Porous sulfur-rich polymer heavy metal adsorbent and preparation method thereof
By introducing dopamine methacrylamide and divinyl monomer crosslinking agents into sulfur polymers and combining them with inorganic salt pore-forming agents, porous sulfur-rich polymers were prepared, which solved the problem of insufficient adsorption capacity of polysulfide polymers for hard metal ions and improved hydrophilicity and adsorption efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU LIAOYUAN ENVIRONMENTAL PROTECTION TECH CO LTD
- Filing Date
- 2026-03-10
- Publication Date
- 2026-05-12
AI Technical Summary
Existing polysulfide polymers have insufficient adsorption capacity for hard metal ions and are highly hydrophobic, which is not conducive to water wetting.
Porous sulfur-rich polymers were prepared by introducing dopamine methacrylamide and divinyl monomer crosslinking agents into sulfur polymers and combining them with inorganic salt porogens. Catechol groups were formed to improve hydrophilicity, and a porous structure was formed by template method.
It improves the adsorption capacity for heavy metal ions such as Fe3+, Ni2+, and Cu2+, broadens the adsorption range, and increases the specific surface area through the porous structure, thereby improving the adsorption efficiency.
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Figure CN122011389A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of heavy metal adsorbent technology, specifically relating to a porous sulfur-rich polymer heavy metal adsorbent and its preparation method. Background Technology
[0002] Heavy metal ions in water, such as mercury(II), copper(II), lead(II), and iron(III), pose a serious threat to the ecological environment and human health. Sulfur, as a cheap and abundant byproduct of the petrochemical industry, can coordinate with heavy metal ions and can be used as a heavy metal adsorbent. However, due to the poor physical properties of elemental sulfur, it cannot be widely used in the adsorption field. In recent years, the preparation of polypolysulfide polymers using the reverse sulfurization method has become one of the most widely used techniques for modifying the properties of elemental sulfur. This technique involves reacting polyene monomers with elemental sulfur to generate stable sulfur-based organic / inorganic polymers. Currently, polysulfide polymers prepared by the antisulfurization method have been widely used in the field of heavy metal adsorption [AngewChem Int Ed, 2016, 55(5): 1714-1718; Chem Commun, 2016, 52(31): 5383-5386; JMater Chem A, 2017, 5(35): 18603-18609].
[0003] However, sulfur only has a strong adsorption effect on soft metal ions such as mercury(II) and silver(II), and its adsorption performance on ions such as iron(III), chromium(III,VI), and copper(II) is poor. In addition, sulfur polymers are highly hydrophobic, which is not conducive to the wetting of water bodies.
[0004] Therefore, overcoming the deficiency of polysulfide polymers in adsorbing hard metal ions is a technical problem that urgently needs to be solved in this field.
[0005] It should be noted that the information disclosed in this background section is only for understanding the background technology of the present application concept, and therefore, the above description is not considered to constitute prior art information. Summary of the Invention
[0006] This disclosure provides at least one porous sulfur-rich polymer heavy metal adsorbent and its preparation method.
[0007] In a first aspect, this disclosure provides a porous sulfur-rich polymer heavy metal adsorbent, prepared from sulfur, dopamine methacrylamide, a divinyl monomer crosslinking agent, and an inorganic salt pore-forming agent; its chemical molecular structure is as follows:
[0008] Wherein, R is a group other than vinyl in the divinyl monomer crosslinking agent, and n ranges from 5 to 100.
[0009] In one optional embodiment, the porosity of the porous sulfur-rich polymer heavy metal adsorbent is 45% to 65%.
[0010] In one alternative embodiment, the divinyl monomer crosslinking agent comprises any one or more combinations of 1,3-diisopropenylbenzene, divinylbenzene, ethylene glycol divinyl ether, divinyl sulfone, and butanediyl glycol divinyl ether.
[0011] In one alternative embodiment, the inorganic salt porogen includes any one or more combinations of sodium chloride, ammonium carbonate, and ammonium bicarbonate.
[0012] Secondly, this disclosure also provides a method for preparing the porous sulfur-rich polymer heavy metal adsorbent as described above, comprising the following steps: S1, heating sulfur to 160-200°C to melt; S2, adding dopamine methacrylamide, divinyl monomer crosslinking agent and inorganic salt pore-forming agent to the molten sulfur, maintaining the temperature for reaction to obtain a homogeneous elastic solid material, and cooling; S3, grinding the homogeneous elastic solid material into particles with a particle size range of 1-10 mm, washing with water to remove the inorganic salt pore-forming agent, and obtaining the porous sulfur-rich polymer heavy metal adsorbent.
[0013] In an alternative embodiment, the weight ratio of the sulfur to the sum of the weights of the dopamine methacrylamide and the divinyl monomer crosslinking agent is not less than 0.5.
[0014] In one optional embodiment, the weight ratio of the dopamine methacrylamide to the divinyl monomer crosslinking agent is 1:1 to 1:3.
[0015] In one optional embodiment, the weight ratio of the inorganic salt pore-forming agent to the sulfur is 0.5 to 0.7.
[0016] In one optional implementation, the number of water washes in S3 is not less than 3.
[0017] Thirdly, this disclosure also provides an application of the porous sulfur-rich polymer heavy metal adsorbent as described above in the field of heavy metal adsorption.
[0018] The beneficial effects of this invention are that the porous sulfur-rich polymer heavy metal adsorbent improves the hydrophilicity of the sulfur polymer by introducing catechol groups into it, making the adsorbent easier to wet with water. The introduction of catechol groups significantly enhances the adsorption capacity of the sulfur polymer for Fe. 3+ Ni 2+ Cu 2+The adsorption capacity of heavy metal ions broadens the adsorption range of sulfur polymer-based adsorbents. From a macroscopic perspective, the porous structure prepared by the inorganic salt porogen template method further increases the specific surface area of the adsorbent, thereby improving the adsorption efficiency.
[0019] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention are realized and obtained through the structures particularly pointed out in the description and the drawings.
[0020] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, preferred embodiments are described below in detail with reference to the accompanying drawings. Attached Figure Description
[0021] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0022] Figure 1 The appearance (left) and scanning electron microscope (SEM) image (right) of the porous sulfur-rich polymer heavy metal adsorbent prepared in Example 1, which is provided for the embodiments of this disclosure. Detailed Implementation
[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, 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.
[0024] As used herein, the phrases “in one embodiment,” “according to one embodiment,” “in some embodiments,” etc., generally refer to the fact that a particular feature, structure, or characteristic following the phrase can be included in at least one embodiment of this disclosure. Therefore, a particular feature, structure, or characteristic can be included in more than one embodiment of this disclosure, such that these phrases do not necessarily refer to the same embodiment. As used herein, the terms “example,” “exemplary,” etc., are used to “serve as an example, instance, or illustration.” Any implementation, aspect, or design described herein as “example” or “exemplary” is not necessarily to be construed as preferred or superior to other implementations, aspects, or designs. Rather, the use of the terms “example,” “exemplary,” etc., is intended to present concepts in a specific manner.
[0025] In this document, as used herein, expressions such as “at least one of…” modify the entire list of elements when following a list of elements, rather than individual elements in the list. For example, the expression “at least one of a, b, and c” should be understood to include only a, only b, only c, both a and b, both a and c, both b and c, or all of a, b, and c.
[0026] The terminology used herein is for the purpose of describing specific exemplary configurations only and is not intended to be limiting. As used herein, the singular articles “a,” “an,” and “the” may also be intended to include plural forms unless otherwise clearly stated herein. The terms “comprising,” “including,” and “having” are inclusive and thus specify the presence of features, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and / or combinations thereof. The method steps, processes, and operations described herein should not be construed as requiring them to be performed in the specific order discussed or shown, unless specifically identified as such. Additional or alternative steps may be employed.
[0027] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.
[0028] This disclosure provides a porous sulfur-rich polymer heavy metal adsorbent, prepared from sulfur, dopamine methacrylamide, divinyl monomer crosslinking agent, and inorganic salt pore-forming agent; its chemical molecular structure is as follows:
[0029] Wherein, R is a group other than vinyl in the divinyl monomer crosslinking agent, and n ranges from 5 to 100.
[0030] In some embodiments, specifically, the porosity of the porous sulfur-rich polymer heavy metal adsorbent is 45% to 65%.
[0031] In some embodiments, specifically, the divinyl monomer crosslinking agent includes any one or more combinations of 1,3-diisopropenylbenzene, divinylbenzene, ethylene glycol divinyl ether, divinyl sulfone, and butanediyl glycol divinyl ether.
[0032] In some embodiments, specifically, the inorganic salt porogen includes any one or more combinations of sodium chloride, ammonium carbonate, and ammonium bicarbonate.
[0033] This disclosure also provides a method for preparing the porous sulfur-rich polymer heavy metal adsorbent as described above, comprising the following steps: S1, heating sulfur to 160-200°C to melt; S2, adding dopamine methacrylamide, divinyl monomer crosslinking agent and inorganic salt pore-forming agent to the molten sulfur, maintaining the temperature for reaction to obtain a homogeneous elastic solid material, and cooling; S3, grinding the homogeneous elastic solid material into particles with a particle size range of 1-10 mm, washing with water to remove the inorganic salt pore-forming agent, and obtaining the porous sulfur-rich polymer heavy metal adsorbent.
[0034] In some embodiments, specifically, the weight ratio of the sulfur to the sum of the weights of the dopamine methacrylamide and the divinyl monomer crosslinking agent is not less than 0.5.
[0035] In some embodiments, specifically, the weight ratio of the dopamine methacrylamide to the divinyl monomer crosslinking agent is 1:1 to 1:3.
[0036] In some embodiments, specifically, the weight ratio of the inorganic salt pore-forming agent to the sulfur is 0.5 to 0.7.
[0037] In some embodiments, specifically, the number of times the water is washed in S3 is not less than 3 times.
[0038] This disclosure also provides an application of the porous sulfur-rich polymer heavy metal adsorbent as described above in the field of heavy metal adsorption.
[0039] Example 1: The porous sulfur-rich polymer-based heavy metal adsorbent in this example is prepared from sulfur, dopamine methacrylamide, 1,3-diisopropenylbenzene crosslinking agent, and sodium chloride pore-forming agent. The preparation steps are as follows: S1, heat 6g of sulfur to 180℃ to melt it; S2, add 2g dopamine methacrylamide, 2g 1,3-diisopropenylbenzene crosslinking agent and 3.5g sodium chloride porogen and continue the reaction for 45min to obtain a homogeneous elastic solid material, and then cool it; S3. The homogeneous elastic solid material is ground into 5 mm particles and then washed with water three times to remove the inorganic salt pore-forming agent, thus obtaining a porous sulfur-rich polymer heavy metal adsorbent.
[0040] Example 2: The porous sulfur-rich polymer-based heavy metal adsorbent in this example is prepared from sulfur, dopamine methacrylamide, 1,3-diisopropenylbenzene crosslinking agent, and sodium chloride pore-forming agent. The preparation steps are as follows: S1, heat 7g of sulfur to 160℃ to melt it; S2, add 2g dopamine methacrylamide, 1g 1,3-diisopropenylbenzene crosslinking agent and 4.2g sodium chloride porogen and continue the reaction for 60min to obtain a homogeneous elastic solid material, and then cool it; S3. The homogeneous elastic solid material is ground into 1 mm particles and then washed with water 3 times to remove the inorganic salt pore-forming agent, thus obtaining a porous sulfur-rich polymer heavy metal adsorbent.
[0041] Example 3: The porous sulfur-rich polymer-based heavy metal adsorbent in this example was prepared from sulfur, dopamine methacrylamide, 1,3-diisopropenylbenzene crosslinking agent, and sodium chloride pore-forming agent. The preparation steps are as follows: S1, heat 5g of sulfur to 200℃ to melt it; S2, add 3.33g dopamine methacrylamide, 1.67g 1,3-diisopropenylbenzene crosslinking agent and 4.2g sodium chloride porogen and continue the reaction for 30min to obtain a homogeneous elastic solid material, and then cool it; S3. The homogeneous elastic solid material is ground into 10 mm particles and then washed with water three times to remove the inorganic salt pore-forming agent, thus obtaining a porous sulfur-rich polymer heavy metal adsorbent.
[0042] Example 4 The porous sulfur-rich polymer-based heavy metal adsorbent in this example was prepared from sulfur, dopamine methacrylamide, ethylene glycol divinyl ether, and ammonium carbonate as a pore-forming agent. The preparation steps are as follows: S1, heat 6g of sulfur to 180℃ to melt it; S2, add 2g dopamine methacrylamide, 2g ethylene glycol divinyl ether crosslinking agent and 3.5g ammonium carbonate porogen and continue the reaction for 45 min to obtain a homogeneous elastic solid material, and then cool it; S3. The homogeneous elastic solid material is ground into 5 mm particles and then washed with water three times to remove the inorganic salt pore-forming agent, thus obtaining a porous sulfur-rich polymer heavy metal adsorbent.
[0043] Comparative Example 1: This comparative example of a porous sulfur-rich polymer-based heavy metal adsorbent was prepared from sulfur, dopamine methacrylamide, and sodium chloride as a pore-forming agent. The preparation steps are as follows: S1, heat 8g of sulfur to 180℃ to melt it; S2, add 2g of divinylbenzene crosslinking agent and 3.5g of sodium chloride porogen and continue the reaction for 45 min to obtain a homogeneous elastic solid material, and then cool it; S3. The homogeneous elastic solid material is ground into 5 mm particles and then washed with water three times to remove the inorganic salt pore-forming agent, thus obtaining a porous sulfur-rich polymer heavy metal adsorbent.
[0044] Comparative Example 2: This comparative example of a porous sulfur-rich polymer-based heavy metal adsorbent was prepared from sulfur, divinylbenzene crosslinking agent, and sodium chloride pore-forming agent. The preparation steps are as follows: S1, heat 5g of sulfur to 200℃ to melt it; S2, add 3.33g dopamine methacrylamide and 4.2g sodium chloride porogen and continue the reaction for 30min to obtain a homogeneous elastic solid material, and then cool it; S3. The homogeneous elastic solid material is ground into 5 mm particles and then washed with water three times to remove the inorganic salt pore-forming agent, thus obtaining a porous sulfur-rich polymer heavy metal adsorbent.
[0045] Specifically, the adsorption performance of heavy metal ions of the heavy metal adsorbents obtained in Examples 1-4 and Comparative Examples 1 and 2 was compared, with an ion concentration of 1 mmol. The results are shown in Table 1.
[0046] Table 1
[0047] Specifically, the porous sulfur-rich polymer heavy metal adsorbents prepared in Examples 1-4 generally exhibited adsorption efficiencies of over 90% for heavy metal ions, demonstrating excellent adsorption performance. Comparative Example 1, a porous sulfur-rich heavy metal adsorbent without dopamine methacrylamide, showed significantly weakened adsorption capacity for heavy metal ions due to its relatively poor hydrophilicity. Comparative Example 2, a porous sulfur-rich heavy metal adsorbent without divinyl monomer crosslinking agent, also showed weakened adsorption capacity for heavy metal ions because it failed to form an effective aggregated structure, resulting in a decrease in specific area and porosity.
[0048] In summary, this porous sulfur-rich polymer heavy metal adsorbent improves the hydrophilicity of the sulfur polymer by introducing catechol groups, making the adsorbent easier to wet with water. The introduction of catechol groups significantly enhances the adsorption capacity of the sulfur polymer for Fe. 3+ Ni 2+ Cu 2+ The adsorption capacity of heavy metal ions broadens the adsorption range of sulfur polymer-based adsorbents; from a macroscopic perspective, the porous structure further increases the specific surface area of the adsorbent, thereby improving the adsorption efficiency.
[0049] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.
Claims
1. A porous sulfur-rich polymer heavy metal adsorbent, characterized in that, It is prepared from sulfur, dopamine methacrylamide, divinyl monomer crosslinking agent and inorganic salt pore-forming agent; Its chemical molecular structure is: ； Wherein, R is a group other than vinyl in the divinyl monomer crosslinking agent, and n ranges from 5 to 100.
2. The porous sulfur-rich polymer heavy metal adsorbent as described in claim 1, characterized in that, The porosity of the porous sulfur-rich polymer heavy metal adsorbent is 45% to 65%.
3. The porous sulfur-rich polymer heavy metal adsorbent as described in claim 1, characterized in that, The divinyl monomer crosslinking agent includes any one or more combinations of 1,3-diisopropenylbenzene, divinylbenzene, ethylene glycol divinyl ether, divinyl sulfone, and butanediol divinyl ether.
4. The porous sulfur-rich polymer heavy metal adsorbent as described in claim 1, characterized in that, The inorganic salt porogen includes any one or more combinations of sodium chloride, ammonium carbonate, and ammonium bicarbonate.
5. A method for preparing a porous sulfur-rich polymer heavy metal adsorbent as described in any one of claims 1-4, characterized in that, Includes the following steps: S1, heat the sulfur to 160-200℃ to melt it; S2, dopamine methacrylamide, divinyl monomer crosslinking agent and inorganic salt pore-forming agent are added to molten sulfur, the reaction is kept at a certain temperature to obtain a homogeneous elastic solid material, and then cooled; S3, the homogeneous elastic solid material is ground into particles with a particle size range of 1 to 10 mm, and the inorganic salt pore-forming agent is removed by water washing to obtain a porous sulfur-rich polymer heavy metal adsorbent.
6. The preparation method according to claim 5, characterized in that, The weight ratio of the sulfur to the sum of the weights of the dopamine methacrylamide and the divinyl monomer crosslinking agent is not less than 0.
5.
7. The preparation method according to claim 5, characterized in that, The weight ratio of the dopamine methacrylamide to the divinyl monomer crosslinking agent is 1:1 to 1:
3.
8. The preparation method according to claim 5, characterized in that, The weight ratio of the inorganic salt pore-forming agent to the sulfur is 0.5 to 0.
7.
9. The preparation method according to claim 5, characterized in that, The number of times water is washed in S3 shall not be less than 3.
10. An application of the porous sulfur-rich polymer heavy metal adsorbent as described in any one of claims 1-4 in the field of heavy metal adsorption.