CN114057603A - O-hydroxy ketoxime compound and preparation method and application thereof - Google Patents

O-hydroxy ketoxime compound and preparation method and application thereof Download PDF

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CN114057603A
CN114057603A CN202111210851.5A CN202111210851A CN114057603A CN 114057603 A CN114057603 A CN 114057603A CN 202111210851 A CN202111210851 A CN 202111210851A CN 114057603 A CN114057603 A CN 114057603A
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hydroxy
formula
compound
hydroxyketoxime
ketone
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李方旭
周晓彤
林日孝
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/38—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

The invention relates to an o-hydroxy ketoxime compound and a preparation method and application thereof. The o-hydroxy ketoxime compound has a structural formula shown as a formula (I) or a formula (II):
Figure DDA0003308775560000011
the o-hydroxyoxime compound provided by the invention has adjacent hydroxyl and oximino structures and is reacted with R1、R2And R3The radicals forming a particular hydrophobeThe water structure has better chelating ability for metal ions, particularly has excellent chelating ability for Cu (II), and has excellent flotation effect; compared with salicylaldoxime, the recovery rate is improved by 1-30%, and the method can be widely applied to the flotation of copper oxide.

Description

O-hydroxy ketoxime compound and preparation method and application thereof
Technical Field
The invention relates to the field of flotation reagents and preparation thereof, and more particularly relates to an o-hydroxy ketoxime compound and a preparation method and application thereof.
Technical Field
2-hydroxy ketoxime, 3-hydroxy aldoxime, 3-hydroxy ketoxime, hydroximic acid are each other for the isomeric relation, its intramolecular O and N atom have lone pair electron, can interact with d, f molecular orbit of the metal ion and form five-membered ring chelate. The oxime compound has the collecting capability of high-efficiency chelation on rare metal oxide minerals, and has the advantages of good selectivity, strong collecting force and the like.
Li(Li L,Zhao J,Xiao Y,et al.Flotation performance and adsorption mechanism of malachite with tert-butylsalicylaldoxime[J]Separation and Purification Technology,2018,210.) reports the flotation performance studies of t-butyl salicylaldoxime on malachite. The results show that tert-butyl salicylaldoxime can be used for sorting malachite, calcite and quartz. Lu yuxi (Lu Y, Wang S, Zhong H. optimization of relational hydraulic acid for casting flow: Application of structural modification under principal of isometrism [ J]Minerals Engineering 167) using nitrobenzene as the starting material and zinc dust/NH4Cl is a reducing agent to produce phenylhydroxylamine; then reacting with acyl chloride to obtain N-phenyl formaldehyde acid. Test results show that the hydroximic acid compound has good collecting performance on cassiterite. Sun Q (Sun Q, Lu Y, Wang S, et al. A novel surfactant 2- (benzylthio) -acetohydroxamic acid: Synthesis, flow property and adsorption property to silicate, calcite and quartz [ J ]]Applied Surface Science,2020,522:146509.) 2- (benzylthio) -acetic acid was obtained by esterification and oximation using 2- (benzylthio) acetic acid as the starting material. Test results show that the hydroximic acid can well separate cassiterite, calcite and quartz. Qi J (Qi J, Y Dong, Liu S, et al. A selective flow of casting ite with a dithiocarbonate-hydroxide molecule and its adsorption mechanism [ J]Applied Surface Science,2021,538: 147996) using octylamine, methyl acrylate, hydroxylamine and carbon disulfide as raw materials, completing carbon chain growth, oximation and xanthation by 'one-pot method', finally synthesizing N- [ (3-hydroxyamino) -propoxy]-N-octyl dithiocarbamate. The test results show thatThe hydroximic acid and xanthic acid bifunctional collecting agent can well separate cassiterite and calcite.
From the research results, through reasonable molecular construction, the oxime compound has good collecting performance on the nonferrous metal minerals. The spatial arrangement and assembly of the N, O atoms in the hydrophilic group are key factors affecting the flotation properties of the collector. At present, salicylaldoxime is a common collecting agent, can realize the flotation separation of copper oxide minerals, but the flotation effect of salicylaldoxime still has certain promotion space.
Li (Fan-Xu LI, Zhou X T, Lin R X. flow performance and adsorption mechanism of novel 1- (2-hydroxyphenyl) hex-2-en-1-one oxide flow selector to maleic [ J ]. Transactions of non-reactants Society of China,2020,30(10):2792 and 2801.) uses 2-hydroxyacetophenone and butyraldehyde as raw materials to synthesize 1- (2-hydroxyphenyl) hex-2-en-1-one oxime through aldol condensation and oximation reactions. Test results show that the compound can form a hydrophobic six-membered ring chelate with Cu atoms on the surface of the malachite, so that the hydrophilicity of the malachite is changed, and the floating recovery of the malachite is realized. But the price of the selected raw material 2-hydroxyacetophenone is higher and the synthesis cost is high.
The development of the oxime compound with wide substrate source, excellent synthesis economy and excellent flotation effect has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an o-hydroxy ketoxime compound. The o-hydroxy ketoxime compound provided by the invention has adjacent hydroxyl and oxime group structures and is in contact with R1、R2The groups form a specific hydrophobic structure, have good chelating capacity for metal ions, particularly have excellent chelating capacity for Cu (II), and have excellent flotation effect; compared with salicylaldoxime, the recovery rate is improved by 10-30%, so that the method can be widely applied to the flotation of copper oxide. In addition, in the preparation method, the selected raw materials have wide sources and low cost, the reaction process can be continuously operated, the reaction condition is mild, the operation is simple, and the industrial production is easy to realize.
Another object of the present invention is to provide a process for producing the above-mentioned o-hydroxyketoxime compound.
The invention also aims to provide application of the o-hydroxy ketoxime compound as a collector in ore dressing.
In order to achieve the purpose, the invention adopts the following technical scheme:
an o-hydroxy ketoxime compound having the formula shown in formula (I) or formula (II):
Figure BDA0003308775540000021
wherein R is1Is alkyl or unsaturated hydrocarbon group containing double bond; r2,、R3Independently selected from H, alkyl or unsaturated hydrocarbon containing double bond.
The o-hydroxyoxime compound provided by the invention has adjacent hydroxyl and oximino structures and is reacted with R1、R2、R3The group (or H, phenyl and cyclohexyl) forms a specific hydrophobic structure, has good chelating capacity for metal ions, particularly has excellent chelating capacity for Cu (II), and has excellent flotation effect; compared with salicylaldoxime, the recovery rate is improved by 10-30%, so that the method can be widely applied to the flotation of copper oxide.
Preferably, said R is1、R2And R3Wherein the alkyl groups are independently selected from C1～8An alkyl group.
More preferably, the alkyl group is ethyl or propyl.
Preferably, said R is1、R2And R3Wherein the double bond-containing unsaturated hydrocarbon group is independently selected from C3～7Unsaturated hydrocarbon groups containing double bonds.
Preferably, the unsaturated hydrocarbon group containing a double bond is furyl or phenyl.
Preferably, the o-hydroxy ketoxime compound has the formula:
Figure BDA0003308775540000031
the preparation method of the o-hydroxy ketoxime compound comprises the following steps:
s11: mixing aldehyde shown as a formula (III) and aldehyde or ketone shown as a formula (IV) in a solvent, stirring under a catalyst, and reacting to obtain an o-hydroxyketone compound shown as a formula (V);
Figure BDA0003308775540000032
s12: mixing an o-hydroxy ketone compound and a nitrogen-containing precursor, adjusting the pH to 7-8, and carrying out an ammoximation reaction under a catalyst to obtain an o-hydroxy ketoxime compound shown in a formula (I);
the reaction process is as follows:
Figure BDA0003308775540000033
or, S21: mixing benzaldehyde and cyclohexanone in a solvent, stirring under the action of a catalyst, and reacting to obtain (1-hydroxycyclohexyl) (phenyl) ketone;
s22: mixing (1-hydroxycyclohexyl) (phenyl) ketone and a nitrogen-containing precursor, adjusting the pH value to 7-8, and carrying out an ammoximation reaction under the presence of a catalyst to obtain an o-hydroxy ketoxime compound shown in a formula (II).
The invention provides a new synthetic route for preparing o-hydroxy ketoxime compounds: in S11 or S21, carbon chain extension and hydroxyl introduction of short-chain aldehyde are realized through cross coupling, and then an o-hydroxy ketoxime compound is obtained through ammoximation reaction of S2. The preparation method provided by the invention obtains the o-hydroxy ketoxime compound through cross coupling and ammoximation one-pot reaction, has wide sources of reaction substrates, can be continuously operated in the reaction process, has mild reaction conditions and simple operation, and is easy for industrial production.
Preferably, the catalyst in S11 or S21 is one or more of benzothiazole or modified benzothiazole.
Preferably, the solvent in S11 or S21 is one or more of methanol, ethanol or acetonitrile.
Preferably, the molar ratio of the aldehyde shown in the formula (III), the aldehyde or the ketone shown in the formula (IV) and the solvent in S11 is 1: 0.01-0.05: 5-10.
Preferably, the molar ratio of the benzaldehyde, the cyclohexanone and the solvent in S21 is 1: 0.01-0.05: 5-10.
Preferably, the aldehyde or ketone shown in formula (iii) is one or more of formaldehyde, propionaldehyde, butyraldehyde, caprylic aldehyde, or furfural.
Preferably, the temperature of the reaction in S11 or S21 is 50-70 ℃.
Preferably, the molar ratio of the o-hydroxyarylenone to the nitrogen-containing precursor in S21 is 1: 1-1.3.
Preferably, the molar ratio of the (1-hydroxycyclohexyl) (phenyl) ketone to the nitrogen-containing precursor in S22 is 1: 1-1.3.
Preferably, the molar ratio of the o-hydroxyarylenone to the catalyst in S21 is 1: 0.01-1.5.
Preferably, the molar ratio of the (1-hydroxycyclohexyl) (phenyl) methanone to the catalyst in S22 is 1: 0.01-1.5.
Preferably, the catalyst in S12 or S22 is one or more of alkali or titanium silicalite molecular sieves.
Preferably, the nitrogen-containing precursor in S12 or S22 is one or more of hydroxylamine hydrochloride, hydroxylamine sulfate or ammonia water.
Preferably, the temperature of the ammoximation reaction in S2 is 30-50 ℃.
The product obtained by the preparation method can be used as a collecting agent for flotation without additional purification and separation.
The application of the o-hydroxy ketoxime compound as a collector in ore dressing is also within the protection scope of the invention.
Preferably, the beneficiated ore is copper oxide ore.
The invention also claims a flotation method, which comprises the following steps: grinding raw ore to particles, preparing into ore pulp, adding an alkaline agent and the o-hydroxy ketoxime compound, and performing rough concentration or fine concentration and scavenging to obtain the o-hydroxy ketoxime compound.
According to the invention, the o-hydroxy ketoxime compound is used as the collecting agent, so that the flotation effect is excellent; compared with salicylaldoxime, the recovery rate is improved by 1-30%.
In addition, the o-hydroxy ketoxime compound can be dispersed in alkali liquor or solvent oil for dropwise use, and has the advantages of convenient operation, strong collecting capability and small medicament dosage.
Milling, roughing, concentrating and scavenging can be carried out under controlled conditions conventional in the art.
Preferably, the mass fraction of the particles with the particle size of-0.074 mm after the raw ore is ground is 60-85%.
Preferably, the mass concentration of the ore pulp is 25-40%.
Preferably, the alkaline agent is one or more of sodium carbonate, lime or sodium hydroxide.
Preferably, the regulator is one or more of water glass, sodium hexametaphosphate, sodium fluoroaluminate, sodium carbonate, lime or sodium hydroxide.
Preferably, the dosage of the o-hydroxyoxime compound medicament is 200-1200 g/t.
The o-hydroxyoxime compound provided by the invention has strong collecting capability and small medicament dosage.
Compared with the prior art, the invention has the following beneficial effects:
the o-hydroxy ketoxime compound provided by the invention has adjacent hydroxyl and oxime group structures and is in contact with R1、R2The groups form a specific hydrophobic structure, have good chelating capacity for metal ions, particularly have excellent chelating capacity for Cu (II), and have excellent flotation effect; compared with salicylaldoxime, the recovery rate is improved by 1-30%, so that the method can be widely applied to the flotation of copper oxide ores.
In addition, the preparation method provided by the invention obtains the o-hydroxy ketoxime compound through cross coupling and ammoximation one-pot reaction, the reaction substrate source is wide, the reaction process can be continuously operated, the reaction condition is mild, the operation is simple, and the industrial production is easy to realize.
Drawings
FIG. 1 is an IR spectrum of 2-hydroxy-1-phenylethane-1-monoxime as provided in example 1;
FIG. 2 is an IR spectrum of 2-hydroxy-1-phenylbutan-1-oxime as provided in example 2;
FIG. 3 is an IR spectrum of 2-hydroxy-1-phenylpentane-1-oxime as provided in example 3;
FIG. 4 is an IR spectrum of 5-hydroxyoctyl-4-monoxime as provided in example 4;
FIG. 5 is an IR spectrum of (1-hydroxycyclohexyl) (phenyl) methyl ketoxime as provided in example 5;
FIG. 6 is an infra-red spectrum of 2- (furan-2-yl) -2-hydroxy-1-phenylethane-1-monoxime as provided in example 6;
FIG. 7 is an IR spectrum of a chelate of 2-hydroxy-1-phenylbutane-1-monoxime-Cu (II) provided in example 2;
FIG. 8 is an IR spectrum of 2-hydroxy-1-phenylbutan-1-one oxime as provided in example 2 before and after exposure to malachite;
FIG. 9 is a schematic representation of 2 hydroxy-1-phenylethane-1-monoxime as provided in example 1;
FIG. 10 is a mass spectrum of 2-hydroxy-1-phenylpentane-1-oxime as provided in example 3;
FIG. 11 is a mass spectrum of 5-hydroxyoctyl-4-monoxime as provided in example 4;
FIG. 12 is a mass spectrum of (1-hydroxycyclohexyl) (phenyl) methyl oxime as provided in example 5.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
2-this example provides an o-hydroxy ketoxime compound: 2-hydroxy-1-phenylethane-1-monoxime of the formula:
Figure BDA0003308775540000061
the compound is prepared by the following preparation method: adding 50mmol of o-hydroxybenzaldehyde, 50mmol of formaldehyde, 250mmol of methanol and 0.5mmol of modified benzothiazole into a reactor, uniformly mixing, and gradually dropwise adding NaOH (0.05mol) under stirring at 50 ℃ to obtain (2-hydroxy-1-phenyl) ethan-1-one. Gradually dropwise adding 0.055mol hydroxylamine hydrochloride aqueous solution into the reactor, adjusting pH to 7.0-8.0, controlling reaction temperature at 40 deg.C, reacting for 6 hr, acidifying with concentrated sulfuric acid, removing reaction solvent to obtain 7.8g 2-hydroxy-1-phenyl ethyl-1-monoxime, with yield of 45.8%
Example 2
This example provides an o-hydroxy ketoxime compound: 2-hydroxy-1-phenylbutan-1-monoxime, having the formula:
Figure BDA0003308775540000062
the compound is prepared by the following preparation method: adding 50mmol of o-hydroxybenzaldehyde, 50mmol of propionaldehyde, 250mmol of methanol and 0.5mmol of modified benzothiazole into a reactor, uniformly mixing, and gradually dropwise adding NaOH (0.05mol) under stirring at 50 ℃ to obtain (2-hydroxy-1-phenyl) butan-1-one. Gradually dropwise adding 0.055mol of hydroxylamine hydrochloride aqueous solution into the reactor, adjusting the pH to 7.0-8.0, controlling the reaction temperature to be 40 ℃, reacting for 6 hours, acidifying with concentrated sulfuric acid, and removing the reaction solvent to obtain 9.8g of 2-hydroxy-1-phenylbutane-1-monoxime, wherein the yield is 82.8%.
Example 3
This example provides an o-hydroxy ketoxime compound: 2-hydroxy-1-phenylpentane-1-monoxime of the formula:
Figure BDA0003308775540000063
the compound is prepared by the following preparation method: adding 50mmol of benzaldehyde, 50mmol of butyraldehyde, 200mmol of ethanol and 0.5mmol of benzothiazole into a reactor, uniformly mixing, and gradually dropwise adding KOH (0.06mol) while stirring at 65 ℃ to obtain (2-hydroxyphenyl) pentan-1-one. 0.06mol of hydroxylamine sulfate, the pH value of which is adjusted to 7.0-8.0, 2-hydroxy-1-phenylpentan-1-one obtained by the above reaction and 40mL of water are mixed, the reaction temperature is controlled at 40 ℃, the reaction is carried out for 4.5 hours, the mixture is acidified by concentrated sulfuric acid, the reaction solvent is removed, and 12.4g of 2-hydroxy-1-phenylpentan-1-monoxime is obtained, wherein the yield is 88.6%.
Example 4
This example provides an o-hydroxy ketoxime compound: 5-hydroxy-4-octyl ketoxime, the structural formula is:
Figure BDA0003308775540000071
the compound is prepared by the following preparation method: adding 0.05mol of butyraldehyde and 0.5mol of acetonitrile into a reactor, uniformly mixing, and gradually dropwise adding 32% NaOH (0.075mol)) while stirring at 60 ℃ to obtain the 5-hydroxyoctanone. 0.075mol of ammonia water and hydrogen peroxide are added, 2.00g of titanium silicalite molecular sieve, 5-hydroxyoctanone obtained by the reaction is mixed with 40mL of water, the reaction temperature is controlled at 50 ℃, the mixture is reacted for 3 hours, concentrated sulfuric acid is used for acidification, the reaction solvent is removed, 10.2g of 5-hydroxy-4-octyl ketoxime is obtained, and the yield is 76.8%.
Example 5
This example provides an o-hydroxy ketoxime compound: (1-hydroxycyclohexyl) (phenyl) ketoxime of the formula:
Figure BDA0003308775540000072
the compound is prepared by the following preparation method: 0.05mol of benzaldehyde, 0.06mol of cyclohexanone and 0.5mol of methanol are added into a reactor and mixed evenly, 32% NaOH (0.075mol) is gradually added dropwise while stirring at 60 ℃ to obtain (1-hydroxycyclohexyl) (phenyl) ketone. 0.03mol of hydroxylamine sulfate, (1-hydroxycyclohexyl) (phenyl) methanone obtained by the above reaction and 40mL of water were reacted at 40 ℃ for 3 hours, acidified with concentrated sulfuric acid, and the reaction solvent was removed to obtain 8.9g of 5-hydroxyoctyl-4-monoxime, in a yield of 71.6%.
Example 6
This example provides an o-hydroxy ketoxime compound: 2- (furan-2-yl) -2-hydroxy-1-phenylethane-1-monoxime of the formula:
Figure BDA0003308775540000081
the compound is prepared by the following preparation method: 0.05mol of benzaldehyde, 0.06mol of furfural and 0.5mol of ethanol are added into a reactor and mixed uniformly, 32 percent NaOH (0.075mol) is gradually added dropwise while stirring at 60 ℃ to obtain the 2- (furan-2-yl) -2-hydroxy-1-phenylethane-1-ketone. 0.06mol of hydroxylamine hydrochloride, 5-hydroxyoctanone obtained by the above reaction and 40mL of water were mixed, the reaction temperature was controlled at 45 ℃ and the reaction was carried out for 3 hours, and then, acidification was carried out with concentrated sulfuric acid and the reaction solvent was removed to obtain 11.8g of 5-hydroxyoctyl-4-monooxime, with a yield of 90.4%.
The o-hydroxy ketoxime compounds prepared in examples 1 to 6 were characterized as follows:
FIG. 1 is an IR spectrum of 2-hydroxy-1-phenylethane-1-monoxime as provided in example 1;
FIG. 2 is an IR spectrum of 2-hydroxy-1-phenylbutan-1-oxime as provided in example 2;
FIG. 3 is an IR spectrum of 2-hydroxy-1-phenylpentane-1-oxime as provided in example 3;
FIG. 4 is an IR spectrum of 5-hydroxyoctyl-4-monoxime as provided in example 4;
FIG. 5 is an IR spectrum of (1-hydroxycyclohexyl) (phenyl) methyl ketoxime as provided in example 5;
FIG. 6 is an infra-red spectrum of 2- (furan-2-yl) -2-hydroxy-1-phenylethane-1-monoxime as provided in example 6;
FIG. 9 is a mass spectrum of 2 hydroxy-1-phenylethane-1-oxime as provided in example 1;
FIG. 10 is a mass spectrum of 2-hydroxy-1-phenylpentan-1-oxime as provided in example 3;
FIG. 11 is a mass spectrum of 5-hydroxyoctyl-4-monoxime as provided in example 4;
FIG. 12 is a mass spectrum of (1-hydroxycyclohexyl) (phenyl) methyl oxime as provided in example 5;
from the infrared spectrum and the mass spectrum, it can be known that the corresponding compound has been successfully prepared in examples 1 to 6.
Application examples 1 to 6
The application example provides flotation of copper oxide by the o-hydroxyoxime compound, and the specific process is as follows.
The copper oxide raw ore mainly contains copper minerals such as chalcocite, malachite, and peacock stone, and the gangue minerals mainly include quartz, calcite, feldspar, and the like. Grinding raw ore by a rod mill to obtain a material with the content of-0.075 mm and the content of 63.8%, roughing, 200g/t of water glass, 200g/t of sodium fluosilicate and a collecting agent.
Collecting agents selected in application examples 1 to 6 are the o-hydroxy ketoxime compounds in examples 1 to 3 respectively; in addition, salicylaldoxime is used as a collecting agent, and a flotation experiment is carried out under the same addition amount so as to compare the flotation effect. Results of flotation tests are shown in table 1.
TABLE 1 copper oxide flotation comparative test results
Figure BDA0003308775540000091
As can be seen from Table 1, compared with salicylaldoxime, the recovery rate of copper in copper concentrate is improved by 1-30% by using the collector provided by the invention under the condition of the same medicament dosage.
The chelate compound in FIG. 7 was obtained by mixing 0.01mol/L of aqueous Cu ion solution (20mL) and 0.01mol/L of 2-hydroxy-1-phenylbutan-1-monoxime (20mL) at natural pH. From the figure, it can be observed that C-N undergoes blue shift (1673 → 1683 cm)-1). The chemical agent is shown to have obvious chemical action with Cu ions.
The chelate in fig. 8 was prepared by mixing 2.00g of malachite and 0.01mol/L of 2-hydroxy-1-phenylbutan-1-monoxime (20mL) at pH 9. From the figure, it can be observed that characteristic peaks of-hydroxy-1-phenylbutan-1-monoxime appear at 3076, 2958, 1594. This means that the negatively charged malachite (isoelectric at pH around 8.3) surface has 2-hydroxy-1-phenylbutan-1-monoxime adsorption, and also indicates that the agent interacts with copper ions on the malachite surface to produce non-electrostatic adsorption.
Finally, it should be noted that the above embodiments are only representative examples of the present invention. Obviously, the technical solution of the present invention is not limited to the above-described embodiments, and many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the present disclosure are to be considered within the scope of the claims of the present invention.

Claims (10)

1. An o-hydroxyketoxime compound having a structural formula represented by formula (I) or formula (II):
Figure FDA0003308775530000011
wherein R is1Is alkyl or unsaturated hydrocarbon group containing double bond; r2,、R3Independently selected from H, alkyl or unsaturated hydrocarbon containing double bond.
2. The o-hydroxyketoxime compound according to claim 1, wherein R is1、R2And R3Wherein the alkyl groups are independently selected from C1～8An alkyl group.
3. The o-hydroxyketoxime compound according to claim 1, wherein R is1、R2And R3Wherein the double bond-containing unsaturated hydrocarbon group is independently selected from C3～7Unsaturated hydrocarbon groups containing double bonds.
4. The o-hydroxyketoxime compound according to claim 3, wherein the double bond-containing unsaturated hydrocarbon group is a furyl group or a phenyl group.
5. The o-hydroxyketoxime compound according to any one of claims 1 to 4, wherein the o-hydroxyketoxime compound has the following structural formula:
Figure FDA0003308775530000012
6. a process for producing an o-hydroxyketoxime compound according to any one of claims 1 to 5, which comprises the steps of:
s11: mixing aldehyde shown as a formula (III) and aldehyde or ketone shown as a formula (IV) in a solvent, stirring under a catalyst, and reacting to obtain an o-hydroxyketone compound shown as a formula (V);
Figure FDA0003308775530000013
s12: mixing an o-hydroxy ketone compound and a nitrogen-containing precursor, adjusting the pH to 7-8, and carrying out an ammoximation reaction under a catalyst to obtain an o-hydroxy ketoxime compound shown in a formula (I);
or S21: mixing benzaldehyde and cyclohexanone in a solvent, stirring under the action of a catalyst, and reacting to obtain (1-hydroxycyclohexyl) (phenyl) ketone;
s22: mixing (1-hydroxycyclohexyl) (phenyl) ketone and a nitrogen-containing precursor, adjusting the pH value to 7-8, and carrying out an ammoximation reaction under the presence of a catalyst to obtain an o-hydroxy ketoxime compound shown in a formula (II).
7. The preparation method of claim 6, wherein in S11 or S21, the catalyst is one or more of benzothiazole or modified benzothiazole; the solvent is one or more of methanol, ethanol or acetonitrile; the molar ratio of the aldehyde shown in the formula (III), the aldehyde or ketone shown in the formula (IV) and the solvent is 1: 0.01-0.05: 5-10; the molar ratio of the benzaldehyde to the cyclohexanone to the solvent is 1: 0.01-0.05: 5-10; the reaction temperature is 50-70 ℃.
8. The method according to claim 6, wherein the molar ratio of the o-hydroxyarylenone to the nitrogen-containing precursor in S12 or S22 is 1:1 to 1.3; the molar ratio of the (1-hydroxycyclohexyl) (phenyl) ketone to the nitrogen-containing precursor is 1: 1-1.3; the catalyst is one or more of alkali or titanium silicalite molecular sieves; the nitrogen-containing precursor is one or more of hydroxylamine hydrochloride, hydroxylamine sulfate or ammonia water; the temperature of the ammoximation reaction is 30-50 ℃.
9. Use of an o-hydroxy ketoxime compound according to any one of claims 1 to 5 as a collector in mineral separation.
10. The use according to claim 9, characterized in that the ore in beneficiation is copper oxide ore.
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