Water-resistant and pressure-resistant enabled solid waste solidification material, and preparation method and application thereof

Abstract

The application discloses an anti-water and anti-pressure enabled solid waste curing material and a preparation method and application thereof, and comprises the following components in percentage by mass: polyglycerol fatty acid ester 5-15 %, acetic acid 10-20 %, fatty alcohol polyoxyethylene ether 35-50 %, polyvinyl alcohol 3-5 %, sodium lignosulfonate 3-5 %, and emulsified paraffin 15-30 %. The acetylated product generated by esterification reaction of polyglycerol fatty acid ester and acetic acid is used as a core skeleton, the electron-rich carboxyl group of which forms a stable coordination bond with heavy metal ions; the ether bond of the fatty alcohol polyoxyethylene ether cooperates with the phenolic hydroxyl group of the sodium lignosulfonate to capture fluoride and manganese ions through hydrogen bond-coordination bimodulus effect; the long-chain alkanes of the emulsified paraffin directionally wrap the chelate to form a hydrophobic barrier, thereby completely blocking the leaching path of harmful substances; the chelation-encapsulation-hydrophobic triple stabilization mechanism constructed in combination with a four-stage organic polymerization process provides technical support for the large-scale application of waste-free city construction.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lithium residue energy-saving and environmental protection, and particularly relates to a water-resistant and compression-resistant energy-assisted solid waste curing material and a preparation method and application thereof. BACKGROUND

[0002] With the rapid rise of the new energy industry, the lithium salt industry has developed vigorously, but at the same time, a large amount of lithium residue has been generated, and the problem of its storage has become increasingly prominent. At present, the lithium residue resource is low in resource utilization degree and narrow in application range, and it is difficult to achieve large-scale consumption, which has become a major pain point for the development of the industry.

[0003] The lithium residue is of a soil yellow appearance and is in a powder state after drying, and has a large specific surface area and a porous structure. After high-temperature roasting, the chemical properties are stable, and the main components are SiO2, Al2O3, CaO, etc. In recent years, the soilization of lithium residue has become a key direction, and exploration is carried out for problems such as heavy metal pollution, unbalanced nutrition, pH adjustment, microbial activity, and long-term stability, aiming to open up a new way for large-scale consumption of lithium residue ecological regression. However, existing chelating agents are mostly aimed at a single metal (such as Cr 6+ ), and lack the ability to cooperatively fix multiple ions; the soil curing agent (CJ / T 486-2015) cannot solve the problem of long-term sealing of harmful ions.

[0004] The water-resistant and compression-resistant energy-assisted new material for soil solidification is formed by polymerization of a plurality of materials with special performance characteristics through a special process, is rich in active ingredients, and when acting on soil and slag particles, a series of physical and chemical reactions occur, and in the process of stimulating modification-linking reconstruction-curing and shaping, the mixture is densely aggregated, so that the engineering performance of hard compression resistance and water resistance stability is obtained. Therefore, designing a new water-resistant and compression-resistant energy-assisted new material for soil solidification is a problem to be solved at present. SUMMARY

[0005] The present application provides a water-resistant and compression-resistant energy-assisted solid waste curing material and a preparation method and application thereof, to overcome the problems of heavy metal ion migration pollution and insufficient resource utilization intensity in the prior art.

[0006] In order to achieve the above-mentioned purpose, the technical scheme of the embodiment of the present application is:

[0007] The first aspect of the present application provides a water-resistant and compression-resistant energy-assisted solid waste curing material, which is prepared by including the following components with mass percentage:

[0008] Polyglycerol fatty acid ester 5-15 %, acetic acid 10-20 %, fatty alcohol polyoxyethylene ether 35-50 %, polyvinyl alcohol 3-5 %, sodium lignosulfonate 3-5 %, emulsified paraffin 15-30 %.

[0009] Preferably in combination with the second aspect, the preparation is made by including the following components with the following mass percentage: polyglycerol fatty acid ester 5%, acetic acid 20%, fatty alcohol polyoxyethylene ether 45%, polyvinyl alcohol 3%, sodium lignosulfonate 4%, emulsified paraffin wax 23%.

[0010] The second aspect of the present application provides a method for preparing the water-resistant and compression-resistant enabled solid waste solidification material of the first aspect, comprising:

[0011] Esterification is performed on the polyglycerol fatty acid ester and acetic acid, and the acid value of the solution during the reaction is controlled within a preset acid value threshold range, after which a first reaction solution is obtained;

[0012] A basic solution is slowly added dropwise to the first reaction solution, and after the pH of the solution is adjusted to be alkaline, a second reaction solution is obtained;

[0013] Fatty alcohol polyoxyethylene ether, polyvinyl alcohol solution, and sodium lignosulfonate solution are sequentially added to the second reaction solution, and after reaction, a mixed solution is obtained;

[0014] After the mixed solution is cooled to a preset temperature range, emulsified paraffin wax is added for reaction, and a water-resistant and compression-resistant enabled solid waste solidification material is obtained after cooling.

[0015] Preferably in combination with the second aspect, the temperature range of the esterification reaction is 80-110 ℃, and the reaction time is 1-3 h.

[0016] Preferably in combination with the second aspect, the preset acid value threshold range is 35-50 mg KOH / g.

[0017] Preferably in combination with the second aspect, the basic solution includes one or more of sodium bicarbonate and sodium hydroxide.

[0018] Preferably in combination with the second aspect, the reaction temperature of the fatty alcohol polyoxyethylene ether is 65-75 ℃, and the reaction time is 20 min.

[0019] Preferably in combination with the second aspect, the pre-dissolution temperature of the polyvinyl alcohol solution is 85 ℃, and the solid-liquid ratio is 1:15; the pre-dissolution temperature of the sodium lignosulfonate solution is 40-50 ℃, and the solid-liquid ratio is 1:5.

[0020] The third aspect of the present application provides an application of the water-resistant and compression-resistant enabled solid waste solidification material of any one of the first aspect or the water-resistant and compression-resistant enabled solid waste solidification material prepared by any one of the methods of the second aspect in non-burned building materials.

[0021] The fourth aspect of the present application provides a non-burned brick containing the water-resistant and compression-resistant enabled solid waste solidification material of any one of the first aspect or the water-resistant and compression-resistant enabled solid waste solidification material prepared by any one of the methods of the second aspect.

[0022] Compared with the prior art, the advantages or beneficial effects of the embodiments of the present application at least include:

[0023] The anti-water and anti-pressure enabled solid waste curing material provided by the present application can give the curing material excellent reaction activity based on the active chemical bonds and organic functional groups rich in the molecular structure of the contained compounds, so as to achieve the effect of precisely capturing free metal particles and non-metal ions in lithium residue and chelating reaction. Specifically, the acetylated product generated by the esterification reaction of polyglycerol fatty acid ester and acetic acid can be used as a core skeleton, and the rich electron carboxyl groups thereof can form stable coordination bonds with heavy metal ions (such as thallium and beryllium); the ether bond of the fatty alcohol polyoxyethylene ether cooperates with the phenolic hydroxyl group of sodium lignosulfonate to capture fluoride and manganese ions through hydrogen bond-coordination bimodal action; the long alkane chain of the emulsified paraffin can directionally wrap the chelate and form a hydrophobic barrier to completely block the leaching path of harmful substances; the above components can effectively capture free metal particles and non-metal ions in lithium residue and chelate, achieving the effect of multi-ion synergistic fixation; at the same time, the hydrogen on the molecular structure is easy to be replaced by halogen elements such as fluorine, the oxygen atom and halogen elements are easy to be combined with thallium, and the carbon atom and halogen elements are easy to react with beryllium to generate covalent carbides, oxides and halides (such as fluorocarbons, beryllium carbide, alkyl thallium, halogenated organic thallium, etc.) of organic chain structure, and generate compounds; in addition, most of the materials contained in the curing material are hydrophobic, which can exist stably in the natural environment for a long time, effectively avoiding the problem of deliquescence of thallium oxide, thallium hydroxide and conventional salts, and will not dissolve in water to cause secondary pollution and harm, thereby significantly improving the environmental safety and material stability in the solid waste treatment process.

[0024] The present application fundamentally solves the problems of heavy metal ion migration pollution and insufficient resource utilization in solid waste (lithium residue, coal gangue, phosphogypsum, etc.), and the constructed "chelation-encapsulation-hydrophobic" triple stabilization mechanism, combined with the four-stage organic polymerization process, provides technical support for the construction of "waste-free city" that can be scaled up. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 SEM image of Example 3 provided by the present application;

[0026] Figure 2 FT-IR image of Example 3 provided by the present application;

[0027] Figure 3 H 1 -NMR image of Example 3 provided by the present application;

[0028] Figure 4 C 13 -NMR image of Example 3 provided by the present application;

[0029] Figure 5 The solid waste mechanism diagram of the solidified agent provided by the present application for treating lithium residue is shown. DETAILED DESCRIPTION

[0030] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings, and the described embodiments should not be regarded as limiting the present application. All other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0031] In the following description, “some embodiments” are related to a subset of all possible embodiments, but it can be understood that “some embodiments” can be the same subset or different subsets of all possible embodiments, and can be combined with each other without conflict. Unless otherwise defined, all technical and scientific terms used in the embodiments of the present application have the same meanings as those commonly understood by those skilled in the technical field to which the embodiments of the present application belong. The terms used in the embodiments of the present application are only for the purpose of describing the embodiments of the present application, and are not intended to limit the present application.

[0032] In the following description of the embodiments of the present application, the terms “include”, “contain”, “have” and “comprise” and the like are all open terms, that is, they mean to include but not limited to.

[0033] It should be noted that all raw materials / reagents in the embodiments of the present application can be purchased on the market or prepared according to conventional methods well known to those skilled in the art; the term “and / or” in the embodiments of the present application is only used to describe the association relationship of the associated objects, which means that there can be three relationships, for example, A and / or B means that there are three cases of A alone, B alone and A and B together, wherein A and B can be singular or plural, and the character “ / ” generally represents an “or” relationship between the associated objects before and after it.

[0034] In the following description of the embodiments of the present application, the term “at least one” means one or more, and “multiple” means two or more. “At least one of the following” or similar expressions means any combination of these items, including any combination of single item or multiple items. For example, “at least one of a, b or c”, or “at least one of a, b and c”, can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b and c can be single or multiple.

[0035] Those skilled in the art shall understand that in the following description of the embodiments of the present application, the order of the serial numbers does not mean the order of execution, and part or all of the steps can be executed in parallel or in sequence, and the execution order of each process shall be determined according to its function and inherent logic, and shall not constitute any limitation on the implementation process of the embodiments of the present application.

[0036] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The singular forms "a" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0037] Those skilled in the art shall understand that the numerical range in the embodiments of the present application shall be understood as also specifically disclosing each intermediate value between the upper limit and the lower limit of the range. Each smaller range between any stated value and stated range of intermediate values and any other stated value or intermediate value within the stated range is also included in the present application. The upper limit and lower limit of these smaller ranges can be independently included or excluded from the range.

[0038] Unless otherwise specified, the technical / scientific terms used herein have the same meaning as generally understood by those skilled in the art of the present application. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the embodiments or test examples of the present application. All documents mentioned in this specification are generally incorporated by reference to disclose and describe the methods and / or materials related to the documents. In the event of conflict between the content of this specification and any incorporated document, the content of this specification shall prevail.

[0039] It should be noted that all raw materials and / or reagents in the embodiments of the present application are purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0040] In a first aspect, the embodiments of the present application provide an anti-water and anti-pressure enabled solid waste solidification material, which is prepared by including components with the following mass percentage:

[0041] Polyglycerol fatty acid ester 5-15 %, acetic acid 10-20 %, fatty alcohol polyoxyethylene ether 35-50 %, polyvinyl alcohol 3-5 %, sodium lignosulfonate 3-5 %, emulsified paraffin 15-30 %.

[0042] In specific embodiments, it is prepared by including components with the following mass percentage: polyglycerol fatty acid ester 5 %, acetic acid 20 %, fatty alcohol polyoxyethylene ether 45 %, polyvinyl alcohol 3 %, sodium lignosulfonate 4 %, emulsified paraffin 23 %.

[0043] It is necessary to point out that the polyglycerol fatty acid ester and the fatty alcohol polyoxyethylene ether are combined as surfactants in the component, which jointly builds a strong emulsifying, wetting, penetrating and dispersing system, ensuring that the hydrophobic paraffin can be uniformly and stably dispersed and effectively infiltrated and wrapped around the solid waste particles.

[0044] The PVA and sodium lignosulfonate in the component act as a bonding framework, which is used to provide the main mechanical strength and structural integrity to bond and fix the solid waste particles and functional components.

[0045] The emulsified paraffin in the component acts as a hydrophobic barrier, which is used to provide the core waterproof performance, and its effect depends on the uniform dispersion and spreading of the surfactant.

[0046] The acetic acid provides a suitable acidic chemical environment for the whole system, ensuring the functional performance of the key components, and possibly neutralizing the alkaline interferents in the solid waste.

[0047] The sodium lignosulfonate in the component plays an important role in dispersing the solid waste particles, assisting in bonding and strengthening, and improving the process performance.

[0048] The water-resistant and pressure-resistant enabled solid waste curing material provided by the present application can impart excellent reactivity to the curing material based on the active chemical bonds and organic functional groups rich in the molecular structure of the contained compounds, so as to achieve the effect of precisely capturing free metal particles and non-metal ions in lithium slag and chelating reaction. Specifically, the acetylated product generated by the esterification reaction of polyglycerol fatty acid ester and acetic acid can be used as a core framework, and the rich electron carboxyl group thereof can form a stable coordination bond with heavy metal ions (such as thallium and beryllium); the ether bond of the fatty alcohol polyoxyethylene ether cooperates with the phenolic hydroxyl group of the sodium lignosulfonate to capture fluoride and manganese ions through hydrogen bond-coordination bimodality; the alkane long chain of the emulsified paraffin can directionally wrap the chelate and form a hydrophobic barrier to completely block the leaching path of harmful substances; the above components can effectively capture free metal particles and non-metal ions in lithium slag and chelate, achieving the effect of multi-ion synergistic fixation; at the same time, the hydrogen on the molecular structure is easy to be replaced by halogen elements such as fluorine, the oxygen atom and halogen elements are easy to be combined with thallium, and the carbon atom and halogen elements are easy to react with beryllium to generate covalent carbides, oxides and halides (such as fluorocarbons, beryllium carbide, alkyl thallium, halogenated organic thallium, etc.) of organic chain structure, generating compounds; in addition, most of the materials contained in the curing material are hydrophobic, which can exist stably in the natural environment for a long time, effectively avoiding the problem of deliquescence of thallium oxide, thallium hydroxide and conventional salts, and will not dissolve in water to cause secondary pollution and harm, significantly improving the environmental safety and material stability in the solid waste treatment process.

[0049] In a second aspect, the present application provides a preparation method of the water-resistant and pressure-resistant enabled solid waste curing material, which comprises:

[0050] esterifying polyglycerol fatty acid ester and acetic acid, and controlling the acid value of the solution in the reaction process within a preset acid value threshold range, and then obtaining a first reaction liquid;

[0051] slowly adding a basic solution to the first reaction liquid, adjusting the pH of the solution to be alkaline, and then obtaining a second reaction liquid;

[0052] adding fatty alcohol polyoxyethylene ether, polyvinyl alcohol solution, and sodium lignosulfonate solution to the second reaction liquid in sequence, and then obtaining a mixed liquid after reaction;

[0053] cooling the mixed liquid to a preset temperature range, adding emulsified paraffin for reaction, and then cooling to obtain a water-resistant and pressure-resistant enabled solid waste solidification material.

[0054] In specific embodiments, the temperature range of the esterification reaction is preferably 80-110°C, and the reaction time is preferably 1-3 hours.

[0055] In the present application, if the esterification temperature is lower than 80°C, the esterification reaction rate will slow down significantly, resulting in incomplete reaction of polyglycerol fatty acid ester and acetic acid. The residual unreacted raw materials will cause the effective active ingredients in the first reaction liquid to be insufficient. This will directly affect the subsequent neutralization reaction with the alkaline solution and the synergistic effect of various additives, ultimately leading to a decrease in the crosslinking density of the solidification material and a decrease in water resistance and compressive strength. If the temperature is higher than 110°C, on the one hand, it will accelerate the volatilization loss of acetic acid, disrupting the material ratio balance of the reaction system; on the other hand, it may cause thermal decomposition or oxidation side reactions of polyglycerol fatty acid ester, generating unstable impurity components. These impurities will interfere with the efficiency of the subsequent chelation reaction, leading to a decrease in the stability of the molecular structure of the solidification material, weakening the compressive performance, and significantly reducing the ability to capture metal ions in lithium slag.

[0056] If the reaction time is less than 1 hour, the esterification reaction has not been fully carried out, and the amount of ester bonds generated in the system is insufficient, which will cause the functional group activity of the first reaction liquid to be low. This will affect the binding efficiency of the subsequent components such as fatty alcohol polyoxyethylene ether and polyvinyl alcohol, making the network structure of the solidification material loose, the water resistance poor, and it is difficult to form a firm overall structure when solidifying lithium slag, resulting in insufficient compressive strength.

[0057] If the reaction time exceeds 3 hours, excessive reaction will cause excessive crosslinking of ester bonds in the system, causing the viscosity of the first reaction liquid to abnormally increase. This will affect the uniformity when adjusting the pH value of the subsequent alkaline solution, as well as the dispersion effect of various additives, ultimately causing uneven distribution of components in the solidification material, and obvious differences in local water resistance and compressive performance, resulting in a decrease in overall performance stability.

[0058] In specific embodiments, the preset acid value threshold range is preferably 35-50 mg KOH / g.

[0059] In the present application, too high acid value means that too much unreacted acetic acid or acidic intermediate remains in the system, resulting in too strong acidity of the first reaction solution. When the pH is adjusted by subsequent dropwise addition of a basic solution, more alkali agent is consumed, not only increasing the cost, but also possibly releasing a large amount of heat due to local intense neutralization reaction, destroying the stability of the system (such as initiating thermal decomposition of some components), leading to uneven dispersion of subsequent additives (such as polyvinyl alcohol, sodium lignosulfonate). In addition, excessive acidic substances can react with subsequent fatty alcohol polyoxyethylene ether and emulsified paraffin wax (such as emulsifier hydrolysis, wax acidolysis), destroying the ordered arrangement of hydrophobic groups. The hydrophobic network of the final material is incomplete, and water molecules can easily penetrate, significantly reducing the water resistance.

[0060] In the present application, too low acid value means that esterification reaction is excessive, too many ester bonds are generated between polyglycerol fatty acid ester and acetic acid, and even excessive intermolecular crosslinking occurs, resulting in a sudden increase in the viscosity of the first reaction solution. This can lead to uneven diffusion of the subsequent basic solution, local deviation in pH adjustment, and insufficient dissolution and dispersion of additives such as fatty alcohol polyoxyethylene ether, resulting in uneven composition of the final material.

[0061] In specific embodiments, the basic solution is at least one of sodium bicarbonate and sodium hydroxide.

[0062] In specific embodiments, the reaction temperature of the fatty alcohol polyoxyethylene ether is preferably 65-75 ℃, and the reaction time is preferably 20 min.

[0063] In the present application, if the temperature is lower than 65 ℃, the molecular motion activity of the fatty alcohol polyoxyethylene ether is insufficient, making it difficult to fully diffuse in the second reaction solution and form stable intermolecular forces with the ester products in the system. This can result in insufficient emulsification and dispersion function, making it difficult for subsequent components such as polyvinyl alcohol and sodium lignosulfonate to disperse uniformly, and the final material is prone to local composition enrichment or vacancy, reducing the uniformity of water resistance and compressive strength. If the temperature is higher than 75 ℃, the ether bond of the fatty alcohol polyoxyethylene ether may be thermally degraded, resulting in a change in the hydrophilic-lipophilic balance value, significantly reducing the emulsification capacity. At the same time, high temperature can accelerate the oxidation reaction of some components in the system, generating polar impurities, destroying the ordered arrangement of hydrophobic groups, and reducing the water resistance of the material; in addition, excessive thermal motion can also affect the stability of the intermolecular crosslinking structure, leading to a decrease in the compressive strength of the material.

[0064] In the present application, if the reaction time is less than 20 min, the fatty alcohol polyoxyethylene ether fails to fully act on the system, and cannot form a stable micellar structure in the liquid phase, so that the subsequent addition of polyvinyl alcohol, sodium lignosulfonate and other polymer chains cannot be uniformly dispersed through the bridging effect. This will cause the formation of local weak areas in the material, which is prone to stress concentration when stressed, and the compressive strength is reduced; at the same time, uneven distribution of hydrophobic components will cause local defects in the water resistance of the material, and water permeation is prone to occur. If the reaction time exceeds 20 min, the excessive reaction of the fatty alcohol polyoxyethylene ether in the system will cause excessive aggregation of the fatty alcohol polyoxyethylene ether, forming large-size micelles, which will destroy the dispersion balance of the system. This will cause the material to form a non-uniform microstructure after curing, some areas have increased brittleness due to excessive hydrophobic components, and some areas have weakened water resistance due to the exposure of hydrophilic components, the overall performance stability is reduced, and the expected water resistance and pressure resistance effect cannot be achieved.

[0065] In specific embodiments, the pre-dissolution temperature of the polyvinyl alcohol solution is preferably 85℃, and the solid-liquid ratio is preferably 1:15.

[0066] In specific embodiments, the pre-dissolution temperature of the sodium lignosulfonate solution is preferably 40-50℃, and the solid-liquid ratio is preferably 1:5.

[0067] In a third aspect, the embodiments of the present application provide an application of the water-resistant and pressure-resistant enabled solid waste curing material of any one of the first aspect or the water-resistant and pressure-resistant enabled solid waste curing material prepared by any one of the method of the second aspect in non-burned building materials.

[0068] In a fourth aspect, the embodiments of the present application provide a non-burned brick comprising the water-resistant and pressure-resistant enabled solid waste curing material of any one of the first aspect or the water-resistant and pressure-resistant enabled solid waste curing material prepared by any one of the method of the second aspect.

[0069] The technical method of the present application will be further described below in conjunction with specific embodiments.

[0070] The present application also provides an application method of the water-resistant and pressure-resistant enabled solid waste curing material, which is specifically as follows:

[0071] Non-burned brick process: solid waste raw material 80% + curing agent 0.2%-0.5% + quicklime 0.3% → mixing and pressing → natural curing (no need to be sintered).

[0072] Road base: solid waste instead of gravel + curing agent 0.3% → mixing and paving → compaction (meet the standard of CJJ / T 286-2018).

[0073] It should be noted that the above-mentioned solid waste raw materials include but are not limited to lithium slag and the like.

[0074] Example 1

[0075] A preparation method of a new anti-water and anti-pressure enabled solid waste curing material, the method comprising the following steps:

[0076] (1) Raw material ratio (mass percentage): polyglycerol fatty acid ester: 8%, acetic acid: 15%, fatty alcohol polyoxyethylene ether: 40%, polyvinyl alcohol: 4%, sodium lignosulfonate: 5%, emulsified paraffin wax: 28%.

[0077] (2) Preparation steps:

[0078] Stage one: esterification reaction, polyglycerol fatty acid ester and acetic acid are put into the reactor and slowly heated to 105 ℃, and the reaction is kept for 2.5 h, and the end point control: the acid value is reduced from 180 mg KOH / g to 45 mg KOH / g.

[0079] Stage two: system neutralization, cooling to 75 ℃, slowly adding 10% NaHCO3 solution, adjusting pH to 7.0.

[0080] Stage three: building emulsion system, adding fatty alcohol polyoxyethylene ether (75 ℃, stirring for 20 min), adding 85 ℃ pre-solubilized polyvinyl alcohol solution (solid-liquid ratio 1:15) into the system, and then adding 40 ℃ pre-solubilized sodium lignosulfonate solution (solid-liquid ratio 1:5) into the system.

[0081] Stage four: emulsified paraffin wax integration, cooling to 55 ℃, adding emulsified paraffin wax drop by drop, constant temperature stirring for 25 min, and cooling to get light yellow viscous liquid.

[0082] (3) Application effect:

[0083] Table 1 Application effect of example 1

[0084]

[0085] Example 2

[0086] (1) Raw material ratio (mass percentage): polyglycerol fatty acid ester: 12%, acetic acid: 18%, fatty alcohol polyoxyethylene ether: 35%, polyvinyl alcohol: 5%, sodium lignosulfonate: 3%, emulsified paraffin wax: 27%.

[0087] (2) Preparation step process innovation point:

[0088] Stage one: esterification enhancement, polyglycerol fatty acid ester and acetic acid are put into the reactor and slowly heated to 115 ℃ for 2 h, and the end point control: the acid value is reduced to 35 mg KOH / g.

[0089] Stage two: neutralization optimization, cooling to 80 ℃, and adjusting pH to 7.2 by using 10% NaOH solution (avoiding CO2 bubbles).

[0090] Stage three: build emulsion system, 85 ℃ pre-solubility of polyvinyl alcohol solution (solid-liquid ratio 1:15) added 0.1 % antifoam agent (to prevent stirring foaming) into the system, fatty alcohol polyoxyethylene ether was added twice (70 % first, then 30 %) 75 ℃ stirring 20 min, then 40 ℃ pre-solubility of sodium lignosulfonate solution (solid-liquid ratio 1:5) was added to the system.

[0091] Stage four: emulsified wax integration, cooling to 58 ℃, slowly (2 mL / min) injected emulsified wax, synchronous ultrasonic dispersion (40 kHz) for 15 min, curing for 24 h, and cooling to get light yellow viscous liquid.

[0092] (3) Application effect:

[0093] Table 2 Application effect of example 2

[0094]

[0095] Example 3

[0096] (1) Raw material ratio (mass percent): polyglycerol fatty acid ester: 5 %, acetic acid: 20 %, fatty alcohol polyoxyethylene ether: 45 %, polyvinyl alcohol: 3 %, sodium lignosulfonate: 4 %, emulsified wax: 23 %.

[0097] (2) Process adjustment:

[0098] Stage one: low temperature esterification, polyglycerol fatty acid ester and acetic acid were put into the reactor with condensation reflux device, slowly heated to 100 ℃ for 3 h (to protect heat-sensitive components), and the end point control: acid value was reduced to 50 mg KOH / g.

[0099] Stage two: accurate neutralization of the system, pH online monitor was used to control the dropping speed of NaHCO3.

[0100] Stage three: build low temperature emulsion system, fatty alcohol polyoxyethylene ether was added at 65 ℃ (to protect ether bond activity), maintained for 20 min, 85 ℃ pre-solubility of polyvinyl alcohol (solid-liquid ratio 1:5) solution was added, the reaction system was stirred at 70 ℃ for 25 min (to prevent PVA precipitation), then 40 ℃ pre-solubility of sodium lignosulfonate (solid-liquid ratio 1:5) solution was slowly added, and stirred for 15 min until homogeneous.

[0101] Stage four: emulsified wax integration, cooling to 52 ℃, emulsified wax was added in three batches (each batch interval 8 min), each batch was synchronously ultrasonic dispersed (40 kHz) for 15 min, then curing for 24 h, and cooling to get light yellow viscous liquid.

[0102] (3) Application effect:

[0103] Table 3 Application effect of Example 3

[0104]

[0105] Example 4

[0106] (1) Raw material ratio (mass percentage): polyglycerol fatty acid ester: 15 %, acetic acid: 10 %, fatty alcohol polyoxyethylene ether: 50 %, polyvinyl alcohol: 4 %, sodium lignosulfonate: 5 %, emulsified paraffin: 16 %.

[0107] (2) Process adjustment:

[0108] Stage one: polyglycerol fatty acid ester and acetic acid are put into a reactor with a condensation reflux device for staged esterification reaction, 80 °C pre-reaction for 1 h (activation of hydroxyl group) → 110 °C main reaction for 1.5 h, end point control: acid value is reduced to 50 mg KOH / g.

[0109] Stage two: system neutralization and strengthening, double alkali method is adopted (first NaHCO3 is used to adjust pH to 5.0 to eliminate strong acidity, and then NaOH is used to adjust pH to 7.0).

[0110] Stage three: emulsification system is constructed, fatty alcohol polyoxyethylene ether (75 °C stirring for 20 min) is added, 0.5 % glycerol is added during pre-solubilization of polyvinyl alcohol at 85 °C (to accelerate hydration), and then 50 °C pre-solubilized sodium lignosulfonate solution (solid-liquid ratio 1:5) is added to the system.

[0111] Stage four: emulsified paraffin integration, temperature is reduced to 60 °C, emulsified paraffin is added in three batches (interval of 8 min), each batch is synchronously ultrasonically dispersed (40 kHz) for 15 min, then it is aged for 24 h, and a light yellow viscous liquid is obtained after cooling.

[0112] (3) Application effect:

[0113] Table 4 Application effect of Example 4

[0114]

[0115] According to the application effect of the above-mentioned embodiments 1-4, embodiment 1 is taken as a basic scheme (initial effect), which includes: lithium slag treatment: using “0.3% solidifying agent + 0.3% quicklime”, the harmful substance reduction multiple is low (fluorine 3.51 times, thallium 2.80 times, beryllium 1200 times, manganese 1800 times), the compressive strength of the non-burned brick is greater than or equal to 20 MPa, and the environmental protection and engineering performance are at a starting level; phosphogypsum treatment: “0.3L / m³ solidifying agent + 6% cement” reduces the heavy metal leaching rate by 92%, but the 7-day compressive strength is only 1.8 MPa, the harmful substance residue is high and the strength is weak; coal gangue treatment: using 0.4% solidifying agent alone realizes the standard of radioactivity, the strength of the water permeable brick is greater than or equal to 12 MPa, the safety reaches the standard but the engineering performance is conservative; the core problem is that the harmful substance treatment efficiency is insufficient and the material strength does not reach the ideal standard.

[0116] Embodiment 2 is taken as a comprehensive optimization (short-term improvement), which includes: lithium slag: under the same formula, the harmful substance treatment efficiency is significantly improved - the fluorine is reduced to 4.01 times, the beryllium / manganese reaches 1500 times / 2200 times (increased by 25%-45% compared with embodiment 1), and the compressive strength jumps to greater than or equal to 24 MPa, proving the potential of the formula; phosphogypsum: the leaching rate reduction amplitude is increased to 96%, the 7-day compressive strength is increased to 2.0 MPa, and the short-term safety and strength are improved simultaneously; coal gangue: the strength of the water permeable brick is broken through to greater than or equal to 14 MPa (+16.7%), and the engineering applicability is enhanced; the key progress is that the environmental protection and engineering indicators are improved, but there is a lack of long-term performance data, and the durability of the phosphogypsum is questionable.

[0117] Embodiment 3: comprehensive breakthrough (optimal performance), which includes: lithium slag: harmful substance control reaches the peak - fluorine (4.14 times), thallium (3.23 times), beryllium (1586 times), and manganese (2375 times) are all the highest values in the four tables, and the compressive strength is greater than or equal to 22 MPa (maintaining a high level); phosphogypsum: the scheme is adjusted to “0.3L / m³ solidifying agent + 6% cement”, realizing two breakthroughs: ① the leaching rate is reduced by 98% (the best among the four embodiments); ② the 28-day compressive strength (5.0-6.3 MPa) is provided for the first time, far exceeding the 7-day strength (1.8-2.0 MPa) of other tables, proving the long-term stability; coal gangue: the strength is greater than or equal to 13 MPa, which is slightly lower than that of embodiment 2 but maintains the standard of radioactivity; the core advantage is that the harmful substance treatment efficiency is comprehensive leading (lithium slag pollutant reduction amplitude, phosphogypsum 98% leaching rate); the only long-term strength data (phosphogypsum 28-day strength) is provided, and the engineering reliability is significantly improved; the balance between environmental protection and long-term performance is the best.

[0118] Example 4: Performance fluctuation (strength priority, environmental protection concession), including: lithium residue: compressive strength creates a new high (≥25 MPa), but harmful substance treatment efficiency falls - fluorine (3.80 times), beryllium (1406 times), manganese (2015 times) are lower than Example 2, Example 3, sacrificing environmental protection effect for strength improvement; phosphogypsum: leaching rate decreased by 94% (weaker than 96% in Table 2, 98% in Table 3), 7-day compressive strength 1.9 MPa, key indicators retrogress; coal gangue: strength regression ≥13 MPa, radioactivity continues to meet standards; prominent contradiction: lithium residue compressive strength is optimized to 25 MPa, but phosphogypsum environmental protection and engineering performance are inferior to Example 2, Example 3, overall performance is uneven.

[0119] In summary, Example 3 has the best performance, the specific reasons are as follows:

[0120] Long-term strength (28 days) data of phosphogypsum - core indicator of engineering application;

[0121] Overall leading harmful substance treatment efficiency (especially phosphogypsum 98% and lithium residue Be / Mn).

[0122] Example 3 has 98% leaching rate reduction of phosphogypsum + 28-day strength data as the core advantage, combined with overall leading harmful substance treatment of lithium residue, becomes the only solution that takes into account high environmental protection standards and long-term engineering reliability. Although the lithium residue in Example 4 has higher strength, its environmental protection indicators have regressed and the performance of phosphogypsum has declined, and the overall value is not as good as Example 3.

[0123] From Figure 1 , it can be known that SEM shooting and analysis of the solidifying agent from different angles show that the solidifying agent has a hollow tubular structure. Its particles are uniformly dispersed, which should be the emulsification effect of fatty alcohol polyoxyethylene ether.

[0124] From Figure 2 , it can be known that it has ester group stretching vibration at 1700 cm -1 around wave number, reflecting the existence of ester group in polyglycerol fatty acid ester; 3300 cm -1 has a wide peak reflecting the association state of PVA hydroxyl group 1470 cm -1 nearby double peak reflects the bending vibration of methylene in emulsified paraffin.

[0125] From Figure 3 and Figure 4 , it can be known that Figure 3 and Figure 4 are the hydrogen spectrum and carbon spectrum of the solidifying agent respectively, where the strong peaks of the two figures reflect the existence of ester group in glycerol fatty acid ester, combined with Figure 2 proving that the emulsification reaction is successful.

[0126] Figure 5The solid waste mechanism diagram of the solidifying agent for treating lithium residue is shown in the figure. The carboxylic acid captures ions, the carboxylic acid ionizes into carboxyl ions, and the carboxyl ions are selectively complexed into insoluble salts through coordination bonds, so as to fix the soluble heavy metals and block the migration; the polyglycerol ester is halogenated to generate hydrophobic halogenated polyglycerol ester, the hydrophobic halogenated polyglycerol ester wraps solid waste particles to form a hydrophobic layer, blocks the penetration of water molecules, and inhibits the leaching of pollutants; the organic components in the solid waste react with halogen at high temperature to generate covalent carbides, and the heavy metals are permanently solidified in the high-hardness structure or generate volatile halides, and the pollutants are removed through gas-solid separation; in the emulsified paraffin system, the paraffin emulsion seals thallium ions in hydrophobic droplets, and completely blocks the release of thallium ions.

[0127] Table 5 is a summary table of the detection results of the solidifying agent on different samples, and the pH performance test and the content detection results of fluoride, beryllium, thallium and manganese of sample 1# and sample 2# of the unfired brick sample treated by the solidifying agent are compared with those of the lithium residue without treatment.

[0128] Table 5 is a summary table of the detection results of the solidifying agent on different samples, and the pH performance test and the content detection results of fluoride, beryllium, thallium and manganese of sample 1# and sample 2# of the unfired brick sample treated by the solidifying agent are compared with those of the lithium residue without treatment.

[0129]

[0130] Table 6 and Table 7 are respectively a summary table of the detection results of the compressive strength of phosphogypsum and a summary table of the detection results of the field compressive strength and thickness, and the specific contents are shown in Table 6 and Table 7.

[0131] Table 8 and Table 9 are respectively a summary table of the field density data and a summary table of the field moisture content data, and the specific contents are shown in Table 8 and Table 9.

[0132]

[0133]

[0134]

[0135] The field is 700m 2 The average maximum dry density is 1.86g / cm 3 , and the average compaction coefficient is 96%, and the field detection report is qualified.

[0136] Table 10 is a summary table of the leaching liquid detection method and detection results of sample 2# of the unfired brick, and the specific contents are shown in Table 10.

[0137]

[0138] In summary, based on the chemical behavior characteristics of heavy metal ions in solid waste, a method for preparing a water-resistant and pressure-resistant enabling type solidifying agent by organic polymerization is innovatively developed by constructing a multi-functional chelating system through molecular design, and the method can realize the following breakthrough progress through four-stage precise control process (esterification, neutralization, emulsification and paraffin integration):

[0139] Chelation mechanism innovation: the acetylated product generated by esterification reaction of polyglycerol fatty acid ester and acetic acid is the core skeleton, its electron-rich carboxyl group forms a stable coordination bond with heavy metal ions (such as thallium, beryllium); the ether bond of fatty alcohol polyoxyethylene ether cooperates with the phenolic hydroxyl group of sodium lignosulfonate to capture fluoride and manganese ions through hydrogen bond-coordination bimodal action; the long alkane chain of emulsified paraffin directionally wraps the chelate to form a hydrophobic barrier, completely blocking the leaching path of harmful substances.

[0140] The present application fundamentally solves the problem of heavy metal ion migration pollution and insufficient resource utilization intensity in solid waste (lithium slag, coal gangue, phosphogypsum, etc.), and the constructed "chelation-encapsulation-hydrophobic" triple stabilization mechanism, combined with the four-stage organic polymerization process, provides technical support for the construction of "waste-free city" that can be applied on a large scale.

[0141] In addition, the present application has been certified by third-party detection (report number: FX2024-444-1), and has been successfully applied in Yan'an coal gangue roadbed, Anhui phosphogypsum consolidation body and other projects, providing an efficient, economic and green industrialization path for solid waste resource utilization.

[0142] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, any skilled person in the art can easily think of changes or replacements within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A water-resistant, compression-resistant, and energized solid waste solidification material, characterized in that, Prepared by including components with the following mass percentage: Polyglycerol fatty acid ester 5-15 %, acetic acid 10-20 %, fatty alcohol polyoxyethylene ether 35-50 %, polyvinyl alcohol 3-5 %, sodium lignosulfonate 3-5 %, emulsified paraffin 15-30 %.

2. The water-resistant, compression-resistant, energized solid waste solidification material of claim 1, wherein, Prepared by including components with the following mass percentage: Polyglycerol fatty acid ester 5 %, acetic acid 20 %, fatty alcohol polyoxyethylene ether 45 %, polyvinyl alcohol 3 %, sodium lignosulfonate 4 %, emulsified paraffin 23 %.

3. A method of preparing the water-resistant, compression-resistant, and energy- enabled solid waste solidification material of claim 1, characterized in that, Comprising: Esterification of polyglycerol fatty acid ester and acetic acid, and controlling the acid value of the solution during the reaction within a preset acid value threshold range, then obtaining a first reaction solution; Slowly adding a basic solution to the first reaction solution, adjusting the pH of the solution to be alkaline, then obtaining a second reaction solution; Adding fatty alcohol polyoxyethylene ether, polyvinyl alcohol solution, and sodium lignosulfonate solution to the second reaction solution in sequence, and after reaction, obtaining a mixed solution; Cooling the mixed solution to a preset temperature range, then adding emulsified paraffin for reaction, and cooling to obtain a water-resistant and pressure-resistant enabled solid waste solidification material.

4. The method of claim 3, wherein the anti-water and anti-pressure enabled solid waste solidification material is prepared by mixing the solid waste with the water-absorbing material and the pressure-absorbing material. The temperature range of the esterification reaction is 80-110 ℃, and the reaction time is 1-3 h.

5. The method of claim 3, wherein the anti-water and anti-pressure enabled solid waste solidification material is prepared by mixing the solid waste with the water-absorbing and pressure-absorbing material, and the binder. The preset acid value threshold range is 35-50 mg KOH / g.

6. The method of claim 3, wherein the anti-water and anti-pressure enabled solid waste solidification material is prepared by mixing the solid waste with the water-absorbing and pressure-absorbing material, the water-absorbing and pressure-absorbing material being prepared by mixing the water-absorbing material and the pressure-absorbing material. The basic solution includes one or more of sodium bicarbonate and sodium hydroxide.

7. The method of claim 3, wherein the anti-water and anti-pressure enabled solid waste solidification material is prepared by mixing the solid waste with the water-absorbing and pressure-absorbing material, the water-absorbing and pressure-absorbing material being prepared by mixing the water-absorbing material and the pressure-absorbing material. The reaction temperature of the fatty alcohol polyoxyethylene ether is 65-75 ℃, and the reaction time is 20 min.

8. The method of claim 3, wherein the anti-water and anti-pressure enabled solid waste solidification material is prepared by mixing the solid waste with the water-absorbing and pressure-absorbing material, the water-absorbing and pressure-absorbing material being prepared by mixing the water-absorbing material and the pressure-absorbing material. The pre-dissolution temperature of the polyvinyl alcohol solution is 85 ℃, and the solid-liquid ratio is 1:15; the pre-dissolution temperature of the sodium lignosulfonate solution is 40-50 ℃, and the solid-liquid ratio is 1:

5.

9. The use of a water-resistant and pressure-resistant enabled solid waste solidification material prepared by any one of the methods of claims 3-8 in non-burned building materials.

10. A non-burnt brick, characterized by, A water-resistant and pressure-resistant enabled solid waste solidification material prepared by any one of the methods of claims 3-8.

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