CN112044605B - Titanium selection medicament and titanium selection method - Google Patents
Titanium selection medicament and titanium selection method Download PDFInfo
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- CN112044605B CN112044605B CN201910490084.4A CN201910490084A CN112044605B CN 112044605 B CN112044605 B CN 112044605B CN 201910490084 A CN201910490084 A CN 201910490084A CN 112044605 B CN112044605 B CN 112044605B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000010936 titanium Substances 0.000 title claims abstract description 92
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 92
- 239000003814 drug Substances 0.000 title claims abstract description 24
- 238000010187 selection method Methods 0.000 title claims abstract description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 16
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 16
- 108010077895 Sarcosine Proteins 0.000 claims abstract description 9
- -1 oleoyl sodium glycinate Chemical compound 0.000 claims abstract description 7
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims abstract description 6
- 239000004247 glycine and its sodium salt Substances 0.000 claims abstract description 6
- 229940029258 sodium glycinate Drugs 0.000 claims abstract description 6
- 229940048098 sodium sarcosinate Drugs 0.000 claims abstract description 6
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 claims abstract description 3
- 230000002000 scavenging effect Effects 0.000 claims description 124
- 239000012535 impurity Substances 0.000 claims description 104
- 230000002378 acidificating effect Effects 0.000 claims description 50
- 238000000926 separation method Methods 0.000 claims description 42
- 238000005188 flotation Methods 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000002283 diesel fuel Substances 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012141 concentrate Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- VLKIFCBXANYYCK-GMFCBQQYSA-M sodium;2-[methyl-[(z)-octadec-9-enoyl]amino]acetate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC([O-])=O VLKIFCBXANYYCK-GMFCBQQYSA-M 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 239000008396 flotation agent Substances 0.000 claims description 10
- 229940065859 sodium cocoyl glycinate Drugs 0.000 claims description 10
- IKGKWKGYFJBGQJ-UHFFFAOYSA-M sodium;2-(dodecanoylamino)acetate Chemical compound [Na+].CCCCCCCCCCCC(=O)NCC([O-])=O IKGKWKGYFJBGQJ-UHFFFAOYSA-M 0.000 claims description 10
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical group CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 9
- BLDIAFVPLYNUIE-KVVVOXFISA-M sodium;2-[[(z)-octadec-9-enoyl]amino]acetate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC(=O)NCC([O-])=O BLDIAFVPLYNUIE-KVVVOXFISA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 7
- 239000000203 mixture Chemical group 0.000 claims description 5
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims 2
- JIGPTDXPKKMNCN-UHFFFAOYSA-N 1-(5-butylsulfonyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea Chemical group CCCCS(=O)(=O)C1=NN=C(N(C)C(=O)NC)S1 JIGPTDXPKKMNCN-UHFFFAOYSA-N 0.000 claims 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ODQMOSYKHALMPU-UHFFFAOYSA-N benzylarsonic acid Chemical compound O[As](O)(=O)CC1=CC=CC=C1 ODQMOSYKHALMPU-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 229910052611 pyroxene Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000012991 xanthate Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- 238000010408 sweeping Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater 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
- B03D1/018—Mixtures of inorganic and organic 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
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a titanium selection medicament and a titanium selection method, and belongs to the technical field of titanium selection. The titanium selection medicament comprises a component A and a component B which are packaged in independent units, wherein the component A is at least one of oleoyl sodium glycinate, oleoyl sodium sarcosinate, cocoyl sodium glycinate and cocoyl sodium sarcosinate; the component B is at least one of oxalic acid, sulfamic acid and sodium fluosilicate. The titanium-selecting medicament does not contain extremely toxic arsines, has low medicament dosage, is beneficial to the health of workers, is easier to treat sewage, and has low requirement on equipment. The titanium selecting agent has good titanium selecting effect and less dosage, and the dosage of the titanium selecting agent is reduced by about 30 percent compared with the prior titanium selecting agent, so the cost is lower.
Description
Technical Field
The invention relates to a titanium selection medicament and a titanium selection method, and belongs to the technical field of titanium selection.
Background
As shown in fig. 3, in the prior art, a titanium-containing in-flotation raw ore is subjected to acidic impurity removal pretreatment and flotation to remove a part of impurities, and then a titanium separation agent is added under an acidic condition for flotation, wherein the general flotation comprises rough concentration, scavenging and concentration, and finally titanium concentrate is obtained. The existing titanium ore pretreatment method is to add reagents such as butyl xanthate and No. 2 oil into raw material ore containing titanium under an acidic condition, and remove foam impurities through a primary coarse sweeping and secondary sweeping process.
There are many existing flotation reagents, including arsines, fatty acids, phosphines, hydroxamic acids, and the like. However, for various reasons, the current industrial application is widely mixtures of arsenic species and fatty acids, such as benzylarsonic acid. However, arsines are highly toxic and harmful to the health of workers, so that the requirements for equipment are high, and the treatment of waste water containing toxic arsines is troublesome.
Chinese patent application No. 2014101358112 discloses a titanium-selecting flotation reagent and a titanium-selecting flotation method for weathered ilmenite, wherein weathered ilmenite is crushed to be below 100 meshes, an activating agent is added according to the mass ratio of 160 g/t-400 g/t, and ore grinding is carried out to be-0.074 mm; adjusting the concentration of the ore pulp to 40%; adding 2500-4500 g/t of regulator and 1800-4000 g/t of auxiliary regulator in sequence, and stirring for 2 minutes; then adding 2500-4800 g/t of collecting agent and 60-180 g/t of auxiliary collecting agent in sequence; roughing for 8-10 minutes, scavenging for 8-10 minutes, selecting for 3-6 minutes, and selecting again for 2-5 minutes. Roughing, scavenging, selecting, and performing one roughing and two refining to obtain the titanium concentrate with grade of 48-52% and recovery rate of 80-82%. However, the dosage of the medicament is high, the generated waste is more, the cost is high, and the types of the medicament are too many, which brings great difficulty to the flotation operation and the optimization of technical and economic indexes.
The Chinese patent application with the application number of 2017105468736 discloses a combined collector for flotation of pyroxene type ilmenite as well as a preparation method and application thereof, wherein the combined collector consists of a component A, a component B and water, wherein the component A is oleic acid or oxidized paraffin soap, and the component B is a primary amine salt or quaternary ammonium salt; wherein the weight ratio of the component A to the component B is 9: 1-12: 1, and the weight ratio of the sum of the weight of the component A and the component B to the weight of water is 1: 4-19; the raw ore grade of the pyroxene type ilmenite ore is not higher than 18 percent. But the dosage of the combined collecting agent is 1800-2200 g/t of raw ore. The dosage of the medicament is high, the generated waste is more, the cost is high, and due to the introduction of the amine collecting agent, the equivalent pyroxene impurities are removed under the acidic condition, and meanwhile, the equivalent ilmenite is lost. Because ilmenite is also recovered by amine collectors under acidic conditions.
Disclosure of Invention
The first problem to be solved by the invention is to provide a new titanium-selecting medicament.
In order to solve the first technical problem, the titanium selection medicament comprises a component A and a component B which are packaged in independent units, wherein the component A is at least one of sodium oleoyl glycinate, sodium oleoyl sarcosinate, sodium cocoyl glycinate and sodium cocoyl sarcosinate; the component B is at least one of oxalic acid, sulfamic acid and sodium fluosilicate; the mass ratio of the component A to the component B to the diesel oil is preferably 3-5: 5-8;
preferably, the titanium selection agent further comprises diesel oil, and the mass ratio of the component A to the component B to the diesel oil is 3-5: 5-8: 5-10.
Preferably, the total mass of the sodium oleoyl sarcosinate, the sodium cocoyl glycinate and the sodium cocoyl sarcosinate is 0-20 wt% of the component A, and the mass of the sodium oleoyl glycinate is 80-100 wt% of the component A.
More preferably, the mass of the sodium oleoyl glycinate accounts for 80wt% of the component A, the total mass of the sodium oleoyl sarcosinate, the sodium cocoyl glycinate and the sodium cocoyl sarcosinate accounts for 20wt% of the component A, the mass of the sodium oleoyl sarcosinate accounts for 5-10 wt% of the component A, the mass of the sodium cocoyl sarcosinate accounts for 5-10 wt% of the component A, and the mass of the sodium cocoyl sarcosinate accounts for 5-10 wt% of the component A.
Preferably, the mass of the oxalic acid, the sulfamic acid and the sodium fluosilicate is respectively 15-25 wt%, 15wt% and 60-70 wt% of the component B.
Preferably, the mass of the oxalic acid, the sulfamic acid and the sodium fluosilicate is 15wt%, 15wt% and 70 wt% of the component B respectively.
Preferably, the mass of the oxalic acid, the sulfamic acid and the sodium fluosilicate is respectively 25 wt%, 15wt% and 60 wt% of the component B.
The second technical problem to be solved by the invention is to provide a titanium selection method.
In order to solve the second technical problem, the titanium selection method comprises rough selection, scavenging and fine selection, wherein the titanium selection agent is uniformly mixed with the titaniferous ore pulp and then rough selection is carried out, and the titanium selection agent is adopted for titanium selection in the method;
the use method of the titanium selection medicament comprises the following steps: the component B is uniformly mixed with the titaniferous ore pulp, and then the component A is added.
The same as the prior art, the roughing needs to keep the titaniferous ore pulp in an acidic state with the pH value lower than 7 by using sulfuric acid, and a small amount of diesel oil can be preferably added, wherein the diesel oil can be added before the addition of the component A and the component B, can be added after the addition of the component A or the component B, and can be added into the ore pulp simultaneously with the component A or the component B. The amount of diesel oil is similar to the prior art, and the raw ore containing titanium: the mass ratio of the diesel oil is about 600: 0.3-0.6.
Preferably, the component B is added earlier than the component A for more than 0.5 min.
Preferably, the mass ratio of the component A, the component B and the titanium-containing ore pulp to the float raw ore is as follows: 3-5: 5-8: 10000.
Preferably, said TiO is added to the float ore2The grade is 14-23%.
More preferably, the scavenging comprises a first scavenging and a second scavenging, and the titaniferous ore pulp and a titanium selection agent are mixed and then sequentially subjected to roughing, first scavenging and second scavenging; the foam products of the first scavenging and the second scavenging return to the first roughing and the first scavenging respectively, and the ore pulp of the first roughing and the first scavenging enters the first scavenging and the second scavenging respectively;
the fine separation is to obtain titanium concentrate by sequentially carrying out first fine separation, second fine separation, third fine separation and fourth fine separation on the foam products subjected to the rough separation, wherein the foam products subjected to the first fine separation, the second fine separation and the third fine separation respectively enter the second fine separation, the third fine separation and the fourth fine separation; and the ore pulp of the third concentration and the ore pulp of the fourth concentration return to the second concentration and the third concentration respectively, and the ore pulp of the first concentration returns to the first scavenging, and the ore pulp of the second concentration returns to the roughing.
Preferably, the titanium separation method further comprises the step of removing impurities by sulfur flotation from the float crude ore, wherein the impurities by sulfur flotation comprise alkaline sulfur flotation and acidic sulfur flotation, and the alkaline sulfur flotation comprises the following steps:
mixing titanium-containing float-entering raw ore with an alkali flotation agent, and sequentially performing alkaline impurity removal roughing, an alkaline impurity removal scavenging I and an alkaline impurity removal scavenging II under an alkaline condition, wherein ore pulp of the alkaline impurity removal roughing and the alkaline impurity removal scavenging I respectively enters the alkaline impurity removal scavenging I and the alkaline impurity removal scavenging II;
the acid sulfur flotation and impurity removal method comprises the following steps: mixing the ore pulp of the second alkaline impurity removal scavenging and the acid flotation reagent, and then sequentially carrying out first acidic impurity removal roughing, first acidic impurity removal scavenging and second acidic impurity removal scavenging under an acidic condition, wherein the ore pulp of the first acidic impurity removal roughing, the first acidic impurity removal scavenging and the second acidic impurity removal scavenging respectively enters the first acidic impurity removal scavenging, the second acidic impurity removal scavenging and the roughing;
wherein the acidic condition is a pH of less than 7 and the basic condition is a pH of greater than 7;
preferably, the alkali flotation agent is butyl xanthate, 2# oil and sodium hydroxide; the acid flotation agent is butyl xanthate, 2# oil and sulfuric acid.
Has the advantages that:
1. the titanium-selecting medicament does not contain extremely toxic arsines, has small medicament dosage, is beneficial to the health of workers, is easier to treat sewage, and has low requirement on equipment.
2. The titanium selecting method has good titanium selecting effect and less dosage of the titanium selecting medicament, and the dosage of the titanium selecting medicament is reduced by about 30 percent compared with the prior titanium selecting medicament, so the cost is lower.
Drawings
FIG. 1 is a flow diagram 1 of a preferred titanium selection process of the present invention;
FIG. 2 is a flow diagram 2 of a preferred titanium selection process of the present invention;
FIG. 3 is a flow chart of a prior art titanium selection process.
Detailed Description
In order to solve the first technical problem, the titanium selection medicament comprises a component A and a component B which are packaged in independent units, wherein the component A is at least one of sodium oleoyl glycinate, sodium oleoyl sarcosinate, sodium cocoyl glycinate and sodium cocoyl sarcosinate; the component B is at least one of oxalic acid, sulfamic acid and sodium fluosilicate; the mass ratio of the component A, the component B and the diesel oil is preferably 3-5: 5-8;
preferably, the titanium selection agent further comprises diesel oil, and the mass ratio of the component A to the component B to the diesel oil is 3-5: 5-8: 5-10.
Preferably, the total mass of the sodium oleoyl sarcosinate, the sodium cocoyl glycinate and the sodium cocoyl sarcosinate is 0-20 wt% of the component A, and the mass of the sodium oleoyl glycinate is 80-100 wt% of the component A.
More preferably, the mass of the sodium oleoyl glycinate accounts for 80wt% of the component A, the total mass of the sodium oleoyl sarcosinate, the sodium cocoyl glycinate and the sodium cocoyl sarcosinate accounts for 20wt% of the component A, the mass of the sodium oleoyl sarcosinate accounts for 5-10 wt% of the component A, the mass of the sodium cocoyl sarcosinate accounts for 5-10 wt% of the component A, and the mass of the sodium cocoyl sarcosinate accounts for 5-10 wt% of the component A.
Preferably, the mass of the oxalic acid, the sulfamic acid and the sodium fluosilicate is respectively 15-25 wt%, 15wt% and 60-70 wt% of the component B.
Preferably, the mass of the oxalic acid, the sulfamic acid and the sodium fluosilicate is 15wt%, 15wt% and 70 wt% of the component B respectively.
Preferably, the mass of the oxalic acid, the sulfamic acid and the sodium fluosilicate is respectively 25 wt%, 15wt% and 60 wt% of the component B.
The second technical problem to be solved by the invention is to provide a titanium selection method.
In order to solve the second technical problem, the titanium selection method comprises rough selection, scavenging and fine selection, wherein the titanium selection agent is uniformly mixed with the titaniferous ore pulp and then rough selection is carried out, and the titanium selection agent is adopted for titanium selection in the method;
the use method of the titanium selection medicament comprises the following steps: the component B is uniformly mixed with the titaniferous ore pulp, and then the component A is added.
The same as the prior art, the roughing needs to use sulfuric acid to keep the titaniferous ore pulp in an acidic state with the pH value lower than 7, and a small amount of diesel oil can be preferably added, wherein the diesel oil can be added before the addition of the A and the B, can be added after the addition of the A or the B component, and can be added into the ore pulp simultaneously with the A or the B component. The amount of diesel oil is similar to the prior art, and the raw ore containing titanium: the mass ratio of the diesel oil is about 600: 0.3-0.6.
Preferably, the component B is added earlier than the component A by more than 0.5 min.
The time interval of the component B added earlier than the component A by more than 0.5min can be more than 0.5min at the same feed inlet, and the component B can be controlled to be mixed with the titanium ore earlier than the component A by more than 0.5min by the adding positions of the component B and the component A.
Preferably, the mass ratio of the component A, the component B and the titanium-containing ore pulp to the float raw ore is as follows: 3-5: 5-8: 10000.
Preferably, the TiO of the float ore2The grade is 14-23%.
More preferably, the scavenging comprises a first scavenging and a second scavenging, and the titaniferous ore pulp and a titanium selection agent are mixed and then sequentially subjected to roughing, first scavenging and second scavenging; the foam products of the first scavenging and the second scavenging return to the first roughing and the first scavenging respectively, and the ore pulp of the first roughing and the first scavenging enters the first scavenging and the second scavenging respectively;
the fine separation is to obtain titanium concentrate by sequentially carrying out first fine separation, second fine separation, third fine separation and fourth fine separation on the foam products subjected to the rough separation, wherein the foam products subjected to the first fine separation, the second fine separation and the third fine separation respectively enter the second fine separation, the third fine separation and the fourth fine separation; and the ore pulp of the third concentration and the ore pulp of the fourth concentration return to the second concentration and the third concentration respectively, and the ore pulp of the first concentration returns to the first scavenging, and the ore pulp of the second concentration returns to the roughing.
The flotation reagent has good flotation effect and high separation degree of impurities and titanium, the grade of titanium of the ore pulp after the first selection is closer to that of the first scavenging, and the returning of the ore pulp after the first selection to the first scavenging can greatly reduce the roughing load, improve the efficiency of the titanium selection process, save energy consumption and further reduce cost.
Preferably, the titanium separation method further comprises the step of removing impurities by sulfur flotation from the float crude ore, wherein the impurities by sulfur flotation comprise alkaline sulfur flotation and acidic sulfur flotation, and the alkaline sulfur flotation comprises the following steps:
mixing titanium-containing flotation raw ore with an alkali flotation agent, and sequentially carrying out alkaline impurity removal roughing, alkaline impurity removal scavenging I and alkaline impurity removal scavenging II under an alkaline condition, wherein ore pulp of the alkaline impurity removal roughing and the alkaline impurity removal scavenging I respectively enters the alkaline impurity removal scavenging I and the alkaline impurity removal scavenging II;
the acid sulfur flotation and impurity removal method comprises the following steps: mixing the ore pulp of the second alkaline impurity removal scavenging and the acid flotation reagent, and then sequentially carrying out first acidic impurity removal roughing, first acidic impurity removal scavenging and second acidic impurity removal scavenging under an acidic condition, wherein the ore pulp of the first acidic impurity removal roughing, the first acidic impurity removal scavenging and the second acidic impurity removal scavenging respectively enters the first acidic impurity removal scavenging, the second acidic impurity removal scavenging and the roughing;
wherein the acidic condition is a pH of less than 7 and the basic condition is a pH of greater than 7;
preferably, the alkali flotation agent is butyl xanthate, 2# oil and sodium hydroxide; the acid flotation agent is butyl xanthate, 2# oil and sulfuric acid.
The newly added alkali flotation impurity removal agents comprise the butyl xanthate, the No. 2 oil and the sodium hydroxide, the acid flotation impurity removal agents comprise the butyl xanthate, the No. 2 oil and the sulfuric acid, and different pH values are also provided, so that more kinds of impurities can be removed. The whole titanium selection process has higher efficiency, saves more energy and has little pollution to the environment.
The dosage of the butyl xanthate and the 2# oil is the same as that of the existing acid flotation impurity removal.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the invention to the embodiments described.
TiO of raw material titanium ore used in examples and comparative examples of the present invention2The grade is 18.92 percent, the size of the raw material ilmenite particles is the conventional titanium selection granularity, namely, the mass content of-200 meshes is 45-75 percent. .
Example 1
As shown in FIG. 1, 600g of TiO was added2Adding water into the float raw ore with the grade of 18.92 percent to prepare titanium-containing ore pulp with the concentration of 55 percent, and mixing the pulp with an acid flotation reagent: 0.12g of xanthate, 0.048g of 2# oil and 12g of 5% dilute sulfuric acid are mixed and then sequentially subjected to acid impurity removal roughing, first acid impurity removal scavenging and second acid impurity removal scavenging under the acid condition that the pH value is less than 7, foam products of the acid impurity removal roughing, first acid impurity removal scavenging and second acid impurity removal scavenging are discarded as impurities, ore pulp of the acid impurity removal roughing and first acid impurity removal scavenging respectively enters the first acid impurity removal scavenging and the second acid impurity removal scavenging, the ore pulp of the second acid impurity removal scavenging is mixed with 0.5g of diesel oil, 0.4g of component B containing 15wt% of oxalic acid, 15wt% of sulfamic acid and 70 wt% of sodium fluosilicate for 0.5min and then 0.3g of component A is added, the mass of sodium oleoyl glycinate in the component A is 80wt%, the mass of sodium oleoyl sarcosinate is 10wt%, the sodium cocoyl glycinate is 5wt% and the sodium cocoyl sarcosinate is 5wt%, and the ore pulp mixed with the component A is subjected to roughing, the ore pulp after the roughing is sequentially subjected to first scavenging and second scavenging, foams of the first scavenging and the second scavenging are respectively returned to the first roughing and the first scavenging, and the ore pulp of the first roughing and the first scavenging enters the first scavenging and the second scavenging; the ore pulp of the second scavenging is the tailings and is discarded; the roughly selected foam product is sequentially subjected to first selection, second selection, third selection and fourth selection to obtain titaniumConcentrate, namely, respectively feeding foam products of first concentration, second concentration and third concentration into second concentration, third concentration and fourth concentration; and returning the ore pulp of the third concentration and the ore pulp of the fourth concentration to the second concentration and the third concentration respectively, returning the ore pulp of the first concentration to the first scavenging, and returning the ore pulp of the second concentration to the rough concentration.
The titanium concentrate TiO is obtained by the concentration2The grade is 47.5-49%, and the recovery rate is 85-86%. The cost of the titanium concentrate titanium-selecting agent is 90 yuan/ton concentrate.
Example 2
As shown in FIG. 2, 600g of TiO was added2Adding water into the float raw ore with the grade of 18.92 percent to prepare titanium-containing ore pulp with the concentration of 45 percent, and mixing the pulp with an alkaline flotation reagent: mixing 0.12g of xanthate, 0.048g of No. 2 oil and 1g of 10% sodium hydroxide, then sequentially carrying out alkaline impurity removal roughing, alkaline impurity removal scavenging I and alkaline impurity removal scavenging II under the alkaline condition that the pH value is greater than 7, discarding foam products of the alkaline impurity removal roughing, the alkaline impurity removal scavenging I and the alkaline impurity removal scavenging II as impurities, sequentially feeding ore pulp of the alkaline impurity removal roughing and the alkaline impurity removal scavenging I into the alkaline impurity removal scavenging I and the alkaline impurity removal scavenging II, mixing the ore pulp of the alkaline impurity removal scavenging II with an acid flotation agent 0.12g of xanthate, 0.048g of No. 2 oil and 12g of 5% sulfuric acid, sequentially carrying out acidic impurity removal roughing, acidic impurity removal scavenging I and acidic impurity removal scavenging II under the acidic condition that the pH value is less than 7, discarding foam of the acidic impurity removal roughing, acidic impurity removal scavenging I and acidic impurity removal scavenging II, sequentially feeding the ore pulp of the acidic impurity removal roughing, acidic impurity removal scavenging I and acidic impurity removal scavenging II, Acid impurity removal and scavenging II, mixing the ore pulp of the acid impurity removal and scavenging II with 0.4g of a component B containing 25 wt% of oxalic acid, 15wt% of sulfamic acid and 60 wt% of sodium fluosilicate for 0.5min, then adding 0.18g of a component A and 0.5g of diesel oil for uniformly mixing, then roughing, wherein the mass of oleoyl sodium glycinate in the component A is 80wt%, oleoyl sodium sarcosinate is 10wt%, cocoyl sodium glycinate 5wt% and cocoyl sodium sarcosinate 5wt%, sequentially carrying out first scavenging and second scavenging on the ore pulp after roughing, returning foams of the first scavenging and the second scavenging to the first scavenging and the second scavenging respectively, and respectively entering the first scavenging and the second scavenging; the ore pulp of the second scavenging is the tailings and is discarded; the roughly selected foam is sequentially subjected to first selection and second selectionSecondly, selecting the third step and the fourth step to obtain titanium concentrate, and enabling foams of the first step, the second step and the third step to enter the second step, the third step and the fourth step respectively; and returning the ore pulp of the third concentration and the ore pulp of the fourth concentration to the second concentration and the third concentration respectively, returning the ore pulp of the first concentration to the first scavenging, and returning the ore pulp of the second concentration to the rough concentration.
The titanium concentrate TiO is obtained by the concentration2The grade is 48-49%, and the recovery rate is 88-89%. The cost of the titanium concentrate titanium-selecting agent is 55 yuan/ton concentrate.
Comparative example 1
As shown in fig. 3, the difference from example 1 is that the flotation reagent is a mixture of the existing reagents of benzylarsonic acid and oleic acid soap, benzylarsonic acid: the mass ratio of the oleic acid soap is as follows: 2:8, returning the ore pulp of the first concentration to the rough concentration of the previous stage, and returning the ore pulp of the second concentration to the first concentration, and the rest is the same as the embodiment 1.
The titanium concentrate TiO is obtained by the concentration2The grade is 47-47.5%, and the recovery rate is 82-83%. The cost of the titanium concentrate titanium-selecting agent is 100-120 yuan per ton of concentrate.
As can be seen from the examples 1 and 2 and the comparative example 1, the flotation effect of the medicament titanium is good, and the consumption of the collecting agent is greatly reduced by adopting the process.
Claims (13)
1. The titanium selection agent is characterized by consisting of a component A, a component B and diesel oil which are packaged in independent units, wherein the component A is at least one of oleoyl sodium glycinate, oleoyl sodium sarcosinate, cocoyl sodium glycinate and cocoyl sodium sarcosinate; the component B is sulfamic acid, or a composition of oxalic acid and sulfamic acid, or a composition of sulfamic acid and sodium fluosilicate, or a composition of oxalic acid, sulfamic acid and sodium fluosilicate; the mass ratio of the component A to the component B to the diesel oil is 3-5: 5-8: 5-10.
2. The titanium-selecting medicament of claim 1, wherein the total mass of sodium oleoyl sarcosinate, sodium cocoyl glycinate and sodium cocoyl sarcosinate is 0-20 wt% of component A, and the mass of sodium oleoyl glycinate is 80-100 wt% of component A.
3. The titanium-selecting medicament of claim 2, wherein the mass of the sodium oleoyl glycinate is 80wt% of component A, the total mass of the sodium oleoyl sarcosinate, the sodium cocoyl glycinate and the sodium cocoyl sarcosinate is 20wt% of component A, the mass of the sodium oleoyl sarcosinate is 5-10 wt% of component A, the mass of the sodium cocoyl glycinate is 5-10 wt% of component A, and the mass of the sodium cocoyl sarcosinate is 5-10 wt% of component A.
4. The agent for selecting titanium according to any one of claims 1 to 3, wherein the oxalic acid, the sulfamic acid and the sodium fluosilicate account for 15 to 25 wt%, 15wt% and 60 to 70 wt% of the component B, respectively.
5. The titanium selecting agent as defined in claim 4, wherein the mass of oxalic acid, sulfamic acid and sodium fluosilicate is 15wt%, 15wt% and 70 wt% of component B respectively.
6. The titanium selecting agent as defined in claim 4, wherein the mass of oxalic acid, sulfamic acid and sodium fluosilicate is 25 wt%, 15wt% and 60 wt% of component B respectively.
7. The titanium selection method comprises rough selection, scavenging and fine selection, wherein a titanium selection agent is uniformly mixed with titaniferous ore pulp and then rough selection is carried out, and the method is characterized in that the titanium selection agent of any one of claims 1-6 is adopted to select titanium;
the use method of the titanium selection medicament comprises the following steps: the component B is uniformly mixed with the titaniferous ore pulp, and then the component A is added.
8. A method for titanium selection according to claim 7 wherein component B is added earlier than component A by more than 0.5 min.
9. The titanium selecting method according to claim 7, wherein the mass ratio of the component A, the component B and the titanium-containing ore pulp entering the float ore is as follows: 3-5: 5-8: 10000.
10. A process according to claim 9, wherein the TiO is carried into the float ore2The grade is 14-23%.
11. The titanium selecting method according to claim 7 or 8, wherein the scavenging comprises a first scavenging and a second scavenging, and the titaniferous ore pulp and a titanium selecting agent are mixed and then sequentially subjected to roughing, first scavenging and second scavenging; the foam products of the first scavenging and the second scavenging return to the first roughing and the first scavenging respectively, and the ore pulp of the first roughing and the first scavenging enters the first scavenging and the second scavenging respectively;
the fine separation is to obtain titanium concentrate by sequentially carrying out first fine separation, second fine separation, third fine separation and fourth fine separation on the foam products subjected to the rough separation, wherein the foam products subjected to the first fine separation, the second fine separation and the third fine separation respectively enter the second fine separation, the third fine separation and the fourth fine separation; and the ore pulp of the third concentration and the ore pulp of the fourth concentration return to the second concentration and the third concentration respectively, and the ore pulp of the first concentration returns to the first scavenging, and the ore pulp of the second concentration returns to the roughing.
12. The titanium separation method according to claim 9, further comprising subjecting the float ore to sulfur flotation and impurity removal, wherein the sulfur flotation and impurity removal comprises alkaline sulfur flotation and impurity removal and acidic sulfur flotation and impurity removal, and the alkaline sulfur flotation and impurity removal is as follows:
mixing titanium-containing flotation raw ore with an alkali flotation agent, and sequentially carrying out alkaline impurity removal roughing, alkaline impurity removal scavenging I and alkaline impurity removal scavenging II under an alkaline condition, wherein ore pulp of the alkaline impurity removal roughing and the alkaline impurity removal scavenging I respectively enters the alkaline impurity removal scavenging I and the alkaline impurity removal scavenging II;
the acid sulfur flotation and impurity removal method comprises the following steps: mixing the ore pulp of the second alkaline impurity removal scavenging and the acid flotation reagent, and then sequentially carrying out first acidic impurity removal roughing, first acidic impurity removal scavenging and second acidic impurity removal scavenging under an acidic condition, wherein the ore pulp of the first acidic impurity removal roughing, the first acidic impurity removal scavenging and the second acidic impurity removal scavenging respectively enters the first acidic impurity removal scavenging, the second acidic impurity removal scavenging and the roughing;
wherein the acidic condition is a pH of less than 7 and the basic condition is a pH of greater than 7.
13. The titanium separation method according to claim 12, wherein the alkali flotation agent is butyl xanthate, 2# oil, sodium hydroxide; the acid flotation agent is buthiuron, 2# oil and sulfuric acid.
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