CN108503563B - Preparation method of hydroximic acid salt collecting agent - Google Patents
Preparation method of hydroximic acid salt collecting agent Download PDFInfo
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- CN108503563B CN108503563B CN201810510460.7A CN201810510460A CN108503563B CN 108503563 B CN108503563 B CN 108503563B CN 201810510460 A CN201810510460 A CN 201810510460A CN 108503563 B CN108503563 B CN 108503563B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/10—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of six-membered aromatic rings
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
- C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
- C07C259/08—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of rings other than six-membered aromatic rings
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- 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
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- 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
Abstract
The invention provides a preparation method of a hydroximic acid salt collecting agent, which comprises the following specific steps: carrying out grinding reaction on a diester compound shown in a formula (I) and a hydroxylamine salt compound shown in a formula (II) under the action of alkali to obtain a hydroximic acid salt shown in a formula (III) and a dihydric alcohol compound shown in a formula (IV); each of said R1Independently an aromatic group, a cycloalkyl group or an alkyl group; the R is2Is- (CH)2)n-or- (CH)2)n‑O‑(CH2)n-, each n is independently 1 ~ 10, NH2OH.M includes hydroxylamine hydrochloride, hydroxylamine-O-sulfonate or hydroxylamine nitrate; the base comprises sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydrogen phosphate or sodium dihydrogen phosphate; said Y is+Including Na+Or K+(ii) a The alkyl, aryl, cycloalkyl, - (CH)2)n-and- (CH)2)n‑O‑(CH2)n-may be further optionally mono-or polysubstituted, identically or differently, by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, alkyl, alkoxy or aryl. The preparation method has the advantages of simple process, short reaction time, simple process, high efficiency and no pollution.
Description
Technical Field
The invention relates to the technical field of preparation of mineral flotation collecting agents, in particular to a preparation method of a hydroximic acid salt collecting agent.
Background
Hydroximic acid is a common desiliconization flotation collector in industry, is easy to chelate with metal ions due to the structural particularity of the hydroximic acid, has good selectivity on metal oxide ores, and is applied to the flotation of minerals such as bauxite, ilmenite, tin ore, copper oxide ore and the like. The synthetic method of hydroximic acid comprises an hydroxylamine method, a nitroalkane rearrangement method, a nitroalkane reduction method, a nitroso compound and aldehyde reaction preparation method and the like, wherein the hydroxylamine method is the most commonly used method in industrial production. The hydroxylamine method is to use carboxylic acid OR its derivative R-CO-L (L is OH, O, OR, Cl, Br, NH)2Etc.) and hydroxylamine as raw materials, and a method for nucleophilic substitution reaction under alkaline conditions, havingHas the advantages of simple process, low technological requirement, easy control of synthesis conditions, etc.
In the conventional synthetic method of hydroximic acid, carboxylic acid lower alcohol ester and hydroxylamine are generally used for reaction in an alkaline solvent, and the solvent commonly used for hydroximic reaction is water or methanol, for example, patent CN102513218A discloses a preparation method of a collecting agent for bauxite flotation, which comprises the steps of mixing caustic soda solution, hydroxylamine sulfate solution and methyl benzoate according to a certain proportion to react to obtain a hydroximic acid salt product, wherein the reaction is completed in a water solvent system; patent CN103922968A discloses a method for preparing hydroxamic acid or hydroxamic acid salt, in which a base is added to a methanol solution of hydroxylamine hydrochloride under stirring, and then an organic carboxylic acid methyl ester is added to perform a reaction, which is performed in a methanol solvent system, and which has a higher yield compared to an aqueous system.
The traditional synthetic methods of the hydroximic acid have advantages, but have the following problems: 1) the traditional method is generally carried out in a large amount of solvent systems, and subsequent recovery treatment of the solvent is inevitably required; 2) in the traditional method, lower alcohol esters such as methyl monocarboxylate are generally used as raw materials, volatile lower alcohol such as methanol is inevitably generated in the reaction process, the amount of the methanol is small, the methanol is not easy to collect, and the influence on the environment is not ignored; 3) because of the volatile property of lower alcohol, the traditional method does not take alcohol generated by reaction as a product, and the obtained hydroximic acid (salt) product is completely dry powder, so that direct granulation is inconvenient, and the dust pollution is large and the splashing waste is serious in the preparation and use processes.
Disclosure of Invention
Aiming at the technical problems in the related art, the invention provides a preparation method of a hydroximic acid salt collecting agent. The preparation method has the advantages of high reaction efficiency, environmental protection, no harm, no solvent, no generation of volatile alcohol in the reaction process, direct granulation of reaction products and no addition of adhesive.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
on one hand, the invention provides a preparation method of a hydroximic acid salt collecting agent, which comprises the following specific processes:
carrying out grinding reaction on a diester compound shown in a formula (I) and a hydroxylamine salt compound shown in a formula (II) under the action of alkali to obtain a hydroximic acid salt shown in a formula (III) and a dihydric alcohol compound shown in a formula (IV);
each of said R1Independently an aromatic group, a cycloalkyl group or an alkyl group;
the R is2Is- (CH)2)n-or- (CH)2)n-O-(CH2)n-；
Each n is independently 1-10;
the NH2OH.M includes hydroxylamine hydrochloride, hydroxylamine-O-sulfonate or hydroxylamine nitrate;
the base comprises sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydrogen phosphate or sodium dihydrogen phosphate;
said Y is+Including Na+Or K+；
The alkyl, aryl, cycloalkyl, - (CH)2)n-and- (CH)2)n-O-(CH2)n-may be further optionally mono-or polysubstituted, identically or differently, by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, alkyl, alkoxy or aryl.
Further, each of said R1Independently is C6～12Aryl radical, C3～12Cycloalkyl or C1～12An alkyl group;
the alkyl, aryl and cycloalkyl can be further optionally substituted by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl and C1～12Alkyl radical, C1～12Alkoxy or C6～12Aryl is monosubstituted or polysubstituted by the same or different.
Further, each of said R1Independently is C6～12Aryl radical, C3～8Cycloalkyl or C1～8An alkyl group;
the alkyl, aryl and cycloalkyl can be further optionally substituted by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl and C1～6Alkyl radical, C1～6Alkoxy or C6～12Aryl is monosubstituted or polysubstituted by the same or different.
Further, each of said R1Independently phenyl, cyclohexane, methyl, ethyl, isopropyl, n-propyl, n-butyl, n-pentyl, or n-octyl;
the phenyl, cyclohexane, methyl, ethyl, isopropyl, n-propyl, n-butyl, n-pentyl and n-octyl radicals may further optionally be mono-or polysubstituted, identically or differently, by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, tert-butoxy, phenyl, p-tert-butylphenyl, o-hydroxyphenyl, naphthyl.
Further, said R2Is- (CH)2)n-or- (CH)2)n-O-(CH2)n-; each n is independently 2-8;
the- (CH)2)n-or- (CH)2)n-O-(CH2)n-may further optionally be substituted by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, C1～6Alkyl radical, C1～6Alkoxy radical, C6～12Aryl radical, C1～6alkyl-C (═ O) -O-or C6～12aryl-C (═ O) -O-C1～6alkyl-O-monosubstitution or polysubstitution, which may be identical or different.
Further, each n is independently 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
Furthermore, the molar ratio of the ester group in the diester compound shown in the formula (I) to the hydroxylamine salt compound shown in the formula (II) to the alkali is 1: 2.1-2.8: 4.2-5.6.
Preferably, the ester compound shown in formula (I) includes diethylene glycol dibenzoate, dipropylene glycol dibenzoate, ethylene glycol dibenzoate, 1, 3-propylene glycol dibenzoate, ethylene glycol dicaprylate, or ethylene glycol dicyclohexyl formate.
Further, the grinding reaction is carried out in a reaction apparatus comprising one of a ball mill, a rod mill, or a mortar.
Furthermore, the ball milling speed of the ball mill is 500-1500 r/min.
Further, the initial reaction temperature in the reaction device for the grinding reaction is 15-70 ℃. Preferably 25 to 50 ℃.
Further, the reaction time of the grinding reaction is 10-90 min. Preferably 15-40 min.
Salts produced during the grinding reaction according to the invention, e.g. sodium chloride, Na2SO4KCl, or K2SO4The inorganic salt or glycol, which does not need to be separated, can be used as a part of the product without influencing the product performance, wherein the glycol, such as diethylene glycol, can be used as a granulation binder and a secondary collector.
The invention has the beneficial effects that:
the invention provides a preparation method of a hydroximic acid salt collecting agent, which utilizes the temperature required by the sustainable reaction of reaction heat generated in the grinding process, the initial reaction temperature is generally 25-50 ℃, additional heat source supply is not needed, the energy is saved, the consumption is reduced, and the production efficiency is high. The reaction time is short, the reaction can be completed within 10-90 min, the preparation process is simple, the production efficiency is high, and the yield of the hydroximic acid salt is over 80 percent. The raw materials of the invention are ground to prepare the hydroximic acid salt and the dihydric alcohol compound without the participation of a solvent, and no volatile lower alcohol such as methanol and the like and wastewater are generated in the reaction process, thereby thoroughly avoiding the pollution of the methanol and the wastewater to the environment. The reaction product dihydric alcohol can be used as a granulation adhesive and an auxiliary collector, separation is not needed, and the product can be directly granulated.
The preparation method has the advantages of simple process, short reaction time, simple process, low energy consumption, high efficiency and no pollution.
Detailed Description
Definitions and general terms
The invention will be described in detail in the literature corresponding to the identified embodiments, and the examples are accompanied by the graphic illustrations of structural formulae and chemical formulae. The present invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the present invention as defined by the appended claims. Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein which can be used in the practice of the present invention. The present invention is in no way limited to the description of methods and materials. There are many documents and similar materials that may be used to distinguish or contradict the present application, including, but in no way limited to, the definition of terms, their usage, the techniques described, or the scope as controlled by the present application.
The following definitions shall apply unless otherwise indicated. For the purposes of the present invention, the chemical elements are defined in accordance with the periodic Table of the elements, CAS version and the handbook of Chemicals, 75, thEd, 1994. In addition, the general principles of Organic Chemistry are described in "Organic Chemistry," Thomas Sorrell, University Science Books, Sausaltito: 1999, and "March's Advanced Organic Chemistry," by Michael B.Smith and Jerry March, John Wiley & Sons, New York: 2007, all of which are hereby incorporated by reference.
The term "comprising" is open-ended, i.e. includes the elements indicated in the present invention, but does not exclude other elements.
Compounds as described herein may be optionally substituted with one or more substituents, such as compounds of the general formula in the present invention, or compounds of the type specifically exemplified, sub-classes, and encompassed by the present invention. It is understood that the term "optionally substituted" may be used interchangeably with the term "substituted or unsubstituted". In general, the term "optionally," whether preceded by the term "substituted," indicates that one or more hydrogen atoms in a given structure are replaced with a particular substituent. Unless otherwise indicated, an optional substituent group may have one substituent substituted at each substitutable position of the group. When more than one position in a given formula can be substituted with one or more substituents selected from a particular group, the substituents may be substituted at each position, identically or differently. Wherein said substituent may be, but is not limited to, hydrogen, F, Cl, Br, I, nitro, cyano, oxo (═ O), hydroxy, alkyl, hydroxyalkyl, alkylamino, aminoalkyl, haloalkoxy, cycloalkyl, amino, aryl, heterocyclyl, heteroaryl, alkenyl, alkynyl, cycloalkyloxy, alkoxy, alkoxyalkyl, haloalkyl, -COOH, and the like.
The term "alkyl" as used herein includes saturated straight or branched chain monovalent hydrocarbon groups of 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or 1 to 6 carbon atoms, or 1 to 4 carbon atoms, or 1 to 3 carbon atoms, or 1 to 2 carbon atoms, wherein the alkyl groups may independently be optionally substituted with one or more substituents described herein. Further examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methyl-2-butyl, 3-methyl-1-butyl, 2-methyl-1-butyl, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3-dimethyl-2-butyl, 2-pentyl, 3-pentyl, 2-, N-heptyl and n-octyl, and the like. The term "alkyl" and its prefix "alkane" as used herein, both include straight and branched saturated carbon chains. The term "alkylene" is used herein to denote a saturated divalent hydrocarbon radical resulting from the elimination of two hydrogen atoms from a straight or branched chain saturated hydrocarbon, examples of which include, but are not limited to, methylene, ethylene, and isopropylene, and the like.
The term "alkoxy" or "alkyloxy" as used herein, refers to an alkyl group, as defined herein, attached to the main carbon chain through an oxygen atom, in some embodiments, the alkoxy group is C1-4An alkoxy group; examples include, but are not limited to, methoxy, ethoxy, propoxy, and butoxy, and the like. And the alkoxy groups may independently be unsubstituted or substitutedSubstituted with one or more substituents as described herein.
The term "cycloalkyl" denotes a monovalent or polyvalent saturated monocyclic, bicyclic or tricyclic carbocyclic ring system containing from 3 to 12 carbon atoms, but in no way comprising an aromatic ring. In one embodiment, the cycloalkyl group contains 3 to 12 carbon atoms; in another embodiment, cycloalkyl contains 3 to 8 carbon atoms; in yet another embodiment, the cycloalkyl group contains 3 to 6 carbon atoms. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The cycloalkyl groups may be independently unsubstituted or substituted with one or more substituents described herein.
The term "aryl" denotes a monocyclic, bicyclic and tricyclic carbon ring system containing 6 to 14 ring atoms, or 6 to 12 ring atoms, or 6 to 10 ring atoms, wherein at least one ring is aromatic, wherein each ring comprises 3 to 7 atoms in the ring and has one or more attachment points to the rest of the molecule. The term "aryl" may be used interchangeably with the term "aryl". Examples of the aryl group may include phenyl, naphthyl and anthracenyl. The aryl group may independently be optionally substituted with one or more substituents described herein.
As used herein, the terms "a," "an," "the," and similar terms used in the context of the present invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
In addition, it should be noted that, unless otherwise expressly indicated, the descriptions used throughout this document "each.. independently" and "each.. independently" are interchangeable and should be construed broadly to mean that the particular options expressed between the same symbols do not affect each other in the same group. For example, in the same formula, formula (I), multiple R1The specific options of (a) are not affected; as another example, - (CH)2)n-O-(CH2)nThe specific options of a plurality n are not affected by each other.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a UV spectrum of benzohydroxamic acid;
FIG. 2 Infrared Spectrum of the sodium benzohydroxamate product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1
Taking 0.5mol of diethylene glycol dibenzoate as a reference, putting analytically pure diethylene glycol dibenzoate, hydroxylamine hydrochloride and sodium hydroxide into an SM-0.5L type stirring ball mill in sequence according to the mol ratio of 1: 2.6: 5.0, stirring at the speed of 800r/min, reacting at the initial temperature of 32 ℃ for 30min, and tabletting the reacted white solid product in a 769YP-15A powder tabletting machine to obtain phi 5 x 8(mm) sodium benzoate particles. The yield of sodium benzohydroxamate was 86.41%. The ultraviolet spectrum of the acidified product is shown in figure 1; the infrared spectrum of the product was directly measured as shown in FIG. 2.
Example 2
Taking 1.0mol of diethylene glycol dibenzoate as a reference, sequentially putting industrial diethylene glycol dibenzoate, hydroxylamine hydrochloride and sodium hydroxide into an WZM three-roll ball mill according to the mol ratio of 1: 2.6: 5.0, stirring at 1400r/min, reacting at an initial temperature of 32 ℃ for 40min, and tabletting the reacted white solid product in a 769YP-15A powder tabletting machine to obtain phi 5 x 8(mm) sodium benzoate particles. The yield of sodium benzohydroxamate was 80.21%.
Example 3
Taking 0.05mol of diethylene glycol dibenzoate as a reference, sequentially putting analytically pure diethylene glycol dibenzoate, hydroxylamine hydrochloride and sodium hydroxide into a mortar according to the mol ratio of 1: 2.6: 5.0, manually grinding and reacting for 15min at the initial temperature of 33 ℃, and tabletting a white solid product after reaction in a 769YP-15A powder tabletting machine to obtain phi 5 x 8(mm) sodium benzoate particles. The yield of sodium benzohydroxamate was 88.91%. .
Example 4
Taking 0.05mol of diethylene glycol dibenzoate as a reference, sequentially putting analytically pure diethylene glycol dibenzoate, hydroxylamine hydrochloride and sodium hydroxide into a mortar according to the mol ratio of 1: 2.2: 4.4, manually grinding and reacting for 15min at the initial temperature of 33 ℃, wherein the product is white solid powder, and tabletting the white solid product after reaction in a 769YP-15A powder tabletting machine to obtain phi 5 x 8(mm) sodium benzoate particles. The yield of sodium benzohydroxamate was 82.25%.
Example 5
Based on 0.05mol of ethylene glycol dibenzoate, the ethylene glycol dibenzoate, hydroxylamine hydrochloride and sodium hydroxide are sequentially put into a mortar according to the mol ratio of 1: 2.6: 5.2, and are manually ground and reacted for 30min at the initial temperature of 35 ℃, so that the product is white solid powder, and the yield of the sodium benzoate is 85.39%.
Example 6
Based on 0.5mol of ethylene glycol dibenzoate, the ethylene glycol dibenzoate, hydroxylamine hydrochloride and sodium hydroxide are sequentially put into an SM-0.5L type stirring ball mill according to the mol ratio of 1: 2.6: 5.2, the stirring speed is 800r/min, the reaction is carried out for 40min at the initial temperature of 35 ℃, the product is white solid powder, and the yield of the sodium benzoate is 80.33%.
Example 7
Based on 0.5mol of ethylene glycol dicaprylate, the ethylene glycol dicaprylate, hydroxylamine hydrochloride and sodium hydroxide are sequentially put into a mortar according to the mol ratio of 1: 2.6: 5.2, and react for 30min at the initial temperature of 40 ℃, so that the product is solid powder, and the yield of the sodium octyl hydroxamate is 80.45%.
Example 8
Based on 0.5mol of ethylene glycol dicyclohexyl formate, the ethylene glycol dicyclohexyl formate, hydroxylamine hydrochloride and sodium hydroxide are sequentially put into a mortar according to the mol ratio of 1: 2.6: 5.2, and react for 30min at the initial temperature of 40 ℃, so that the product is solid powder, and the yield of the sodium cyclohexylmethylhydroxamate is 82.66%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a hydroximic acid salt collecting agent is characterized by comprising the following specific steps:
carrying out grinding reaction on a diester compound shown in a formula (I) and a hydroxylamine salt compound shown in a formula (II) under the action of alkali to obtain a hydroximic acid salt shown in a formula (III) and a dihydric alcohol compound shown in a formula (IV);
each of said R1Independently an aromatic group, a cycloalkyl group or an alkyl group;
the R is2Is- (CH)2)n-or- (CH)2)n-O-(CH2)n-；
Each n is independently 1-10;
the NH2OH.M includes hydroxylamine hydrochloride, hydroxylamine-O-sulfonate or hydroxylamine nitrate;
the base comprises sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydrogen phosphate or sodium dihydrogen phosphate;
said Y is+Including Na+Or K+；
The alkyl, aryl, cycloalkyl, - (CH)2)n-and- (CH)2)n-O-(CH2)n-may be further optionally mono-or polysubstituted, identically or differently, by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, alkyl, alkoxy or aryl.
2. The method of preparing a hydroxamate collector according to claim 1, wherein each R is1Independently is C6～12Aryl radical, C3～12Cycloalkyl or C1～12An alkyl group;
the alkyl, aryl and cycloalkyl can be further optionally substituted by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl and C1～12Alkyl radical, C1～12Alkoxy or C6～12Aryl is monosubstituted or polysubstituted by the same or different.
3. The method of preparing a hydroxamate collector according to claim 1, wherein each R is1Independently is C6～12Aryl radical, C3～8Cycloalkyl or C1～8An alkyl group;
the alkyl, aryl and cycloalkyl can be further optionally substituted by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl and C1～6Alkyl radical, C1～6Alkoxy or C6～12Aryl is monosubstituted or polysubstituted by the same or different.
4. The method of preparing a hydroxamate collector according to claim 2 or 3, wherein each R is1Independently is phenyl, cyclohexane, methyl, ethyl, isopropyl, n-propyl, n-butyl, n-pentyl orN-octyl;
the phenyl, cyclohexane, methyl, ethyl, isopropyl, n-propyl, n-butyl, n-pentyl and n-octyl radicals may further optionally be mono-or polysubstituted, identically or differently, by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, tert-butoxy, phenyl, p-tert-butylphenyl, o-hydroxyphenyl, naphthyl.
5. The method of preparing a hydroxamate collector according to claim 1, wherein R is2Is- (CH)2)n-or- (CH)2)n-O-(CH2)n-; each n is independently 2-8;
the- (CH)2)n-or- (CH)2)n-O-(CH2)n-may further optionally be substituted by hydrogen, fluorine, chlorine, bromine, hydroxyl, amino, carboxyl, C1～4Alkyl radical, C1～4Alkoxy or C6～12Aryl is monosubstituted or polysubstituted by the same or different.
6. The preparation method of the hydroximic acid salt collecting agent according to claim 1, wherein the molar ratio of the diester compound represented by the formula (I), the hydroxylamine salt compound represented by the formula (II) and the base is 1: 2.1-2.8: 4.2-5.6.
7. The method for preparing the hydroximate collector according to claim 1, wherein the diester compound represented by the formula (I) comprises diethylene glycol dibenzoate, dipropylene glycol dibenzoate, ethylene glycol dibenzoate, 1, 3-propylene glycol dibenzoate, ethylene glycol dicaprylate or ethylene glycol dicyclohexyl formate.
8. The method of preparing a hydroxamate collector according to claim 1, wherein the grinding reaction is carried out in one of a reaction apparatus comprising a ball mill, a rod mill, or a mortar;
the trituration reaction was carried out at room temperature.
9. The preparation method of the hydroxamate collector according to claim 1, wherein the reaction time of the grinding reaction is 10-90 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810510460.7A CN108503563B (en) | 2018-05-24 | 2018-05-24 | Preparation method of hydroximic acid salt collecting agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810510460.7A CN108503563B (en) | 2018-05-24 | 2018-05-24 | Preparation method of hydroximic acid salt collecting agent |
Publications (2)
| Publication Number | Publication Date |
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| CN108503563B true CN108503563B (en) | 2019-12-20 |
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| CN110947522B (en) * | 2018-09-26 | 2021-04-02 | 中南大学 | Sulfur nitrogen-hydroximic acid bifunctional collecting agent and application thereof |
| CN109761836B (en) * | 2019-02-21 | 2020-05-15 | 中南大学 | Preparation method of amide compound |
| CN111068926B (en) * | 2019-11-12 | 2021-06-29 | 中南大学 | Hydroximic acid-alkyl sulfuric acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN110721815B (en) * | 2019-11-12 | 2021-07-27 | 中南大学 | Hydroximic acid-sulfonic acid multi-ligand metal complex collecting agent and preparation method and application thereof |
| CN111495601A (en) * | 2020-04-20 | 2020-08-07 | 武汉理工大学 | Combined collecting agent and method for removing pyrite and pyrrhotite from high-sulfur iron concentrate |
| CN112209852B (en) * | 2020-11-03 | 2022-08-30 | 湖南中医药大学 | Method for preparing hydroxamic acid compound by peroxide |
| CN112246441B (en) * | 2020-11-03 | 2021-08-31 | 中南大学 | Flotation composite collecting agent and preparation method and application thereof |
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| CN1303444A (en) * | 1998-05-27 | 2001-07-11 | Cytec技术有限公司 | Mineral collector compositions of fatty hydroxamic acid in admixture with oil and process of making same |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
| WO2017091552A1 (en) * | 2015-11-25 | 2017-06-01 | Cytec Industries Inc. | Collector compositions and methods of using same in mineral flotation processes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303444A (en) * | 1998-05-27 | 2001-07-11 | Cytec技术有限公司 | Mineral collector compositions of fatty hydroxamic acid in admixture with oil and process of making same |
| WO2017091552A1 (en) * | 2015-11-25 | 2017-06-01 | Cytec Industries Inc. | Collector compositions and methods of using same in mineral flotation processes |
| CN106423573A (en) * | 2016-10-28 | 2017-02-22 | 江西理工大学 | Application method of ester-based hydroximic acid collecting agent to mineral flotation |
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