CN1169775C - Poly-basic aromatic carboxylic acid for flotation and its preparing method - Google Patents
Poly-basic aromatic carboxylic acid for flotation and its preparing method Download PDFInfo
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- CN1169775C CN1169775C CNB011068264A CN01106826A CN1169775C CN 1169775 C CN1169775 C CN 1169775C CN B011068264 A CNB011068264 A CN B011068264A CN 01106826 A CN01106826 A CN 01106826A CN 1169775 C CN1169775 C CN 1169775C
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Abstract
The present invention relates to a polybasic aromatic carboxylic acid for floatation and a preparing method thereof. The present invention uses gallic acid, monochloroacetic acid and sodium hydroxide as raw material, and the hydroxyl etherification reaction of gallic acid phenol is realized by using a Bunsen valve sealing device and controlling reaction conditions; 3, 4, 5-tricarboxyl methoxybenzoic acid as a new floatation agent is prepared. The preparing method of the present invention has the characteristics of easy material source, simple operation, and high reaction yield; when the compound prepared in the present invention is used for floating of single mineral calcite, diaspore, pyrite and actual mineral-diaspore, a good floating inhibiting performance is formed; the present invention can also be used as an inhibitor for various oxidation minerals, particularly minerals containing calcium and magnesium.
Description
[technical field] the present invention relates to a kind of poly-basic aromatic carboxylic acid flotation reagent that is applied in the ore dressing field.
[background technology] flotation reagent molecule is made up of polar group and nonpolar group two portions, polar group is hydrophilic, it is the part that agent molecule and mineral are had an effect, so also claim the parent solid base, nonpolar group then constitutes the hydrophobic grouping of agent molecule, show the hydrophobic ability of agent molecule,, and flotation reagent is divided into collecting agent, inhibitor and pore forming material according to the relative size of polar group and nonpolar group.
The wetting ability of phenoxy acetic acid compounds molecule is stronger, it not only contains the extremely strong carboxyl of wetting ability, also containing ehter bond and certain hydrophilic phenyl ring than strongly hydrophilic, so just in time meet the requirement of depressing agent on its structure, might be the depressing agent of multiple oxidized ore.Mainly contain phenoxy acetic acid in the phenoxy acetic acid compounds at present, m-, o-or p-two (carboxymethoxyl) benzene, 1,2,3-three (carboxymethoxyl) benzene, their preparation method utilizes aldehydes matter, as phenol and dihydroxy-benzene, with Monochloro Acetic Acid William's nurse inferior (Williamson) reaction takes place under alkaline condition and makes, but also there is bigger problem at present in its synthetic aspect: the one, and the operation complexity, reaction process is long, and the 2nd, reaction yield is not high, and product selectivity is lower.In such etherification reaction, the oxidation of phenolic hydroxyl group and the hydrolysis of Monochloro Acetic Acid are their topmost side reactions, the oxidation that reduces phenolic hydroxyl group will reduce reaction system exactly as far as possible and contact with air, but traditional mercury seal device complicated operation not only, and potential the damaging effect of mercury.
[summary of the invention] the present invention is a raw material with gallic acid, Monochloro Acetic Acid and sodium hydroxide, and a kind of poly-basic aromatic carboxylic acid for flotation is provided---3,4, and 5-tricarboxylic methoxybenzoic acid and preparation method thereof.
Its name of poly-basic aromatic carboxylic acid provided by the present invention is called: 3,4, and 5-tricarboxylic methoxybenzoic acid, molecular formula: C
13H
12O
11Molecular weight: 344.1, its structural formula is:
Relevant physical properties: the grey powder, decomposition temperature: 218 ℃, acid dissociation constant: pK
13.53, pK
24.02, pK
39.80, pK
41 0.57.
The present invention is a main raw material with gallic acid, Monochloro Acetic Acid and sodium hydroxide, by the certain reaction condition, realize the etherification reaction of phenolic hydroxyl group in the gallic acid molecule, the total proportioning mol ratio of raw material in the etherification procedure is a gallic acid: Monochloro Acetic Acid: sodium hydroxide=1: 3.2～3.5: 8.5～9.5, they are chemical pure or analytical reagent.Principal reaction process and processing condition are as follows: (1) adds the distilled water mixing that weight is 3～4 times of gallic acid weight in the gallic acid for preparing, Monochloro Acetic Acid, slowly shake, and makes it to become pasty state uniformly.(2) slowly add 10%～20% sodium hydroxide solution, make the mashed prod dissolving, the limit edged cools off in frozen water, makes the temperature of system be no more than 40 ℃, adds that the pH of solution is controlled at 9.5～11.5 after the sodium hydroxide.If after adding the sodium hydroxide solution of amounts of reactants, the pH of system does not reach claimed range, and then available distilled water or 40% sodium hydroxide solution are adjusted.(3) heating is stirred, and heats 40～60 minutes down at 80 ℃～100 ℃.(4) be cooled to room temperature, to pH2～3, separate out gray precipitate, in frozen water, be cooled to below 5 ℃ with 1: 1 hcl acidifying, suction filtration, washing gets thick product.(5) with distilled water thick product being carried out recrystallization purifies.50 ℃～70 ℃ following vacuum-dryings get product, detect at last, analyze.
In heating and whipping process, reflux and the sealing whipping appts for guaranteeing carrying out smoothly of etherification reaction, adopting, and the Bunsen valve tightness system is housed in the upper end of reflux condensing tube.The Bunsen valve tightness system is to insert one section Glass tubing at the center of a soft rubber ball, overlaps the rubber tubing that a bit of the other end is sealing on the Glass tubing again, with blade standardized longitudinal slit on rubber tubing.
With 3,4,5-tricarboxylic methoxybenzoic acid is made into certain density solution, is applied to respectively investigate its flotation rejection in calcite, diaspore and the FLOTATION OF PYRITE process.The flotation oil acid sodium of calcite is made collecting agent, and the flotation of diaspore is made collecting agent with amino dodecane, and FLOTATION OF PYRITE is made collecting agent with butyl xanthate, add new synthetic 3 respectively, 4,5-tricarboxylic methoxybenzoic acid solution is made inhibitor, when collecting agent concentration is 5 * 10
-4Mol/L～5 * 10
-3Mol/L, the concentration of inhibitor is 1 * 10
-5Mol/L～1 * 10
-4Mol/L, flotation pH are 8.5～11.0 o'clock, and the rate of recovery of calcite is 1.0～2.0%, and the rate of recovery of diaspore is 20.0～25.0%, and the pyritous rate of recovery is 35.0～40.0%.With 3,4,5-tricarboxylic methoxybenzoic acid is applied to the Counterfloatating desiliconization of bauxite ore as inhibitor, and the content of aluminum oxide is 67.1%～67.4% in the raw ore, the alumina silica ratio 7.53～7.76 of concentrate, and the rate of recovery of aluminum oxide is 71.6%～80.4%.
Compare with existing flotation reagent, the present invention has the following advantages and positively effect:
1 the present invention is a raw material with gallic acid, Monochloro Acetic Acid and sodium hydroxide, by adopting Bunsen valve tightness system and control reaction conditions, realized the etherification reaction of gallic acid phenolic hydroxyl group, prepared a kind of novel flotation reagent 3,4,5-tricarboxylic methoxybenzoic acid;
2 preparation methods of the present invention have that raw material is easy to get, simple to operate, characteristics that reaction yield is high;
The used Bunsen valve tightness system of 3 the present invention has not only reached the purpose of sealed reaction system, and compares with traditional mercury seal device, has tangible improvement;
4 with 3,4,5-tricarboxylic methoxybenzoic acid is applied in the flotation of single mineral calcite, diaspore and pyrite and actual ore diaspore, embodied flotation rejection preferably, wherein to obviously be better than rejection to sulphide ores to the rejection of oxidized ore, so can be used as the particularly inhibitor of calcite of oxidized ore, thereby aspect depressing agent, opened up new field;
5 the present invention also can be used as the particularly inhibitor of calcic, magnesium mineral of other various oxidized ores.
[embodiment]
1 implements preferred plan of the present invention is: take by weighing 0.1mol (17.0g) gallic acid and 0.33mol (31.2g) Monochloro Acetic Acid mixes in 500mL, add 50mL earlier and boil boiled-out water, shake and make it to become white mashed prod uniformly, the NaOH solution that slowly splashes into 270mL 10% then is (with dissolution of sodium hydroxide to boiling in the boiled-out water, now with the current) in, the limit edged shakes in frozen water, make system temperature below 40 ℃, the pH value of the NaOH solution regulation system with 40% makes it to be controlled at 10.5～11 (needing 40% NaOH solution 10mL approximately).Adopt and reflux and the sealing whipping appts, load onto the Bunsen valve tightness system in the upper end of the reflux condensation mode mouth of pipe, heating, stir, heated and stirred is 50 minutes in 90 ℃ of hot water baths, is cooled to room temperature and adds 1: 1 hcl acidifying, this moment occurs gray precipitate, continue to add hydrochloric acid to pH～2.Frozen water cooling, suction filtration, precipitation with twice of 80mL distilled water wash after, use 100mL distilled water recrystallization twice again, suction filtration, fully take out branchs that anhydrate after, 60 ℃ of following vacuum-dryings, at last must product 25.1g, productive rate 72.8%.
2 monomineralic flotation are carried out on XFG--76 type hanging groove formula flotation machine, and flotation machine rotating speed 1650r/min, simple ore thing granularity-0.074mm ± 0.037mm, pH measure and use PHSJ-4 type pH meter.
The preferred plan of implementing flotation is:
(a) flotation of calcite: get calcite 2g in the 50mL flotation cell, add water 40mL and stir 2min, add 4 * 10
-3The synthetic inhibitor 1mL of mol/L stirs 2min, and adjusting pH with the sodium hydroxide of 0.1mol/L is 10.27, adds 4 * 10 again
-3The sodium oleate 1mL of mol/L stirs 2min, scrapes bubble 3min at last.Dry foam down, reclaim calcite 0.02g, the rate of recovery 1.0% for 90 ℃.
B) flotation of diaspore: the operating process of flotation is identical with the flotation of calcite, just changes collecting agent into dodecylamine hydrochloride, and adjusting pH is 9.24, scrapes bubble 5min at last, reclaims diaspore 0.4g, the rate of recovery 20.0%.
C) FLOTATION OF PYRITE: get pyrite 2g, put into the CQ50 ultrasonic cleaner and clean 5min, place flotation cell then, add water 40mL, add 4 * 10
-3The synthetic inhibitor 1mL of mol/L stirs 2min, and adjusting pH with the sodium hydroxide of 0.1mol/L is 10.60, adds 2 * 10 again
-4The butyl xanthate 1mL of mol/L stirs 2min, adds pore forming material 2# oil 0.2uL and stirs 1min, scrapes bubble 3min at last.After the oven dry, get pyrite 0.64g, the rate of recovery 35.0%.
Claims (3)
1. poly-basic aromatic carboxylic acid for flotation, it is characterized in that: compound name is called 3,4,5-tricarboxylic methoxybenzoic acid, molecular formula C
13H
12O
11, molecular weight 344.1, its structural formula is:
2. method for preparing the described poly-basic aromatic carboxylic acid of claim 1, it is characterized in that: with gallic acid, Monochloro Acetic Acid and sodium hydroxide is main raw material, realize the etherification reaction of phenolic hydroxyl group in the gallic acid molecule, the total proportioning mol ratio of raw material in the etherification procedure is a gallic acid: Monochloro Acetic Acid: sodium hydroxide=1: 3.2～3.5: 8.5～9.5, the principal reaction process is as follows: (1) adds the distilled water mixing that weight is 3～4 times of gallic acid weight in the gallic acid for preparing, Monochloro Acetic Acid, slowly shake, make it to become pasty state uniformly; (2) slowly add 10%～20% sodium hydroxide solution, make the mashed prod dissolving, the limit edged cools off in frozen water, makes the temperature of system be no more than 40 ℃, add that the pH of solution is controlled at 9.5～11.5 after the sodium hydroxide, carry out pH with the sodium hydroxide solution of distilled water or 40% and adjust; (3) heating is stirred, and heats 40～60 minutes down at 80 ℃～100 ℃; (4) be cooled to room temperature, to pH2～3, separate out gray precipitate, in frozen water, be cooled to below 5 ℃ with 1: 1 hcl acidifying, suction filtration, washing gets thick product; (5) with distilled water thick product is carried out recrystallization and purify, 50 ℃～70 ℃ following vacuum-dryings get product, detect at last, analyze.
3. device that is used for the described method of claim 2, it is characterized in that: in heating and whipping process, for guaranteeing carrying out smoothly of etherification reaction, adopt and reflux and the sealing whipping appts, and the Bunsen valve tightness system is housed in the upper end of reflux condensing tube, the Bunsen valve tightness system is to insert one section Glass tubing at the center of a soft rubber ball, overlaps the rubber tubing that a bit of the other end is sealing on the Glass tubing again, and a longitudinal slit is arranged on rubber tubing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011068264A CN1169775C (en) | 2001-01-09 | 2001-01-09 | Poly-basic aromatic carboxylic acid for flotation and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011068264A CN1169775C (en) | 2001-01-09 | 2001-01-09 | Poly-basic aromatic carboxylic acid for flotation and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1364754A CN1364754A (en) | 2002-08-21 |
| CN1169775C true CN1169775C (en) | 2004-10-06 |
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| CNB011068264A Expired - Fee Related CN1169775C (en) | 2001-01-09 | 2001-01-09 | Poly-basic aromatic carboxylic acid for flotation and its preparing method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PE20130498A1 (en) * | 2010-01-14 | 2013-04-22 | Teebee Holdings Pty Ltd | FLOTATION REAGENTS |
| CN102329237A (en) * | 2011-06-24 | 2012-01-25 | 灌南伊斯特化工有限公司 | Production process of 2-chloro-5-nitrobenzoic acid |
| CN106975573B (en) * | 2017-03-13 | 2018-08-21 | 中南大学 | Carbon inhibitor and its application in a kind of copper-sulphide ores floatation process |
| CN109465112B (en) * | 2018-11-16 | 2021-02-19 | 鞍山市天翔工业科技有限公司 | Chelate amphoteric collector, preparation method thereof and composition consisting of chelate amphoteric collector and fatty acid |
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