CN110898996B - Fluorite ore collecting agent and preparation method and application thereof - Google Patents
Fluorite ore collecting agent and preparation method and application thereof Download PDFInfo
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- CN110898996B CN110898996B CN201811082200.0A CN201811082200A CN110898996B CN 110898996 B CN110898996 B CN 110898996B CN 201811082200 A CN201811082200 A CN 201811082200A CN 110898996 B CN110898996 B CN 110898996B
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 239000010436 fluorite Substances 0.000 title claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- -1 fatty acid ester Chemical class 0.000 claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 40
- 239000000194 fatty acid Substances 0.000 claims description 40
- 229930195729 fatty acid Natural products 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000004665 fatty acids Chemical class 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000002250 absorbent Substances 0.000 claims description 19
- 230000002745 absorbent Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 claims description 13
- KPFSGNRRZMYZPH-UHFFFAOYSA-M potassium;2-chloroacetate Chemical compound [K+].[O-]C(=O)CCl KPFSGNRRZMYZPH-UHFFFAOYSA-M 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000006473 carboxylation reaction Methods 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000007112 amidation reaction Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910003202 NH4 Inorganic materials 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 125000005466 alkylenyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000005188 flotation Methods 0.000 abstract description 33
- 230000008014 freezing Effects 0.000 abstract description 4
- 238000007710 freezing Methods 0.000 abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 229910052500 inorganic mineral Inorganic materials 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 8
- 229910001950 potassium oxide Inorganic materials 0.000 description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 7
- 239000005642 Oleic acid Substances 0.000 description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229920000263 Rubber seed oil Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000001094 effect on targets Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- BOWVQLFMWHZBEF-KTKRTIGZSA-N oleoyl ethanolamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCO BOWVQLFMWHZBEF-KTKRTIGZSA-N 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- RPOHBMAQTOJHKM-UHFFFAOYSA-M sodium;2-chloropropanoate Chemical compound [Na+].CC(Cl)C([O-])=O RPOHBMAQTOJHKM-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a fluorite mine collecting agent, which contains a formula (I)
) A compound of the structure
(ii) a Wherein: r1、R2Is C1~C20An alkyl, alkenyl or aryl group of (a); n is 1-10, M is H, Na, K or NH4. The invention also discloses a preparation method of the fluorite ore collecting agent. The fluorite ore collecting agent has the characteristics of good water solubility, good dispersibility, strong freezing resistance and the like, is good in selection and strong in collecting capability when being used as a fluorite ore flotation collecting agent, and still has high flotation efficiency at the temperature lower than 10 ℃.
Description
Technical Field
The invention belongs to the field of mineral flotation, and relates to a novel fluorite ore collecting agent and a preparation method thereof.
Background
Fluorite ore is the main source of fluorine in various industrial fluorine products at present, is used as an important non-metallic mineral raw material, and has a very close relationship with the development of national economy in China. Although the total amount of fluorite mineral resources is rich in China, poor ores are rich and few ores are rich, and along with continuous mining, the composition of ores is increasingly complex, and the properties of symbiotic minerals and fluorites are very similar, so that the beneficiation difficulty of the fluorite ores is increasingly high. In addition, in recent years, higher requirements are placed on the purity of fluorite concentrates, and the more efficient flotation technology and method are forced to be found. For the development of fluorite ore, besides the improvement of the flotation process, another important way is to research and develop a more efficient collecting agent.
The collecting agent mainly used in the domestic fluorite ore dressing production is mainly fatty acid, and the fatty acid and the saponified product thereof can effectively separate target minerals and gangue minerals due to the carboxyl functional groups. Since the higher fatty acid is solid at normal temperature, insoluble in water and inconvenient to use, oleic acid and its modified product and oxidized paraffin soap are currently the most commonly used in industrial flotation of fluorite ore. Chinese patent (publication No. CN101712014A) discloses a method for sectional flotation of single fluorite ore with multiple impurities by using alkaline oleic acid, neutral oleic acid and acidic oleic acid respectively; chinese patent (publication number: CN104475263A) discloses a combined collector with fatty acid as a main component; chinese patent (publication No. CN104525380A) discloses a collector prepared from rubber seed oil for flotation of fluorite mine tailings.
Oleic acid and oxidized paraffin soap are used as collecting agents in fluorite ores because of strong collecting capacity and low price. However, the collecting agent has obvious defects in flotation, such as low selectivity, low freezing resistance, layering after long-term storage, and poor water solubility and dispersibility at normal temperature, so that the collecting agent needs to be emulsified or the flotation pulp needs to be heated (maintained at 40 ℃), and the heating flotation not only increases energy consumption, but also brings inconvenience to production operation and management. Thus. The research and development of the low-temperature and high-efficiency collecting agent have important significance.
At present, the amide ether carboxylic acid compounds are reported, mainly used as a mild surfactant and used in the field of daily chemical industry, and the amide ether carboxylic acid compounds as fluorite ore flotation collectors are not reported. The amide ether carboxylic acid compound has good performances of dispersing, foaming, foam assisting, washing and the like, and has mildness and safety. French patent (publication: FR1875917) combines alkylamidoether carboxylic acids with fatty esters as a detergent cosmetic; chinese patent (publication No. CN1441662A) discloses a self-foaming cleansing gel consisting of an amidoethercarboxylic acid in combination with other anionic surfactants; chinese patent publication No. CN102120928A discloses a chemical mechanical abrasive in which amide ether carboxylic acid is an important component. The amide ether carboxylic acid is prepared by carboxylating alkanolamide or alkanolamide polyoxyethylene ether, but the purity of the compound in the fields is higher, so the synthesis process is more complicated, the synthesis conditions are harsher, and the purification is needed after the synthesis. If the amido ether carboxylic acid compounds are used for the fluorite ore collecting agent, fatty acid can be used as an initial raw material, fatty acid monoethanolamide is synthesized firstly, and then the fatty acid monoethanolamide is carboxylated to obtain the fluorite ore collecting agent.
Disclosure of Invention
The invention aims to provide a carboxylic acid compound with amide groups and ether groups, which is used as a fluorite ore flotation collector and has good selectivity, water solubility and dispersibility, aiming at the defects of poor selectivity, poor dispersibility, poor freezing resistance and the like of oleic acid and oxidized paraffin which are common collectors for fluorite ores at present.
Another object of the present invention is to provide a process for producing an amidoethercarboxylic acid-based compound, which is simple in procedure, easy to operate and low in cost.
Still another object of the invention is to provide the application of the amide ether carboxylic acid compound as a fluorite ore flotation collector.
The object of the present invention is achieved by the following means. The invention relates to a fluorite mine collecting agent, which is characterized in that the collecting agent contains a compound with a structure shown in a formula (I);
wherein: r1、R2Is C1～C20An alkyl, alkenyl or aryl group of (a); n is 1-10, M is H, Na, K or NH4。R1Preferably C10～C18Alkyl or alkenyl of R2Preferably methyl, ethyl or phenyl. n is preferably 2.
The invention also provides a preparation method of the fluorite ore collecting agent in the technical scheme, which is characterized in that the synthesis steps of the compound with the structure shown in the formula (I) are as follows:
(1) carrying out amidation reaction on fatty acid or fatty acid ester and alcohol amine;
(2) and (2) performing a carboxylation reaction on the product obtained in the step (1) and sodium chloroacetate, potassium chloroacetate, ammonium chloroacetate or p-chlorobenzoic acid under the action of a catalyst to obtain the product.
The catalyst in step (2) is preferably potassium hydroxide or sodium hydroxide. It is preferable to add a water-carrying agent or an absorbent in the step (2) to remove the water produced by the reaction. The water-carrying agent is preferably one of benzene, toluene or xylene; the water absorbent is preferably one of soda lime, anhydrous calcium chloride or anhydrous sodium sulfate.
The invention also discloses the application of the fluorite ore collecting agent in the technical scheme, which is characterized in that the compound with the structure shown in the formula (I) is used as the fluorite ore collecting agent in fluorite ore. The compound with the structure shown in the formula (I) is used as a fluorite ore collecting agent alone or is combined with other fluorite ore collecting agents.
The compound with the structure shown in the formula (I) provided by the invention is an amide ether carboxylic acid compound. As mentioned above, the amide ether carboxylic acid compound can be obtained by performing amidation reaction on fatty acid or fatty acid ester and alcohol amine to obtain an intermediate alcohol amide compound, and performing carboxylation reaction on the intermediate and sodium chloroacetate, potassium chloroacetate, ammonium chloroacetate or p-chlorobenzoic acid under the action of a catalyst sodium hydroxide or strong potassium oxide. In a preferred scheme, the molar ratio of the fatty acid to the alcohol amine is preferably 1: 1; the molar ratio of the alcohol amide compound to the sodium chloroacetate, the potassium chloroacetate, the ammonium chloroacetate or the p-chlorobenzoic acid is 1: 1; the molar ratio of the alcohol amide compound to the sodium hydroxide or the strong potassium oxide is 1: 2. Water carrying agent or absorbent is added in the carboxylation reaction to remove water generated in the reaction, so that the reaction yield can be improved.
The method for preparing the compound amide ether carboxylic acid represented by the formula (I) preferably comprises the following specific steps:
(1) synthesis of intermediate alcohol amide compound: adding fatty acid into a reaction container, raising the temperature of the reactor to 160-180 ℃, adding alcohol amine into a reaction system, and reacting for 6-8 hours at the temperature. Wherein the molar ratio of the fatty acid to the alcohol amine is 1: 1.
(2) Carboxylation reaction of alcohol amide compound: sequentially adding fatty acid monoethanolamide, a catalyst and a water-carrying agent or a water absorbent into a reaction container, adding sodium chloroacetate, potassium chloroacetate or ammonium chloroacetate under stirring, and reacting at 50-80 ℃ for 3-5 hours. Wherein the molar ratio of the fatty acid monoethanolamide to the sodium chloroacetate and the potassium chloroacetate or the ammonium chloroacetate is 1:1, the catalyst is sodium hydroxide or strong potassium oxide, and the molar ratio of the fatty acid monoethanolamide to the sodium hydroxide or the strong potassium oxide is 1: 2.
(3) And (3) post-treatment: if the water-carrying agent is used in the reaction, the water-carrying agent is removed by reduced pressure distillation after the reaction is finished; if the absorbent is used in the reaction, the absorbent is filtered off when the reaction is finished.
Compared with the prior art, the invention has the following advantages:
according to the invention, the amide ether carboxylic acid compound is used for the fluorite ore flotation collector for the first time, carboxyl and amide groups in the compound molecule have a synergistic adsorption effect on target minerals, the collection capability on the target minerals can be improved, and the introduction of the ether group into the compound molecule is beneficial to improving the hydrophilicity and the dispersibility of the compound molecule, so that the collector is suitable for low-temperature flotation. Compared with the defects of low fatty acid separation, poor dispersibility, weak freezing resistance, need of heating flotation and the like in the prior art, the amido ether carboxylic acid collector disclosed by the invention has the advantages of good water solubility, easiness in dispersion in flotation pulp, convenience in use, good selectivity to target ores, capability of performing flotation at normal temperature or even low temperature and capability of reducing the ore dressing cost. In addition, the invention provides a preparation method of the amido ether carboxylic acid collector, which has the advantages of low cost, simple flow and easy operation.
Drawings
FIG. 1 is an infrared spectrum of sodium oleic monoethanolamide ether carboxylate;
FIG. 2 is an infrared spectrum of sodium laureth carboxylate;
fig. 3 is a flow diagram of a flotation process for fluorite ore.
Detailed Description
The invention is further illustrated by, but is not limited to, the following examples. All parts and percentages in the examples are by mass unless otherwise specified.
Example 1, a fluorite ore collector, which contains a compound having a structure represented by formula (I);
wherein: r1、R2Is C1～C20An alkyl, alkenyl or aryl group of (a); n is 1-10, M is H, Na, K or NH4。
Example 2, a fluorite ore collector, which contains a compound having a structure represented by formula (I);
R1is C10～C18Alkyl or alkenyl of R2Is methyl, ethyl or phenyl; n is 2.
Example 3, the method for preparing a fluorite ore collector described in example 1 or 2, the compound having the structure represented by formula (I) is synthesized as follows:
(1) carrying out amidation reaction on fatty acid or fatty acid ester and alcohol amine;
(2) and (2) performing a carboxylation reaction on the product obtained in the step (1) and sodium chloroacetate, potassium chloroacetate, ammonium chloroacetate or p-chlorobenzoic acid under the action of a catalyst to obtain the product.
In the step (2), the catalyst is potassium hydroxide or strong sodium oxide; and (3) simultaneously adding a water-carrying agent or an absorbent in the step (2) to remove water generated in the reaction. The water-carrying agent is one of benzene, toluene or xylene; the water absorbent is one of soda lime, anhydrous calcium chloride or anhydrous sodium sulfate.
Example 4, the method for preparing a fluorite ore collector described in example 1 or 2, the compound having the structure represented by formula (I) is synthesized as follows:
(1) synthesis of intermediate alcohol amide compound: adding fatty acid or fatty acid ester into a reaction vessel, raising the temperature of the reactor to 160 ℃, adding alcohol amine into the reaction system, and reacting for 6 hours at the temperature; wherein the molar ratio of the fatty acid to the alcohol amine is 1: 1;
(2) carboxylation reaction of alcohol amide compound: sequentially adding fatty acid monoethanolamide, a catalyst and a water-carrying agent or a water absorbent into a reaction container, adding sodium chloroacetate, potassium chloroacetate or ammonium chloroacetate under stirring, and reacting at 50 ℃ for 5 hours; wherein the molar ratio of the fatty acid monoethanolamide to the sodium chloroacetate and the potassium chloroacetate or the ammonium chloroacetate is 1:1, the catalyst is sodium hydroxide or strong potassium oxide, and the molar ratio of the fatty acid monoethanolamide to the sodium hydroxide or the strong potassium oxide is 1: 2.
(3) And (3) post-treatment: when the water-carrying agent is used in the reaction, the water-carrying agent is removed by reduced pressure distillation after the reaction is finished; when the absorbent is used in the reaction, the absorbent is filtered off when the reaction is finished.
Example 5, the method for preparing a fluorite ore collector described in example 1 or 2, the compound having the structure represented by formula (I) is synthesized as follows:
(1) synthesis of intermediate alcohol amide compound: adding fatty acid or fatty acid ester into a reaction vessel, raising the temperature of the reactor to 180 ℃, adding alcohol amine into the reaction system, and reacting for 8 hours at the temperature; wherein the molar ratio of the fatty acid to the alcohol amine is 1: 1;
(2) carboxylation reaction of alcohol amide compound: sequentially adding fatty acid monoethanolamide, a catalyst and a water-carrying agent or a water absorbent into a reaction container, adding sodium chloroacetate, potassium chloroacetate or ammonium chloroacetate under stirring, and reacting at 80 ℃ for 3 hours; wherein the molar ratio of the fatty acid monoethanolamide to the sodium chloroacetate and the potassium chloroacetate or the ammonium chloroacetate is 1:1, the catalyst is sodium hydroxide or strong potassium oxide, and the molar ratio of the fatty acid monoethanolamide to the sodium hydroxide or the strong potassium oxide is 1: 2.
(3) And (3) post-treatment: when the water-carrying agent is used in the reaction, the water-carrying agent is removed by reduced pressure distillation after the reaction is finished; when the absorbent is used in the reaction, the absorbent is filtered off when the reaction is finished.
The prepared compound with the structure shown in the formula (I) is used as a fluorite ore collecting agent in fluorite ore. The compound with the structure shown in the formula (I) is used as a fluorite ore collecting agent alone or is combined with other fluorite ore collecting agents.
Example 6, preparation experiment of sodium oleate monoethanolamide ether carboxylate:
282 parts of oleic acid are introduced into a reactor with stirring, the temperature is raised to 160 ℃ and 61 parts of monoethanolamine are added to the reactor and reacted at 160 ℃ for 7 hours. And (3) reducing the temperature of the reactor by 60 ℃, adding 80 parts of sodium hydroxide, 0.5L of toluene and 116.5 parts of sodium chloroacetate into the reactor, reacting for 3 hours at 60 ℃, and removing the toluene by reduced pressure distillation after the reaction is finished to obtain the sodium oleic monoethanolamide ether carboxylate. The IR spectrum of the sodium oleic monoethanolamide ether carboxylate is shown in FIG. 1.
Example 7, preparation experiment of sodium laureth carboxylate:
200 parts of lauric acid was charged into a reactor equipped with a stirring device, the temperature was raised to 170 ℃, 61 parts of monoethanolamine was added to the reactor, and the reaction was carried out at 170 ℃ for 8 hours. And (3) reducing the temperature of the reactor by 60 ℃, adding 80 parts of sodium hydroxide, 0.5L of toluene and 116.5 parts of sodium chloroacetate into the reactor, reacting for 3 hours at 60 ℃, and removing the toluene by reduced pressure distillation after the reaction is finished to obtain the sodium laureth glycolate. The IR spectrum of the sodium laureth carboxylate is shown in FIG. 2.
Example 8 Replacing the sodium chloroacetate of example 6 for sodium chloropropionate can yield R2Sodium oleic monoethanolamide ether carboxylate which is ethyl.
Example 9 replacement of sodium chloroacetate from example 6 to p-chlorobenzoic acid affords R2Of phenyl radicalsOleic acid monoethanolamide ether carboxylic acid.
Example 10, preparation of mixed collector:
adding 50 parts of oxidized paraffin soap into a reactor with a stirring device, heating to the temperature of more than 80 ℃, adding 50 parts of the oleic acid monoethanolamide ether carboxylic acid sodium synthesized in the example 6, and uniformly stirring to obtain the mixed collector PF-55.
Example 11: flotation test of fluorite ore in Zhejiang at different temperatures
CaF in raw ore of fluorite ore in Zhejiang2The 36.20% grade flotation process flow chart is shown in figure 3. Grinding fluorite ore to-200 meshes accounting for-65% by using an ore grinding machine, adding water for mixing until the concentration of ore pulp is 30%, adding 1.5kg/t of sodium carbonate for mixing for 1-2 minutes, adding 1.0kg/t of water glass for mixing for 1-2 minutes, adding 0.6kg/t of collecting agent for mixing for 1-2 minutes, and performing primary roughing operation at 25 ℃ and 8 ℃. The flotation results of different collectors at 25 ℃ are shown in table 1, and the flotation results of different collectors at 8 ℃ are shown in table 2.
TABLE 1 flotation results for different collectors at 25 deg.C flotation temperature
TABLE 2 flotation results for different collectors at a flotation temperature of 8 deg.C
As can be seen from tables 1 and 2, the flotation performance of the three collectors prepared by the method is superior to that of the common collector sodium oleate, and the grade and recovery rate of the obtained concentrate are improved under the same use amount of the collectors. Comparing table 1 and table 2, when the flotation is carried out at low temperature, the flotation performance of the two types of collector of the amide ether carboxylic acid is not changed greatly, the combined collector of the amide ether carboxylic acid is added, the upper amount is reduced, the recovery rate is reduced by 2.97%, the flotation effect of the collector sodium oleate is poor, the collecting performance and the sorting performance are reduced, and the recovery rate is reduced by 28.07%. The amido ether carboxylic acid collector can be used for low-temperature flotation of fluorite ore.
Claims (9)
1. The application of the compound used as the fluorite ore collector is characterized in that the compound is prepared by the following formula (A)
) The compound with the structure is used as a fluorite ore collecting agent;
（
）
wherein: r1、R2Is C1~C20An alkyl, alkenyl or aryl group of (a); n is 1-10, M is H, Na, K or NH4。
2. Use according to claim 1, characterized in that: r1Is C10~C18Alkyl or alkenyl of R2Is methyl, ethyl or phenyl.
3. Use according to claim 1 or 2, characterized in that: n is 2.
4. Use according to claim 1, characterized in that the formula (la), (lb) and (lb), (lb) and (lb) as (lb) in (lb) a (lb)
) The compound with the structure is used as a fluorite ore collecting agent independently or is combined with other fluorite ore collecting agents.
5. A method of preparing a fluorite ore collector for use according to claim 1, wherein the collector is of the formula (I), (II), (III), (IV), (
) The synthesis steps of the compound with the structure are as follows:
(1) carrying out amidation reaction on fatty acid or fatty acid ester and alcohol amine;
(2) and (2) performing a carboxylation reaction on the product obtained in the step (1) and sodium chloroacetate, potassium chloroacetate, ammonium chloroacetate or p-chlorobenzoic acid under the action of a catalyst to obtain the product.
6. The method of claim 5, wherein: in the step (2), the catalyst is potassium hydroxide or sodium hydroxide.
7. The method of claim 5, wherein: and (3) adding a water carrying agent or a water absorbent in the step (2) to remove water generated in the reaction.
8. The method of claim 7, wherein: the water-carrying agent is one of benzene, toluene or xylene; the water absorbent is one of soda lime, anhydrous calcium chloride or anhydrous sodium sulfate.
9. The preparation method according to claim 5, characterized by comprising the following specific steps:
(1) synthesis of intermediate alcohol amide compound: adding fatty acid or fatty acid ester into a reaction container, heating the temperature of the reactor to 160-180 ℃, adding alcohol amine into the reaction system, and reacting for 6-8 hours at the temperature; wherein the molar ratio of the fatty acid to the alcohol amine is 1: 1;
(2) carboxylation reaction of alcohol amide compound: sequentially adding fatty acid monoethanolamide, a catalyst and a water-carrying agent or a water absorbent into a reaction container, adding sodium chloroacetate and potassium chloroacetate or ammonium chloroacetate under stirring, and reacting at 50-80 ℃ for 3-5 hours; wherein the molar ratio of the fatty acid monoethanolamide to the sodium chloroacetate and the potassium chloroacetate or the ammonium chloroacetate is 1:1, the catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the fatty acid monoethanolamide to the sodium hydroxide or the potassium hydroxide is 1: 2;
(3) and (3) post-treatment: when the water-carrying agent is used in the reaction, the water-carrying agent is removed by reduced pressure distillation after the reaction is finished; when the water absorbent is used in the reaction, the water absorbent is filtered off when the reaction is finished.
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