Modified graphene oxide material and preparation method thereof and application in metal ore selection

Abstract

The present invention relates to the technical field of metal beneficiation and heavy metal wastewater treatment, and in particular to modified graphene oxide material and its preparation method and application in metal ore selection. The present invention adopts aminohydroxamic acid, aminotriazolethione, aminohydroxamic acid and alkyldiamine, aminotriazolethione and alkyldiamine to modify graphene oxide respectively, and obtains hydroxamic acid modified graphene oxide material, azolethione modified graphene oxide material, amino-hydroxamic acid modified graphene oxide material, amino-azolethione modified graphene oxide material; using modified graphene oxide material, at least one valuable metal in copper, zinc, antimony, silver and gold minerals can be flotation recovered; using modified graphene oxide material, at least one metal ion in copper, zinc, antimony, lead, silver and gold can also be adsorbed.

Description

Technical Field

[0001] The invention relates to the technical field of mining and ore dressing for improving the recovery rate of mineral resources, and in particular to a modified graphene oxide material and a preparation method thereof and an application thereof in metal ore dressing. Background Art

[0002] In recent years, due to the continuous increase in demand for non-ferrous metal mineral resources and intensified mining, non-ferrous metal minerals have become poor and mixed. At the same time, with the rapid development of the electronic battery, metallurgy and mining industries, heavy metal electroplating wastewater, washing wastewater, etching waste liquid in circuit board preparation, mining and flotation process wastewater contain a large amount of heavy metals. The wastewater containing heavy metals is seriously polluted, difficult to control and difficult to manage, mainly manifested in the serious exceeding of the content of heavy metals such as copper, lead, zinc and cadmium.

[0003] For the efficient recycling of mineral resources, the structure of flotation collectors can be improved to achieve efficient and selective recovery of non-ferrous metal minerals. However, flotation collectors for non-ferrous metal minerals are mostly organic compounds, and organic wastewater will inevitably be produced during the flotation process, damaging the surrounding ecological environment. There are many different treatment methods for heavy metal ion wastewater. Common treatment methods include adsorption and chemical precipitation. Adsorption is a simple and efficient way to treat heavy metals, but it requires the development of new, efficient and recyclable adsorbents. The chemical precipitation process only transfers heavy metal ions and cannot selectively recover heavy metal precipitates.

[0004] Therefore, solving the problem of selective adsorption and recovery of heavy metal ions and their precipitates in wastewater with excessive organic matter during mineral flotation recovery and developing new recyclable nano-collectors or adsorbents are urgent research topics to be addressed.

[0005] Most of the existing flotation collectors were developed decades ago, and their effective groups are thiol (sulfide minerals) and oxime (oxide minerals), etc., which cannot achieve ideal results in terms of selectivity and collection capacity. For the adsorption of heavy metal ions, commonly used adsorbents are activated carbon, zeolite, activated alumina, lignite coke and bentonite, etc., which have poor selectivity and adsorption effects. It is very necessary to innovatively combine flotation collectors with adsorbents to achieve simultaneous capture and adsorption, and to achieve the recycling of capture and adsorbents, thereby effectively reducing the discharge of organic wastewater and improving the utilization efficiency of mineral and metal resources.

[0006] As a new type of carbon material with excellent performance, graphene oxide has good adsorption effect on many heavy metal ions and can be used to remove metal ions in water. At the same time, its adsorption effect can be enhanced by compounding with other materials. It is widely used in the field of water treatment. In addition, the development of conjugated chelating collectors with hydroxamic acid groups and triazolethione is also the latest research trend in flotation separation of valuable minerals in recent years. In view of the excellent metal chelating properties and flotation performance of hydroxamic acid and triazolethione compounds, as well as the adsorption capacity and recycling performance of graphene oxide nanomatrix structure, how to effectively combine the two to achieve simultaneous capture and adsorption is the current difficulty. Summary of the invention

[0007] In view of the above-mentioned technical deficiencies, the present invention provides a modified graphene oxide material, a preparation method thereof and an application thereof in metal ore selection. The present invention respectively uses aminohydroxamic acid, aminotriazolethione, aminohydroxamic acid and alkyldiamine, aminotriazolethione and alkyldiamine to modify graphene oxide, thereby obtaining hydroxamic acid modified graphene oxide material, azolethione modified graphene oxide material, amino-hydroxamic acid modified graphene oxide material and amino-azolethione modified graphene oxide material; the modified graphene oxide material can be used to flotation and recover at least one valuable metal in copper-containing, zinc-containing, antimony-containing, silver-containing and gold-containing minerals; the modified graphene oxide material can also be used to adsorb at least one metal ion in copper, zinc, antimony-containing, lead, silver and gold-containing minerals.

[0008] To achieve the above object, the technical solution of the present invention is as follows:

[0009] A class of modified graphene oxide materials, the modified graphene oxide materials include hydroxamic acid modified graphene oxide materials, azolethione modified graphene oxide materials, amino-hydroxamic acid modified graphene oxide materials, amino-azolethione modified graphene oxide materials, the structure of the hydroxamic acid modified graphene oxide material is shown in formula (I), the structure of the azolethione modified graphene oxide material is shown in formula (II), the structure of the amino-hydroxamic acid modified graphene oxide material is shown in formula (III), and the structure of the amino-azolethione modified graphene oxide material is shown in formula (IV):

[0010]

[0011] In formula (I) and formula (III), R is the same, and R is selected from a C1-C17 straight chain or branched alkane group, a C2-C17 olefin group, a C6-C12 aromatic group, or a Alkoxy ether group of the structure;

[0012] In formula (II) and formula (IV), R1 is the same, and R1 is selected from hydrogen, amino, C1-C17 straight chain or branched alkane, C2-C17 olefin, C6-C12 aromatic, Alkoxy ether group of the structure or containing The chelating functional groups of the structure;

[0013] In the structure, R 1 is selected from ethylene or propylene, n is an integer of 1-3, R 2 A hydrocarbon group selected from C1-C17;

[0014] In the structure, R 3 A C1-C17 straight chain or branched alkane group, a C2-C17 olefin group, a C6-C12 aromatic group, or a Alkoxy ether group of the structure;

[0015] In formula (III) and formula (IV), R2 is the same, and R2 is selected from C2-C10 straight chain or branched alkane groups, C2-C10 olefin groups, and C6-C12 aromatic groups.

[0016] Preferably, in the formula (I) and formula (III), R is selected from a C3-C8 straight chain or branched alkane group, a C2-C8 olefin group, a C6-C10 aromatic group or a Alkoxy ether group of the structure;

[0017] In formula (II) and formula (IV), R1 is selected from hydrogen, amino, C3-C8 straight chain or branched alkane, C2-C8 olefin, C6-C10 aromatic, Alkoxy ether group of the structure or containing The chelating functional groups of the structure;

[0018] In the structure, R1 is ethylene, n is an integer of 1-3, and R2 is selected from a C3-C8 hydrocarbon group;

[0019] In the structure, R 3 A C3-C8 straight chain or branched alkane group, a C2-C8 olefin group, a C6-C10 aromatic group or a Alkoxy ether group of the structure;

[0020] In formula (III) and formula (IV), R2 is selected from a C2-C8 straight chain or branched alkane group, a C2-C8 olefin group, or a C6-C10 aromatic group.

[0021] Preferably, in formula (I) and formula (III), R is selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, hexyl, heptyl, octyl, phenyl, benzyl, phenethyl, propenyl, allyl, butenyl, isobutenyl, dibutenyl, hexenyl, phenylpropenyl, butoxy, isobutoxy or hexoxy;

[0022] In formula (II) and formula (IV), R1 is selected from hydrogen, amino, methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, vinyl, propenyl, phenyl, benzyl, phenethyl, propenyl, allyl, butenyl, isobutenyl, dibutenyl, hexenyl, phenylpropenyl, butoxy, isobutoxy, hexyloxy, isobutylxanthate or hexyldithiocarbamate;

[0023] In formula (III) and formula (IV), R2 is selected from ethyl, n-propyl, isobutyl, n-hexyl, vinyl, propenyl, phenyl, benzyl or phenethyl.

[0024] The present invention also protects a method for preparing a modified graphene oxide material. The hydroxamic acid-modified graphene oxide material is prepared according to the following steps:

[0025] S1, dissolving the hydroxylamine compound in a solvent, then adding caustic soda thereto, and reacting at 0-15° C. for 30-40 minutes to obtain a free hydroxylamine solution;

[0026] Wherein, the hydroxylamine compound is selected from hydroxylamine hydrochloride or hydroxylamine sulfate;

[0027] S2. Under alkaline conditions, add amino acid methyl ester hydrochloride to the free hydroxylamine solution of step S1, react at 10° C. for 3-4 hours, and then react at 20-30° C. for 1-1.5 hours to obtain a hydroxamic acid solution;

[0028] S3, acidifying the hydroxamic acid solution in step S2 by cooling, filtering, and evaporating the solvent to obtain aminohydroxamic acid;

[0029] S4, mixing the aminohydroxamic acid of step S3 with graphene oxide, and reacting them under reflux at 60-70° C. for 8-9 hours, and then filtering, washing and drying to obtain a hydroxamic acid-modified graphene oxide material.

[0030] Preferably, the molar ratio of the hydroxylamine compound in step S1, the caustic soda in step S1, and the amino acid methyl ester hydrochloride in step S2 is (1.0-1.1): (2.1-4.2): (1.0-1.1);

[0031] In the step S4, the mass ratio of graphene oxide to aminohydroxamic acid is (0.7-0.8): (2.9-3.0).

[0032] Preferably, the cooling and acidification method in step S3 is: cooling the hydroxamic acid solution in step S2 to 0-5°C in an ice bath, then adding concentrated sulfuric acid dropwise to the hydroxamic acid solution, and controlling the temperature not to exceed 10°C, acidifying to a pH of 7-8, and stirring at 5-10°C for 30-45 minutes.

[0033] The present invention also protects a method for preparing a modified graphene oxide material. The amino-hydroxamic acid modified graphene oxide material is prepared according to the following steps:

[0034] The aminohydroxamic acid and alkyl diamine prepared in step S3 are mixed with graphene oxide, and the mixture is refluxed at 60-70° C. for 8-9 hours, and then filtered, washed, and dried to obtain an amino-hydroxamic acid modified graphene oxide material;

[0035] Among them, the mass ratio of graphene oxide, aminohydroxamic acid and alkyl diamine is (0.7-0.8):(2.9-3.0):(0.52-1.04).

[0036] The present invention also protects a method for preparing a modified graphene oxide material, wherein the azolethione modified graphene oxide material is prepared according to the following steps:

[0037] (1) dissolving a disulfide salt compound in an alcohol solvent, then adding a chlorocarboxylate thereto, and reacting at 10-20° C. for 2-5 hours to obtain an ester compound;

[0038] Wherein, the dithio salt compound is selected from dithioformate, dithiocarbamate or dithiophosphate; the alcohol solvent is methanol or ethanol; the molar ratio of the dithio salt compound to the chlorocarboxylic acid ester is (1.0-1.3): (1.5-2.5);

[0039] (2) adding hydrazine hydrate to the ester compound of step (1) at 0-5° C., then heating to 60-65° C. and reflux for 6-7 hours to obtain a hydrazide compound;

[0040] Wherein, the molar ratio of the ester compound to the hydrazine hydrate is (1.0-1.3): (1.2-2.5);

[0041] (3) Continue to cool to 0-5°C, add carbon disulfide to the hydrazide compound of step (2) under alkaline conditions, and react at 15-20°C for 3-5h, add hydrazine hydrate dropwise again, continue to reflux at 60-65°C for 6-8h, acidify to pH 3-5, cool, filter, and dry to obtain aminotriazolethione;

[0042] Wherein, the molar ratio of hydrazide compound, carbon disulfide and hydrazine hydrate is (1.0-1.3): (1.5-2.5): (1.2-2.5);

[0043] (4) mixing the aminotriazolethione of step (3) with graphene oxide, and reacting the mixture under reflux at 60-65° C. for 8-9 hours, and then filtering, washing, and drying to obtain an azolethione-modified graphene oxide material;

[0044] Wherein, the mass ratio of graphene oxide to aminotriazolethione is (0.7-0.8):(2.9-3.0).

[0045] The present invention also protects a method for preparing a modified graphene oxide material. The amino-oxathione modified graphene oxide material is prepared according to the following steps:

[0046] After mixing aminotriazolethione, alkyldiamine and graphene oxide, the mixture is refluxed at 60-65° C. for 8-9 hours, and then filtered, washed and dried to obtain amino-thionethione modified graphene oxide material;

[0047] Among them, the mass ratio of graphene oxide, aminotriazolethione and alkyldiamine is (0.7-0.8):(2.9-3.0):(0.52-1.04).

[0048] The present invention also protects the use of modified graphene oxide materials in the preparation of ore valuable metal collectors or adsorbents, using the modified graphene oxide materials to flotation recover at least one valuable metal in copper, zinc, antimony, silver, and gold-containing minerals; or using the modified graphene oxide materials to adsorb at least one metal ion among copper, zinc, antimony, lead, silver, and gold.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) The hydroxamic acid and oxathione structures in the present invention are highly selective ligands that can selectively react with metals to form chelate rings, thereby enhancing their stability and selectivity for metal chelation. From the perspective of flotation and adsorption principles, the hydrophobic groups in the hydroxamic acid and oxathione modified graphene oxide, the carbon chain length, the branched structure or the position and number of oxygen atoms in the alkyl / alkoxy groups involved are easily regulated, which is beneficial for improving and regulating the flotation recovery or adsorption of metal minerals or metal elements;

[0051] The present invention innovatively combines hydroxamic acid or triazolethione compounds with graphene oxide to further optimize its structure. The introduction of hydroxamic acid and triazolethione structures further improves the selectivity and chelating properties of graphene oxide for metals, realizes the selective recovery of valuable minerals or metals in complex low-grade minerals and multi-metal coexisting wastewater, improves the harm of heavy metal ions to the environment, and improves the comprehensive utilization rate of mineral resources.

[0052] (2) The present invention innovatively combines hydroxamic acid and azolethione structures with graphene oxide to prepare a new type of highly selective valuable metal flotation collector or adsorbent, which is particularly suitable for the enrichment and recovery of at least one valuable metal among copper, zinc, antimony, silver and gold. Compared with the collectors or adsorbents commonly used in the prior art, the recovery rate and selectivity of the valuable metals can be improved.

[0053] (3) The present invention obtains hydroxamic acid-modified graphene oxide material and oxathiolide-modified graphene oxide material, which are used as adsorbents for valuable metals in metal mineral beneficiation processes and heavy metal wastewater, respectively, and further recovered and recycled by physical and chemical means, thereby reducing the discharge of organic wastewater and effectively solving the environmental problems caused by it.

[0054] (4) The present invention also prepares amino-azolethione modified graphene oxide materials and amino-isohydroxamic acid modified graphene oxide materials. The introduction of amino groups with different carbon chain structures can regulate the hydrophilic-hydrophobic properties of the modified graphene oxide materials. At the same time, the amino groups can also serve as coordination active centers to improve the ability to interact with metals during flotation or adsorption, thereby improving the flotation and adsorption efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 is the infrared spectrum of graphene oxide used in the embodiments of the present invention;

[0056] Figure 2 This is the infrared spectrum of phenylalanine hydroxamic acid prepared in Example 1 of the present invention;

[0057] Figure 3 This is the infrared spectrum of the phenylalanine hydroxamic acid modified graphene oxide material prepared in Example 1 of the present invention;

[0058] Figure 4 The synthetic route of the hydroxamic acid-modified nano-graphene oxide material of the present invention;

[0059] Figure 5 The present invention provides a synthetic route for the azolethione-modified nano-graphene oxide material. DETAILED DESCRIPTION

[0060] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work belong to the protection scope of the present invention. The experimental methods described in the embodiments of the present invention are conventional methods unless otherwise specified.

[0061] The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the following reagents and raw materials, unless otherwise specified, are commercially available.

[0062] All parts and percentages in the examples of the present invention refer to mass unless otherwise specified. The flotation capture of minerals or the adsorption of valuable metals in heavy metal wastewater in the examples are conventional processes, and the only difference from the prior art is that the modified graphene oxide material prepared in Examples 1-6 of the present invention is used to replace the conventional collector or adsorbent to capture and adsorb heavy metals. Figure 1 The infrared characteristic absorption peaks and their attributions of graphene oxide are shown in Table 1.

[0063] Table 1 Infrared characteristic absorption peaks and attributions of graphene oxide in the examples

[0064]

[0065]

[0066] Example 1

[0067] The preparation method of phenylalanine hydroxamic acid modified graphene oxide comprises the following steps:

[0068] S1. Add 3.66 parts of hydroxylamine hydrochloride to a mechanically stirred reaction bottle at a temperature below 10°C, and add 80 parts of methanol as a solvent, slowly stir for 30 minutes to prepare a solution, then add 4.22 parts of NaOH solid, and after the addition, react at 15°C with slow stirring for 30 minutes, use NaOH to free hydroxylamine to obtain a free hydroxylamine solution;

[0069] S2, weigh 2.1 parts of NaOH into a reaction bottle, adjust the solution to be alkaline to promote the reaction, control the reaction temperature to less than 10°C, weigh 10.79 parts of L-phenylalanine methyl ester hydrochloride and add it to the reaction bottle, after the addition, react at 10°C for 3.5h, after the reaction is completed, heat to 30°C and continue to react for 1h to obtain a hydroxamic acid solution;

[0070] S3, after the reaction is completed, cool to 5°C in an ice bath, transfer concentrated sulfuric acid, acidify the hydroxamic acid solution, control the temperature not to exceed 10°C, acidify to pH 7.5, stop adding sulfuric acid, continue stirring at 10°C for 30 minutes, filter, and rotary evaporate the filtrate to obtain phenylalanine hydroxamic acid;

[0071] S4, prepare 4 mg / mL graphene oxide solution, mix 3 parts of phenylalanine hydroxamic acid with the graphene oxide solution, stir and reflux continuously for 8 hours at 60° C. and 200 parts of water as solvent, after the reaction is completed, filter to obtain phenylalanine hydroxamic acid modified graphene oxide; its structural formula is as follows:

[0072]

[0073] Malachite with a particle size of -0.076 mm to +0.038 mm was floated for 10 min using a phenylalanine hydroxamic acid modified graphene oxide collector, wherein the concentration of the phenylalanine hydroxamic acid modified graphene oxide collector was 0.1 g / L, the pH value of the pulp was 7.0, the concentration of the frother methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. At this time, the flotation recovery rate of malachite reached 65.8%. Figure 2 The characteristic absorption peaks of phenylalanine hydroxamic acid infrared spectrum and their attribution are shown in Table 2. Figure 3 The infrared characteristic absorption peaks and their attributions of phenylalanine hydroxamic acid modified graphene oxide are shown in Table 3.

[0074] Table 2 Infrared characteristic absorption peaks and attributions of phenylalanine hydroxamic acid in Example 1

[0075] <![CDATA[Wave number (cm -1 )]]> Possible attribution 3243 OH, NH stretching vibration overlapping peaks 3029 Aromatic ring CH stretching vibration peak 2857 <![CDATA[-CH2- symmetric stretching vibration peak]]> 1947,1871,1804,1703 Benzene ring skeleton vibration peak 1613 C=O stretching vibration peak 1405 <![CDATA[-CH2-Deformed Vibration]]> 1131 CN, NO stretching vibration peaks superposition 752,698,615 Monosubstituted aromatic ring -CH out-of-plane vibration peak

[0076] Table 3 Infrared characteristic absorption peaks and attributions of phenylalanine hydroxamic acid modified graphene oxide in Example 1

[0077] <![CDATA[Wavenumber (cm -1 )]]> Possible attribution 3247 OH, NH stretching vibration overlapping peaks 3028 Aromatic ring CH stretching vibration peak 2914 <![CDATA[-CH2- asymmetric stretching vibration peak]]> 1950,1895,1821,1772 Benzene ring skeleton vibration peak 1703 C=O stretching vibration peak 1604 C-OH stretching vibration peak 1410 <![CDATA[-CH2-Deformed Vibration <!-- 7 -->]]> 1064 CN, NO stretching vibration peaks superposition 749,696,666,614 Monosubstituted aromatic ring -CH out-of-plane vibration peak

[0078] Example 2

[0079] The preparation method of 2,6-diamino-7-hydroxamic acid modified graphene oxide comprises the following steps:

[0080] S1. Add 3.66 parts of hydroxylamine hydrochloride to a reaction bottle equipped with a mechanical stirrer at a temperature less than 10°C, add 80 parts of methanol as a solvent, slowly stir for 35 minutes to prepare a solution, add 4.22 parts of NaOH solid, and after the addition, react at 10°C with slow stirring for 35 minutes, use NaOH to free hydroxylamine to obtain a free hydroxylamine solution;

[0081] S2, weigh 2.1 parts of NaOH into a reaction bottle, control the reaction temperature to less than 10°C, weigh 11.66 parts of L-lysine methyl ester hydrochloride into the reaction bottle, after the addition, react at 10°C for 3h, after the reaction is completed, heat to 35°C and continue to react for 1h to obtain a hydroxamic acid solution;

[0082] S3, after the reaction is completed, cool to 5°C in an ice bath, transfer concentrated sulfuric acid, acidify the hydroxamic acid solution, control the temperature not to exceed 10°C, acidify to pH 7, stop adding sulfuric acid, continue stirring at 10°C for 40 minutes, filter, and rotary evaporate the filtrate to obtain 2,6-diamino-7-hydroxamic acid;

[0083] S4, prepare 4 mg / mL graphene oxide solution, mix 3 parts of 2,6-diamino-7-hydroxamic acid with the graphene oxide solution, and continuously stir and reflux for 8.5 hours at 65° C. and 200 parts of water as solvent. After the reaction is completed, filter to obtain 2,6-diamino-7-hydroxamic acid modified graphene oxide collector; its structural formula is as follows:

[0084]

[0085] Malachite with a particle size of -0.076 mm to +0.038 mm was floated for 10 minutes using 2,6-diamino-7-hydroxamic acid modified graphene oxide collector; the concentration of 2,6-diamino-7-hydroxamic acid modified graphene oxide collector was 0.1 g / L, the pH value of the slurry was 7.0, the concentration of the frother methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. At this time, the flotation recovery rate of malachite reached 72.3%.

[0086] Example 3

[0087] The preparation method of 1-amino-7-hydroxamic acid modified graphene oxide comprises the following steps:

[0088] S1. Add 3.66 parts of hydroxylamine hydrochloride to a reaction bottle equipped with mechanical stirring at a temperature less than 10°C, add 80 parts of methanol as a solvent, slowly stir for 40 minutes to prepare a solution, add 4.22 parts of NaOH solid, and after the addition, react at 0°C with slow stirring for 40 minutes, use NaOH to free hydroxylamine to obtain a free hydroxylamine solution;

[0089] S2, weigh 2.1 parts of NaOH into a reaction bottle, control the reaction temperature to less than 10°C, weigh 9.08 parts of 6-aminocaproic acid methyl ester hydrochloride into the reaction bottle, after the addition, react at 10°C for 4h, after the reaction is completed, heat to 20°C and continue to react for 1.5h to obtain a hydroxamic acid solution;

[0090] S3, after the reaction is completed, cool to 5°C in an ice bath, transfer concentrated sulfuric acid, acidify the hydroxamic acid solution, control the temperature not to exceed 10°C, acidify to pH 8, stop adding sulfuric acid, continue stirring at 10°C for 40 minutes, filter, and rotary evaporate the filtrate to obtain 1-amino-7-hydroxamic acid;

[0091] S4, prepare 4 mg / mL graphene oxide solution, mix 3 parts of 1-amino-7-hydroxamic acid with the graphene oxide solution, stir and reflux continuously for 9 hours at 70° C. and 200 parts of water as solvent, after the reaction is completed, filter to obtain 1-amino-7-hydroxamic acid modified graphene oxide collector; its structural formula is as follows:

[0092]

[0093] Malachite with a particle size of -0.076 mm to +0.038 mm was floated for 10 minutes using a 1-amino-7-hydroxamic acid modified graphene oxide collector; the concentration of the 1-amino-7-hydroxamic acid modified graphene oxide collector was 0.1 g / L, the pH value of the slurry was 7.0, the concentration of the frother methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. At this time, the flotation recovery rate of malachite reached 68.7%.

[0094] The synthetic route diagram of Example 1-3 is as follows Figure 4 shown.

[0095] Example 4

[0096] The preparation of amino-hydroxamic acid modified graphene oxide material comprises the following steps:

[0097] The same as steps 1-3 of Example 1, except that:

[0098] S4, prepare a 4 mg / mL graphene oxide solution, mix 3 parts of phenylalanine hydroxamic acid, 1.04 parts of ethylenediamine with the graphene oxide solution and react together to obtain a phenylalanine hydroxamic acid and ethylenediamine mixed modified graphene oxide collector, that is, an amino-hydroxamic acid modified graphene oxide material, wherein the addition of ethylenediamine can adjust the hydrophobic properties of the product structure after the reaction, and the amino-hydroxamic acid modified graphene oxide material collector has the following structural formula:

[0099]

[0100] Malachite with a particle size of -0.076 mm to +0.038 mm was floated for 10 minutes using a mixed modified graphene oxide collector of phenylalanine hydroxamic acid and ethylenediamine; the concentration of the mixed modified graphene oxide collector of phenylalanine hydroxamic acid and ethylenediamine was 0.6 g / L, the pH value of the slurry was 7.0, the concentration of the frother methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. At this time, the flotation recovery rate of malachite reached 81.2%.

[0101] Example 5

[0102] The preparation of amino-hydroxamic acid modified graphene oxide material comprises the following steps:

[0103] The same as steps 1-3 of Example 1, except that the amount of ethylenediamine is replaced from 1.04 parts to 0.52 parts, as shown below:

[0104] S4, preparing 4 mg / mL of graphene oxide solution, mixing 3 parts of phenylalanine hydroxamic acid and 0.52 parts of ethylenediamine with the graphene oxide solution and reacting them together to obtain a mixed modified graphene oxide collector of phenylalanine hydroxamic acid and ethylenediamine.

[0105] Malachite with a particle size of -0.076 mm to +0.038 mm was floated for 10 minutes using a mixed modified graphene oxide collector of phenylalanine hydroxamic acid and ethylenediamine; the concentration of the mixed modified graphene oxide collector of phenylalanine hydroxamic acid and ethylenediamine was 0.6 g / L, the pH value of the slurry was 7.0, the concentration of the frother methyl isobutyl carbinol (MIBC) was 15 mg / L, and the N2 gas flow rate was 200 mL / min. At this time, the flotation recovery rate of malachite reached 75.3%.

[0106] Example 6

[0107] The preparation of aminotriazolethione modified graphene oxide material containing C(=S)—O structure comprises the following steps:

[0108] S1. First, add 23.76 parts of methanol as a solvent at 5°C, then add 17.22 parts of sodium butyl xanthate, then dropwise add 10.85 parts of methyl chloroacetate, raise the temperature to 15°C and react for 3 hours to obtain an ester compound containing a C(=S)-O structure;

[0109] S2. At 0°C, 10.02 parts of hydrazine hydrate were added dropwise to the ester compound containing the C(=S)-O structure. After completion, the temperature was raised to 60°C and refluxed for 7 hours to prepare a hydrazide compound containing the C(=S)-O structure.

[0110] S3, continue to add 6.73 parts of potassium hydroxide to the hydrazide compound at 0°C to obtain alkaline conditions, and after the addition, continue to add 11.50 parts of carbon disulfide at this temperature, react at 20°C for 3h, and then drop 10.02 parts of hydrazine hydrate to the liquid again, gradually raise the temperature to 60°C and reflux for 8h. After the reaction is completed, cool to room temperature, acidify with hydrochloric acid to pH 3, filter and dry after cooling to obtain aminotriazolethione containing C(=S)-O structure;

[0111] S4, prepare a 4 mg / mL graphene oxide solution, mix 3 parts of aminotriazolethione containing C(=S)-O structure with the graphene oxide solution, and continuously stir and reflux for 8 hours at 60° C. and 200 parts of water as a solvent. After the reaction is completed, filter to obtain the desired aminotriazolethione modified graphene oxide collector containing C(=S)-O structure; its structural formula is as follows:

[0112]

[0113] Using amino-triazolethione modified graphene oxide collector containing C(=S)-O structure to remove Cu 2+ Adsorption experiment of copper metal in solution, Cu 2+ The solution concentration is 50 mg / L, 200 mg / L of collector solution is added, the temperature is 25°C, the pH is 4, and the adsorption time is 60 minutes. At this time, the adsorption rate of copper ions can reach 70%. The adsorption rate of unmodified graphene oxide (i.e., graphene oxide) is only 45% under the same conditions.

[0114] The synthetic route of this embodiment is as follows Figure 5 shown.

[0115] Example 7

[0116] The preparation of amino-triazolethione modified graphene oxide material comprises the following steps:

[0117] S1. First, add 23.76 parts of methanol as a solvent at 0°C, then add 17.22 parts of sodium butyl xanthate, then dropwise add 16.275 parts of methyl chloroacetate, raise the temperature to 10°C and react for 5 hours to obtain an ester compound containing a C(=S)-O structure;

[0118] S2, at 5°C, 15 parts of hydrazine hydrate were added dropwise to the liquid, and after completion, the temperature was raised to 60°C, and refluxed for 7 hours to prepare a hydrazide compound containing a C(=S)-O structure;

[0119] S3, continue to add 7.2 parts of potassium hydroxide to the hydrazide compound at 5°C to obtain alkaline conditions, and after the addition, continue to add 11.50 parts of carbon disulfide at this temperature, react at 20°C for 3h, and then drop 10.02 parts of hydrazine hydrate to the liquid again, gradually raise the temperature to 60°C, reflux for 8h, and after the reaction is completed, cool to room temperature, acidify with hydrochloric acid to pH 5, and after cooling, filter and dry to obtain aminotriazolethione containing C(=S)-O structure;

[0120] S4, prepare 4 mg / mL graphene oxide solution, mix 3 parts of aminotriazolethione containing C(=S)-O structure, ethylenediamine and graphene oxide solution, stir and reflux continuously for 9 hours at 60° C. and 200 parts of water as solvent, after the reaction is completed, filter to obtain the desired amino-triazolethione modified graphene oxide collector; its structural formula is as follows:

[0121]

[0122] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A modified graphene oxide material, characterized in that: The modified graphene oxide material includes hydroxamic acid modified graphene oxide material, azolethione modified graphene oxide material, amino-hydroxamic acid modified graphene oxide material, amino-azolethione modified graphene oxide material, the structure of the hydroxamic acid modified graphene oxide material is shown in formula (I), the structure of the azolethione modified graphene oxide material is shown in formula (II), the structure of the amino-hydroxamic acid modified graphene oxide material is shown in formula (III), and the structure of the amino-azolethione modified graphene oxide material is shown in formula (IV): In formula (I) and formula (III), R is the same, and R is selected from a C1-C17 straight chain or branched alkane group, a C2-C17 olefin group, a C6-C12 aromatic group, or a Alkoxy ether group of the structure; In formula (II) and formula (IV), R1 is the same, and R1 is selected from hydrogen, amino, C1-C17 straight chain or branched alkane, C2-C17 olefin, C6-C12 aromatic, Alkoxy ether group of the structure or containing , , The chelating functional groups of the structure; In the structure, R 1 is selected from ethylene or propylene, n is an integer of 1-3, R 2 A hydrocarbon group selected from C1-C17; , , In the structure, R 3 A C1-C17 straight chain or branched alkane group, a C2-C17 olefin group, a C6-C12 aromatic group, or a Alkoxy ether group of the structure; In formula (III) and formula (IV), R2 is the same, and R2 is selected from C2-C10 straight chain or branched alkane groups, C2-C10 olefin groups, and C6-C12 aromatic groups.

2. The modified graphene oxide material according to claim 1, characterized in that: In the formula (I) and formula (III), R is selected from a C3-C8 straight chain or branched alkane group, a C2-C8 olefin group, a C6-C10 aromatic group or a Alkoxy ether group of the structure; In formula (II) and formula (IV), R1 is selected from hydrogen, amino, C3-C8 straight chain or branched alkane, C2-C8 olefin, C6-C10 aromatic, Alkoxy ether group of the structure or containing , , The chelating functional groups of the structure; In the structure, R 1 is ethylene, n is an integer of 1-3, R 2 A hydrocarbon group selected from C3-C8; , , In the structure, R 3 A C3-C8 straight chain or branched alkane group, a C2-C8 olefin group, a C6-C10 aromatic group or a Alkoxy ether group of the structure; In formula (III) and formula (IV), R2 is selected from a C2-C8 straight chain or branched alkane group, a C2-C8 olefin group, or a C6-C10 aromatic group.

3. The modified graphene oxide material according to claim 2, characterized in that: In formula (I) and formula (III), R is selected from n-propyl, n-butyl, isobutyl, hexyl, heptyl, octyl, phenyl, benzyl, phenethyl, propenyl, allyl, butenyl, isobutenyl, dibutenyl, hexenyl or phenylpropenyl; In formula (II) and formula (IV), R1 is selected from hydrogen, amino, n-propyl, n-butyl, isobutyl, n-pentyl, vinyl, propenyl, phenyl, benzyl, phenethyl, propenyl, allyl, butenyl, isobutenyl, dibutenyl, hexenyl or phenylpropenyl; In formula (III) and formula (IV), R2 is selected from ethyl, n-propyl, isobutyl, n-hexyl, vinyl, propenyl, phenyl, benzyl or phenethyl.

4. The method for preparing the modified graphene oxide material according to claim 1, characterized in that: The hydroxamic acid-modified graphene oxide material is prepared according to the following steps: S1, dissolving a hydroxylamine compound in a solvent, then adding caustic soda thereto, and reacting at 0-15° C. for 30-40 minutes to obtain a free hydroxylamine solution; Wherein, the hydroxylamine compound is selected from hydroxylamine hydrochloride or hydroxylamine sulfate; S2. Under alkaline conditions, add amino acid methyl ester hydrochloride to the free hydroxylamine solution of step S1, react at 10° C. for 3-4 hours, and then react at 20-30° C. for 1-1.5 hours to obtain a hydroxamic acid solution; S3, acidifying the hydroxamic acid solution in step S2 by cooling, filtering, and evaporating the solvent to obtain aminohydroxamic acid; S4, mixing the aminohydroxamic acid of step S3 with graphene oxide, and subjecting the mixture to reflux reaction at 60-70° C. for 8-9 hours, and then filtering, washing and drying to obtain a hydroxamic acid-modified graphene oxide material.

5. The method for preparing the modified graphene oxide material according to claim 4, characterized in that: The molar ratio of the hydroxylamine compound in step S1, the caustic soda in step S1, and the amino acid methyl ester hydrochloride in step S2 is (1.0-1.1): (2.1-4.2): (1.0-1.1); In the step S4, the mass ratio of graphene oxide to aminohydroxamic acid is (0.7-0.8): (2.9-3.0).

6. The method for preparing the modified graphene oxide material according to claim 4, characterized in that: The cooling and acidification method in step S3 is: cooling the hydroxamic acid solution in step S2 to 0-5°C in an ice bath, then adding concentrated sulfuric acid dropwise to the hydroxamic acid solution, and controlling the temperature not to exceed 10°C, acidifying to a pH of 7-8, and stirring at 5-10°C for 30-45 minutes.

7. The method for preparing the modified graphene oxide material according to claim 1, characterized in that: The amino-hydroxamic acid modified graphene oxide material is prepared according to the following steps: A1, dissolving a hydroxylamine compound in a solvent, then adding caustic soda thereto, and reacting at 0-15° C. for 30-40 minutes to obtain a free hydroxylamine solution; Wherein, the hydroxylamine compound is selected from hydroxylamine hydrochloride or hydroxylamine sulfate; A2. Under alkaline conditions, add amino acid methyl ester hydrochloride to the free hydroxylamine solution of step A1, react at 10° C. for 3-4 hours, and then react at 20-30° C. for 1-1.5 hours to obtain a hydroxamic acid solution; A3, acidifying the hydroxamic acid solution in step A2 by cooling, filtering, and evaporating the solvent to obtain aminohydroxamic acid; A4, mixing the aminohydroxamic acid, alkyl diamine and graphene oxide obtained in step A3, reflux reacting at 60-70° C. for 8-9 hours, filtering, washing and drying to obtain an amino-hydroxamic acid modified graphene oxide material; Among them, the mass ratio of graphene oxide, aminohydroxamic acid and alkyl diamine is (0.7-0.8):(2.9-3.0):(0.52-1.04).

8. The method for preparing the modified graphene oxide material according to claim 1, characterized in that: The oxathiophene-modified graphene oxide material is prepared according to the following steps: (1) dissolving a disulfide salt compound in an alcohol solvent, then adding a chlorocarboxylic acid ester thereto, and reacting at 10-20° C. for 2-5 h to obtain an ester compound; Wherein, the dithio salt compound is selected from dithioformate, dithiocarbamate or dithiophosphate; the alcohol solvent is methanol or ethanol; the molar ratio of the dithio salt compound to the chlorocarboxylic acid ester is (1.0-1.3): (1.5-2.5); (2) adding hydrazine hydrate to the ester compound of step (1) at 0-5°C, then heating to 60-65°C and reflux for 6-7h to obtain a hydrazide compound; Wherein, the molar ratio of the ester compound to hydrazine hydrate is (1.0-1.3): (1.2-2.5); (3) Continue to cool to 0-5°C, add carbon disulfide to the hydrazide compound of step (2) under alkaline conditions, and react at 15-20°C for 3-5h, then dropwise add hydrazine hydrate, continue to reflux at 60-65°C for 6-8h, acidify to pH 3-5, cool, filter, and dry to obtain aminotriazolethione; Wherein, the molar ratio of hydrazide compound, carbon disulfide and hydrazine hydrate is (1.0-1.3): (1.5-2.5): (1.2-2.5); (4) mixing the aminotriazolethione of step (3) with graphene oxide, and subjecting the mixture to reflux reaction at 60-65° C. for 8-9 hours, and then filtering, washing, and drying to obtain an azolethione-modified graphene oxide material; Among them, the mass ratio of graphene oxide to aminotriazolethione is (0.7-0.8): (2.9-3.0).

9. The method for preparing the modified graphene oxide material according to claim 1, characterized in that: The amino-oxathione modified graphene oxide material is prepared according to the following steps: B1. dissolving a disulfide salt compound in an alcohol solvent, then adding a chlorocarboxylate thereto, and reacting at 10-20° C. for 2-5 h to obtain an ester compound; Wherein, the dithio salt compound is selected from dithioformate, dithiocarbamate or dithiophosphate; the alcohol solvent is methanol or ethanol; the molar ratio of the dithio salt compound to the chlorocarboxylic acid ester is (1.0-1.3): (1.5-2.5); B2, adding hydrazine hydrate to the ester compound in step B1 at 0-5°C, then heating to 60-65°C and reflux for 6-7h to obtain a hydrazide compound; Wherein, the molar ratio of the ester compound to hydrazine hydrate is (1.0-1.3): (1.2-2.5); B3, continue to cool to 0-5 ° C, add carbon disulfide to the hydrazide compound of step B2 under alkaline conditions, and react at 15-20 ° C for 3-5 hours, add hydrazine hydrate dropwise thereto again, continue to reflux at 60-65 ° C for 6-8 hours, acidify to pH 3-5, cool, filter, and dry to obtain aminotriazolethione; Wherein, the molar ratio of hydrazide compound, carbon disulfide and hydrazine hydrate is (1.0-1.3): (1.5-2.5): (1.2-2.5); B4, after mixing the aminotriazolethione, alkyldiamine and graphene oxide of step B3, reflux reaction at 60-65° C. for 8-9 hours, and then filtering, washing and drying to obtain amino-thionethione modified graphene oxide material; Among them, the mass ratio of graphene oxide, aminotriazolethione and alkyldiamine is (0.7-0.8):(2.9-3.0):(0.52-1.04).

10. Use of the modified graphene oxide material according to claim 1 in preparing a collector or adsorbent for valuable metals in ores, characterized in that: The modified graphene oxide material is used to flotation-recover at least one valuable metal in copper, zinc, antimony, silver and gold-containing minerals; or the modified graphene oxide material is used to adsorb at least one metal ion among copper, zinc, antimony, lead, silver and gold.

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