CN109465112B - Chelate amphoteric collector, preparation method thereof and composition consisting of chelate amphoteric collector and fatty acid - Google Patents
Chelate amphoteric collector, preparation method thereof and composition consisting of chelate amphoteric collector and fatty acid Download PDFInfo
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- CN109465112B CN109465112B CN201811368165.9A CN201811368165A CN109465112B CN 109465112 B CN109465112 B CN 109465112B CN 201811368165 A CN201811368165 A CN 201811368165A CN 109465112 B CN109465112 B CN 109465112B
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 14
- 239000000194 fatty acid Substances 0.000 title claims abstract description 14
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 14
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 title claims description 4
- 239000013522 chelant Substances 0.000 title description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 19
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 14
- 238000006193 diazotization reaction Methods 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 8
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims abstract description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- JVUOZFIKJGZTCN-UHFFFAOYSA-N 4-aminophenol;sodium Chemical compound [Na].NC1=CC=C(O)C=C1 JVUOZFIKJGZTCN-UHFFFAOYSA-N 0.000 claims abstract description 5
- LSBDFXRDZJMBSC-UHFFFAOYSA-N Amide-Phenylacetic acid Natural products NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 21
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 235000010288 sodium nitrite Nutrition 0.000 claims description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 3
- 229960003656 ricinoleic acid Drugs 0.000 claims description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 125000003368 amide group Chemical group 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000005188 flotation Methods 0.000 description 30
- 238000001816 cooling Methods 0.000 description 21
- 239000002253 acid Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 4
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- -1 2-hydroxy-6-amino-4-hexyloxybenzoic acid Chemical compound 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001612 separation test Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a chelating amphoteric collector and a preparation method thereof. The collecting agent contains alkyl, ether, phenyl, hydroxyl, amido and carboxyl, wherein the length of the alkyl is C5～C16. The preparation method comprises the steps of reacting p-aminophenol with sodium ethoxide to generate p-aminophenol sodium, and reacting with 1-chloroalkane to generate p-alkoxyaniline; under the action of nitric acid and sulfuric acid, 2, 6-dinitro-4-alkoxy phenylacetamide is generated; diazotization, namely substituting diazo group by cyano under copper powder and potassium cyanide, and performing acidic hydrolysis to generate 2, 6-dinitro-4-alkoxy benzoic acid; selectively reducing a nitro group by using sodium sulfide and ammonium chloride, carrying out diazotization reaction, and carrying out acidic hydrolysis to generate 2-hydroxy-6-nitro-4-alkoxy benzoic acid; reducing to generate the target product 2-hydroxy-6-amido-4-alkoxy benzoic acid. The chelating amphoteric collector has good collecting capacity, selectivity and low temperature resistance, and can be combined with various fatty acids to form a composite collector.
Description
Technical Field
The invention relates to a chelating amphoteric collector and a preparation method thereof, belonging to the technical field of beneficiation reagents.
Background
At present, the quantity of easily-selected iron ores is less and less, most of the iron ores have the characteristics of poor quality, impurity and fineness, and the higher iron ore concentrate grade and the higher metal recovery rate are difficult to obtain simultaneously by adopting common gravity separation and magnetic separation. In order to adapt to the change of the characteristics of iron ores, a reverse flotation process is adopted as a main method for obtaining high-grade iron ore concentrate and metal recovery rate, the core content of the process is a medicament system, and a collecting agent is also the key in the medicament system. The current poor iron ore adopts the collectors which are mostly fatty acid and modified compounds thereof, the flotation temperature of the collectors is generally 30-45 ℃, and the normal flotation temperature can be maintained by heating the collectors by a boiler. In order to obtain high-quality beneficiation effect, some distinctive collectors have been synthesized in recent years. For example, publication No. [ CN 101543805a ] proposes two oxygen-oxygen chelate type collectors of α -hydroxy fatty acids and β -hydroxy fatty acids, which are mainly used for direct flotation, and can form oxygen-oxygen chelate with mineral surface groups during flotation. Publication No. [ CN 101088623a ] proposes an ether amine cationic collector, which can reduce the kinds of chemicals and lower the flotation temperature, but has the disadvantages of high flotation froth viscosity and sensitivity to slime. In order to further improve the collecting capability and selectivity of the collecting agent, the collecting agent containing both an oxygen-oxygen chelating ring and an oxygen-nitrogen chelating ring is synthesized, meanwhile, the ether group and the phenyl group can change the dispersibility of the collecting agent, the beneficiation temperature can be obviously reduced, and the collecting agent can further improve the performance of the iron ore collecting agent.
Disclosure of Invention
The invention aims to synthesize an amphoteric collecting agent which has a novel structure and stable performance, can form two chelate rings of oxygen-oxygen and oxygen-nitrogen with activated gangue simultaneously, and has good collecting capability and selectivity so as to meet the actual requirements of reverse flotation of lean, impure and fine iron ores.
The invention provides a chelating amphoteric collector, which has the following structural general formula:
r is C5～C16Alkyl group of (1).
Further, in the above technical scheme, R is C5～C16Linear or branched alkyl groups of (1).
Further, in the above technical solution, the chelating amphoteric collector further comprises a fatty acid, and the fatty acid is selected from at least one of vegetable oleic acid, ricinoleic acid, animal oleic acid, and synthetic fatty acid.
Further, in the technical scheme, the chelating amphoteric collector is characterized in that the fatty acid accounts for 1-99% by mass, and the amphoteric collector accounts for 1-99% by mass.
The invention provides a preparation method of the chelating amphoteric collector, which comprises the following steps:
(1) p-aminophenol reacts with sodium ethoxide to generate p-aminophenol sodium, and then reacts with 1-chloroalkane to generate p-alkoxyaniline;
(2) protecting amine group by using acetic anhydride, and generating 2, 6-dinitro-4-alkoxy phenylacetamide under the action of nitric acid and sulfuric acid;
(3) acid hydrolysis, namely diazotization under the conditions of sodium nitrite and sulfuric acid, substitution of a diazo group by a cyano group under copper powder and potassium cyanide, and acid hydrolysis to generate 2, 6-dinitro-4-alkoxy benzoic acid;
(4) selectively reducing a nitro group by using sodium sulfide and ammonium chloride, carrying out diazotization reaction, and carrying out acidic hydrolysis to generate 2-hydroxy-6-nitro-4-alkoxy benzoic acid;
(5) reducing under the action of iron powder and hydrochloric acid to generate the target product 2-hydroxy-6-amido-4-alkoxy benzoic acid.
The amphoteric collecting agent provided by the invention has the characteristics of simple synthesis process, easiness in operation and the like.
Compared with the prior art, the chelating amphoteric collector has the following advantages:
(1) easy to dissolve in water and good in dispersibility;
(2) when the flotation temperature is 5 ℃, the flotation index which is 30 ℃ higher than that of other collectors can be obtained;
(3) the collecting capacity is strong, and the selectivity is high;
(4) the amount of the collecting agent can be reduced.
In the invention, during flotation, the mass percentage of the NaOH aqueous solution is 5 percent; the mass percentage of the corn starch water solution is 2 percent; the mass percentage content of the calcium oxide aqueous solution is 2 percent; the mass percentage of the chelating amphoteric collector aqueous solution is 2%.
The present invention will be further described below with reference to the synthesis method, but the present invention is not limited thereto.
Drawings
FIG. 1 is a process for preparing chelating amphoteric collector reverse flotation saddle-hill iron ore by adopting the invention.
Detailed Description
The collector for the iron ore provided by the invention is a chelating amphoteric collector, the main component of the collector is 2-hydroxy-6-amino-4-alkoxy benzoic acid, the collector contains alkyl, ether, phenyl, hydroxyl, amino and carboxyl, the length of the alkyl is C5～C16。
The preparation method of the chelating amphoteric collector provided by the invention comprises the following steps: p-aminophenol reacts with sodium ethoxide to generate p-aminophenol sodium, and then reacts with 1-chloroalkane to generate p-alkoxyaniline; protecting amine group by using acetic anhydride, and generating 2, 6-dinitro-4-alkoxy phenylacetamide under the action of nitric acid and sulfuric acid; acid hydrolysis, namely diazotization under the conditions of sodium nitrite and sulfuric acid, substitution of a diazo group by a cyano group under copper powder and potassium cyanide, and acid hydrolysis to generate 2, 6-dinitro-4-alkoxy benzoic acid; selectively reducing a nitro group by using sodium sulfide and ammonium chloride, carrying out diazotization reaction, and carrying out acidic hydrolysis to generate 2-hydroxy-6-nitro-4-alkoxy benzoic acid; reducing under the action of iron powder and hydrochloric acid to generate the target product 2-hydroxy-6-amido-4-alkoxy benzoic acid.
The invention adopts a synthesis method comprising the following steps:
(1) p-aminophenol reacts with sodium ethoxide to generate p-aminophenol sodium, and then reacts with 1-chloroalkane to generate p-alkoxyaniline;
(2) protecting amine group by using acetic anhydride, and generating 2, 6-dinitro-4-alkoxy phenylacetamide under the action of nitric acid and sulfuric acid;
(3) acid hydrolysis, namely diazotization under the conditions of sodium nitrite and sulfuric acid, substitution of a diazo group by a cyano group under copper powder and potassium cyanide, and acid hydrolysis to generate 2, 6-dinitro-4-alkoxy benzoic acid;
(4) selectively reducing a nitro group by using sodium sulfide and ammonium chloride, carrying out diazotization reaction, and carrying out acidic hydrolysis to generate 2-hydroxy-6-nitro-4-alkoxy benzoic acid;
(5) reducing under the action of iron powder and hydrochloric acid to generate the target product 2-hydroxy-6-amido-4-alkoxy benzoic acid.
The synthetic route is as follows:
example 1
Adding a certain amount of sodium ethoxide into a flask, adding equimolar p-aminophenol, adding equimolar 1-chlorohexane, refluxing for 2 hours, cooling to room temperature, adding equimolar acetic anhydride, refluxing for 1 hour, cooling, adding mixed acid in batches, reacting for 50 minutes at 56-59 ℃, cooling, pouring the reaction mixture into a separating funnel, and separating an acid layer. Cooling the organic layer to 0-2 deg.c in ice salt bath, slowly dropping cooled sodium nitrite solution, adding copper powder and potassium cyanide, heating to 67-68 deg.c, stirring for 2 hr, adding certain amount of dilute sulfuric acid and stirring for 2 hr. After cooling, the reaction mixture was poured into a separatory funnel and the acid layer was separated. Sodium sulfide and ammonium chloride are respectively added into the organic layer, the temperature is raised to 83-85 ℃, and the reaction is carried out for 2 hours under the stirring. Cooling to 0-2 deg.c in ice salt bath, dropping cooled sodium nitrite solution slowly, oscillating, adding certain amount of dilute sulfuric acid and stirring for 2 hr to produce 2-hydroxy-6-nitro-4-alkoxy benzoic acid. After cooling, the reaction mixture was poured into a separatory funnel and the acid layer was separated. Washing the organic layer with water, drying, adding a certain amount of iron powder and concentrated hydrochloric acid, heating to 82-83 ℃, and reacting for 2 hours under stirring to obtain the product 2-hydroxy-6-amino-4-hexylalkoxybenzoic acid.
The float feed mixed magnetic fine grade is 46.53 percent. In a laboratory, an XFD type single-groove flotation machine (0.75L) is used as a flotation test machine, 200g of mixed magnetic concentrate is weighed in a 0.75L flotation groove, water is added to the flotation groove to be close to the scale, and the flotation machine is started. Then, 4.5mL of NaOH aqueous solution, 11.2mL of corn starch aqueous solution, 3.5mL of calcium oxide aqueous solution and 8.9mL of collector (65% by mass of 2-hydroxy-6-amino-4-hexyloxybenzoic acid + 35% by mass of vegetable oil acid) aqueous solution are sequentially added. At 10 ℃, a one-coarse one-fine three-sweep reverse flotation separation test is carried out. Finally, flotation concentrate grade of 68.5 percent and flotation tailing grade of 89.2g and flotation tailing grade of 13.41 percent and flotation tailing weight of 64.5g are obtained.
Example 2
Adding a certain amount of sodium ethoxide into a flask, adding equimolar p-aminophenol, adding equimolar 1-chlorodecane, refluxing for 3 hours, cooling to room temperature, adding equimolar acetic anhydride, refluxing for 1 hour, cooling, adding mixed acid in batches, reacting for 50 minutes at the temperature of 58-60 ℃, cooling, pouring a reaction mixture into a separating funnel, and separating an acid layer. Cooling the organic layer to 1-2 deg.c in ice salt bath, slowly dropping cooled sodium nitrite solution, adding copper powder and potassium cyanide, heating to 68-70 deg.c, stirring for 2 hr, adding certain amount of dilute sulfuric acid and stirring for 1 hr. After cooling, the reaction mixture was poured into a separatory funnel and the acid layer was separated. Sodium sulfide and ammonium chloride are respectively added into the organic layer, the temperature is raised to 83-85 ℃, and the reaction is carried out for 2 hours under the stirring. Cooling to 1-2 ℃ by using an ice salt bath, slowly dripping the cooled sodium nitrite solution, oscillating, adding a certain amount of dilute sulfuric acid, and stirring for 1 hour to generate the 2-hydroxy-6-nitro-4-alkoxy benzoic acid. After cooling, the reaction mixture was poured into a separatory funnel and the acid layer was separated. Washing the organic layer with water, drying, adding a certain amount of iron powder and concentrated hydrochloric acid, heating to 83-85 ℃, and reacting for 2.5 hours under stirring to obtain the product 2-hydroxy-6-amino-4-decyloxy benzoic acid.
In this example, the same grade of iron ore as in example 1 was used, and 4.6mL of aqueous NaOH solution, 11.5mL of aqueous corn starch solution, 3.4mL of aqueous calcium oxide solution and 8.2mL of aqueous collector (82% by mass of 2-hydroxy-6-amino-4-hexylalkoxybenzoic acid + 18% by mass of ricinoleic acid) solution were added in this order by the same beneficiation process. At the temperature of 8 ℃, a one-coarse-one-fine-three-sweep reverse flotation separation test is carried out. Finally, flotation concentrate grade of 68.6 percent and flotation tailing grade of 92.1g and weight of 63.8g are obtained.
Example 3
Adding a certain amount of sodium ethoxide into a flask, adding equimolar p-aminophenol, adding equimolar 1-chlorododecane, refluxing for 4 hours, cooling to room temperature, adding equimolar acetic anhydride, refluxing for 1 hour, cooling, adding mixed acid in batches, reacting for 50 minutes at 56-58 ℃, cooling, pouring the reaction mixture into a separating funnel, and separating an acid layer. Cooling the organic layer to 2-3 deg.c in ice salt bath, slowly dropping cooled sodium nitrite solution, adding copper powder and potassium cyanide, heating to 66-67 deg.c, stirring for 2 hr, adding certain amount of dilute sulfuric acid and stirring for 1.5 hr. After cooling, the reaction mixture was poured into a separatory funnel and the acid layer was separated. Sodium sulfide and ammonium chloride are respectively added into the organic layer, the temperature is raised to 83-84 ℃, and the reaction is carried out for 2 hours under the stirring. Cooling to 2-3 deg.c in ice salt bath, dropping cooled sodium nitrite solution slowly, oscillating, adding certain amount of dilute sulfuric acid and stirring for 1.5 hr to produce 2-hydroxy-6-nitro-4-alkoxy benzoic acid. After cooling, the reaction mixture was poured into a separatory funnel and the acid layer was separated. Washing the organic layer with water, drying, adding a certain amount of iron powder and concentrated hydrochloric acid, heating to 82-83 ℃, and reacting for 2 hours under stirring to obtain the product 2-hydroxy-6-amino-4-dodecyloxybenzoic acid.
In this example, the same grade of iron ore as in example 1 was used, and 4.7mL of aqueous NaOH solution, 11.6mL of aqueous corn starch solution, 3.9mL of aqueous calcium oxide solution and 9.3mL of aqueous collector (91% by mass of 2-hydroxy-6-amino-4-hexylalkoxybenzoic acid + 9% by mass of synthetic fatty acid) solution were sequentially added by the same beneficiation process. At 16 ℃, a one-coarse one-fine three-sweep reverse flotation separation test is carried out. Finally, the flotation concentrate grade is 67.9 percent, the weight of the flotation concentrate grade is 102.1g, the flotation tailing grade is 12.52 percent, and the weight of the flotation tailing grade is 70.2 g.
Claims (5)
1. A chelating amphoteric collector is characterized in that the collector has the following structural general formula:
r is C5～C16Alkyl group of (1).
2. The chelating amphoteric collector according to claim 1, characterized in that: r is a group containing C5～C16Linear or branched alkyl groups of (1).
3. The preparation method of the chelating amphoteric collector according to claim 1, characterized by comprising the steps of:
(1) p-aminophenol reacts with sodium ethoxide to generate p-aminophenol sodium, and then reacts with 1-chloroalkane to generate p-alkoxyaniline;
(2) protecting amine group by using acetic anhydride, and generating 2, 6-dinitro-4-alkoxy phenylacetamide under the action of nitric acid and sulfuric acid;
(3) acid hydrolysis, namely diazotization under the conditions of sodium nitrite and sulfuric acid, substitution of a diazo group by a cyano group under copper powder and potassium cyanide, and acid hydrolysis to generate 2, 6-dinitro-4-alkoxy benzoic acid;
(4) selectively reducing a nitro group by using sodium sulfide and ammonium chloride, carrying out diazotization reaction, and carrying out acidic hydrolysis to generate 2-hydroxy-6-nitro-4-alkoxy benzoic acid;
(5) reducing under the action of iron powder and hydrochloric acid to generate the target product 2-hydroxy-6-amido-4-alkoxy benzoic acid.
4. A composition consisting of the chelating amphoteric collector of claim 1 or 2 and a fatty acid selected from at least one of vegetable oleic acid, ricinoleic acid, animal oleic acid or synthetic fatty acids.
5. The composition according to claim 4, wherein the fatty acid is 1-99% by mass, and the amphoteric collector is 1-99% by mass.
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| CN114276276A (en) * | 2021-07-05 | 2022-04-05 | 天津天宝翔科技有限公司 | Chelating rare earth collecting agent and preparation method thereof |
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| US3890222A (en) * | 1974-06-12 | 1975-06-17 | Vojislav Petrovich | Froth flotation method for recovery of minerals by means of alkali or ammonium alkyl alkylaryl, and aryl sulfinates as froth flotation reagents |
| US5015415A (en) * | 1990-06-27 | 1991-05-14 | Goze Jean M | N,N-disubstituted phthalamic acids and their ammonium salts, and their uses thereof as surfactants, emulsifiers, and conditioning agents in shampoos |
| IL133121A (en) * | 1998-12-08 | 2004-06-20 | Dow Agrosciences Llc | Process for making 2-alkyl-3-hydroxybenzoic acids |
| CN1169775C (en) * | 2001-01-09 | 2004-10-06 | 中南大学 | Poly-basic aromatic carboxylic acid for flotation and its preparing method |
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