Glycylpropylamine compounds, preparation methods thereof and applications thereof as flotation agents

Abstract

The present invention discloses a structure of a glycosylpropylamine compound, as shown in structural general formula (I), structural general formula (II) or structural 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 life and industrial demands, and is an essential basic industry for the sustainable development of the national economy. With the rapid development of 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 becoming increasingly greater. Due to its advantages such as 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 achieved 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, the separation of minerals such as mica from silicic acid, and the separation of oxidized lead-zinc ores.

[0003] Most of the commonly used amine flotation agents are currently prepared from non-renewable resources such as petroleum and coal, and have problems such as toxicity and poor 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. Currently, 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 method for preparing a glycosylpropylamine compound. The present invention uses glucosamide / alkyl glycoside as a raw material, first reacts with acrylonitrile under the condition of a solid base as a catalyst to obtain an 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 method for preparing 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 vacuum 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 increase 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 into a 250 ml flask. After adding the raw materials, start stirring and heat to 60 ºC. Then, dropwise add 1.33 g (25 mmol) of acrylonitrile. After adding acrylonitrile dropwise, continue the reaction for 9 h. After hot filtration, cool down and evaporate the solvent with a rotary evaporator to obtain 3-hexadecyl glucoside oxypropionitrile.

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

[0040] Example 2: 3-N-methyl-N-dodecyl glucamide oxypropylamine

[0041]

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

[0043] Add 150 mL of cyclohexane, 10 g of 3-N-methyl-N-dodecyl glucamide oxypropionitrile, 0.7 g of Raney-Ni catalyst, and 0.5 g of inhibitor NH₃·H₂O into a high-pressure reactor, and displace with N₂ three times. Start stirring, heat up to 75 ºC, 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 with a rotary evaporator to obtain the product 3-N-methyl-N-dodecyl glucamide oxypropylamine, and the measured content is 93%.

[0044] Example 3: 3-octyl glucamide oxypropylamine

[0045]

[0046] Add 150 mL of cyclohexane, 10 g (32.5 mmol) of octyl glucamide, and 0.1 g of sodium hydroxide into 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 adding acrylonitrile dropwise, continue the reaction for 5 h. After hot filtration, cool down and evaporate the solvent using a rotary evaporator to obtain 3-octyl glucamidooxypropionitrile.

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

[0048] Example 4: 3-dodecyl glucosyloxypropylamine

[0049]

[0050] Add 150 mL of cyclohexane, 10 g (28.3 mmol) of dodecyl glucoside, and 0.08 g of sodium hydroxide into 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 adding acrylonitrile dropwise, continue the reaction for 8 h. After hot filtration, cool down and evaporate the solvent using a rotary evaporator to obtain 3-dodecyl glucosyloxypropionitrile.

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

[0052] Example 5: 3-N-methyl-N-decyl glucamidooxypropylamine

[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, add 1.52 g (28.6 mmol) of acrylonitrile dropwise. After adding all the acrylonitrile, 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. Replace the air with N₂ three times. Start stirring and heat to 75 °C. 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 biodegradability 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-cell flotation machine, and the main shaft rotation speed is 1230 r / min. Weigh 3 g of minerals each time and put them 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 (II), , wherein, n is selected from 7 - 15.

2. The structure of the glycosylpropylamine compound according to claim 1 is: 3 - octylcarbamoyloxypropylamine, 。 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 in 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, 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 material is discharged. After hot filtration, the solvent is removed by vacuum distillation to obtain the product 3 - alkylglycosyloxypropylamine; The alkyl glycoside compound is one or a combination of several of alkyl glucamide or alkyl glycoside.

5. The preparation method of the glycosylpropylamine 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 glycosylpropylamine 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 glycylpropylamine 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 glycylpropylamine 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 method for preparing the glycylpropylamine 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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