CN115286748B - Mineral dissociation agent and preparation method and application thereof - Google Patents
Mineral dissociation agent and preparation method and application thereof Download PDFInfo
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- CN115286748B CN115286748B CN202210977053.3A CN202210977053A CN115286748B CN 115286748 B CN115286748 B CN 115286748B CN 202210977053 A CN202210977053 A CN 202210977053A CN 115286748 B CN115286748 B CN 115286748B
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Abstract
The invention provides a mineral dissociation agent and a preparation method and application thereof. The mineral dissociating agent comprises a polymer of an unsaturated ether monomer and an unsaturated carboxylic acid monomer, and a C1-C5 saturated carboxylic acid. The mineral dissociation agent can enable different minerals in the waste residue to be dissociated more easily, so that the separation efficiency of the different minerals in the waste residue is improved, and the activity of the waste residue, the recovery of valuable resources and the utilization value of the waste residue are improved.
Description
Technical Field
The invention belongs to the fields of additive synthesis and solid waste resource utilization, and in particular relates to a mineral dissociation agent and a preparation method and application thereof.
Background
The recycling of waste residues is an important way for improving the utilization efficiency of mineral resources, protecting the environment and realizing the aim of double carbon. However, waste residues such as gas slag, steel slag, copper slag and the like generally contain a plurality of different minerals, and utilization of the waste residues may only need one or more minerals, but other associated minerals are often tightly connected with the target minerals and are difficult to separate. The method not only reduces the utilization value and the use effect of the waste residue, for example, the existence of inert magnetite in the copper residue reduces the activity of the copper residue, but also wastes the associated minerals. Therefore, how to separate different minerals in copper slag is a problem to be solved.
However, the traditional mineral separation method is mainly limited by combining grinding, flotation and magnetic separation technologies, and most of traditional grinding aids and flotation agents are amine, alcohol and lipid alkaline compounds, and the alkaline grinding aids and the flotation agents are difficult to have strong chemical reaction with alkaline minerals in waste residues, so that the mineral separation capability is weak, and the separation efficiency is low. However, there is no report on the dissociating agent of different minerals in the waste residue.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a mineral dissociation agent and a preparation and application method thereof, aiming at enabling different minerals in waste residues to be dissociated more easily, improving the separation efficiency of different minerals in the waste residues, and improving the activity of the waste residues, the recovery of valuable resources and the utilization value of the waste residues.
In order to achieve the purpose of the invention, the following technical scheme is adopted.
In a first aspect, the present invention provides a mineral debonding agent comprising a polymer of unsaturated ether monomers and unsaturated carboxylic acid monomers and a C1-C5 saturated carboxylic acid.
In some embodiments, the unsaturated ether monomer is selected from one or more of methylallyl polyoxyethylene ether, allyl polyoxyethylene ether, and isopentenyl polyoxyethylene ether. In some embodiments, the unsaturated ether-based monomer is methylallyl polyoxyethylene ether (TPEG) and/or isopentenyl polyoxyethylene ether.
In some embodiments, the unsaturated carboxylic monomer is selected from one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and maleic anhydride. In some embodiments, the unsaturated carboxylic monomer is one or more of acrylic acid, maleic acid, and maleic anhydride.
In some embodiments, the C1-C5 saturated carboxylic acid is selected from one or more of acetic acid or trifluoroacetic acid. In some embodiments, the C1-C5 saturated carboxylic acids are formic acid and acetic acid.
In some embodiments, the ratio of the mass of the polymer of the unsaturated ether-based monomer and unsaturated carboxylic acid-based monomer to the mass of the saturated carboxylic acid of C1-C5 is (0.1-5): 1, for example, may be 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, or any value therebetween. In some preferred embodiments, the ratio of the mass of the polymer of the unsaturated ether-based monomer and the unsaturated carboxylic acid-based monomer to the mass of the saturated C1-C5 carboxylic acid is (0.3-3): 1.
in some embodiments, the mass ratio of the unsaturated ether-based monomer to the unsaturated carboxylic acid-based monomer is (2-15): 1, for example, may be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, or any value therebetween. In some preferred embodiments, the mass ratio of the unsaturated ether-based monomer to the unsaturated carboxylic acid-based monomer is (3-10): 1.
in some embodiments, the mass ratio of the C1-C5 saturated carboxylic acid to the unsaturated carboxylic acid monomer is (1-20): 1, for example, may be 1:1, 2.5:1, 5:1, 7.5:1, 10:1, 12.5:1, 15:1, 17.5:1, 20:1, or any value therebetween. In some embodiments, the mass ratio of the C1-C5 saturated carboxylic acid to the unsaturated carboxylic acid monomer is (2-12): 1.
in some embodiments, the mass ratio of formic acid to acetic acid in the C1-C5 saturated carboxylic acid is (1.5-15): 1 may be, for example, 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, or any value therebetween. In some embodiments, the mass ratio of formic acid to acetic acid in the C1-C5 saturated carboxylic acid is (2-10): 1.
in some embodiments, the polymer of unsaturated ether monomers and unsaturated carboxylic acid monomers includes the product of a polymerization reaction of an unsaturated ether monomer and an unsaturated carboxylic acid monomer in the presence of a chain transfer agent and an initiator.
In some embodiments, the chain transfer agent comprises at least one of thioglycolic acid, 3-mercaptopropionic acid, sodium bisulfite, or sodium methallyl sulfonate, preferably thioglycolic acid.
In some embodiments, the initiator is selected from at least one of hydrogen peroxide, persulfate, 2-hydroxy-2-sulfinylacetic acid, water-soluble azo initiator, preferably hydrogen peroxide.
In the invention, the carboxyl (-COOH) of formic acid and acetic acid provides an acidic environment and is connected with the unsaturated ether monomer and the polymer of unsaturated carboxylic acid monomer through hydrogen bonds and the like, so that the formed hydrogen bonds and the like enable the formic acid and the acetic acid to have a certain slow release effect, and the problem that dissociated minerals are uneven due to too fast reaction is avoided. Meanwhile, the formic acid reacts with waste residues to generate calcium formate, and the calcium formate has an early strength effect on cement hydration. Acetic acid reacts with waste residue to generate calcium acetate, and has a certain delay effect on cement hydration. Thus, formic acid is used in an amount of the main component. After the dissociating agent is used, the polymer of the unsaturated ether monomer and the unsaturated carboxylic acid monomer has excellent dispersing function.
In some embodiments, the mass ratio of the initiator to the unsaturated ether monomer is (0.001-0.5): 1 may be, for example, 0.001:1, 0.002:1, 0.005:1, 0.008:1, 0.01:1, 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, or any value therebetween. In some embodiments, the mass ratio of the initiator to the unsaturated ether monomer is (0.002-0.3): 1.
in some embodiments, the mass ratio of the chain transfer agent to the unsaturated ether monomer is (0.001-0.5): 1 may be, for example, 0.001:1, 0.002:1, 0.005:1, 0.008:1, 0.01:1, 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, or any value therebetween. In some embodiments, the mass ratio of the initiator to the unsaturated ether monomer is (0.002-0.3): 1.
in some embodiments, the mineral dissociation agent includes a polymer of formula (I) and a C1-C5 saturated carboxylic acid.
In a second aspect, the invention provides a method for preparing the mineral dissociating agent according to the first aspect, comprising the steps of polymerizing an unsaturated ether monomer and an unsaturated carboxylic acid monomer in a solution, and mixing a C1-C5 saturated carboxylic acid with the solution before or after polymerization.
In some embodiments, the method of preparation includes mixing a C1-C5 saturated carboxylic acid, an unsaturated ether monomer, an unsaturated carboxylic acid monomer, a chain transfer agent, an initiator, and water to perform a polymerization reaction.
In some embodiments, the C1-C5 saturated carboxylic acids include acetic acid and formic acid.
In some embodiments, the C1-C5 saturated carboxylic acid is 25-60 (e.g., 25, 30, 35, 40, 45, 50, 55, or 60) parts by weight, the unsaturated ether monomer is 20-50 (e.g., 20, 25, 30, 35, 40, 45, or 50) parts by weight, the unsaturated carboxylic acid monomer is 3-10 (e.g., 3, 4, 5, 6, 7, 8, 9, or 10) parts by weight, the chain transfer agent is 0.1-0.6 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, or 0.6) parts by weight, the initiator is 0.1-0.6 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, or 0.6) parts by weight, and the water is 10-35 (e.g., 10, 15, 20, 25, 30, or 35) parts by weight.
In some embodiments, the C1-C5 saturated carboxylic acid comprises 5-10 (e.g., 5, 6, 7, 8, 9, or 10) parts acetic acid and 20-50 (e.g., 20, 25, 30, 35, 40, 45, or 50) parts formic acid.
In some embodiments, the method comprises the steps of:
s1: providing a first mixed solution containing C1-C5 saturated carboxylic acid, unsaturated ether monomer and water, a second mixed solution containing unsaturated carboxylic acid monomer, chain transfer agent and water, and a third mixed solution containing initiator and water;
s2: and mixing the second mixed solution and the third mixed solution with the first mixed solution at the same time, and carrying out polymerization reaction to obtain the mineral dissociation agent.
In some embodiments, the first mixed solution contains 5-10 parts of acetic acid, 20-50 parts of formic acid, 20-50 parts of unsaturated ether monomer and 5-15 parts of water.
In some embodiments, the second mixture contains 3-10 parts unsaturated carboxylic acid monomer, 0.1-0.6 parts chain transfer agent, 3-10 parts water.
In some embodiments, the third mixture contains 0.1 to 0.6 parts initiator and 3 to 10 parts water.
In some embodiments, the mixing is performed by dropwise addition.
In some embodiments, step S2 further comprises curing the product of the polymerization reaction for 20-120 minutes.
The mineral dissociation agent is prepared by adopting a low-temperature aqueous solution free radical polymerization method.
In some embodiments, the preparation method of the present invention comprises the steps of: firstly, 5 to 10 parts of acetic acid, 20 to 50 parts of formic acid, 20 to 50 parts of methylallyl polyoxyethylene ether (TPEG) and 5 to 15 parts of water are weighed into a three-neck flask and stirred for dissolution. Then, a mixed solution of 3 to 10 parts of acrylic acid, 0.3 to 0.6 part of thioglycollic acid, 3 to 10 parts of water is added dropwise to the stirred three-necked flask over 10 to 30 minutes, for example, 15 minutes, while a mixed solution of 0.3 to 0.6 part of hydrogen peroxide and 3 to 10 parts of water is added dropwise to the stirred three-necked flask over 10 to 40 minutes, for example, 20 minutes. Curing for 20-60min, such as 30min, to obtain the dissociation agent.
In a third aspect, the present invention provides the use of a mineral breaker according to the first aspect or a mineral breaker prepared by a method of preparation according to the second aspect in mineral separation.
In some embodiments, the mineral comprises a copper slag mineral or a steel slag mineral.
In some embodiments, the mineral breaker is used in an amount of 0.05% to 2% by weight of the mineral waste residue to be separated.
In some embodiments, the mineral dissociation agent is applied by grinding the mineral waste residue for 10-20 minutes, weighing the dissociation agent according to the mass fraction of 0.05% -2% of the mineral waste residue, adding the dissociation agent into the mineral waste residue, and grinding for 10-20 minutes to obtain the mineral waste residue with different minerals dissociated from each other.
In some embodiments, the mineral waste residue after grinding and dissociation can be separated into different minerals by adopting technologies such as floatation, magnetic separation and the like. The use of the dissociation agent can make the active minerals and inert minerals in the mineral waste residues easier to separate, the separation efficiency can be improved by 50-200%, and the active mineral content and valuable resource recovery and utilization value of the mineral waste residues are obviously improved.
Compared with the existing dissociating agent, the mineral dissociating agent has the following advantages:
(1) The dissociation agent has strong adaptability, and is particularly suitable for separating different minerals in waste residues such as copper slag, steel slag and the like;
(2) The dissociation agent has the advantages of simple synthesis method, low dosage and obvious separation effect improvement;
(3) The use of the dissociation agent can reduce the use of other additives in the follow-up flotation agent and magnetic separation process, and obviously reduce the cost;
(4) The dissociation agent can lead the connection interfaces of different mineral crystals in solid wastes such as copper slag and the like to generate cracks, so that minerals are spontaneously dissociated from each other;
(5) The dissociating agent can obviously improve the activity of the mineral waste residues treated by the dissociating agent.
Drawings
Fig. 1 illustrates a schematic flow diagram of mineral waste residue treatment with a mineral debonding agent according to some embodiments of the present application.
Fig. 2 shows XRD patterns of the mineral breaker-treated steel slag prepared according to comparative example 2 and examples 5 to 8 of the present application.
Fig. 3 shows the results of hydrothermal tests of mineral breaker-treated steel slag prepared according to comparative example 2 and examples 5 to 8 of the present application.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a method for synthesizing and applying a copper slag mineral dissociation agent, which improves the separation efficiency of inert and active minerals in copper slag, and improves the activity of waste slag, the recovery of valuable resources and the value of waste slag.
The test index is the mass fraction of the residual slag, the slag is separated through a magnetic separation technology, the mass fraction of the separated residual slag is calculated, the magnetically inert minerals after magnetic separation are extracted, the non-magnetic active minerals are left, and when the two phases are mutually wrapped and are difficult to separate, the two phases are simultaneously extracted through magnetic separation, and the remaining residual active minerals are reduced.
Comparative example 1
Comparison group experiment: and (3) weighing triethanolamine which is a conventional grinding aid according to the mass fraction of 0.05% of copper slag, adding the triethanolamine into the waste slag, grinding for 20 minutes, separating the copper slag by adopting a magnetic separation technology, and measuring the mass fraction of the residual slag to be 25%.
Example 1
First, 5 parts of acetic acid, 20 parts of formic acid, 45 parts of TPEG and 10 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 10 parts of acrylic acid, 0.4 parts of thioglycollic acid, 4 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes, while a mixed solution of 0.6 parts of hydrogen peroxide and 5 parts of deionized water was added dropwise to the stirred three-necked flask over 20 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociating agent.
During application, the copper slag is ground for 10 minutes, then a dissociation agent is weighed according to the mass fraction of 0.05% of the copper slag, the dissociation agent is added into the waste slag, grinding is continued for 10 minutes, then the copper slag is separated by adopting a magnetic separation technology, and the mass fraction of the residual slag is measured to be 37%.
Example 2
First, 10 parts of acetic acid, 30 parts of formic acid, 35 parts of TPEG and 5 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 10 parts of acrylic acid, 0.5 part of thioglycollic acid, 4 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes, while a mixed solution of 0.5 part of hydrogen peroxide and 5 parts of deionized water was added dropwise to the stirred three-necked flask over 20 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociating agent.
During application, the copper slag is ground for 10 minutes, then a dissociation agent is weighed according to the mass fraction of 0.1% of the waste slag, the dissociation agent is added into the waste slag, grinding is continued for 10 minutes, then the copper slag is separated by adopting a magnetic separation technology, and the mass fraction of the residual slag is measured to be 49%.
Example 3
First, 10 parts of acetic acid, 35 parts of formic acid, 30 parts of TPEG and 5 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 5 parts of acrylic acid, 0.6 part of thioglycollic acid, and 4 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes, while a mixed solution of 0.4 part of hydrogen peroxide and 10 parts of deionized water was added dropwise to the stirred three-necked flask over 20 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociating agent.
During application, the copper slag is ground for 15 minutes, then a dissociation agent is weighed according to 1% of the copper slag by mass, the dissociation agent is added into the copper slag, grinding is continued for 20 minutes, then the copper slag is separated by adopting a magnetic separation technology, and the mass fraction of the residual slag is measured to be 65%.
Example 4
First, 10 parts of acetic acid, 50 parts of formic acid, 20 parts of TPEG and 5 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 5 parts of acrylic acid, 0.5 part of thioglycollic acid, 4 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes, while a mixed solution of 0.5 part of hydrogen peroxide and 5 parts of deionized water was added dropwise to the stirred three-necked flask over 20 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociating agent.
During application, the copper slag is ground for 10 minutes, then a dissociation agent is weighed according to the mass fraction of 0.05% of the copper slag, the copper slag is continuously ground for 10 minutes, then the copper slag is separated by adopting a magnetic separation technology, and the mass fraction of the residual slag is measured to be 63%.
From the above results, it was found that, compared with comparative example 1, the use of the dissociation agent of the present invention significantly increases the residual slag mass fraction of the copper slag, the residue is mainly a mineral such as a non-magnetic active silicate, and the increase in the residue content indicates a significant increase in the separation effect of the magnetic iron mineral from the non-magnetic mineral.
Comparative example 2
45 parts of TPEG and 35 parts of deionized water were first weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 5 parts of acrylic acid, 0.25 part of thioglycollic acid, 5 parts of deionized water was added dropwise to the stirred three-necked flask over 10 minutes, while a mixed solution of 0.25 part of hydrogen peroxide and 9.5 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociation agent SS-1.
Example 5
First, 5 parts of acetic acid, 20 parts of formic acid, 45 parts of TPEG and 10 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 5 parts of acrylic acid, 0.25 part of thioglycollic acid, 5 parts of deionized water was added dropwise to the stirred three-necked flask over 10 minutes, while a mixed solution of 0.25 part of hydrogen peroxide and 9.5 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociation agent SS-2.
Example 6
First, 5 parts of acetic acid, 35 parts of formic acid, 35 parts of TPEG and 5 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 5 parts of acrylic acid, 0.2 part of thioglycollic acid, 5 parts of deionized water was added dropwise to the stirred three-necked flask over 10 minutes, while a mixed solution of 0.2 part of hydrogen peroxide and 9.6 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociation agent SS-3.
Example 7
First, 5 parts of acetic acid, 40 parts of formic acid, 30 parts of TPEG and 5 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 5 parts of acrylic acid, 0.2 part of thioglycollic acid, 5 parts of deionized water was added dropwise to the stirred three-necked flask over 10 minutes, while a mixed solution of 0.2 part of hydrogen peroxide and 9.6 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociation agent SS-4.
Example 8
First, 10 parts of acetic acid, 50 parts of formic acid, 20 parts of TPEG and 5 parts of deionized water were weighed into a three-necked flask and dissolved with stirring. Then, a mixed solution of 6 parts of acrylic acid, 0.2 parts of thioglycollic acid, 4 parts of deionized water was added dropwise to the stirred three-necked flask over 10 minutes, while a mixed solution of 0.2 parts of hydrogen peroxide and 9.6 parts of deionized water was added dropwise to the stirred three-necked flask over 15 minutes. Curing for 0.5 hour after the completion of the dripping to obtain the dissociation agent SS-5.
Test case
Firstly grinding the waste slag for 10-20 minutes (steel slag or directly using 100-200 meshes of steel slag powder), then weighing a dissociation agent according to 0.05% -2% of the steel slag by mass, adding the dissociation agent into the waste slag, and continuously grinding for 10-20 minutes to obtain the steel slag with mutually dissociated rates of different minerals. Or by a process as shown in fig. 1.
XRD testing was performed on the treated steel slag, and the results are shown in FIG. 2. The results show that the dissociating agent has a certain degree of decomposition on the free calcium oxide.
The activity effect of the steel slag powder is tested by adopting a TAM Air hydration calorimeter of TA Instruments company, the hydration temperature is 20 ℃, the water-gel ratio is 0.3, firstly, the steel slag powder and water are mixed and stirred for 2 minutes, then, the corresponding comparative sample water is weighed, and meanwhile, the water is put into an instrument detection channel, and the recording time is 72 hours. The experimental results are shown in FIG. 3.
From fig. 3, it is found that the hydration heat value of the steel slag treated by the dissociating agent is far higher than that of the steel slag treated by the untreated group for 72 hours, which indicates that the activity of the steel slag is obviously improved after the steel slag is treated by the dissociating agent.
While certain exemplary embodiments of the present application have been illustrated and described, the present application is not limited to the disclosed embodiments. Rather, one of ordinary skill in the art will recognize that certain modifications and changes may be made to the described embodiments without departing from the spirit and scope of the present application, as described in the appended claims.
Claims (29)
1. A mineral dissociating agent comprises a polymer of unsaturated ether monomers and unsaturated carboxylic acid monomers and C1-C5 saturated carboxylic acid,
the unsaturated ether monomer is selected from one or more of methyl allyl polyoxyethylene ether, allyl polyoxyethylene ether and isopentenyl polyoxyethylene ether;
the unsaturated carboxylic acid monomer is selected from one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid and maleic anhydride;
the C1-C5 saturated carboxylic acid is selected from one or more of formic acid, acetic acid or trifluoroacetic acid;
the ratio of the mass of the polymer of the unsaturated ether monomer and the unsaturated carboxylic acid monomer to the mass of the saturated carboxylic acid of C1-C5 is (0.1-5): 1, a step of;
the mass ratio of the unsaturated ether monomer to the unsaturated carboxylic acid monomer is (2-15): 1.
2. the mineral breaker of claim 1, wherein the C1-C5 saturated carboxylic acid is selected from formic acid and acetic acid.
3. The mineral dissociation agent of claim 1, wherein the ratio of the mass of said polymer of unsaturated ether-based monomer and unsaturated carboxylic acid-based monomer to the mass of said saturated C1-C5 carboxylic acid is (0.3-3): 1.
4. the mineral dissociation agent according to claim 1, wherein the mass ratio of the unsaturated ether-based monomer to the unsaturated carboxylic acid-based monomer is (3-10): 1.
5. the mineral dissociation agent of claim 1, wherein the mass ratio of said C1-C5 saturated carboxylic acid to said unsaturated carboxylic acid monomer is (1-20): 1.
6. the mineral dissociation agent of claim 1, wherein the mass ratio of said C1-C5 saturated carboxylic acid to said unsaturated carboxylic acid monomer is (2-12): 1.
7. the mineral dissociation agent of claim 1, wherein the mass ratio of formic acid to acetic acid in said C1-C5 saturated carboxylic acid is (1.5-15): 1.
8. the mineral dissociation agent of claim 1, wherein the mass ratio of formic acid to acetic acid in said C1-C5 saturated carboxylic acid is (2-10): 1.
9. the mineral debonding agent of any of claims 1 to 8 wherein the polymer of unsaturated ether monomers and unsaturated carboxylic acid monomers comprises the product of a polymerization reaction of an unsaturated ether monomer and an unsaturated carboxylic acid monomer in the presence of a chain transfer agent and an initiator.
10. The mineral debonding agent of claim 9 wherein the chain transfer agent comprises at least one of thioglycolic acid, 3-mercaptopropionic acid, sodium bisulfite, or sodium methallyl sulfonate.
11. The mineral dissociation agent of claim 9, in which said initiator is selected from at least one of hydrogen peroxide, persulfates, 2-hydroxy-2-sulfinylacetic acid, water-soluble azo initiators.
12. The mineral dissociation agent of claim 9, wherein the mass ratio of said initiator to said unsaturated ether monomer is (0.001-0.5): 1.
13. the mineral dissociation agent of claim 9, in which the mass ratio of said initiator to said unsaturated ether monomer is (0.002-0.3): 1.
14. the mineral dissociation agent of claim 9, wherein the mass ratio of said chain transfer agent to said unsaturated ether monomer is (0.001-0.5): 1.
15. the mineral dissociation agent of claim 9, wherein the mass ratio of said chain transfer agent to said unsaturated ether monomer is (0.002-0.3): 1.
16. a process for the preparation of a mineral debonding agent according to any of claims 1 to 15, comprising polymerizing unsaturated ether monomers and unsaturated carboxylic acid monomers in a solution, and mixing a C1-C5 saturated carboxylic acid with the solution before or after polymerization.
17. The method according to claim 16, wherein the method comprises mixing a C1-C5 saturated carboxylic acid, an unsaturated ether monomer, an unsaturated carboxylic acid monomer, a chain transfer agent, an initiator, and water, and performing polymerization.
18. The method of claim 17, wherein the C1-C5 saturated carboxylic acid comprises acetic acid and formic acid.
19. The production method according to claim 17, wherein the saturated carboxylic acid of C1 to C5 is 25 to 60 parts by weight, the unsaturated ether-based monomer is 20 to 50 parts by weight, the unsaturated carboxylic acid-based monomer is 3 to 10 parts by weight, the chain transfer agent is 0.1 to 0.6 part by weight, the initiator is 0.1 to 0.6 part by weight, and the water is 10 to 35 parts by weight.
20. The process of claim 19, wherein the C1-C5 saturated carboxylic acid comprises 5-10 parts acetic acid and 20-50 parts formic acid.
21. The method of preparation according to claim 17, characterized in that the method comprises the steps of:
s1: providing a first mixed solution containing C1-C5 saturated carboxylic acid, unsaturated ether monomer and water, a second mixed solution containing unsaturated carboxylic acid monomer, chain transfer agent and water, and a third mixed solution containing initiator and water;
s2: and mixing the second mixed solution and the third mixed solution with the first mixed solution at the same time, and carrying out polymerization reaction to obtain the mineral dissociation agent.
22. The method according to claim 21, wherein the first mixed solution contains 5 to 10 parts of acetic acid, 20 to 50 parts of formic acid, 20 to 50 parts of unsaturated ether monomer and 5 to 15 parts of water.
23. The method according to claim 21, wherein the second mixed solution contains 3 to 10 parts of the unsaturated carboxylic acid monomer, 0.1 to 0.6 part of the chain transfer agent, and 3 to 10 parts of water.
24. The method of claim 21, wherein the third mixture comprises 0.1 to 0.6 parts of initiator and 3 to 10 parts of water.
25. The method of claim 21, wherein the mixing is performed by dropwise addition.
26. The method of claim 21, wherein step S2 further comprises curing the product of the polymerization reaction for 20-120 minutes.
27. Use of a mineral breaker according to any one of claims 1 to 15 or prepared according to the method of preparation of any one of claims 16 to 26 in mineral separation.
28. Use according to claim 27, characterized in that the mineral separation is copper slag mineral separation or steel slag mineral separation.
29. The use according to claim 27, wherein the mineral breaker is used in an amount of 0.05% -2% by weight of the mineral waste residue to be separated.
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