A method of stabilizing a barium-containing adsorbent

Abstract

This application relates to a method for stabilizing a barium-containing adsorbent, comprising: S1 reacting the barium-containing adsorbent with an SO4-containing adsorbent. 2‑ A stabilization reaction is carried out by mixing an aqueous solution of a barium adsorbent with SO4 in the aqueous solution of the barium adsorbent. 2‑ The molar ratio of the substances is greater than or equal to 10:1; the main component of the barium-containing adsorbent is a barium-containing FAU-type molecular sieve; S2 separates the solid and liquid phases to obtain a stabilized adsorbent and a first liquid tail liquid. This invention utilizes the physicochemical properties of a barium-containing adsorbent (mainly a barium-containing FAU-type molecular sieve) to produce SO4 with a significantly lower molar amount of barium than that in the barium-containing adsorbent. 2‑ The molar amount stabilizes the above solid particles. The mass concentration of barium element and compounds in the leachate of the stabilized barium-containing adsorbent is lower than the hazardous component concentration limit (100 mg / L) specified in GB 5085.3~2007, and also lower than the hazardous waste permissible landfill control limit (85 mg / L, a necessary condition for entry into flexible landfills) specified in GB 18598~2019.

Description

Technical Field

[0001] This invention relates to a method for stabilizing barium-containing adsorbents. Specifically, it relates to a method for treating barium-containing adsorbents with a stabilizing agent to reduce the mass concentration of barium elements and compounds in the leachate of the stabilized barium-containing adsorbent to below the allowable landfill control limit for hazardous waste (85 mg / L, a necessary condition for entry into flexible landfills). Background Technology

[0002] Most existing stabilization methods for barium-containing solid waste target barium slag, which is an alkaline solid waste residue produced by high-temperature carbon reduction and leaching of barite as raw material. Its main components are water-soluble barium salts (mainly BaS) and acid-soluble barium salts (mainly BaCO3).

[0003] However, in the simulated moving bed adsorption separation of PX, the barium-containing adsorbent (with Ba as the active component) 2+ Exchange-modified FAU-type molecular sieves differ significantly from water-soluble and acid-soluble barium salts in their physicochemical properties, including but not limited to: the Ba element in the molecular sieve is located within specific supercages, β-cages, or hexagonal prism cages constructed from the silicon, aluminum, and oxygen atomic framework; adsorbents used in adsorption separation also possess microstructures represented by pores. Therefore, processing them using conventional methods is difficult and costly. Summary of the Invention

[0004] This application provides a method for stabilizing a barium-containing adsorbent, comprising:

[0005] S1 causes the barium-containing adsorbent to react with the SO4-containing adsorbent. 2- A stabilization reaction is carried out by mixing an aqueous solution of a barium adsorbent with SO4 in the aqueous solution of the barium adsorbent. 2- The molar ratio of the substances is greater than or equal to 10:1; the main component of the barium-containing adsorbent is a barium-containing FAU-type molecular sieve;

[0006] S2 separates the solid and liquid phases to obtain the stabilized adsorbent and the first liquid tail liquid.

[0007] In one embodiment, the method of this application further includes:

[0008] S3 Wash the stabilized adsorbent to obtain the second liquid tail liquid.

[0009] The first liquid phase tail liquid and / or the second liquid phase tail liquid are treated and then used as part of the stabilizer aqueous solution.

[0010] In one embodiment, the Ba element in the barium-containing adsorbent reacts with the SO4 in the stabilizer solution. 2-The molar ratio of the substances is 10:1 to 41:1, preferably 13:1 to 41:1, and even more preferably 20:1 to 41:1.

[0011] In one embodiment, the total pore volume of the barium-containing adsorbent is 0.25~0.32 cm³. 3 / g, micropore volume is 0.23~0.30cm³ 3 / g.

[0012] In one embodiment, the molar ratio of silicon to aluminum atoms in the barium-containing adsorbent is 1.0 to 2.0, more preferably 1.3 to 1.6.

[0013] In one embodiment, the particle diameter of the barium-containing adsorbent is ≤2mm, preferably ≤1.2mm.

[0014] In one embodiment, the mass fraction of BaO in the barium-containing adsorbent is 30% to 37% of the dry basis of the adsorbent.

[0015] In one embodiment, the aqueous stabilizer solution does not contain mercury, lead, cadmium, chromium, copper, zinc, beryllium, nickel, or arsenic.

[0016] In one embodiment, the stabilizer aqueous solution contains one or more of sodium ions, potassium ions, and lithium ions, more preferably one or more of sodium ions and potassium ions.

[0017] In one embodiment, the volume ratio of the stabilizer aqueous solution to the barium adsorbent solid is ≥0.7, preferably 0.7~2.0; the reaction temperature is ≥10℃, preferably 10℃~60℃; and the reaction time is ≥10 minutes, preferably 10~60 minutes.

[0018] The method of this invention utilizes the physicochemical properties of barium-containing adsorbents (mainly FAU-type molecular sieves containing barium) to produce SO4 with a significantly lower molar amount of barium element than that in barium-containing adsorbents. 2-The molar amount stabilizes the aforementioned solid particles. The mass concentration of barium and its compounds in the leachate of the stabilized barium-containing adsorbent is lower than the hazardous component concentration limit (100 mg / L) specified in GB 5085.3~2007, and also lower than the permissible landfill control limit for hazardous waste specified in GB 18598~2019 (85 mg / L, a necessary condition for flexible landfill access). Because flexible landfills have advantages such as low cost, relatively mature technology, and simple operation, this invention avoids a series of costs associated with constructing and using rigid landfills for treating waste paraxylene adsorbents. Meanwhile, the stabilization reaction tail liquid and washing tail liquid generated during the stabilization process of the present invention can be recycled, achieving low wastewater and low curing agent usage; no inorganic acid is introduced, making it safe and environmentally friendly; a variety of soluble sulfates can be selected as curing agents, and wastewater containing sulfate ions can be used as curing agents to achieve waste-to-waste treatment; with appropriate equipment (reactor, filter press, etc.), large-scale and continuous stabilization of barium-containing adsorbents can be achieved in industrial production, which has extremely strong practical value. Attached Figure Description

[0019] Figure 1 A flowchart illustrating the method of this application is shown. Detailed Implementation

[0020] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0021] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments. Although various aspects of embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated otherwise.

[0022] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0023] This application provides a method for stabilizing barium-containing adsorbents, including:

[0024] S1 causes the barium-containing adsorbent to react with the SO4-containing adsorbent. 2- A stabilization reaction is carried out by mixing an aqueous solution of a stabilizing agent, wherein the Ba element in the barium-containing adsorbent reacts with the SO4 in the stabilizing agent solution. 2- The molar ratio of the substances is greater than or equal to 10:1; the main component of the barium-containing adsorbent is a barium-containing FAU-type molecular sieve;

[0025] S2 separates the solid and liquid phases to obtain the stabilized adsorbent and the first liquid tail liquid.

[0026] Figure 1 A process flow diagram of the method of this application is shown. The following is in conjunction with... Figure 1 The method described in this application is explained.

[0027] The total pore volume of the barium-containing adsorbent used in this application is 0.25~0.32 cm³. 3 / g, micropore volume is 0.23~0.30cm³ 3 / g.

[0028] The barium-containing adsorbent is primarily composed of barium-containing FAU-type molecular sieves. Preferably, the molar ratio of silicon to aluminum atoms in the barium-containing adsorbent is 1.0 to 2.0, more preferably 1.3 to 1.6. Specifically, the barium-containing adsorbent is used for separating p-xylene, particularly for separating p-xylene from a C8 aromatic hydrocarbon mixed feed using a simulated moving bed adsorption separation process. The mass fraction of BaO in the barium-containing adsorbent is 30% to 37% (on a dry basis), for example, 34% to 37%.

[0029] When the particle diameter of the barium adsorbent is too large, the effectiveness of the stabilization method described in this invention may be reduced. If necessary, the particle diameter of the barium adsorbent material to be treated can be reduced by means including but not limited to pulverization. In one embodiment, the particle diameter of the barium adsorbent (material to be treated) is ≤2 mm, preferably ≤1.2 mm.

[0030] The method in this application uses SO4-containing... 2- An aqueous solution of a stabilizing agent is used to react with a barium-containing adsorbent for stabilization. In this application, the adsorbent contains SO4. 2- The stabilizing agent aqueous solution contains metal cations including but not limited to Na + K + Li + Simultaneously, it must be able to ensure that the mass concentration of barium and its compounds in the leachate of the adsorbent is lower than the hazardous component concentration limits specified in GB 5085.3~2007, and lower than the hazardous waste permissible landfill control limits specified in GB 18598~2019. Furthermore, the stabilizing agent aqueous solution must not contain mercury, lead, cadmium, chromium, copper, zinc, beryllium, nickel, or arsenic.

[0031] Stabilization of common water-soluble barium salts typically requires a relatively high amount of SO4. 2- For example, SO4 2- The amount of barium ions is in an equimolar ratio, or even in excess. In this application, the Ba element in the barium-containing adsorbent and the SO4 in the stabilizer solution are... 2-The molar ratio of the substances is greater than or equal to 10:1, preferably 10:1 to 41:1, more preferably 13:1 to 41:1, and even more preferably 20:1 to 41:1. In terms of stoichiometry, relative to the amount of Ba in the barium-containing adsorbent, the amount of SO4 in the stabilizer... 2- The amount of substance is far lower than the molar ratio of the two to form barium sulfate. However, the inventors of this application unexpectedly discovered that, relative to the amount of Ba in the barium-containing adsorbent, even the amount of SO4 in the stabilizer used... 2- The stoichiometric amount is far from sufficient to effectively stabilize Ba. This reduces the amount of stabilizer needed. Furthermore, a wide variety of soluble sulfates are available as stabilizers; even wastewater containing sulfate ions can be used, achieving waste-to-waste treatment.

[0032] According to the present invention, the mass concentration of barium element and compounds in the leachate of the stabilized barium-containing adsorbent is lower than the hazardous component concentration limit (100 mg / L) specified in GB 5085.3~2007, and also lower than the permissible landfill control limit for hazardous waste specified in GB 18598~2019 (85 mg / L, a necessary condition for flexible landfill access). Because flexible landfills have advantages such as low cost, relatively mature technology, and simple operation, the present invention avoids a series of costs incurred in constructing and using rigid landfills for treating waste paraxylene adsorbents.

[0033] In one embodiment, the volume ratio of the stabilizer aqueous solution to the barium-containing adsorbent solid (the material to be treated) is ≥0.7, preferably 0.7~2.0. Maintaining a certain liquid-to-solid volume ratio is beneficial to the ion exchange process of the barium-containing FAU-type molecular sieve and can improve the stabilization degree of barium in the molecular sieve.

[0034] The stabilization reaction is carried out at a specific reaction temperature and for a specific reaction time. In one embodiment, the reaction temperature is ≥10°C, preferably 10°C to 60°C. The reaction time is ≥10 minutes, for example, 10-60 minutes, preferably 10-40 minutes.

[0035] After the reaction, the solid and liquid phases are separated: the solid and liquid phases in the solid-liquid mixture after the stabilization reaction are separated to obtain the stabilized adsorbent and the first liquid tail liquid after use. The methods for separating the solid and liquid phases include, but are not limited to, filtration and centrifugation.

[0036] In one embodiment, the method of this application further includes: washing the stabilized adsorbent to obtain a second liquid tail liquid. The stabilized adsorbent can be washed with deionized water, and then the solid and liquid phases can be separated by filtration to obtain the second liquid tail liquid.

[0037] After removing floating oil and sediment, the tailings of the first and / or second liquid phases can be recycled as part of the stabilizer aqueous solution after being mixed.

[0038] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0039] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0040] The detection methods for each indicator in the embodiment are as follows:

[0041] (1) Leaching toxicity leaching method: Refer to industry standard HJ / T 299-2007 "Leaching toxicity leaching method for solid waste - sulfuric acid and nitric acid method";

[0042] (2) Method for analyzing the mass concentration of barium and its compounds in leachate: Refer to industry standard HJ 766-2015 "Determination of Metallic Elements in Solid Waste by Inductively Coupled Plasma Mass Spectrometry";

[0043] (3) The dry basis mass of the barium adsorbent refers to the remaining mass of the sample after calcination at 600℃ for 2 hours. The dry basis mass percentage (A) of the barium adsorbent is calculated according to the following formula:

[0044]

[0045] In the formula:

[0046] A – Barium adsorbent content (dry basis, percentage, %)

[0047] M0—Sample mass before ignition at 600℃, in grams (g).

[0048] M i —The remaining mass of the sample after being ignited at 600℃ for 2 hours, in grams (g);

[0049] (4) The specific surface area and pore structure of the adsorbent were determined by static low-temperature capacity adsorption using a fully automated specific surface area and porosity analyzer. The matrix (mesoporous) surface area and micropore volume of the sample were calculated by t-plotting according to SH / T0571; the liquid nitrogen adsorption volume when the relative pressure (P / P0) was about 0.98 was taken as the total pore volume of the sample.

[0050] Example 1

[0051] Small spheres containing barium-containing FAU molecular sieve as the active component were sieved using a 2.0 mm sieve. The undersize portion was used for stabilization experiments (the mass concentration of barium and its compounds in the leachate was 153 mg / L). The main component of the raw material spheres was barium-containing FAU molecular sieve with a silicon-to-aluminum atom molar ratio of 1.3. The barium oxide content in the dry spheres was 36.9%, and the total pore volume was 0.32 cm³. 3 / g, micropore volume is 0.30cm³ 3 / g.

[0052] 97.4 g (105 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 69 mL of 0.070 mol / L Na₂SO₄ aqueous solution was used as a stabilizer. The stabilization reaction temperature was 10℃, and the stabilization reaction time was 40 minutes. The reaction involved the interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer. 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 1.

[0053] The mixture after stabilization reaction was separated into solid and liquid phases by filtration. The solid phase was washed and filtered to obtain stabilized barium-containing FAU molecular sieve, with a barium element and compound mass concentration of 78.9 mg / L in the leachate.

[0054] After filtering to remove insoluble solids and using a separatory funnel to remove trace amounts of oil from the upper layer, the liquid phase and washing water were prepared into a 0.070 mol / L Na₂SO₄ aqueous solution. This prepared aqueous solution was used as a stabilizer to further stabilize barium-containing FAU molecular sieve-based raw material pellets (with properties identical to the stabilized test material described earlier in this example). 97.4 g (10⁵ mL) of raw material pellets (84.58% dry basis mass) sieved through a 2.0 mm sieve was placed in a beaker, and 69 mL of the prepared aqueous solution was used as the stabilizer. The stabilization reaction temperature was 10 °C, and the reaction time was 40 minutes. The mixture after stabilization was filtered to separate into solid and liquid phases. After washing and filtration, the solid phase yielded stabilized barium-containing FAU molecular sieve, with a barium element and compound concentration of 78.3 mg / L in the leachate.

[0055] Example 2

[0056] Small spheres containing barium-containing FAU molecular sieve as the active component were sieved using a 1.2 mm sieve. The undersize portion was used for stabilization experiments (the mass concentration of barium and its compounds in the leachate was 153 mg / L). The main component of the raw material spheres was barium-containing FAU molecular sieve with a silicon-to-aluminum atom molar ratio of 1.3. The barium oxide content in the dry spheres was 36.9%, and the total pore volume was 0.32 cm³. 3 / g, micropore volume is 0.30cm³ 3 / g.

[0057] 69.5 g (75 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 150 mL of 0.070 mol / L Na₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 60℃, and the stabilization time was 30 minutes. The interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer... 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 1.

[0058] The mixture after stabilization reaction was separated into solid and liquid phases by filtration. The solid phase was washed and filtered to obtain stabilized barium-containing FAU molecular sieve, with a barium element and compound mass concentration of 18.4 mg / L in the leachate.

[0059] Example 3

[0060] The same material as in Example 2 was used as the subject of the stabilization experiment.

[0061] 69.5 g (75 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 150 mL of 0.094 mol / L K₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 60℃, and the stabilization time was 30 minutes. The interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer... 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 1.

[0062] The mixture after stabilization reaction was separated into solid and liquid phases by filtration. The solid phase was washed and filtered to obtain stabilized barium-containing FAU molecular sieve, with a barium element and compound mass concentration of 1.7 mg / L in the leachate.

[0063] Example 4

[0064] The same material as in Example 2 was used as the subject of the stabilization experiment.

[0065] 69.5 g (75 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 150 mL of 0.047 mol / L K₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 60℃, and the stabilization time was 30 minutes. The interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer... 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 1.

[0066] The mixture after stabilization reaction was separated into solid and liquid phases by vacuum filtration. After washing and vacuum filtration, the solid phase yielded stabilized barium-containing FAU-type molecular sieves, with a barium element and compound mass concentration of 60.3 mg / L in the leachate.

[0067] Example 5

[0068] The same material as in Example 2 was used as the subject of the stabilization experiment.

[0069] 69.5 g (75 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 150 mL of 0.047 mol / L K₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 60℃, and the stabilization time was 10 minutes. The interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer... 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 1.

[0070] The mixture after stabilization reaction was separated into solid and liquid phases by vacuum filtration. After washing and vacuum filtration, the solid phase yielded stabilized barium-containing FAU-type molecular sieves, with a barium element and compound mass concentration of 70.8 mg / L in the leachate.

[0071] Example 6

[0072] Small spheres containing barium-containing FAU molecular sieve as the active component were sieved using a 1.2 mm sieve. The undersize portion was used for stabilization experiments (the mass concentration of barium and its compounds in the leachate was 153 mg / L). The main component of the raw material spheres was barium-containing FAU molecular sieve with a silicon-to-aluminum atom molar ratio of 1.6. The barium oxide content in the dry spheres was 34.1%, and the total pore volume was 0.25 cm³. 3 / g, micropore volume is 0.23cm³ 3 / g.

[0073] 69.5 g (75 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 150 mL of 0.047 mol / L K₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 60℃, and the stabilization time was 10 minutes. The interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer... 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 1.

[0074] The mixture after stabilization reaction was separated into solid and liquid phases by vacuum filtration. After washing and vacuum filtration, the solid phase yielded stabilized barium-containing FAU-type molecular sieves, with a barium element and compound mass concentration of 65.5 mg / L in the leachate.

[0075] Comparative Example 1

[0076] The same material as in Example 1 was used as the subject of the stabilization experiment.

[0077] 97.4 g (105 mL) of the sieved raw material pellets (dry basis mass percentage of 84.58%) were placed into a beaker, and 69 mL of 0.035 mol / L Na₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 10 °C, and the stabilization time was 40 minutes. The interaction between Ba in the barium-containing FAU molecular sieve and SO₄ in the stabilizer... 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 2.

[0078] After stabilization, the mixture was washed and filtered, and the mass concentration of barium and its compounds in the leachate was 153.2 mg / L.

[0079] Comparative Example 2

[0080] The same material as in Example 2 was used as the subject of the stabilization experiment.

[0081] 62.6 g of sieved raw material pellets (dry basis mass percentage of 84.58%) and 2.9 g of barium chloride were placed in a beaker and mixed evenly. The resulting mixture contained the same molar amount of barium as the material to be treated in Example 2, and the ratio of the molar amount of barium provided by barium chloride to the total molar amount of barium in the mixture was 0.1.

[0082] 150 mL of a 0.070 mol / L Na₂SO₄ aqueous solution was used as a stabilizer. The stabilization temperature was 60 °C, and the stabilization time was 30 minutes. The Ba element in the above barium-containing mixture reacted with the SO₄ in the stabilizer. 2- The molar ratios of the substances and the liquid-to-solid volume ratios of the stabilizer and the barium-containing FAU molecular sieve are shown in Table 2.

[0083] The mixture after stabilization reaction was separated into solid and liquid phases by vacuum filtration. The solid phase was washed and filtered to obtain stabilized barium-containing FAU-type molecular sieves, with a barium element and compound mass concentration of 165.0 mg / L in the leachate.

[0084] A comparison of "Comparative Example 2" and "Example 2" shows that the stabilization method described in this application is not applicable to barium-containing waste residues whose main components are water-soluble barium salts and acid-soluble barium salts: the molar amount of barium in the materials to be treated is the same; in "Example 2", all the barium in the material to be treated comes from the barium-containing adsorbent (the active component is Ba). 2+ In the "Comparative Example 2" material, approximately 10% of the barium element in the material to be treated originated from barium chloride, and approximately 90% of the barium element originated from the barium-containing adsorbent (the active component is Ba). 2+ The mass concentration of barium and its compounds in the leachate of the stabilized adsorbent in "Example 2" is lower than the hazardous component concentration limit specified in GB 5085.3~2007, but the mass concentration of barium and its compounds in the leachate of the stabilized adsorbent in "Comparative Example 2" is much higher than the hazardous component concentration limit specified in GB 5085.3~2007. In the stabilization method of this application (high Ba element and SO4 in the stabilizer solution)... 2- The molar ratio condition) cannot stabilize barium-containing waste residues containing water-soluble barium salts. However, it was unexpectedly found that for FAU-type molecular sieves whose main component is barium, the method of this application works even in solutions with very high levels of Ba and SO42-, even in solutions containing very high levels of stabilizing agent. 2- Barium can be stabilized to meet the required standards even under the conditions of the molar ratio of substances.

[0085] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.

[0086] Table 1 Stabilization reaction parameters involved in the examples

[0087]

[0088] Table 2 Stabilization reaction parameters involved in the comparative examples

[0089]

Claims

1. Stabilization methods for barium-containing adsorbents, including: S1 causes the barium-containing adsorbent to react with the SO4-containing adsorbent. 2- A stabilization reaction is carried out by mixing an aqueous solution of a barium adsorbent with SO4 in the aqueous solution of the barium adsorbent. 2- The molar ratio of the substances is greater than or equal to 10:1; the main component of the barium-containing adsorbent is a barium-containing FAU-type molecular sieve; S2 separates the solid and liquid phases to obtain the stabilized adsorbent and the first liquid tail liquid.

2. The stabilization method according to claim 1, wherein, Also includes: S3 Wash the stabilized adsorbent to obtain the second liquid tail liquid. The first liquid phase tail liquid and / or the second liquid phase tail liquid are treated and then used as part of the stabilizer aqueous solution.

3. The stabilization method according to claim 1, wherein, Ba element in barium adsorbent and SO4 in stabilizer solution 2- The molar ratio of the substances is 10:1 to 41:

1.

4. The stabilization method according to claim 3, wherein, Ba element in barium adsorbent and SO4 in stabilizer solution 2- The molar ratio of the substances is 13:1 to 41:

1.

5. The stabilization method according to claim 4, wherein, Ba element in barium adsorbent and SO4 in stabilizer solution 2- The molar ratio of the substances is 20:1 to 41:

1.

6. The stabilization method according to claim 1, wherein, The total pore volume of the barium-containing adsorbent is 0.25~0.32 cm³. 3 / g, micropore volume is 0.23~0.30cm³ 3 / g.

7. The stabilization method according to claim 6, wherein, The molar ratio of silicon to aluminum atoms in the barium-containing adsorbent is 1.0 to 2.

0.

8. The stabilization method according to claim 7, wherein, The molar ratio of silicon to aluminum atoms in the barium-containing adsorbent is 1.3 to 1.

6.

9. The stabilization method according to claim 6, characterized in that: The particle diameter of the barium-containing adsorbent is ≤2mm.

10. The stabilization method according to claim 9, characterized in that: The particle diameter of the barium-containing adsorbent is ≤1.2mm.

11. The stabilization method according to claim 6, wherein, The mass fraction of BaO in barium-containing adsorbents is 30% to 37% of the dry basis of the adsorbent.

12. The stabilization method according to claim 11, wherein, The mass fraction of BaO in the barium-containing adsorbent is 34% to 37% of the dry basis of the adsorbent.

13. The stabilization method according to any one of claims 1-12, wherein, The stabilizer aqueous solution does not contain mercury, lead, cadmium, chromium, copper, zinc, beryllium, nickel, or arsenic.

14. The stabilization method according to claim 13, wherein, The stabilizer aqueous solution contains one or more of sodium ions, potassium ions, and lithium ions.

15. The stabilization method according to claim 14, wherein, The stabilizer aqueous solution contains one or more of sodium ions and potassium ions.

16. The stabilization method according to any one of claims 1-12, wherein, The volume ratio of the stabilizer aqueous solution to the barium-containing adsorbent solid is ≥0.7; Reaction temperature ≥ 10℃; The reaction time is ≥10 minutes.

17. The stabilization method according to claim 16, wherein, The volume ratio of the stabilizer aqueous solution to the barium-containing adsorbent solid is 0.7~2.

0.

18. The stabilization method according to claim 16, wherein, The reaction temperature between the stabilizer aqueous solution and the barium-containing adsorbent solid is 10℃~60℃.

19. The stabilization method according to claim 16, wherein, The reaction time between the stabilizer aqueous solution and the barium-containing adsorbent solid is 10-60 minutes.

Images