CN115090422A - Amino acid type collecting agent and preparation method and application thereof - Google Patents
Amino acid type collecting agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN115090422A CN115090422A CN202210692133.4A CN202210692133A CN115090422A CN 115090422 A CN115090422 A CN 115090422A CN 202210692133 A CN202210692133 A CN 202210692133A CN 115090422 A CN115090422 A CN 115090422A
- Authority
- CN
- China
- Prior art keywords
- amino acid
- acid type
- collecting agent
- ester hydrochloride
- diethyl ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005188 flotation Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 150000005375 primary alkyl halides Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 235000001014 amino acid Nutrition 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- AJOXZAAREAYBQR-RGMNGODLSA-N diethyl (2s)-2-aminobutanedioate;hydrochloride Chemical compound Cl.CCOC(=O)C[C@H](N)C(=O)OCC AJOXZAAREAYBQR-RGMNGODLSA-N 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- GLFVNTDRBTZJIY-UHFFFAOYSA-N diethyl 2-aminopropanedioate;hydron;chloride Chemical compound Cl.CCOC(=O)C(N)C(=O)OCC GLFVNTDRBTZJIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 229940024606 amino acid Drugs 0.000 description 53
- 235000010755 mineral Nutrition 0.000 description 15
- 239000010445 mica Substances 0.000 description 10
- 229910052618 mica group Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 8
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 8
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 7
- 229910052627 muscovite Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 239000010433 feldspar Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 2
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 2
- GCDPERPXPREHJF-UHFFFAOYSA-N 1-iodododecane Chemical compound CCCCCCCCCCCCI GCDPERPXPREHJF-UHFFFAOYSA-N 0.000 description 2
- FKUQOQPBCHJHAP-UHFFFAOYSA-N 1-iodoundecane Chemical compound CCCCCCCCCCCI FKUQOQPBCHJHAP-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- QYFRTHZXAGSYGT-UHFFFAOYSA-L hexaaluminum dipotassium dioxosilane oxygen(2-) difluoride hydrate Chemical compound O.[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O QYFRTHZXAGSYGT-UHFFFAOYSA-L 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940072033 potash Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229910052637 diopside Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000001308 synthesis method 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
Abstract
The invention belongs to the technical field of flotation reagents, and particularly relates to an amino acid type collecting agent and a preparation method and application thereof. The amino acid type collecting agent provided by the invention comprises raw materials of primary alkyl halide, tetrahydrofuran, amino acid diethyl ester hydrochloride, pyridine anhydrous ethanol and alkali. The preparation method of the amino acid type collecting agent comprises the following steps: taking equimolar primary alkyl halide and amino acid diethyl ester hydrochloride, respectively dissolving the equimolar primary alkyl halide and the amino acid diethyl ester hydrochloride in tetrahydrofuran and pyridine, uniformly mixing the two, stirring for 12-18 hours at 40-60 ℃ to obtain a suspension, centrifuging the suspension to obtain a white paste body, and washing the white paste body for 4-6 times by using deionized water; and (3) uniformly mixing the white paste body and alkali in absolute ethyl alcohol, and stirring for 20-30 minutes to obtain the collecting agent. The amino acid type collector has the characteristics of near neutral optimal pH value in ore pulp, strong collecting capacity, good selectivity, small medicament dosage, low temperature resistance and the like, and has good market popularization prospect.
Description
Technical Field
The invention belongs to the technical field of flotation reagents, and particularly relates to an amino acid type collecting agent and a preparation method and application thereof.
Background
The utilization of the tailings is an effective way for enlarging the source of raw materials and reducing the discharge amount of solid tailings, and the economic value of the tailings is not inferior to the discovery of one or more new ore deposits. Taking molybdenum tailings as an example, the tailings mainly consist of co-associated metals and nonmetallic minerals, and for molybdenum tailings with low co-associated metal mineral content, the current recovery process technology and equipment have difficulties which are difficult to overcome, and the separate recovery of metallic minerals is not always economically feasible. Therefore, the recovery of the nonmetallic minerals in the tailings is of great significance for improving the comprehensive utilization rate of resources and improving the quality and variety of mineral products.
There are various recyclable nonmetallic minerals in tailings, and nonmetallic minerals in tailings in different regions are different, but silicate or carbonate is mainly used. At present, fatty acid and fatty amine are commonly used as collecting agents to float nonmetallic minerals in tailings, but the solubility and the dispersibility of the two are poor at normal temperature, and particularly in the low-temperature environment in winter, heating is often needed to ensure the smooth operation of the flotation process; meanwhile, in order to overcome the defect of poor selectivity of a single collecting agent, the collecting agent and the collecting agent are often combined for use, although the collecting agent shows strong selectivity, the reagent system is complex, a good flotation effect is only shown in a laboratory, and the collecting agent is not applied to actual production.
The amino acid collecting agent is used for improving the traditional fatty acid and fatty amine collecting agent, and an amino group and a carboxyl group are simultaneously introduced into a fatty chain through a chemical modification means, so that the acid-base property of ore pulp can be flexibly adjusted in the flotation process, the ore pulp has the dual properties of a cation or anion collecting agent, and the good selectivity and the good collecting property of target minerals are shown. Meanwhile, due to the introduction of a large number of polar groups, the solubility and the dissociation degree of the collecting agent in water are enhanced, the ionic activity of the collecting agent is improved, and the low-temperature resistance of the amino acid collecting agent is further enhanced. However, the types of amino acid collectors developed at present are few, most of the amino acid collectors are synthesized by a methyl acrylate method, an acrylic acid method, an acrylonitrile method and other methods, and the limitation of the synthesis method results in single raw material source, so that the development of the amino acid collectors is greatly limited. A novel synthesis way is searched, the source of product raw materials is enlarged, and the development of a novel amino acid collecting agent becomes a hotspot of current research.
Disclosure of Invention
The purpose of the invention is: an amino acid type collector is provided. The collecting agent is convenient to use, does not need to be dispersed in acid, alkali or non-polar oil, and has the characteristics of good selectivity, strong collecting capacity and small medicament dosage. The invention also provides a preparation method and application thereof.
The general structural formula of the amino acid type collecting agent is shown as the following formula (I):
in the formula (I), n1 is 7-11; n2 is 0-1; m is Li, Na or K;
the amino acid type collector disclosed by the invention comprises the following raw materials in parts by mole:
wherein:
the structural general formula of the primary alkyl halide is shown as the formula (II):
CH 3 -(CH 2 ) n -X, formula (II);
in the formula (II), n is 7-11; x is Cl, Br or I.
The amino acid diethyl ester hydrochloride is one of aspartic acid diethyl ester hydrochloride or aminomalonic acid diethyl ester hydrochloride.
The alkali is one of lithium hydroxide, sodium hydroxide or potassium hydroxide.
The molar part ratio of the primary alkyl halide to the amino acid diethyl ester hydrochloride is 1: 1.
The preparation method of the amino acid type collecting agent comprises the following steps:
(1) weighing primary alkyl halide, tetrahydrofuran, amino acid diethyl ester hydrochloride, pyridine, absolute ethyl alcohol and alkali according to the molar parts;
(2) adding tetrahydrofuran into the primary alkyl halide and mixing evenly;
(3) adding pyridine into amino acid diethyl ester hydrochloride and uniformly mixing;
(4) uniformly mixing the solution obtained in the step (2) and the solution obtained in the step (3), and stirring to obtain a suspension;
(5) centrifuging the suspension obtained in the step (4) to obtain a white paste body, and washing the white paste body;
(6) and (3) adding alkali into the white paste obtained in the step (5), taking absolute ethyl alcohol as a solvent, and stirring for 20-30 minutes to obtain a white solid, namely the amino acid type collecting agent.
Wherein:
stirring for 12-18 hours at 40-60 ℃ in the step (4) to obtain suspension.
And (5) washing the white paste body for 4-6 times by using deionized water.
The application of the amino acid type collecting agent is mainly applied to enrichment and recovery of non-metal minerals in tailings, the dosage range of the amino acid type collecting agent can be flexibly adjusted according to different target mineral contents, and the dosage of the amino acid type collecting agent is generally 200-800 g added in each ton of flotation tailings.
Compared with the prior art, the invention has the following beneficial effects:
(1) the amino acid type collector is a white solid at normal temperature, is convenient to use, does not need to be dispersed in acid, alkali or non-polar oil, and has the advantages of good selectivity, strong collecting capacity, small medicament consumption and the like.
(2) The preparation method of the amino acid type collecting agent is simple in process and easy for industrial large-scale production.
(3) The application of the amino acid type collecting agent disclosed by the invention is applied to enrichment and recovery of non-metal minerals in tailings, and the amino acid type collecting agent has the characteristics of strong collecting capability, good selectivity, small medicament dosage, low temperature resistance and the like, and has a good market popularization prospect, and the most suitable pH value of the amino acid type collecting agent in ore pulp is close to neutral.
Drawings
FIG. 1 is a scheme for the synthesis of the amino acid type collector prepared in example 1;
FIG. 2 is an infrared spectrum of an amino acid type collector prepared in example 1;
FIG. 3 is a process flow diagram of flotation of muscovite in molybdenum tailings using example 1;
FIG. 4 is a process flow diagram of flotation of potassium feldspar in gold tailings in application example 2;
fig. 5 is a process flow diagram of the application example 3 for flotation of mica in iron tailings.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The amino acid type collector described in this example 1 comprises the following raw materials, by mole:
the general structural formula of the amino acid type collector described in this example 1 is shown as the following formula (I):
in formula (I), n1 ═ 7; n2 ═ 1; m is Na.
The preparation method of the amino acid type collector described in this example 1 consists of the following steps:
adding 20 parts of tetrahydrofuran into 1 part of 1-chlorooctane according to molar parts, adding 20 parts of pyridine into 1 part of diethyl aspartate hydrochloride, uniformly mixing the tetrahydrofuran solution of 1-chlorooctane and the pyridine solution of diethyl aspartate hydrochloride, stirring at 40 ℃ for 12 hours to obtain a suspension, centrifuging the suspension to obtain a white paste body, washing the white paste body for 4 times by using deionized water, adding 2 parts of sodium hydroxide into the washed white paste body, and stirring for 20 minutes by using 10 parts of absolute ethyl alcohol as a solvent to obtain the amino acid type collector.
The synthesis scheme of the amino acid type collecting agent prepared in the example 1 is shown in the attached figure 1; infrared spectroscopy was carried out on the amino acid type collector prepared in example 1 and the resulting infrared spectrum is shown in figure 2, which is 3302.57cm -1 ，1291.52cm -1 The stretching vibration absorption peak of N-H, C-N in secondary amine is 2918.88cm -1 ，2894.72cm -1 is-CH 3 、-CH 2 The antisymmetric telescopic vibration absorption peak of the medium C-H; 1592.95cm -1 、1439.07cm -1 In the carboxyl group>The antisymmetric and symmetric stretching vibration absorption peak of C ═ O shows that 1-chlorooctane and aspartic acid diethyl ester hydrochloride have chemical reaction, and the amino acid type collecting agent in the example 1 is successfully prepared.
Example 2
The amino acid type collector described in this example 2 comprises the following raw materials, by mole:
the general structural formula of the amino acid type collector described in this example 2 is shown in the following formula (I):
formula (I) wherein n1 is 9; n2 ═ 1; m is K.
The preparation method of the amino acid type collector described in this example 2 consists of the following steps:
adding 30 parts of tetrahydrofuran into 1 part of 1-bromodecane according to molar parts, adding 30 parts of pyridine into 1 part of diethyl aspartate hydrochloride, uniformly mixing the tetrahydrofuran solution of 1-bromodecane and the pyridine solution of diethyl aspartate hydrochloride, stirring at 50 ℃ for 18 hours to obtain a suspension, centrifuging the suspension to obtain a white paste, washing the white paste with deionized water for 5 times, adding 2 parts of potassium hydroxide into the washed white paste, and stirring for 25 minutes by using 10 parts of absolute ethyl alcohol as a solvent to obtain the amino acid type collector.
Example 3
The amino acid type collector described in this example 3, in terms of mole parts, includes the following components:
the general structural formula of the amino acid type collector described in this example 3 is shown in the following formula (I):
formula (I) wherein n1 is 11; n2 ═ 1; m is Na.
The preparation method of the amino acid type collector described in this example 3 consists of the following steps:
adding 25 parts of tetrahydrofuran into 1 part of 1-iodododecane, adding 25 parts of pyridine into 1 part of diethyl aspartate hydrochloride, uniformly mixing the tetrahydrofuran solution of the 1-iodododecane and the pyridine solution of the diethyl aspartate hydrochloride, stirring at 60 ℃ for 16 hours to obtain a suspension, centrifuging the suspension to obtain a white paste, washing the white paste with deionized water for 6 times, adding 2 parts of sodium hydroxide into the washed white paste, and stirring for 30 minutes by using 10 parts of absolute ethyl alcohol as a solvent to obtain the amino acid type collector.
Example 4
The amino acid type collector described in this example 4 comprises the following raw materials, by mole:
the general structural formula of the amino acid type collector described in this example 4 is shown in the following formula (I):
in formula (I), n1 ═ 8; n2 ═ 0; m is Na.
The preparation method of the amino acid type collector described in this example 4 consists of the following steps:
adding 25 parts of tetrahydrofuran into 2 parts of 1-bromononane according to molar parts, adding 25 parts of pyridine into 2 parts of diethyl aminomalonate hydrochloride, uniformly mixing a tetrahydrofuran solution of 1-bromononane and a pyridine solution of diethyl aminomalonate hydrochloride, stirring at 55 ℃ for 16 hours to obtain a suspension, centrifuging the suspension to obtain a white paste, washing the white paste with deionized water for 6 times, adding 4 parts of sodium hydroxide into the washed white paste, and stirring with 13 parts of absolute ethyl alcohol as a solvent for 30 minutes to obtain the amino acid type collector.
Example 5
In this example 5, the amino acid type collector comprises the following raw materials, by mole:
the amino acid type collector described in this example 5 has a general structural formula shown in the following formula (I):
formula (I) wherein n1 is 10; n2 ═ 1; m is Li.
The preparation method of the amino acid type collector described in this example 5 consists of the following steps:
adding 30 parts of tetrahydrofuran into 3 parts of 1-iodoundecane, adding 30 parts of pyridine into 3 parts of diethyl aspartate hydrochloride, uniformly mixing a tetrahydrofuran solution of the 1-iodoundecane and a pyridine solution of the diethyl aspartate hydrochloride, stirring at 45 ℃ for 18 hours to obtain a suspension, centrifuging the suspension to obtain a white paste, washing the white paste with deionized water for 6 times, adding 6 parts of sodium hydroxide into the washed white paste, and stirring with 15 parts of absolute ethyl alcohol as a solvent for 25 minutes to obtain the amino acid type collector.
Application example 1
The amino acid type collector prepared in example 1 and the dodecylamine/sodium dodecylsulfonate combined collector are respectively applied to flotation of muscovite in molybdenum tailings.
The ore sample for test is taken from a certain molybdenum ore tailing pond in Liaoning. The minerals in the tailings mainly comprise montmorillonite, diopside, dolomite, muscovite, albite and calcite, wherein the grade of the muscovite is 2.04% (the grade of the muscovite is K) 2 O is the same as below). Grinding the raw tailings until the ore size is-0.074 mm and accounts for 80%, desliming the grinded tailings in advance by adopting a small cone angle cyclone with the diameter of 150mm, carrying out coarse separation on muscovite mica under the conditions that the concentration of flotation pulp is 25%, the temperature of the flotation pulp is 20 ℃, the environment of neutral pulp is adopted, the using amount of sodium silicate is 3000g/t and the using amount of collecting agent is 500g/t, adding 500g/t of sodium silicate in one-time fine separation, and adding 250g/t of collecting agent in one-time scavenging. The flow chart of the flotation process is shown in the attached figure 3. The results of the flotation comparative tests with the dodecylamine/sodium dodecylsulfonate combination collector are shown in table 1. As can be seen from table 1, compared to the dodecylamine/sodium dodecylsulfonate combined collector, the collector of example 1 increased the muscovite grade of the flotation concentrate by 0.34%, and the recovery increased by 3.91%.
Table 1 comparative test for flotation of muscovite mica using the collector of example 1
Application example 2
The amino acid type collector prepared in example 1 and the dodecylamine/sodium oleate combined collector are respectively applied to the flotation of feldspar in gold tailings.
The sample ore is taken from a gold mine tailing pond in Shandong, and the tailings mainly comprise quartz, potassium feldspar and other minerals, wherein the potassium feldspar grade is 9.07 percent (the potassium feldspar grade is K) 2 O is calculated as follows). Grinding the raw tailings until the ore is 80% of minus 0.074mm, carrying out strong magnetic separation to obtain strong magnetic tailings, and taking the strong magnetic tailings as a flotation feed. The concentration of the flotation ore pulp is 35 percent, the flotation test of the potash feldspar is carried out in a neutral ore pulp environment, the using amount of the sodium hexametaphosphate is 200g/t, and the using amount of the collecting agent is 600 g/t. The flow chart of the flotation process is shown in the attached figure 4. The results of the flotation comparative tests with the dodecylamine/sodium oleate combination collector are shown in table 2. As can be seen from table 2, when the temperature of the ore pulp is 20 ℃, compared with the dodecylamine/sodium oleate combined collector, the grade of the potassium feldspar is improved by 0.94% by using the collector of example 1, and the recovery rate is improved by 7.11%. When the temperature of ore pulp is 5 ℃, compared with a dodecylamine/sodium oleate combined collector, by adopting the collector in the embodiment 1, the grade of potassium feldspar is improved by 2.14%, the recovery rate is improved by 17.39%, and the collector in the embodiment 1 has better low-temperature resistance than the dodecylamine/sodium oleate combined collector.
Table 2 comparative test for flotation of potash feldspar using collector of example 2
Application example 3
The amino acid type collecting agent, the diethyl aminomalonate hydrochloride and the sodium oleate/phenylalanine combined collecting agent which are prepared in the example 1 are respectively applied to the separation of mica in certain iron tailings in Shandong province.
The ore sample for test is taken from a certain iron ore tailing pond in Shandong, the tailings mainly comprise magnetite, quartz, feldspar, mica, kaolin, illite and other minerals, wherein the mica grade is 1.23 percent (the muscovite grade is K) 2 O is counted as followsThe same). The tailings are ground, the grinding fineness is controlled to be 90% of-200 meshes, and the ground ore pulp is subjected to pre-desliming through a small cone angle swirler and then enters flotation. The concentration of flotation ore pulp is 20%, the temperature of the ore pulp is 20 ℃, the ore pulp is neutral, the using amount of sodium silicate is 1000g/t, the using amount of collecting agent is 500g/t, and the using amount of sodium hexametaphosphate is 200g/t, and mica rough separation is carried out. 500g/t of sodium silicate is added into the mica in one concentration, and 250g/t of collecting agent is added into the mica in one scavenging. The flow chart of the flotation process is shown in the attached figure 5. The results of the flotation comparative test with the sodium oleate/phenylalanine combination collector are shown in table 3. From table 3, it can be seen that diethyl aminomalonate hydrochloride has almost no collecting ability on mica, and compared with the sodium oleate/phenylalanine combined collector, the grade of mica is improved by 4.50% by using the collector in example 1, and the recovery rate is improved by 27.37%.
Table 3 comparative test of collector flotation mica using example 3
Claims (8)
1. An amino acid type collector characterized in that: the general structural formula is shown as the following formula (I):
in the formula (I), n1 is 7-11; n2 is 0-1; m is Li, Na or K;
the raw materials comprise the following components in parts by mole:
2. a collector of the amino acid type according to claim 1, characterised in that: the structural general formula of the primary alkyl halide is shown as the formula (II):
CH 3 -(CH 2 ) n -X, formula (II);
in the formula (II), n is 7-11; x is Cl, Br or I.
3. A collector of the amino acid type according to claim 1, characterised in that: the amino acid diethyl ester hydrochloride is one of aspartic acid diethyl ester hydrochloride or aminomalonic acid diethyl ester hydrochloride.
4. A collector of the amino acid type according to claim 1, characterised in that: the alkali is one of lithium hydroxide, sodium hydroxide or potassium hydroxide.
5. A method of producing an amino acid type collector according to claim 1, characterized in that: the method comprises the following steps:
(1) weighing primary alkyl halides, tetrahydrofuran, amino acid diethyl ester hydrochloride, pyridine, absolute ethyl alcohol and alkali in parts by mole;
(2) adding tetrahydrofuran into the primary alkyl halide and mixing evenly;
(3) adding pyridine into amino acid diethyl ester hydrochloride and uniformly mixing;
(4) uniformly mixing the solution obtained in the step (2) and the solution obtained in the step (3), and stirring to obtain a suspension;
(5) centrifuging the suspension obtained in the step (4) to obtain a white paste body, and washing the white paste body;
(6) and (3) adding alkali into the white paste obtained in the step (5), taking absolute ethyl alcohol as a solvent, and stirring for 20-30 minutes to obtain a white solid, namely the amino acid type collecting agent.
6. A method of producing an amino acid type collector according to claim 5, characterized in that: stirring for 12-18 hours at 40-60 ℃ in the step (4) to obtain a suspension.
7. A method of producing an amino acid type collector according to claim 5, characterized in that: and (5) washing the white paste body for 4-6 times by using deionized water.
8. Use of an amino acid type collector according to claim 1, wherein: the method is applied to enrichment and recovery of non-metal minerals in tailings, and the using amount of the method is 200-800 g added in each ton of flotation tailings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210692133.4A CN115090422B (en) | 2022-06-17 | 2022-06-17 | Amino acid type collector, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210692133.4A CN115090422B (en) | 2022-06-17 | 2022-06-17 | Amino acid type collector, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115090422A true CN115090422A (en) | 2022-09-23 |
| CN115090422B CN115090422B (en) | 2024-04-26 |
Family
ID=83291727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210692133.4A Active CN115090422B (en) | 2022-06-17 | 2022-06-17 | Amino acid type collector, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115090422B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531605A (en) * | 2009-04-21 | 2009-09-16 | 武汉工程大学 | Aminoaliphatic acid flotation agent and preparation method thereof |
| CN104801426A (en) * | 2015-05-07 | 2015-07-29 | 中南大学 | Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof |
| CN108993439A (en) * | 2018-06-27 | 2018-12-14 | 西南民族大学 | The preparation method of polyurethane/cationic base acid magnetic adsorbent |
| CN109290062A (en) * | 2018-08-07 | 2019-02-01 | 长沙矿山研究院有限责任公司 | A kind of miscible collecting agent of oxide ore flotation and its application method |
| CN113351373A (en) * | 2021-06-04 | 2021-09-07 | 中国地质科学院矿产综合利用研究所 | Flotation collector for spodumene ores and preparation method and application thereof |
| AU2021105063A4 (en) * | 2021-08-06 | 2021-09-30 | Hunan Research Institute For Nonferrous Metals | Method for promoting sulphidizing flotation of copper oxide ore using amino acid |
-
2022
- 2022-06-17 CN CN202210692133.4A patent/CN115090422B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531605A (en) * | 2009-04-21 | 2009-09-16 | 武汉工程大学 | Aminoaliphatic acid flotation agent and preparation method thereof |
| CN104801426A (en) * | 2015-05-07 | 2015-07-29 | 中南大学 | Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof |
| CN108993439A (en) * | 2018-06-27 | 2018-12-14 | 西南民族大学 | The preparation method of polyurethane/cationic base acid magnetic adsorbent |
| CN109290062A (en) * | 2018-08-07 | 2019-02-01 | 长沙矿山研究院有限责任公司 | A kind of miscible collecting agent of oxide ore flotation and its application method |
| CN113351373A (en) * | 2021-06-04 | 2021-09-07 | 中国地质科学院矿产综合利用研究所 | Flotation collector for spodumene ores and preparation method and application thereof |
| AU2021105063A4 (en) * | 2021-08-06 | 2021-09-30 | Hunan Research Institute For Nonferrous Metals | Method for promoting sulphidizing flotation of copper oxide ore using amino acid |
Non-Patent Citations (1)
| Title |
|---|
| 魏德洲，高淑玲，刘文刚: "《新编选矿概论》", 31 October 2012, 冶金工业出版社, pages: 177 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115090422B (en) | 2024-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104741245B (en) | A kind of Novel lepidolite flotation method and a kind of collecting agent and its application | |
| CN101972710B (en) | Double reverse flotation process of middle-low grade phosphorite | |
| CN111672636A (en) | Spodumene ore flotation collector and preparation method and application method thereof | |
| CN105642448A (en) | Method for efficiently separating wolframite concentrate and scheelite concentrate from tungsten ore | |
| CN113522517B (en) | Fluorite ore beneficiation method | |
| CN103331212A (en) | Carbonate phosphorite reverse flotation collecting agent and preparation method thereof | |
| CN111250269B (en) | Novel collector for flotation of low-grade spodumene ores and spodumene ore dressing method | |
| CN111530633A (en) | Novel composite collecting agent for recovering zinc oxide from peat plaza lead zinc oxide ore, preparation method and application | |
| CN107899755B (en) | Synergist for flotation of refractory copper oxide ore | |
| CN106391297B (en) | A kind of beneficiation method of copper and tin sulphide ore | |
| CN109604068A (en) | Combined inhibitor for olivine flotation, preparation method and application thereof | |
| CN115090422A (en) | Amino acid type collecting agent and preparation method and application thereof | |
| CN115090423B (en) | Tannin amide beneficiation aid and preparation method and application thereof | |
| CN106975574A (en) | A kind of collector composition for rutile ore flotation | |
| CN113680534B (en) | Fine iron mineral collector and method for asynchronous flotation of coarse and fine iron ore containing carbonate | |
| CN104801426A (en) | Schiff base caproate mineral flotation collecting agent as well as preparation method and application thereof | |
| CN110976096B (en) | Beneficiation method for rare earth ore | |
| CN103817011A (en) | Carbon inhibitor and application thereof in molybdenum-nickel flotation from high-carbon molybdenum-nickel ores | |
| CN112317134A (en) | Compound dispersant for treating carbonate-containing iron ore and beneficiation method | |
| CN114682388B (en) | Flotation reagent for arsenic-containing dip-dyed gold ore, preparation method and use method | |
| CN110882828A (en) | Beneficiation method for recovering niobium mineral from carbonic acid type pyrochlore | |
| CN113680535B (en) | Alkyl ether group dithiophosphate collecting agent and preparation method and application thereof | |
| CN110773323B (en) | Beneficiation method for borosillimanite type boron ore | |
| CN102872978A (en) | Copper-zinc flotation process for minerals and products | |
| CN103706488A (en) | Reverse flotation technology of phosphate ore in alkaline medium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |