a vacuum filtration device to obtain semi-dry HgCl2 generator, and then place the semi-dry generator in an oven at 105°C for 12 hours to obtain HgCl2 generator.

[0064] Step 4: Place the dried HgCl2 generator in a low-temperature plasma modification device, use 10ppm Cl2 as the modifying gas, discharge power of 160W, discharge time of 30min, and perform low-temperature plasma modification on the dried HgCl2 generator to obtain the low-temperature plasma modified HgCl2 generator.

[0065] Step 5: Regenerate the expired HgCl2 standard gas generator by low-temperature plasma treatment.

[0066] Example 4

[0067] A method for preparing a renewable HgCl2 standard gas generator includes the following steps:

[0068] Step 1: Weigh 15g of MnCl2 and dissolve it in 45ml of deionized water to obtain a 25wt.% MnCl2 solution;

[0069] Step 2: Add 3g TiO2 at a solid-liquid ratio of 1g:20ml; stir evenly, then place on a magnetic stirrer and stir for 8 hours to obtain a mixture;

[0070] Step 3: Filter the mixture on a vacuum filter to obtain a semi-dry HgCl2 generator, and then place the semi-dry generator in an oven at 100°C for 18 hours to obtain the HgCl2 generator.

[0071] Step 4: Place the dried HgCl2 generator in a low-temperature plasma modification device, use 10000ppm HCl as the modifying gas, discharge power of 300W, discharge time of 0.5min, and perform low-temperature plasma modification on the dried HgCl2 generator to obtain a low-temperature plasma modified HgCl2 generator.

[0072] Step 5: Regenerate the expired HgCl2 standard gas generator by low-temperature plasma treatment.

[0073] Example 5

[0074] A method for preparing a renewable HgCl2 standard gas generator includes the following steps:

[0075] Step 1: Weigh 12g of FeCl3 and dissolve it in 48ml of deionized water to obtain a 20wt.% FeCl3 solution;

[0076] Step 2: Add 4g of zeolite at a solid-liquid ratio of 1g:15ml; stir well and then place on a magnetic stirrer to stir for 4 hours to obtain a mixture;

[0077] Step 3: Filter the mixture on a vacuum filter to obtain a semi-dry HgCl2 generator, and then place the semi-dry generator in an oven at 110°C for 8 hours to obtain the HgCl2 generator.

[0078] Step 4: Place the dried HgCl2 generator in a low-temperature plasma modification device, use 5000ppm Cl2 as the modifying gas, discharge power of 50W, discharge time of 10min, and perform low-temperature plasma modification on the dried HgCl2 generator to obtain the HgCl2 generator treated with low-temperature plasma.

[0079] Step 5: Regenerate the expired HgCl2 standard gas generator by low-temperature plasma treatment.

[0080] Example 6

[0081] A method for preparing a renewable HgCl2 standard gas generator includes the following steps:

[0082] Step 1: Weigh 5g of anhydrous CuCl2 and dissolve it in 45ml of deionized water to obtain a 10wt.% CuCl2 solution;

[0083] Step 2: Add 5g of MCM-41 molecular sieve at a solid-liquid ratio of 1g:10ml; after stirring evenly, place on a magnetic stirrer and stir for 6 hours to obtain a mixture;

[0084] Step 3: Filter the mixture using a vacuum filtration device to obtain semi-dry HgCl2 generator, and then place the semi-dry generator in an oven at 105°C for 12 hours to obtain HgCl2 generator.

[0085] Step 4: Place the dried HgCl2 generator in a low-temperature plasma modification device, use a mixed gas of 1000ppm HCl and Cl2 (volume ratio 1:1) as the modification gas, discharge power of 10W, discharge time of 20min, and perform low-temperature plasma modification on the dried HgCl2 generator to obtain a low-temperature plasma modified HgCl2 generator.

[0086] Step 5: Regenerate the expired HgCl2 standard gas generator by low-temperature plasma treatment.

[0087] Application Example 1

[0088] The HgCl2 standard gas generator prepared in step 3 of Example 1 was placed on a fixed-bed test bench to verify its oxidation of Hg. 0 HgCl2 generation capacity. Experimental conditions: HgCl2 generator 25mg, quartz sand bed 500mg, mercury-loaded nitrogen 200ml / min, equilibrium nitrogen 800ml / min, initial Hg... 0 Concentration of 1050±10 μg / m 3 .

[0089] Depend on Figure 2 It can be seen that the HgCl2 standard gas generator prepared in step 3 of Example 1 has high oxidation efficiency and stable oxidation effect in the temperature range of 180 to 220°C, and the HgCl2 generation rate is stable at over 90% within 120 min.

[0090] Application Example 2

[0091] The oxidation efficiency of the low-temperature plasma-modified HgCl2 standard gas generator prepared in Example 2 and the unmodified HgCl2 standard gas generator prepared in Example 1 was tested over a long period (14 h) in a fixed bed. Experimental conditions: 25 mg of both low-temperature plasma-modified and unmodified HgCl2 generators, 500 mg of quartz sand bed material, 200 ml / min of mercury-loaded nitrogen, 800 ml / min of balanced nitrogen, fixed bed temperature of 220 °C, and initial Hg... 0 Concentration of 1050±10ug / m 3 .

[0092] Depend on Figure 3 It can be seen that the HgCl2 standard gas generator prepared in Example 2, after low-temperature plasma modification, exhibits further improvements in both oxidation rate and oxidation time. Compared to Example 1, its initial oxidation efficiency increased from 93.7% to 97.5%, and remained above 90% after 14 hours, while the oxidation efficiency of the unmodified HgCl2 generator in Example 1 was 83.4%.

[0093] Figure 4 This is a graph showing the change in mercury oxidation rate over time for the HgCl2 standard gas generator prepared in Example 3 after low-temperature plasma modification. Figure 4 It can be seen that the Cl2-modified oxidant prepared in Example 3 exhibits excellent oxidation efficiency, which is maintained at 96.1% within 2 hours.

[0094] Application Example 3

[0095] On a fixed bed, the HgCl2 standard gas generator prepared in Example 2 and modified by low-temperature plasma was tested for a long time until it completely failed. Then, 400 ppm HCl was introduced as the modifying gas, and the HgCl2 standard gas generator was subjected to low-temperature plasma discharge for 10 minutes at a discharge power of 160 W to conduct a regeneration test of the HgCl2 standard gas generator and verify its regeneration effect.

[0096] like Figure 5 As shown, the HgCl2 standard gas generator, after plasma regeneration, still possesses high oxidation efficiency. When tested according to the method shown in Application Example 2, the oxidation efficiency remained above 90% for 2 hours. This indicates that its oxidation capacity was effectively restored after regeneration.

[0097] In summary, this invention proposes an HgCl2 standard gas generator and its preparation method. Compared with existing technologies, the method is simple and can stably and reliably generate HgCl2 standard gas with high purity and strong safety. It can well meet the technical requirements of the mercury calibration module in the online continuous mercury monitoring system (Hg-CEMS) and can be applied to the online continuous mercury monitoring system to provide quality control and accuracy control of monitoring data.

[0098] The above are merely preferred embodiments of the present invention and are not intended to limit the implementation methods and protection scope of the present invention. Those skilled in the art should recognize that any equivalent substitutions and obvious changes made based on the content of this specification should be included within the protection scope of the present invention.

Claims

1. A method for preparing a renewable HgCl2 standard gas generator, characterized in that, Includes the following steps: S1. Dissolve the transition metal chloride in water to obtain a solution; S2. Add the non-carbon-based carrier material to the solution and mix thoroughly to obtain a mixture; S3. The mixture is subjected to filtration and drying processes to obtain HgCl2 standard gas generator; S4. The expired HgCl2 standard gas generator is regenerated by low-temperature plasma treatment; the regeneration uses HCl and / or Cl2 as the regeneration gas, the concentration of the regeneration gas is 100~4000ppm, the regeneration time is 5~60min, and the discharge power is 60~400W. The HgCl2 standard gas generator is used in the online mercury monitoring system for mercury-containing flue gas to achieve stable generation of HgCl2 standard gas.

2. The preparation method according to claim 1, characterized in that, In step S1, the mass concentration of the transition metal chloride in the solution is 1 wt.% to 30 wt.%; the transition metal chloride is selected from one or more combinations of FeCl3, CuCl2, and MnCl2.

3. The preparation method according to claim 1, characterized in that, In step S2, the non-carbon-based support material is selected from one or more combinations of porous Al2O3, mesoporous SiO2, TiO2, zeolite, and MCM-41 molecular sieve.

4. The preparation method according to claim 1, characterized in that, In step S2, the mass-to-volume ratio of the non-carbon-based carrier material to the solution is 1:(5~20)g / mL.

5. The preparation method according to claim 1, characterized in that, In step S3, the mixture is first filtered to make it semi-dry, and then dried. The drying temperature is 100~110℃ and the time is 2~24h.

6. The preparation method according to claim 1, characterized in that, Step S3 further includes: using HCl and / or Cl2 as modifying gas to perform low-temperature plasma modification on the HgCl2 generator to improve its chemical activity; the low-temperature plasma modification adopts dielectric barrier discharge, the concentration of the modifying gas is 10~10000ppm, the modification time is 0.5~60min, and the discharge power is 5~300W.

7. A renewable HgCl2 standard gas generator, characterized in that, The HgCl2 generator is prepared by the preparation method according to any one of claims 1-6.

8. Application of a renewable HgCl2 standard gas generator, wherein the HgCl2 generator is prepared by the preparation method according to any one of claims 1-6; characterized in that, Using the HgCl2 standard gas generator as the chlorine source, elemental mercury (Hg) 0 As a mercury source, high-purity, impurity-free HgCl2 standard gas is produced through a gas-solidification chemical reaction under a nitrogen atmosphere.

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