CN108672095A - γ-hydroxy alkyl hydroximic acid and the preparation method and application thereof - Google Patents
γ-hydroxy alkyl hydroximic acid and the preparation method and application thereof Download PDFInfo
- Publication number
- CN108672095A CN108672095A CN201810417146.4A CN201810417146A CN108672095A CN 108672095 A CN108672095 A CN 108672095A CN 201810417146 A CN201810417146 A CN 201810417146A CN 108672095 A CN108672095 A CN 108672095A
- Authority
- CN
- China
- Prior art keywords
- hydroximic acid
- hydroxy alkyl
- acid
- preparation
- alkyl hydroximic
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses γ hydroxy alkyl hydroximic acids and the preparation method and application thereof, γ hydroxy alkyl hydroximic acid chemical structural formulas such as formula（）It is shown, n=4 ~ 7 in formula.It is prepared by following methods：It is 1 according to substance molal quantity:1.1~1.3:2.1 ~ 2.3, third alkyl lactone, hydroxylamine hydrochloride are mixed with alkali, with water as solvent, at 30 ~ 50 DEG C of reaction temperature, reacts 2 ~ 6 hours, is acidified to obtain γ hydroxy alkyl hydroximic acids with sulfuric acid.The preparation condition of the present invention is mild, and synthesis is green and Atom economy is good.The collecting agent has OH and C (O) NH OH bipolarity groups, can emerge efficient as oxide mineral collector and be not required to that foaming agent additionally is added.
Description
Technical field
The invention belongs to floating agent and its preparation fields, relate generally to γ-hydroxy alkyl hydroximic acid and preparation method thereof
With application.
Background technology
Hydroximic acid（Hydroxamic acid）There is very strong chelating to metal ion Cu, Cr, Co, Fe, Mn, W, Sn etc.
Ability uses in mineral engineering usually as the flotation collector of iron oxide ore, black and white tungsten ore, rare earth and tin ore.
Relative to benzyl hydroximic acid and Salicyl Hydroximic Acid, alkyl hydroximic acid（C5-9）Raw material-C5-9Petrochemical industry can be used in carboxylic acid
Heavy oil or alkene in industry are reacted by paraffin oxidation style or alkene carbonyl process to be made, while alkyl hydroximic acid has more preferably
Biodegradable.Ji Junmei（Non-ferrous metal (ore dressing part), 2004 (4):42-44）Have studied alkylhydroxyoximate with
The flotation of ilmenorutile and the mechanism of action.Qu Guosheng（Chinese Mining Industry, 1998 (6):82-84）Have studied C5-9Hydroximic acid is to peace
The flotation of Dongshan iron ore, experiments have shown that in pH values of pulp=10, alkyl hydroximic acid floatation indicators are better than oxidized paraffin wax soap.Cheng Qi（It answers
With chemical industry, 2016,45 (8):1407-1411）Have studied flotation performance and mechanism of the decyl hydroximic acid to ilmenite, experiment knot
Fruit shows that the collecting ability of decyl hydroximic acid is better than octyl hydroximic acid, and collecting agent molecular ion eutectoid content is in mineral surfaces.What
Know beautiful（China rare earth journal, 2016 (2):244-251）Have studied flotation performance of the modified alkyl hydroximic acid to bastnaesite.
Experiments have shown that modified collecting agent（C5-9Hydroximic acid, C5-22Aliphatic acid and solvent naphtha) flotation effect is significantly stronger than 1- hydroxyl -2- naphthalene hydroxyls
Oxime acid and Salicyl Hydroximic Acid.Wang Peipei（China YouSe Acta Metallurgica Sinica (English edition), 2013 (6):1789-1796）Alkane is carried out
Base hydroximic acid（C7, C8, C9）Flotation to Fine cassiterite and its solution chemistry research.Azizi（Colloids &
Surfaces A Physicochemical & Engineering Aspects, 2017）Have studied alkyl hydroximic acid and water glass
Screening test of the glass to calcite, dolomite and ankerite.CN104016883A discloses -2 hexene hydroximic acid of 2- ethyls（C8
Hydroximic acid）And combinations thereof collecting agent and they application.This C8Hydroximic acid is by -2 hexenoic acid one pot process of 2- ethyls, system
Standby mild condition, product are generated without acidification, no waste water.
Relative to unipolarity, bipolarity group can assign hydroximic acid more physico-chemical properties.Such as water solubility, foaming characteristic,
Compatibility, low temperature resistivity and medicament are to mineral collecting ability etc..Jiang Yuren（Hydrometallurgy, 2010, 104(1):
112-118）Bipolarity-alkyl-carbonyl hydroximic acid is had studied to study aluminum silicon mineral flotation performance.CN103301953A is disclosed
Bipolarity -6- aryl amido group hexyl hydroximic acid collecting agents are to black and white tungsten ore, Rare Earth Mine, tin ore, bauxite, ilmenite and firefly
The flotation behavior of stone ore.Such collecting agent carries multiple polar group（Amide groups and oximido）, there is good dispersivity in water
And anti-seismic design, collecting ability is significantly stronger than benzyl hydroximic acid and dosing is small.Seemingly with amide groups hydroximic acid,
CN106423573A discloses a kind of application process of ester group hydroximic acid collecting agent on mineral floating, such medicament has good
Biodegradable.
Invention content
The present invention provides γ-hydroxy alkyl hydroximic acid and preparation method and application.The γ-hydroxy alkyl hydroximic acid is by third
Position alkyl lactone and azanol carry out obtained by hydroxyl oximate ring-opening reaction, and preparation condition is mild, and synthesis is green and Atom economy is good.It should
Collecting agent has-OH and C (O)-NH-OH bipolarity groups, can emerge efficient as oxide mineral collector and be not required to volume
Outer addition foaming agent.
The chemical structural formula of the γ-hydroxy alkyl hydroximic acid is shown below：
N=4 ~ 7 in formula.
Alkyl carbon chain lengths in the γ-hydroxy alkyl hydroximic acid are 9-12.
The γ-hydroxy alkyl hydroximic acid is prepared by following methods：
It is 1 according to substance molal quantity:1.1~1.3:2.1 ~ 2.3, third alkyl lactone, hydroxylamine hydrochloride are mixed with alkali, made with water
Solvent reacts 2 ~ 6 hours at 30 ~ 50 DEG C of reaction temperature, is acidified to obtain γ-hydroxyl-alkyl hydroximic acid with sulfuric acid.
The alkali is sodium hydroxide or potassium hydroxide.
The γ-application of the hydroxy alkyl hydroximic acid as beneficiation collecting agent, for the floating of tungsten ore, Rare Earth Mine or tin ore
Choosing.
γ-hydroxy alkyl hydroximic acid the preparation method and its collecting agent of the present invention has the following advantages：
（1）Synthesis green, does not use toxic organic solvents；
（2）The Atom economy of chemical reaction is good, and no additional organic by-products generate；
（3）Hydroxy alkyl hydroximic acid foaming characteristic is good, foam is sticky, collecting ability is strong by γ-.
Description of the drawings
Fig. 1 is the infrared spectrogram of γ-hydroxynonyl hydroximic acid；
Fig. 2 is the infrared spectrogram of γ-hydroxydecyl hydroximic acid；
Fig. 3 is the infrared spectrogram of γ-hydroxydodecyl hydroximic acid；
Fig. 4 is liquid phase-mass spectrogram of γ-hydroxynonyl hydroximic acid；
Fig. 5 is liquid phase-mass spectrogram of γ-hydroxydecyl hydroximic acid；
Fig. 6 is liquid phase-mass spectrogram of γ-hydroxydodecyl hydroximic acid；
Fig. 7 is the process flow chart of γ-hydroxynonyl hydroximic acid flotation tin ore；
Fig. 8 is the process flow chart of γ-hydroxydecyl hydroximic acid Flotation Wolframite；
Fig. 9 is the process flow chart of γ-hydroxydodecyl hydroximic acid flotation of rare earth.
Specific implementation mode
Embodiment 1
The preparation of γ-hydroxynonyl hydroximic acid.
By 0.11mol hydroxylamine hydrochlorides, 0.21mol sodium hydroxides, third nonalactone of 0.1mol and 40mL water, control reaction temperature
Degree is 30 DEG C, reacts 6 hours, is acidified with the concentrated sulfuric acid, removes reaction dissolvent and obtains crude product 16.80g.It is surveyed by Kjeldahl's method
It is 6.8% to obtain the N content in crude product, reaction yield 81.52%.Crude product is purified by column chromatography（Rf=0.29, EtOAc/
MeOH,9:1).γ-hydroxynonyl hydroximic acid is pale yellow oily liquid, and P=1.14 CLog, can be dissolved in methanol and ethyl alcohol etc. has
Solvent is insoluble in water.Its infrared spectrum is shown in Fig. 1,3242cm-1With the stretching vibration peak of N-H and-OH, 2936 and 2866cm-1
For-CH3With-CH2Asymmetric stretching vibration peak, 1773 and 1642cm-1It is carbon-based（C=O）Stretching vibration peak, 1467cm-1For
C-NH stretching vibration peaks.Product passes through liquid phase-Mass Spectrometer Method（See Fig. 4）, find the molecular ion peak of γ-hydroxydecyl hydroximic acid
Mr:[M+1] 190.1441, MS：[M-16] 173.1368 is the fragment peak of demethyl, MS：[M-32] 157.1224 is to go first
Base, the fragment peak of hydroxyl.
Embodiment 2
The preparation of γ-hydroxydecyl hydroximic acid.
By 0.12mol hydroxylamine hydrochlorides, 0.22mol sodium hydroxides, 0.1mol gamma decalactones and 50mL water, control reaction temperature
Degree is 40 DEG C, reacts 4 hours, is acidified with the concentrated sulfuric acid, removes reaction dissolvent and obtains crude product 19.31g.It is surveyed by Kjeldahl's method
It is 5.6% to obtain the N content in crude product, reaction yield 76.28%.Crude product is purified by column chromatography（Rf=0.35, EtOAc/
MeOH,9:1).γ-hydroxydecyl hydroximic acid is pale yellow oily liquid, and P=1.253 viscosity CLog can be dissolved in methanol and second
The organic solvents such as alcohol, are insoluble in water.Its infrared spectrum is shown in Fig. 2,3197cm-1With the stretching vibration peak of N-H and-OH, 2926 Hes
2856cm-1For-CH3With-CH2Asymmetric stretching vibration peak, 1773 and 1667cm-1It is carbon-based（C=O）Stretching vibration peak,
1467cm-1For C-NH stretching vibration peaks.Product passes through liquid phase-Mass Spectrometer Method（See Fig. 5）, find γ-hydroxydecyl hydroximic acid
Molecular ion peak Mr:[M+1] 204.1596, MS：[M-16] 187.1523 is the fragment peak of demethyl, MS [M-32]：
171.1383 being demethyl, the fragment peak of hydroxyl.
Embodiment 3
The preparation of γ-hydroxydodecyl hydroximic acid.
By 0.13mol hydroxylamine hydrochlorides, 0.23mol potassium hydroxide, third dodecyl lactone of 0.1mol and 60mL water, control
Reaction temperature is 50 DEG C, reacts 2 hours, is acidified with the concentrated sulfuric acid, removes reaction dissolvent and obtains crude product 20.33g.It is fixed by kelvin
It is 5.2% that nitrogen method, which measures the N content in crude product, reaction yield 74.99%.Crude product is purified by recrystallization（H2O/MeOH,
1:1).γ-hydroxydodecyl hydroximic acid is white solid, and 42-44 DEG C of melting range, P=2.311 CLog can be dissolved in methanol and second
The organic solvents such as alcohol, are insoluble in water.Its infrared spectrum is shown in Fig. 1,3237cm-1With the stretching vibration peak of N-H and-OH, 2931 Hes
2856cm-1For-CH3With-CH2Asymmetric stretching vibration peak, 1772 and 1667cm-1It is carbon-based（C=O）Stretching vibration peak,
1467cm-1For C-NH stretching vibration peaks.Product passes through liquid phase-Mass Spectrometer Method（See Fig. 4）, find γ-hydroxydodecyl hydroxyl oxime
The molecular ion peak Mr of acid:[M+1] 232.1915, MS：[M-16] 215.1841 is the fragment peak of demethyl, MS：[M-32]
199.1698 being demethyl, the fragment peak of hydroxyl.
Embodiment 4
γ-flotation of the hydroxynonyl hydroximic acid to tin ore.
Certain technics of cassiterite clay raw ore tin grade 0.5%, granularity 0.074mm accounts for 75%, adds water to size mixing to 30% mass concentration, adds
Enter Na2CO3 300g/t, CMC 100g/t, γ-hydroxynonyl hydroximic acid dosage 280g/t carry out technics of cassiterite clay roughing flotation,
γ-hydroxynonyl hydroximic acid 60g/t is added in once purging selection, and γ-hydroxynonyl hydroximic acid 30g/t is added in secondary scan（Medicament system
Degree is shown in Table 1）.CMC 30g/t are added in primary cleaning, and CMC 20g/t are added in recleaning, and CMC 15g/t are added in triple cleaning, float
Process flow chart is selected to see Fig. 7.The flotation comparative test result of γ-hydroxynonyl hydroximic acid and Salicyl Hydroximic Acid is shown in Table in the present invention
1.As shown in Table 1, using γ-hydroxynonyl hydroximic acid, the rate of recovery of Tin concentrate improves 5.13%.
1 γ of table-hydroxynonyl hydroximic acid Flotation of Cassiterite contrast test
Embodiment 5
γ-flotation of the hydroxydecyl hydroximic acid to black tungsten.
Certain tungsten ore floats sulphur tailing, contains WO to mine3Ore ore grinding to -0.074mm is accounted for 76%, ore flotation by 0.3-0.45 %
Concentration 40%, waterglass 1800g/t, plumbi nitras 350g/t are starched, it is thick to carry out floating sulphur tailing by γ-hydroxydecyl hydroximic acid 175g/t
Choosing, scans and γ-hydroxydecyl hydroximic acid 20g/t is added, and γ-hydroxydecyl hydroximic acid 20g/t is added in secondary scan（Regime of agent
It is shown in Table 2）, acidified sodium silicate 800 g/t is added in primary cleaning, and acidified sodium silicate 600g/t, triple cleaning is added in secondary waterglass
Acidified sodium silicate 500g/t is added, flotation process figure is shown in Fig. 8.γ-hydroxydecyl hydroximic acid in the present invention and benzene first hydroxyl
The flotation comparative test result of oxime acid is shown in Table 2.As shown in Table 2, using γ-hydroxydecyl hydroximic acid, black tungsten floats WO in sulphur tailing3
The rate of recovery improve 5.72%.
The black tungsten contrast test of 2 γ of table-hydroxydecyl hydroximic acid flotation
Embodiment 6
Flotation performance of the γ-hydroxydodecyl hydroximic acid to rare earth
Chinese somewhere rare-earth original ore stone is selected, mainly by bastnaesite, parisite, monazite, barite, fluorite, Fang Xie
The mineral compositions such as stone, orthoclase, quartz, arfvedsonite, aegirine, hornblend, coronadite, biotite and kaolin, REO grades
2.79%.By raw ore after rod mill ore grinding, the material that -0.075mm contents are 80% is obtained, is obtained after high magnetic separation
The high intensity magnetic mineral of REO grades 23 ~ 24% uses high intensity magnetic mineral to be selected in material as flotation.Acidification is added in flotation pulp a concentration of 30%
Waterglass 3000g/t, γ-hydroxydodecyl hydroximic acid 1000g/t, No. 2 oil 80g/t of foaming agent are not added with No. 2 oil, are floated
Select roughing, once purging selection that γ-hydroxydodecyl hydroximic acid 200g/t is added（Regime of agent is shown in Table 2）, primary cleaning acidifying water
Glass 800g/t, recleaning acidified sodium silicate 600g/t, flotation process figure are shown in Fig. 9.γ-hydroxydodecanoic in the present invention
Base hydroximic acid and C5-9Hydroximic acid flotation comparative test result is shown in Table 3.As shown in Table 3, the rate of recovery of REO improves in rare earth ore concentrate
5.05%.
3 γ of table-hydroxydodecyl hydroximic acid flotation of rare earth contrast test
Claims (6)
1. γ-hydroxyl-alkyl hydroximic acid, which is characterized in that chemical structural formula such as formula（）It is shown：
N=4 ~ 7 in formula.
2. γ described in claim 1-hydroxy alkyl hydroximic acid, which is characterized in that the alkyl carbon chain lengths are 9-12.
3.
The preparation method of γ-hydroxy alkyl hydroximic acid described in claim 1-2, which is characterized in that by following methods preparation
At：It is 1 according to substance molal quantity:1.1~1.3:2.1 ~ 2.3, third alkyl lactone, hydroxylamine hydrochloride are mixed with alkali, made with water molten
Agent reacts 2 ~ 6 hours at 30 ~ 50 DEG C of reaction temperature, is acidified to obtain γ-hydroxyl-alkyl hydroximic acid with sulfuric acid.
4. the preparation method of γ according to claim 3-hydroxy alkyl hydroximic acid, which is characterized in that the alkali is hydrogen-oxygen
Change sodium or potassium hydroxide.
5. γ-application of the hydroxy alkyl hydroximic acid as beneficiation collecting agent described in claim 1-4.
6. application according to claim 5, which is characterized in that the beneficiation collecting agent is used for tungsten ore, Rare Earth Mine or tin ore
Flotation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810417146.4A CN108672095A (en) | 2018-05-04 | 2018-05-04 | γ-hydroxy alkyl hydroximic acid and the preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810417146.4A CN108672095A (en) | 2018-05-04 | 2018-05-04 | γ-hydroxy alkyl hydroximic acid and the preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108672095A true CN108672095A (en) | 2018-10-19 |
Family
ID=63802045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810417146.4A Pending CN108672095A (en) | 2018-05-04 | 2018-05-04 | γ-hydroxy alkyl hydroximic acid and the preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108672095A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057614A (en) * | 2021-11-05 | 2022-02-18 | 广东省科学院资源利用与稀土开发研究所 | Hydroximic acid sulfonic acid compound and preparation method and application thereof |
| CN115155824A (en) * | 2022-07-05 | 2022-10-11 | 中南大学 | Beneficiation method for recovering tin from tin-containing fine mud |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU433723A1 (en) * | 1973-06-21 | 1978-09-25 | Горнометаллургический Институт Кольского Филиала Ан Ссср | Flotation method sphene from ores |
| EP0311759A2 (en) * | 1987-10-15 | 1989-04-19 | American Cyanamid Company | Novel collectors and processes for making and using same |
| CN1245798A (en) * | 1998-08-10 | 2000-03-01 | 阿迪尔公司 | New hydroxamic acid compounds, their preparation method and medicine composition containing them |
| CN1300210A (en) * | 1998-05-16 | 2001-06-20 | 英国生物技术药物有限公司 | Hydroxamic acid derivatives as antibacterials |
| CN104016883A (en) * | 2014-05-15 | 2014-09-03 | 中南大学 | 2-ethyl-2-hexenyl hydroximic acid as well as combined collector thereof and application of 2-ethyl-2-hexenyl hydroximic acid and combined collector |
-
2018
- 2018-05-04 CN CN201810417146.4A patent/CN108672095A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU433723A1 (en) * | 1973-06-21 | 1978-09-25 | Горнометаллургический Институт Кольского Филиала Ан Ссср | Flotation method sphene from ores |
| EP0311759A2 (en) * | 1987-10-15 | 1989-04-19 | American Cyanamid Company | Novel collectors and processes for making and using same |
| CN1300210A (en) * | 1998-05-16 | 2001-06-20 | 英国生物技术药物有限公司 | Hydroxamic acid derivatives as antibacterials |
| CN1245798A (en) * | 1998-08-10 | 2000-03-01 | 阿迪尔公司 | New hydroxamic acid compounds, their preparation method and medicine composition containing them |
| CN104016883A (en) * | 2014-05-15 | 2014-09-03 | 中南大学 | 2-ethyl-2-hexenyl hydroximic acid as well as combined collector thereof and application of 2-ethyl-2-hexenyl hydroximic acid and combined collector |
Non-Patent Citations (3)
| Title |
|---|
| 刘殿文: "《氧化铜矿浮选技术》", 31 May 2009, 冶金工业出版社 * |
| 百见熙: "《浮选药剂》", 31 August 1981, 冶金工业出版社 * |
| 魏文德: "《有机化工原料大全（第二版）中卷》", 31 January 1999, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057614A (en) * | 2021-11-05 | 2022-02-18 | 广东省科学院资源利用与稀土开发研究所 | Hydroximic acid sulfonic acid compound and preparation method and application thereof |
| CN115155824A (en) * | 2022-07-05 | 2022-10-11 | 中南大学 | Beneficiation method for recovering tin from tin-containing fine mud |
| CN115155824B (en) * | 2022-07-05 | 2024-01-26 | 中南大学 | Mineral separation method for recovering tin from tin-containing fine mud |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106423573B (en) | Application method of ester hydroxamic acid collecting agent in mineral flotation | |
| CN108906331A (en) | A kind of hydrocarbon amide groups-bis- hydroximic acid compounds and its application in mineral floating | |
| CN108672093A (en) | A kind of collecting agent and its preparation method and application | |
| US4853113A (en) | Froth Flotation of bastnaesite | |
| EP2017009B1 (en) | Reverse iron ore flotation by collectors in aqueous nanoemulsion | |
| CN108672095A (en) | γ-hydroxy alkyl hydroximic acid and the preparation method and application thereof | |
| CN103922968B (en) | Preparation method of hydroxamic acid or hydroxamic acid salt | |
| CN111644270B (en) | Beneficiation process for recovering fluorite from tailings | |
| CN103301952A (en) | 6-aliphatic hydrocarbon amido hexyl hydroximic acid collecting agent and preparation and application methods thereof | |
| CN106955791B (en) | N-alkyl hydroximic acid-dithiocarbamate collecting agent, preparation and application thereof | |
| CN104016883B (en) | 2-ethyl-2-hexenyl hydroximic acid and combined capturing and collecting agent thereof and their application | |
| CN109499773B (en) | Use of amido polycarboxylic acids/hydroximic acids in mineral flotation | |
| CN105013616B (en) | A kind of method that molybdenum concntrate and lead iron concentrate are separated in the lead sulfide mixed concentrate from molybdenum | |
| CN108499742A (en) | Application of the cinnamyl group hydroximic acid in ilmenite and bastnaesite flotation | |
| CN106552717A (en) | A kind of double application processes of the hydroximic acid compound on mineral floating of aromatic series | |
| CN108456153B (en) | Phenylpropanoid hydroximic acid, preparation method thereof and application thereof in tungsten ore flotation | |
| CN105312161B (en) | A kind of lead zinc sulphur bulk flotation separates the preparation method of inhibitor | |
| CN110013916B (en) | Preparation method and application method of bismuth-lead sulfide ore flotation inhibitor | |
| CN109772592A (en) | 2- hydroxyl arone oxime compound as collecting agent in oxide ore flotation application and method for floating | |
| CN107470031A (en) | A kind of preparation method and applications of oxide mineral collector | |
| CN108607678A (en) | A method of from separation molybdenum concntrate and lead concentrate in stone containing wulfenite | |
| CN108554643A (en) | Decyl Salicyl Hydroximic Acid and its application | |
| CN110947521A (en) | Hydrazide flotation collector and preparation method and application thereof | |
| CN107899755B (en) | Synergist for flotation of refractory copper oxide ore | |
| CN103721852A (en) | Manganese carbonate ore floatation agent and floatation 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181019 |