CN113926591A - Multi-efficiency novel reverse flotation inhibitor for iron ore and synthesis and use methods thereof - Google Patents
Multi-efficiency novel reverse flotation inhibitor for iron ore and synthesis and use methods thereof Download PDFInfo
- Publication number
- CN113926591A CN113926591A CN202111003427.3A CN202111003427A CN113926591A CN 113926591 A CN113926591 A CN 113926591A CN 202111003427 A CN202111003427 A CN 202111003427A CN 113926591 A CN113926591 A CN 113926591A
- Authority
- CN
- China
- Prior art keywords
- reverse flotation
- starch
- iron ore
- efficiency
- chitosan mixture
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 226
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 113
- 238000005188 flotation Methods 0.000 title claims abstract description 84
- 239000003112 inhibitor Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 229920001661 Chitosan Polymers 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 69
- 229920002472 Starch Polymers 0.000 claims abstract description 55
- 235000019698 starch Nutrition 0.000 claims abstract description 55
- 239000008107 starch Substances 0.000 claims abstract description 55
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 23
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 23
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 23
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 23
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 21
- 229920000615 alginic acid Polymers 0.000 claims abstract description 21
- 238000007885 magnetic separation Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract 2
- 229940072056 alginate Drugs 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000012141 concentrate Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229920000881 Modified starch Polymers 0.000 claims description 20
- 239000004368 Modified starch Substances 0.000 claims description 20
- 235000019426 modified starch Nutrition 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 17
- 235000013336 milk Nutrition 0.000 claims description 16
- 239000008267 milk Substances 0.000 claims description 16
- 210000004080 milk Anatomy 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229940106681 chloroacetic acid Drugs 0.000 claims description 11
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical group [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 6
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 6
- 239000004571 lime Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000005662 Paraffin oil Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 210000003462 vein Anatomy 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 25
- 229910001608 iron mineral Inorganic materials 0.000 abstract description 19
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 239000006148 magnetic separator Substances 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000005456 ore beneficiation Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229920002261 Corn starch Polymers 0.000 description 8
- 239000008120 corn starch Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 230000002000 scavenging effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- -1 phosphoric acid diester Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000002351 beta-D-glucopyranosyloxy group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B03D1/016—Macromolecular compounds
-
- 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
-
- 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
- B03D1/02—Froth-flotation processes
- B03D1/025—Froth-flotation processes adapted for the flotation of fines
-
- 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
- B03D2201/06—Depressants
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明属于铁矿石选矿领域，主要涉及一种多效能新型铁矿反浮选抑制剂及其合成、使用方法。本发明所述的多效能新型铁矿反浮选抑制剂，是天然淀粉与壳聚糖混合形成的淀粉壳聚糖混合物，和工业羧甲基纤维素、褐藻胶发生交联聚合反应制得，解决了天然淀粉药剂结构单一和选择性差的问题，减少了铁矿反浮选作业对粮食作物的消耗，同时通过改善药剂的分子结构和官能团特性，进一步强化微细粒弱磁性铁矿物的回收。本发明的多效能新型铁矿反浮选抑制剂在强磁选的给矿中加入，提高磁选机对微细粒铁矿物的捕获效率，充分延长了药剂和铁矿物的作用时间，显著提高了药剂对铁矿物的抑制性能。
The invention belongs to the field of iron ore beneficiation, and mainly relates to a novel multi-efficiency iron ore reverse flotation inhibitor and a method for synthesizing and using the same. The multi-efficiency novel iron ore reverse flotation inhibitor described in the present invention is a mixture of starch and chitosan formed by mixing natural starch and chitosan, and is prepared by cross-linking polymerization reaction with industrial carboxymethyl cellulose and alginate. It solves the problems of single structure and poor selectivity of natural starch medicament, reduces the consumption of grain crops by iron ore reverse flotation operation, and further strengthens the recovery of fine-grained weak magnetic iron minerals by improving the molecular structure and functional group characteristics of the medicament. The multi-efficiency new type of iron ore reverse flotation inhibitor of the invention is added to the ore feeding of strong magnetic separation, which improves the capture efficiency of the magnetic separator for fine-grained iron minerals, fully prolongs the action time of the agent and the iron minerals, and significantly improves the efficiency of the magnetic separator. Improves the inhibitory performance of the agent on iron minerals.
Description
Technical Field
The invention belongs to the field of iron ore dressing, and mainly relates to a multi-effect novel iron ore reverse flotation inhibitor and a synthesis and use method thereof.
Background
The micro-fine particle embedded iron ore which is difficult to sort in China has rich resource reserves, and most of the iron ore is in a micro-fine dip-dyeing type. The embedded granularity of the fine dip-dyeing type iron ore is fine, so that the iron minerals in the iron ore are often ground to-20 mu m to achieve monomer dissociation, and the fine iron minerals in the iron ore are difficult to effectively recover by adopting conventional ore dressing equipment and an ore dressing process, so that the fine iron minerals are greatly lost in the sorting process. Therefore, the strategic significance of strengthening the research on the high-efficiency utilization of domestic refractory micro-particle embedded iron ore resources is great. The embedded granularity of the useful iron minerals in the micro-dip-dyed iron ore is fine, so that the iron mineral particles have the characteristics of small particle size, low specific magnetization coefficient and large specific surface area, so that on one hand, the magnetic field force applied to the iron mineral particles in the magnetic separation process is low, and a large amount of useful iron minerals are greatly lost into tailings in the magnetic separation process and cannot be recycled; on the other hand, because the micro-fine iron ore has higher surface energy, the problems of slurry covering, surface conversion, foam, water flow entrainment and the like are caused in the flotation process, the flotation environment is seriously deteriorated, and a large amount of medicament consumption and resource waste are caused.
At present, in the reverse flotation operation of iron ore, the adopted iron ore inhibitor is mainly natural starch extracted from grain crops such as corn, cassava, potato, wheat and the like, and because the natural starch has low content of characteristic functional groups, single medicament structure and poor medicament selectivity, the medicament consumption is high in the using process, a large amount of grain crops are wasted, and the national grain safety is seriously influenced. Therefore, the development of a novel high-efficiency iron ore flotation inhibitor and the change of the use method of the traditional inhibitor are beneficial to the high-efficiency utilization research of refractory micro-particle embedded iron ore resources in China.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a multi-effect novel reverse flotation inhibitor for iron ore, a synthetic method and a using method thereof based on the physicochemical characteristics and the crystal chemical properties of the fine iron ore and the supermolecule hydrogen bond association performance and the hydrophilic performance of a multi-polar functional group polymer agent on the surface of the iron ore, and aims to solve the problem of efficient development and utilization of the fine iron ore.
The multi-effect novel reverse flotation inhibitor for iron ore is prepared by the cross-linking polymerization reaction of a starch chitosan mixture formed by mixing natural starch and chitosan, industrial carboxymethyl cellulose and algin. The modified starch chitosan mixture can also be obtained by modifying the starch chitosan mixture by chlorohydrin and chloroacetic acid and then carrying out polymerization reaction with industrial carboxymethyl cellulose and algin. The preparation process comprises the following steps:
step 1: preparing a starch chitosan mixture or/and a modified starch chitosan mixture:
and mixing the natural starch and the chitosan according to the mass ratio of (1-3) to 1 to obtain the starch chitosan mixture.
Adding the starch chitosan mixture into an ethanol solution with the mass concentration of more than 95% to prepare starch milk with the mass concentration of 20% -40%; continuously stirring the starch milk, adding sodium hydroxide which is 10-20% of the total mass of the starch chitosan mixture for reaction, controlling the reaction temperature to be 40-60 ℃, and reacting for 1-2 h; after reacting for 1-2h, adding chloroacetic alcohol and chloroacetic acid into starch milk according to the mass ratio of (0.5-2):1, wherein the total dosage of the chloroacetic acid and the chloroacetic alcohol is 20-30% of the total mass of the starch chitosan mixture, controlling the reaction temperature to be 50-80 ℃, reacting for 2-4h, neutralizing the starch milk with hydrochloric acid or oxalic acid and other solutions after the reaction is finished, and filtering, washing and drying to obtain the modified starch chitosan mixture.
The modification of the starch chitosan mixture is to improve the selectivity of the starch medicament and the action energy of the starch medicament and iron minerals by etherifying hydroxyl groups in starch and chitosan, improve the molecular structure and functional group characteristics of the finally formed medicament, reduce the problems of single structure and poor selectivity of the natural starch medicament by modification, and further strengthen the recovery of the prepared reverse flotation inhibitor to micro-fine particle weak magnetic iron minerals.
Taking chloroacetic acid as an example, the modified starch has the following chemical reaction formula:
(C6H11O6)n+nNaOH＝(C6H10O6Na)n+nH2O
(C6H10O6Na)n+nClCH2COOH＝(C6H10O6-CH2COOH)n+nNaCl
the chemical reaction formula of the modified chitosan is as follows:
(C6H11NO4)n+nNaOH＝(C6H10NO4Na)n+nH2O
(C6H10NO4Na)n+nClCH2COOH＝(C6H10NO4-CH2COOH)n+nNaCl
step 2: polymerization reaction:
mixing a starch chitosan mixture or/and a modified starch chitosan mixture (which refers to a starch chitosan mixture alone or a modified starch chitosan mixture alone or a mixture of the two, and the starch chitosan mixture or/and the modified starch chitosan mixture is hereinafter referred to as a "mixture") with industrial carboxymethyl cellulose and algin according to a mixture ratio: industrial carboxymethyl cellulose: the mass ratio of the algin is (1-2): 1:2, adding water to prepare an emulsion with the mass concentration of 20-40%, then adding phosphorus oxychloride and sodium chloride for reaction, wherein the adding amount of the phosphorus oxychloride and the sodium chloride is 0.2-1% and 3-5% of the total mass of the mixture, the industrial carboxymethyl cellulose and the algin respectively, adjusting the pH value to 8-10 in the reaction process, controlling the reaction temperature to 60-80 ℃, reacting for 2-4h, neutralizing, filtering, washing and drying after the reaction, and obtaining a filtered solid product which is a multi-efficiency novel iron ore reverse flotation inhibitor, wherein the structural schematic diagram is shown in fig. 1. The multi-effect novel reverse flotation inhibitor for the iron ore can be prepared into an aqueous solution with the mass concentration of 1-5% for later use.
And (2) carrying out polymerization reaction on the mixture, the industrial carboxymethyl cellulose and the algin, respectively generating phosphoric acid diester from hydroxyl in the mixture and hydroxyl in the industrial carboxymethyl cellulose and the algin through phosphorus oxychloride, and further enabling the starch chitosan mixture, the carboxymethyl cellulose and the algin to form a cross-linked structure through free radical polymerization reaction of the phosphoric acid diester. The starch chitosan mixture or/and the modified starch chitosan mixture are polymerized with industrial carboxymethyl cellulose and algin through a cross-linking polymerization reaction, and the chain-shaped polymer is cross-linked into a net shape, so that the molecular structure of the medicament can be further improved, the molecular weight of the medicament is improved, the dosage of the medicament is greatly reduced, the use of starch medicaments of grain crops is greatly reduced, and the consumption of the grain crops in the reverse flotation operation of iron ores is reduced.
The invention also comprises a method for applying the multi-effect novel iron ore reverse flotation inhibitor to iron ore reverse flotation, which comprises the following steps:
on the basis of the process flow of 'grinding classification-low-intensity magnetic separation-high-intensity magnetic separation-mixed magnetic concentrate reverse flotation' of the conventional iron ore, a two-section dosing method is adopted, firstly, the iron ore is ground and classified, the ground and classified product is subjected to low-intensity magnetic separation and high-gradient high-intensity magnetic separation to obtain a mixed magnetic concentrate product, and the multi-efficiency novel iron ore reverse flotation inhibitor is added into the high-intensity magnetic separation ore (namely, low-intensity magnetic tailings) according to the 200g/t of the mass of the ore sample before the high-intensity magnetic separation is carried out; the mixed magnetic concentrate product is prepared into ore pulp with the mass fraction of 30-40%, and the iron concentrate product is obtained by reverse flotation, wherein the reverse flotation inhibitor adopted in the reverse flotation process is the multi-effect novel iron ore reverse flotation inhibitor, and the dosage is 500-800g/t of the mass of the reverse flotation ore sample.
The specific method for carrying out the bulk magnetic concentrate ore pulp reverse flotation by using the multi-effect novel iron ore reverse flotation inhibitor comprises the following steps:
firstly, adding sodium hydroxide to adjust the pH value of ore pulp to 10.5-11.5, then sequentially adding 800g/t of multi-effect novel reverse flotation inhibitor for the iron ore according to the mass of the ore sample, 800g/t of gangue mineral activating agent such as lime or calcium chloride according to the mass of 600-800g/t of the ore sample, 500g/t of sodium oleate or saponified paraffin oil according to the mass of 300-800 g/t of the ore sample as a collecting agent and 30-50g/t of second oil according to the mass of the ore sample as a foaming agent, fully mixing pulp, feeding the mixture into a flotation machine for reverse flotation operation, and sequentially carrying out primary reverse flotation roughing, primary concentration and tertiary scavenging to finally obtain the qualified iron concentrate product.
The invention has the beneficial effects that:
1. in the preparation process of the multi-effect novel iron ore reverse flotation inhibitor, firstly, a characteristic functional group is introduced into a natural starch medicament and a chitosan molecular structure through chemical modification, and in order to solve the problems of single structure and poor selectivity of the natural starch medicament, the modified starch, industrial carboxymethyl cellulose and algin are subjected to polymerization reaction, so that the medicament dosage is greatly reduced, the consumption of grain crops in iron ore reverse flotation operation is reduced, and the recovery of micro-fine particle weak magnetic iron minerals is further enhanced by improving the molecular structure and the functional group characteristics of the medicament.
2. In the using method of the multi-effect novel iron ore reverse flotation inhibitor, the multi-effect novel iron ore reverse flotation inhibitor is firstly added into the feeding ore of the strong magnetic separation through a sectional medicine adding method, and the bridging agglomeration of the high molecular medicament is utilized to enable the micro-fine particle weak magnetic iron ore to form a firm chain and net structure, thereby improving the capture efficiency of the magnetic separator on the micro-fine particle iron ore, meanwhile, as the molecular structure of the medicament contains a large number of multi-polar iron-philic hydrophilic characteristic functional groups, the action time of the medicament and iron minerals can be fully prolonged by adding the medicament in advance, the inhibition performance of the medicament on the iron minerals is remarkably improved, and the firm chain-like and net-like structures formed by the micro-fine iron minerals under the action of the high molecular medicament further reduce the water flow and foam entrainment of the micro-fine iron minerals in the reverse flotation process, reduce the loss of the iron minerals and remarkably improve the separation index.
Drawings
FIG. 1 is a schematic structural diagram of the multi-effect novel reverse flotation depressant for iron ore of the present invention.
FIG. 2 is a process flow diagram in an embodiment of the invention.
Detailed Description
The following examples are given to illustrate the present invention, but are not intended to limit the invention:
example 1
Taking a certain lean magnetite-hematite mixed iron ore in Hebei as a raw material, wherein the TFe grade in an ore sample is 25.64 percent, and SiO2The content is 70.32 percent, and the granularity of the ground ore product is-0.038 mu m accounting for 65.85 percent. The specific implementation steps are as follows:
(1) mixing corn starch and chitosan according to a mass ratio of 1:1 in a hydrothermal constant-temperature reaction kettle to form a starch chitosan mixture, adding the starch chitosan mixture into an ethanol solution with a mass concentration of more than 95%, wherein the using amount of the corn starch is 10kg, preparing starch milk with a mass concentration of 20%, continuously stirring, adding a sodium hydroxide solution with a mass concentration of 10% for reaction, controlling the reaction temperature to be 40 ℃, and reacting for 2 hours.
(2) After reacting for 3 hours, adding chloroethanol and chloroacetic acid into a reaction kettle according to the mass ratio of 0.5:1, wherein the total amount of the chloroethanol and the chloroacetic acid is 20% of the mass of the starch chitosan mixture, controlling the reaction temperature to be 50 ℃, and after reacting for 4 hours, adding the starch milk into an oxalic acid solution with the concentration of 10% for neutralization, filtering, washing and drying to obtain a modified starch chitosan mixture for later use;
(3) mixing a modified starch chitosan mixture, industrial carboxymethyl cellulose and algin according to a mass ratio of 1:1:2 to prepare an emulsion with the concentration of 20%, then adding the modified starch chitosan mixture, the industrial carboxymethyl cellulose and the algin with the total mass of 0.2% of phosphorus oxychloride and 3% of sodium chloride into a reaction kettle to react, regulating the pH value of a solution to be 9.0, controlling the reaction temperature to be 60 ℃, reacting for 2 hours, adding an oxalic acid solution with the concentration of 10% after the reaction is finished to neutralize, filter, wash and dry to obtain a multi-effect novel iron ore reverse flotation inhibitor, and preparing the multi-effect novel iron ore reverse flotation inhibitor into an aqueous solution with the concentration of 5% for later use.
(4) In the process of separating iron ore, as shown in fig. 2, a two-stage dosing method is adopted, firstly, iron ore raw materials are ground and classified, weak magnetic concentrate and weak magnetic tailings are respectively obtained by carrying out primary weak magnetic separation on ground and classified products of the iron ore, a multi-effect novel iron ore reverse flotation inhibitor is added into the weak magnetic tailings (strong magnetic separation feeding ore) according to the mass of an ore sample of 100g/t, high gradient strong magnetic separation is carried out to obtain strong magnetic concentrate and strong magnetic tailings, the two magnetic concentrate products of the weak magnetic concentrate and the strong magnetic concentrate are mixed and pulp-mixed to obtain ore pulp with the mass concentration of 35%, and the following substances are sequentially added into the ore pulp: the method comprises the following steps of (1) carrying out reverse flotation and roughing on the slurry for 3min by using a pH value regulator sodium hydroxide (regulating the pH value of ore slurry to be 11.0), a multi-effect novel iron ore reverse flotation inhibitor (using amount to be 400g/t), an activator lime (using amount to be 600g/t), a collector sodium oleate (using amount to be 300g/t), and a foaming agent No. two oil (using amount to be 30g/t), wherein the roughing time is 4 min; carrying out concentration twice on the roughed concentrate, wherein the using amount of an activator lime is 300g/t, the using amount of a collecting agent sodium oleate is 200g/t, the pH value of ore pulp is controlled to be 11.50, and the concentration time is 3min, so as to obtain the final concentrate of reverse flotation; and (4) carrying out scavenging on the rougher tailings twice, controlling the pH value of the ore pulp to be 11.50, and carrying out scavenging for 3min to obtain the reverse flotation final tailings.
The iron grade of the concentrate finally obtained by the method is 65.5 percent, the iron recovery rate is 94.5 percent, and the results of the primary accounting of technical and economic indexes show that compared with the original conventional iron ore dressing process, the method can increase the iron concentrate yield by 30.84 kilotons every year, reduce the tailing discharge by 18.25 kilotons and reduce the starch consumption by 680 kilotons, meanwhile, the iron grade of the concentrate is increased by 1.25 percent, the iron recovery rate is increased by 8.32 percent, and the economic benefit is increased by about 2.83 million yuan every year.
Example 2
The same as in example 1 elsewhere, except that: the preparation processes of the modified starch chitosan mixture in the steps (1) and (2) are not carried out, the corn starch and the chitosan are directly mixed according to the mass ratio of 1:1 in the step (3) to form the starch chitosan mixture, and the modified starch chitosan mixture in the step (3) is replaced and mixed with the industrial carboxymethyl cellulose and the algin. The proper dosage of the prepared inhibitor in the ore pulp is 900g/t, the iron grade of the obtained ore concentrate is 64.5 percent, the iron recovery rate is 87.63 percent,
comparative example 3
The raw materials and the method are basically the same as example 1, except that the reverse flotation inhibitor is a mixture of corn starch and carboxymethyl cellulose in a mass ratio of (1:1), the appropriate amount of the reverse flotation inhibitor in the ore pulp is 1000g/t, and the iron concentrate finally obtained has an iron grade of 64.25% and an iron recovery rate of 84.54% through detection.
Comparative example 4
The processing raw materials and the method are basically the same as the example 1, but the difference is that the sectional dosing is not adopted, the multi-effect novel reverse flotation inhibitor for the iron ore is only added in the reverse flotation operation, the dosage is 600g/t, the iron ore concentrate finally obtained is detected to have the iron grade of 65.20 percent, and the iron recovery rate is 87.50 percent.
Example 5
The lean magnetic red mixed iron ore in the Anshan area of Liaoning is taken as a raw material, the TFe grade in an ore sample is 29.61%, the content of SiO2 is 68.32%, and the granularity of an ore grinding product is-0.038 mu m and accounts for 75.86%. The specific implementation steps are as follows:
(1) mixing corn starch and chitosan according to a mass ratio of 2:1 in a hydrothermal constant-temperature reaction kettle to form a starch chitosan mixture, adding the starch chitosan mixture into an ethanol solution with a mass concentration of more than 95%, wherein the using amount of the corn starch is 8.5kg, preparing starch milk with a mass concentration of 40%, continuously stirring, adding a sodium hydroxide solution with a mass concentration of 20% for reaction, controlling the reaction temperature to be 60 ℃, and reacting for 1 hour.
(2) After reacting for 1h, adding chloroethanol and chloroacetic acid into a reaction kettle according to the mass ratio of 1:1, wherein the total amount of the chloroethanol and the chloroacetic acid is 30% of the mass of the starch chitosan mixture, controlling the reaction temperature to be 60 ℃, and after reacting for 3h, adding starch milk into an oxalic acid solution with the concentration of 10% for neutralization, filtering, washing and drying to obtain a modified starch chitosan mixture for later use;
(3) mixing a modified starch chitosan mixture, industrial carboxymethyl cellulose and algin according to a mass ratio of 2:1:2 to prepare an emulsion with the concentration of 35%, then adding the modified starch chitosan mixture, the industrial carboxymethyl cellulose and the algin with the total mass of 0.5% of phosphorus oxychloride and 5% of sodium chloride into a reaction kettle to react, regulating the pH value of a solution to be 10.0, controlling the reaction temperature to be 80 ℃, reacting for 4 hours, adding an oxalic acid solution with the concentration of 10% after the reaction is finished to neutralize, filter, wash and dry to obtain a multi-effect novel iron ore reverse flotation inhibitor, and preparing the multi-effect novel iron ore reverse flotation inhibitor into an aqueous solution with the concentration of 5% for later use.
(4) In the process of separating iron ore, a two-stage dosing method is adopted, firstly, the raw material of iron ore is ground and classified, the ground and classified product of iron ore is subjected to one-time low-intensity magnetic separation to respectively obtain low-intensity magnetic concentrate and low-intensity magnetic tailing, a multi-effect novel reverse flotation inhibitor of iron ore is added into the low-intensity magnetic tailing (high-intensity magnetic separation feeding ore) according to the mass of an ore sample of 150g/t, high-gradient high-intensity magnetic separation is carried out to obtain high-intensity magnetic concentrate and high-intensity magnetic tailing, the two magnetic concentrate products of the low-intensity magnetic concentrate and the high-intensity magnetic concentrate are mixed and pulp-mixed to obtain ore pulp with the mass concentration of 30%, and the following substances are sequentially added into the ore pulp: the method comprises the following steps of (1) carrying out reverse flotation and roughing on the slurry for 3min by using a pH value regulator sodium hydroxide (regulating the pH value of ore slurry to be 11.5), a multi-effect novel iron ore reverse flotation inhibitor (using amount is 500g/t), an activator lime (using amount is 800g/t), a collector sodium oleate (using amount is 400g/t), and a foaming agent II oil (using amount is 50g/t), wherein the reverse flotation and roughing are carried out for 5min after the slurry is mixed; carrying out concentration twice on the roughed concentrate, wherein the using amount of an activator lime is 300g/t, the using amount of a collecting agent sodium oleate is 250g/t, the pH value of ore pulp is controlled to be 11.50, and the concentration time is 3min, so as to obtain the final reverse flotation concentrate; and (4) carrying out scavenging on the rougher tailings twice, controlling the pH value of the ore pulp to be 11.50, and carrying out scavenging for 3min to obtain the reverse flotation final tailings.
The iron grade of the concentrate finally obtained by the method is 66.21%, the iron recovery rate is 88.20%, and the results of the primary calculation of technical and economic indexes show that compared with the original conventional iron ore dressing process, the method can increase the iron concentrate yield by 28.85 kilotons every year, reduce the tailing discharge by 20.35 kilotons, reduce the starch consumption by 560 kilotons, simultaneously increase the iron grade of the concentrate by 1.32 percentage points, improve the iron recovery rate by 9.01 percentage points, and increase the economic benefit by about 3.02 million yuan every year.
Example 6
The same as in example 1 elsewhere, except that: the preparation processes of the modified starch chitosan mixture in the steps (1) and (2) are not carried out, the corn starch and the chitosan are directly mixed according to the mass ratio of 2:1 in the step (3) to form the starch chitosan mixture, and the modified starch chitosan mixture in the step (3) is replaced and mixed with the industrial carboxymethyl cellulose and the algin. The prepared inhibitor is suitable for 850g/t in ore pulp, the iron grade of the finally obtained concentrate is 65.21%, and the iron recovery rate is 87.20%
Comparative example 7
The raw materials and the method are basically the same as example 1, except that the reverse flotation inhibitor is a mixture of corn starch and carboxymethyl cellulose in a mass ratio of (1:1), the proper dosage of the inhibitor in the ore pulp is 950g/t, and the finally obtained iron concentrate has an iron grade of 64.89% and an iron recovery rate of 76.19% through detection.
Comparative example 8
The processing raw materials and the method are basically the same as the example 1, but the difference is that the multi-effect novel iron ore reverse flotation inhibitor is only added in the reverse flotation operation without sectional dosing, the dosage is 750g/t, and the iron ore concentrate obtained finally has the iron grade of 65.18 percent and the iron recovery rate of 81.24 percent through detection.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111003427.3A CN113926591B (en) | 2021-08-30 | 2021-08-30 | A novel multi-effect iron ore reverse flotation inhibitor and its synthesis and use methods |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111003427.3A CN113926591B (en) | 2021-08-30 | 2021-08-30 | A novel multi-effect iron ore reverse flotation inhibitor and its synthesis and use methods |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113926591A true CN113926591A (en) | 2022-01-14 |
| CN113926591B CN113926591B (en) | 2023-02-03 |
Family
ID=79274713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111003427.3A Active CN113926591B (en) | 2021-08-30 | 2021-08-30 | A novel multi-effect iron ore reverse flotation inhibitor and its synthesis and use methods |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113926591B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117772421A (en) * | 2024-01-17 | 2024-03-29 | 太原理工大学 | Preparation method and application of high-selectivity iron ore flotation inhibitor |
| WO2024099667A1 (en) * | 2022-11-11 | 2024-05-16 | Clariant International Ltd | Phosphoric acid esters for the beneficiation of magnetic minerals from low-grade ores |
| WO2025050545A1 (en) * | 2023-09-08 | 2025-03-13 | 鞍钢集团北京研究院有限公司 | Beneficiation method for carbonate-containing iron ore |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339331A (en) * | 1980-12-05 | 1982-07-13 | American Cyanamid Company | Crosslinked starches as depressants in mineral ore flotation |
| US4877517A (en) * | 1988-05-02 | 1989-10-31 | Falconbridge Limited | Depressant for flotation separation of polymetallic sulphidic ores |
| US5525212A (en) * | 1995-06-07 | 1996-06-11 | Cytec Technology Corp. | Method of depressing non-sulfide silicate gangue minerals |
| CN101844110A (en) * | 2010-06-11 | 2010-09-29 | 中国地质科学院郑州矿产综合利用研究所 | Sulfide ore flotation layered silicate mineral inhibitor and preparation method thereof |
| CN104014417A (en) * | 2014-05-30 | 2014-09-03 | 鞍钢集团矿业公司 | Beneficiation method for micro-fine iron ore |
| CN104998759A (en) * | 2015-07-29 | 2015-10-28 | 昆明理工大学 | Combined reagent for reverse flotation of microgranular iron ore magnetic concentrate and application method thereof |
-
2021
- 2021-08-30 CN CN202111003427.3A patent/CN113926591B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339331A (en) * | 1980-12-05 | 1982-07-13 | American Cyanamid Company | Crosslinked starches as depressants in mineral ore flotation |
| US4877517A (en) * | 1988-05-02 | 1989-10-31 | Falconbridge Limited | Depressant for flotation separation of polymetallic sulphidic ores |
| US5525212A (en) * | 1995-06-07 | 1996-06-11 | Cytec Technology Corp. | Method of depressing non-sulfide silicate gangue minerals |
| CN101844110A (en) * | 2010-06-11 | 2010-09-29 | 中国地质科学院郑州矿产综合利用研究所 | Sulfide ore flotation layered silicate mineral inhibitor and preparation method thereof |
| CN104014417A (en) * | 2014-05-30 | 2014-09-03 | 鞍钢集团矿业公司 | Beneficiation method for micro-fine iron ore |
| CN104998759A (en) * | 2015-07-29 | 2015-10-28 | 昆明理工大学 | Combined reagent for reverse flotation of microgranular iron ore magnetic concentrate and application method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 程绍凯等: "东鞍山弱磁性铁矿桥联团聚—强磁选技术研究", 《金属矿山》, no. 4, 30 April 2021 (2021-04-30), pages 90 - 95 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024099667A1 (en) * | 2022-11-11 | 2024-05-16 | Clariant International Ltd | Phosphoric acid esters for the beneficiation of magnetic minerals from low-grade ores |
| WO2025050545A1 (en) * | 2023-09-08 | 2025-03-13 | 鞍钢集团北京研究院有限公司 | Beneficiation method for carbonate-containing iron ore |
| CN117772421A (en) * | 2024-01-17 | 2024-03-29 | 太原理工大学 | Preparation method and application of high-selectivity iron ore flotation inhibitor |
| CN117772421B (en) * | 2024-01-17 | 2024-11-15 | 太原理工大学 | Preparation method and application of high-selectivity iron ore flotation inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113926591B (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113926591A (en) | Multi-efficiency novel reverse flotation inhibitor for iron ore and synthesis and use methods thereof | |
| CN104437818B (en) | A kind of beneficiation method of copper-lead-zinc polymetallic ore | |
| CN102443071B (en) | Composite modified starch as hematite reverse flotation inhibitor and preparation method thereof | |
| CN112642575A (en) | Magnetic levitation combined separation method for carbonate-containing lean magnetic hematite mixed iron ore | |
| CN113102114B (en) | Collecting agent for high-sulfur-content fine-fraction gold ore flotation | |
| CN106269212A (en) | A kind of magnetic separation grading system is for the method for extraction of superpure concentrate of magnetite | |
| CN106269286B (en) | Preparation method of sulfonated fatty acid phosphate reverse flotation collector | |
| CN112264183B (en) | Resource treatment method of high-sulfur copper tailings, product and application thereof | |
| WO2019218295A1 (en) | Efficient purification method for high-silicon, high-calcium, high-iron and low-grade brucite | |
| CN113680534B (en) | Fine iron mineral collector and method for asynchronous flotation of coarse and fine iron ore containing carbonate | |
| CN106179723B (en) | A kind of difficulty selects the beneficiation method of Pb-Zn deposits Pb-Zn separation | |
| CN112657672A (en) | Synthesis and use method of organic polymer medicament for reinforcing fine iron mineral recovery | |
| CN103706484A (en) | Preparation method of micro-fine particle cassiterite mineral inhibitor and application of preparation method | |
| CN113798065A (en) | Composite inhibitor for reverse flotation of carbonate-containing iron ore and preparation method and application thereof | |
| CN105013595B (en) | Beneficiation method for producing high-purity kyanite through low-grade kyanite | |
| CN110813521A (en) | A method for recovering carbon, iron and zinc from blast furnace gas ash | |
| CN112575190B (en) | Beneficiation method for copper-nickel separation of complex refractory nickel-copper concentrate | |
| CN117884259B (en) | Multi-metal ore dressing and separating agent and preparation method and application thereof | |
| CN113680536B (en) | A kind of percarbonate iron ore composite modification inhibitor and preparation and use method thereof | |
| CN111039317A (en) | Production method of basic zinc carbonate | |
| CN106000659A (en) | Manganese-magnesium low-grade phosphate flotation process | |
| CN110004263A (en) | A kind of technique of red mud fluidized bed process production Iron concentrate | |
| CN107790292A (en) | A kind of application of salicylide oxime compound in copper oxide mineral flotation | |
| CN111871602B (en) | Waste-free efficient utilization method of hematite ore | |
| CN114669401A (en) | Supermolecule inhibitor for reverse flotation of iron ore and use method |
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 | ||
| GR01 | Patent grant |