Glycylpropylamine compounds, preparation methods thereof and applications as flotation agents

Abstract

The present invention discloses a structure of a glycosylpropylamine compound, as shown in general formula (I), general formula (II) or general formula (III). The present invention also discloses a preparation method of the structure of the glycosylpropylamine compound and its application as a flotation agent. Since the molecular structure of the compound of the present invention contains a glycosyl group, the toxicity of the product will be greatly reduced; and there are also amide bonds and ether bonds that are easily degradable in the molecular structure, so the biodegradability of the product will be greatly improved.

Description

Technical Field

[0001] The present invention relates to a glycosylpropylamine compound, a preparation method thereof, and an application thereof as a flotation agent, belonging to the field of mineral flotation agents. Background Art

[0002] Mining is closely related to various fields such as people's daily lives and industrial demands, and is an indispensable basic industry for the sustainable development of the national economy. With the rapid development of the social economy, the demand for mineral resources is increasing day by day, resulting in the continuous aggravation of the phenomena of miscellaneous, fine, and lean mineral resources. Therefore, the difficulty of mineral extraction is increasing. Due to its high separation efficiency and strong adaptability, flotation technology is currently the most widely used and most promising mineral separation technology. Among them, amine compounds have obtained good application effects in the beneficiation of metal oxide ores, non-metal ores, etc., in the separation of silicates, potassium and sodium salts, the separation of iron oxide ores from quartz, silicates, silicic acids and other minerals from mica, and the separation of oxidized lead-zinc ores.

[0003] Most of the commonly used amine flotation agents at present are prepared from non-renewable resources such as petroleum and coal, and have problems such as toxicity and non-degradability. Therefore, they are not conducive to sustainable development and will cause relatively serious harm to the environment, animals and plants. Therefore, the development of low-toxic and highly degradable amine flotation agent products prepared from natural renewable resources is of great significance for the sustainable development of the mineral flotation process. At present, there is no report on the preparation of glycosylamine compounds using glycosyl products as raw materials. Summary of the Invention

[0004] The purpose of the present invention is to provide a glycosylpropylamine compound, a preparation method thereof, and an application thereof as a flotation agent.

[0005] The present invention provides a structure of a glycosylpropylamine compound, as shown in structural general formula (I), structural general formula (II), or structural general formula (III),

[0006] ,

[0007] wherein, m is selected from 8-14, and n is selected from 7-15.

[0008] The glycosylpropylamine compound of the present invention is preferably selected from the following compounds:

[0009]

[0010] The present invention provides a preparation method of a glycosylpropylamine compound, and its reaction route is,

[0011] ,

[0012] ,

[0013] ,

[0014] Among them, m is selected from 8 - 14, and n is selected from 7 - 15.

[0015] The present invention provides a preparation method of a glycosylpropylamine compound. The present invention uses glucosamide / alkyl glycoside as raw materials, first reacts with acrylonitrile under the condition of a solid base as a catalyst to obtain alkyl glycosylpropionitrile; then, under the condition of Raney-Ni (Raney nickel) as a catalyst, a hydrogenation reaction occurs to synthesize a novel alkyl glycosyl-containing propylamine compound. Since the molecular structure of this product contains a glycosyl group, the toxicity of the product will be greatly reduced; and there are also amide bonds and ether bonds that are easily degradable in the molecular structure, so the biodegradability of the product will be greatly improved, and it can be used as an excellent substitute for alkylpropylamine compounds in mineral re-election and daily washing.

[0016] The present invention provides a preparation method of a glycosylpropylamine compound, and its reaction steps are as follows:

[0017] Step 1: Cyclohexane, an alkyl glycosyl compound, and a solid base catalyst are added to a container according to a mass ratio of (8 - 15):1:(0.5‰ - 5‰), then acrylonitrile is slowly added. After reacting for 5 - 9 h, hot filtration is carried out. After cooling, the solvent is evaporated to obtain 3-alkylglycosyloxypropionitrile.

[0018] Among them, the alkyl glycosyl compound is one or a combination of several of N-methyl-N-alkylglucosamide, alkylglucosamide, or alkyl glycoside.

[0019] Among them, the solid base catalyst is one or two of sodium hydroxide and potassium hydroxide.

[0020] Among them, the reaction temperature is 40 - 80 °C, preferably: 50 - 65 °C.

[0021] Among them, the addition method of acrylonitrile is dropwise addition. Preferably, it is added dropwise at a uniform speed.

[0022] Among them, the molar ratio of acrylonitrile to the alkyl glycosyl compound is 0.9 - 1.3, preferably 1.0 - 1.1.

[0023] Step 2: Cyclohexane, 3-alkylglycosyloxypropionitrile, a Raney-Ni catalyst, and an inhibitor NH₃·H₂O are added to a high-pressure reaction vessel, replaced with N₂, stirred, and heated to 60 - 90 °C. Then, H₂ is introduced into the high-pressure reaction vessel. After reacting for 5 - 9 h, the product is discharged. After hot filtration, the solvent is removed by reduced pressure distillation to obtain the product 3-alkylglycosyloxypropylamine.

[0024] Among them: the mass ratio of cyclohexane to 3-alkylglycosyloxypropionitrile is 8-13:1, preferably 9-12:1.

[0025] Among them: the dosage of Raney-Ni catalyst is 2-12 wt% of the mass of 3-alkylglycosyloxypropionitrile, preferably 2-8%.

[0026] Among them: nitrogen replacement is required before charging hydrogen, preferably 3 times.

[0027] Among them: the reaction temperature is 60-90 °C, preferably 70-85 °C.

[0028] Among them: the reaction pressure is 1.5-4.0 MPa, preferably 1.8-3.5 MPa.

[0029] Preferably: the content of the product 3-alkylglycosyloxypropylamine is calculated according to the national standard GB / T15045-2013 Determination Method of Total Amine, Primary Amine, Secondary Amine and Tertiary Amine in Fatty Alkyl Dimethyl Tertiary Amine, and the purity is greater than 90%.

[0030] The present invention provides an application of a glycosylpropylamine compound as a flotation agent.

[0031] The present invention has the following advantages compared with the prior art:

[0032] 1. The glycosyl is derived from renewable resources, which can replace non-renewable resources such as petroleum and coal, and increases the sustainable development of amine products.

[0033] 2. After adding glycosyl, the amine products have better biocompatibility, lower toxicity, good biodegradability, and are more environmentally friendly.

[0034] 3. Currently common amine collectors have poor solubility in water, so acids must be used to neutralize them to improve their solubility in water. However, the higher the neutralization degree is not necessarily better. A higher neutralization degree can increase the solubility of the flotation agent, but may weaken the flotation behavior. After introducing glycosyl groups into the molecule in the present invention, the water solubility of the molecule can be increased, and acid neutralization is not required, greatly reducing the operation procedures and lowering the use cost.

[0035] 4. The compound described in the present invention has good flotation effect on minerals and can be used as an efficient flotation agent. Specific Embodiments

[0036] Example 1: 3-Hexadecylglycosyloxypropylamine

[0037]

[0038] Add 150 mL of cyclohexane, 10 g (25 mmol) of hexadecyl glucoside, and 0.01 g of sodium hydroxide to a 250 mL flask. After adding the raw materials, start stirring and heat to 60 °C. Then, dropwise add 1.33 g (25 mmol) of acrylonitrile. After adding acrylonitrile, continue the reaction for 9 h. After hot filtration, cool down and evaporate the solvent using a rotary evaporator to obtain 3-hexadecylglucosyloxypropionitrile.

[0039] Add 150 mL of cyclohexane, 10 g of 3-hexadecylglucosyloxypropionitrile, 0.5 g of Raney-Ni catalyst, and 0.5 g of inhibitor NH₃·H₂O to a high-pressure reactor. Replace with N₂ three times. Start stirring, heat to 75 °C, and then introduce H₂ (pressure 2 MPa) into the reactor. After reacting for 5 h, discharge the material. After hot filtration, evaporate the solvent using a rotary evaporator to obtain the product 3-hexadecylglucosyloxypropylamine, and the measured content is 91%.

[0040] Example 2: 3-N-methyl-N-dodecylglucosamideoxypropylamine

[0041]

[0042] Add 150 mL of cyclohexane, 10 g (26.5 mmol) of N-methyl-N-dodecylglucosamide, and 0.05 g of sodium hydroxide to a 250 mL flask. After adding the raw materials, start stirring and heat to 55 °C. Then, dropwise add 1.41 g (26.5 mmol) of acrylonitrile. After adding acrylonitrile, continue the reaction for 7 h. After hot filtration, cool down and evaporate the solvent using a rotary evaporator to obtain 3-N-methyl-N-dodecylglucosamideoxypropionitrile.

[0043] Add 150 mL of cyclohexane, 10 g of 3-N-methyl-N-dodecylglucosamideoxypropionitrile, 0.7 g of Raney-Ni catalyst, and 0.5 g of inhibitor NH₃·H₂O to a high-pressure reactor. Replace with N₂ three times. Start stirring, heat to 75 °C, and then introduce H₂ (pressure 2.5 MPa) into the reactor. After reacting for 7 h, discharge the material. After hot filtration, evaporate the solvent using a rotary evaporator to obtain the product 3-N-methyl-N-dodecylglucosamideoxypropylamine, and the measured content is 93%.

[0044] Example 3: 3-octylglucosamideoxypropylamine

[0045]

[0046] Add 150 mL of cyclohexane, 10 g (32.5 mmol) of octylglucosamide, and 0.1 g of sodium hydroxide to a 250 mL flask. After adding the raw materials, start stirring and heat to 50 °C. Then, dropwise add 1.72 g (32.5 mmol) of acrylonitrile. After dropping acrylonitrile, continue the reaction for 5 h, then perform hot filtration, cool down, and evaporate the solvent using a rotary evaporator to obtain 3-octylglucosamidooxypropionitrile.

[0047] Add 150 mL of cyclohexane, 10 g of 3-octylglucosamidooxypropionitrile, 1 g of Raney-Ni catalyst, and 0.5 g of inhibitor NH₃·H₂O to a high-pressure reactor, and displace with N₂ three times. Start stirring, heat to 75 °C, then introduce H₂ (pressure 2 MPa) into the reactor. After reacting for 9 h, discharge the material, perform hot filtration, and evaporate the solvent using a rotary evaporator to obtain the product 3-octylglucosamidooxypropylamine, and the measured content is 90%.

[0048] Example 4: 3-dodecylglycosyloxypropylamine

[0049]

[0050] Add 150 mL of cyclohexane, 10 g (28.3 mmol) of dodecyl glycoside, and 0.08 g of sodium hydroxide to a 250 mL flask. After adding the raw materials, start stirring and heat to 60 °C. Then, dropwise add 1.50 g (28.3 mmol) of acrylonitrile. After dropping acrylonitrile, continue the reaction for 8 h, then perform hot filtration, cool down, and evaporate the solvent using a rotary evaporator to obtain 3-dodecylglycosyloxypropionitrile.

[0051] Add 150 mL of cyclohexane, 10 g of 3-dodecylglycosyloxypropionitrile, 0.8 g of Raney-Ni catalyst, and 0.5 g of inhibitor NH₃·H₂O to a high-pressure reactor, and displace with N₂ three times. Start stirring, heat to 75 °C, then introduce H₂ (pressure 2.5 MPa) into the reactor. After reacting for 8 h, discharge the material, perform hot filtration, and evaporate the solvent using a rotary evaporator to obtain the product 3-dodecylglycosyloxypropylamine, and the measured content is 95%.

[0052] Example 5: 3-N-methyl-N-decylglucosamidooxypropylamine

[0053]

[0054] Add 150 mL of cyclohexane, 10 g (28.6 mmol) of N-methyl-N-decylglucamide, and 0.06 g of sodium hydroxide to a 250 mL flask. After adding the raw materials, start stirring and heat to 60 °C. Then, dropwise add 1.52 g (28.6 mmol) of acrylonitrile. After adding acrylonitrile dropwise, continue the reaction for 6 h. After hot filtration, cool down and evaporate the solvent using a rotary evaporator to obtain 3-N-methyl-N-decylglucamidooxypropionitrile.

[0055] Add 150 mL of cyclohexane, 10 g of 3-N-methyl-N-decylglucamidooxypropionitrile, 0.9 g of Raney-Ni catalyst, and 0.5 g of inhibitor NH₃·H₂O to a high-pressure reactor, and replace with N₂ three times. Start stirring, heat to 75 °C, and then introduce H₂ (pressure 2 MPa) into the reactor. After reacting for 6 h, discharge the material. After hot filtration, evaporate the solvent using a rotary evaporator to obtain the product 3-N-methyl-N-decylglucamidooxypropylamine, and the measured content is 93%.

[0056] Experimental Example 1:

[0057] According to the national standard GB / T 15818-2018 (Test Method for Biodegradability of Surfactants), the biodegradation performance test results of the samples prepared in the above examples are as follows in the table:

[0058]

[0059] Experimental Example 2:

[0060] Taking quartz ore as a sample, detect the mineral flotation effect of the prepared samples. The specific flotation experiment method is as follows: The single mineral flotation experiment is carried out on an XFG hanging trough flotation machine, and the main shaft rotation speed is 1230 r / min. Each time, weigh 3 g of the mineral and put it into a 40 mL flotation cell, add 30 mL of distilled water, adjust the pulp for 1 min, then add a certain amount of flotation agent solution, stir for 3 min, and float for 5 min. The foam products and the products in the cell are dried and weighed respectively, and the recovery rate is calculated.

[0061] According to the above method, the mineral flotation performance test results of the samples prepared in the above examples are as follows in the table:

[0062] Example Example 1 Example 2 Example 3 Example 4 Example 5 Recovery rate / % 96 98 95 96 97

Claims

1. A structure of a glycosylpropylamine compound, as shown in the general formula (III): , wherein, n is selected from 7 - 15.

2. The glycosylpropylamine compound according to claim 1 is selected from the following compounds: 3 - hexadecylglycosyloxypropylamine ， 3 - dodecylglycosyloxypropylamine 。 3. The preparation method of the glycosylpropylamine compound according to claim 1, and its reaction route is: , wherein, n is selected from 7 - 15.

4. The preparation method of the glycosylpropylamine compound according to claim 1, and its reaction steps are: Step 1: Cyclohexane, an alkyl glycoside compound, and a solid base catalyst are added to a container according to a mass ratio of (8 - 15):1:(0.5‰ - 5‰), and then acrylonitrile is slowly added. After reacting for 5 - 9 h, hot filtration is carried out. After cooling, the solvent is evaporated to obtain 3 - alkylglycosyloxypropionitrile; Step 2: Cyclohexane, 3 - alkylglycosyloxypropionitrile, a Raney - Ni catalyst, and an inhibitor NH₃·H₂O are added to a high - pressure reaction vessel. After purging with N₂ and stirring, when the temperature is raised to 60 - 90 °C, H₂ is introduced into the high - pressure reaction vessel. After reacting for 5 - 9 h, the material is discharged. After hot filtration, the solvent is removed by vacuum distillation to obtain the product 3 - hexadecylglycosyloxypropylamine or 3 - dodecylglycosyloxypropylamine; The alkyl glycoside compound is hexadecyl glycoside or dodecyl glycoside.

5. The preparation method of the glycylpropylamine compound according to claim 4, characterized in that: The solid base catalyst is one or two of sodium hydroxide and potassium hydroxide.

6. The preparation method of the glycosylpropylamine compound according to claim 4, characterized in that: The molar ratio of acrylonitrile to the alkyl glycoside compound is 0.9 - 1.

3.

7. The preparation method of the glycylpropylamine compound according to claim 6, characterized in that: The molar ratio of acrylonitrile to the alkyl glycoside compound is 1.0 - 1.

1.

8. The preparation method of the glycosylpropylamine compound according to claim 4, characterized in that: The mass ratio of cyclohexane to 3 - alkylglycosyloxypropionitrile is 8 - 13:

1.

9. The preparation method of the glycosylpropylamine compound according to claim 8, characterized in that: The mass ratio of cyclohexane to 3 - alkylglycosyloxypropionitrile is 9 - 12:

1.

10. The preparation method of the glycosylpropylamine compound according to claim 4, characterized in that: The dosage of the Raney - Ni catalyst is 2 - 12 wt% of the mass of 3 - alkylglycosyloxypropionitrile.

11. The preparation method of the glycosylpropylamine compound according to claim 4, characterized in that: The dosage of the Raney - Ni catalyst is 2 - 8% of the mass of 3 - alkylglycosyloxypropionitrile.

12. The application of the glycosylpropylamine compound according to claim 1 as a flotation agent.

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