CN118719336B - A method for applying waste kitchen oil to flotation of high-ash difficult-to-separate coal - Google Patents

A method for applying waste kitchen oil to flotation of high-ash difficult-to-separate coal Download PDF

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CN118719336B
CN118719336B CN202411033202.6A CN202411033202A CN118719336B CN 118719336 B CN118719336 B CN 118719336B CN 202411033202 A CN202411033202 A CN 202411033202A CN 118719336 B CN118719336 B CN 118719336B
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flotation
coal
stage
ore pulp
composite collector
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CN118719336A (en
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夏阳超
邢耀文
桂夏辉
曹亦俊
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China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology Beijing CUMTB
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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
    • B03D1/02—Froth-flotation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • 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
    • 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
    • B03D2203/08—Coal ores, fly ash or soot
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

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  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a method for applying kitchen waste oil to flotation of high-ash refractory coal, belongs to the technical field of fine-grain coal flotation, and solves the problems of low selectivity of a collector, low collecting performance, large dosage of a medicament, low yield of clean coal and low grade in the prior art. A method for applying kitchen waste oil to flotation of high ash refractory coal comprises (1) preparing flotation agent by taking kitchen waste oil as raw material to prepare composite collector solution; the method comprises the steps of (1) carrying out primary flotation, namely mixing ore pulp with a composite collector solution, carrying out primary flotation after the ore pulp is mixed with the composite collector solution to be weakly alkaline to obtain clean coal and tailing coal for primary flotation, (3) carrying out secondary flotation, namely adjusting the ore pulp of the primary flotation clean coal to be weakly acidic to carry out secondary flotation to obtain clean coal products and middlings, and (4) carrying out ore grinding dissociation on the middlings for the secondary flotation, and returning the coal slurry to a primary flotation machine. The method reduces the ash content of the clean coal and the consumption of the collecting agent while ensuring the yield of the clean coal.

Description

Method for applying kitchen waste oil to flotation of high-ash refractory coal
Technical Field
The invention relates to the technical field of fine-grain coal flotation, in particular to a method for applying kitchen waste oil to flotation of high-ash refractory coal.
Background
The development and use of high-quality coal resources and the improvement of mechanical coal mining technology lead to the coal presenting a miniaturization trend, and simultaneously, a large amount of gangue is mixed into the coal, so that the problems of high ash content of the coal slime, increased continuous biomass content, poor floatability and difficult coal slime separation are further outstanding. The typical characteristics of high ash refractory coal flotation are high clean coal yield, poor flotation selectivity and serious limitation of ash content exceeding standard on the quality of the final clean coal product.
Research shows that the main reasons for high ash content of the high ash refractory coal clean coal are the existence of adsorption covers, water flow entrainment and coal-mineral intergrowth (such as floatable components) of the fine slime on the surface of the clean coal. Aiming at the difficult problem of high ash content of high-ash refractory coal, the prior art mainly relates to a flotation process strengthening method which comprises efficient size mixing, selective flocculation, inhibitor addition and the like.
In the flotation process, pollutant substances such as fine clay minerals can be adsorbed and covered on the surface of coal, so that the hydrophobicity of the surface of the coal is reduced, the adhesion efficiency of particles and bubbles is reduced, the adsorption of a collector is hindered, and the flotation efficiency is reduced. Clay minerals are fine colloid particles, and are easy to enter flotation clean coal foam along with water flow under the stirring effect, so that clean coal ash is increased. The slurry mixing operation before flotation is beneficial to realizing the dispersion of coal particles and ash particles, strengthening the selective adsorption of flotation agents on the surface of coal, and improving the flotation separation effect of high-ash refractory coal. Certain turbulence and shearing are needed for floatation slurry mixing to realize mineral dispersion and medicament adsorption, so that recovery of clean coal in floatation can be promoted, clean coal ash content is reduced, but the inhibition effect of floatation slurry mixing on floatation clean coal ash content is limited, and coal particles are possibly further crushed.
The selective flocculation means that flocculant such as polyaluminium chloride, polyacrylamide and the like is added in flotation slurry mixing to realize flocculation of fine clay minerals, thereby reducing mineral entrainment and fine mud cover in the flotation process. However, the coal is often subjected to hydrophobic flocculation in preference to the clay mineral, so that the selective flocculation of the clay mineral is difficult to realize in coal flotation. Inhibitors such as modified starch, sodium silicate, sodium hexametaphosphate and the like can be added into ore pulp to destroy or weaken the adsorption of minerals to a collector, enhance the surface hydrophilicity of the minerals and achieve the purpose of improving flotation, but have higher requirements on the types and the dosage of the inhibitors.
The existing flotation process strengthening method is difficult to adapt to the requirements of separation and quality improvement of difficult-to-separate coal slime with high ash content and complex cloth, and the flotation process lacks adaptation to material property change.
Disclosure of Invention
In view of the above analysis, the embodiment of the invention aims to provide a method for applying kitchen waste oil to flotation of high-ash refractory coal, which is used for solving at least one of the problems of low selectivity, low collection performance, large dosage of reagents, low yield of clean coal, low grade of clean coal and the like of the existing collector.
On one hand, the embodiment of the invention provides a method for applying kitchen waste oil to flotation of high-ash refractory coal, which comprises the following steps:
(1) Preparing a flotation reagent, namely preparing a composite collector solution by taking kitchen waste oil as a raw material;
(2) The primary flotation, namely mixing ore pulp with a composite collector solution, fully mixing the ore pulp, keeping the pH value of the ore pulp to be weak alkaline, pumping the alkaline ore pulp into a primary flotation machine for flotation, and obtaining refined coal and tailing coal subjected to primary flotation through roughing;
(3) The second-stage flotation, namely sending the flotation clean coal generated by the first-stage flotation machine into the second-stage flotation machine, adjusting the pH value of ore pulp to be weak acid, generating clean coal and middling through the second-stage flotation machine, and enabling the second-stage flotation clean coal to enter a dehydration link to become a clean coal product;
(4) And the continuous body dissociation recleaning, namely, the secondary flotation machine picks middlings, enters a ball mill for selective grinding and dissociation, so that the middlings are fully dissociated, and the coal slurry is returned to the primary flotation machine to be mixed with the feed for flotation.
Specifically, in the step (1), the kitchen waste oil is used as a molecular substance of a tail chain of the composite collector, and the preparation method of the composite collector solution comprises the following steps:
step 1, removing impurities and dehydrating kitchen waste oil, mixing with an intermediate aqueous solution, and adjusting the pH of the mixed solution to 7.5-8.5;
And2, stirring the mixed solution in the step 1 to obtain the composite collector solution with the solute molecules of the Gemini-like structure.
Further, the molar ratio of the kitchen waste oil to the intermediate aqueous solution is 2:1.
Specifically, the Gemini-like structure is formed by 1 intermediate and 2 tail chain molecules under the action of static electricity, and is a composite collector in an assembled state.
The kitchen waste oil is used as tail chain molecule, which accords with the general structural formulaThe Gemini-like structure accords with the general formula:。
Further, in the step (3), the pH value of the weak acid ore pulp is 5.5-6.0 in the second-stage flotation.
Specifically, in the weak acid pulp, the intermediate and tail chain molecules of the composite collector are in a depolymerized state.
Notably, the 2 tail molecules are the same or different.
On the other hand, the embodiment of the invention also provides a high-ash refractory coal composite collector which is used for flotation of the high-ash refractory coal and comprises 1 intermediate and 2 tail chain molecules, wherein the chemical structural general formula of the high-ash refractory coal composite collector is as follows: The general structural formula of the intermediate is R1 in the intermediate structure contains part of N, S, O, C atoms, the total number of non-hydrogen atoms in R1 is 2-8, R2 contains N atoms or N, C atoms, and the total number of atoms is 1-3.
Further, the tail chain molecular structure general formula is: The 2 tail chain molecules are the same or different, wherein R3 is a polar group of the tail chain molecule, and is deprotonated-COOH or-SO 3H, n is the carbon chain length of the tail chain molecule, and the numerical value is 6-18.
Illustratively, the Gemini-structure-imitated composite collector comprises:
,
,
。
compared with the prior art, the invention has at least one of the following beneficial effects:
1. Aiming at the characteristics of high ash content and complex components of high-ash refractory coal, the invention adopts kitchen waste oil to prepare and obtain tail chain molecular substances of the composite collector, the kitchen waste oil is rich in unsaturated acids such as oleic acid, linoleic acid, linolenic acid and the like, the adsorption effect of unsaturated carboxylic acid and the coal surface is stronger, the flotation separation is more facilitated, and the preparation of the tail chain molecular substances from the kitchen waste oil has certain economical efficiency and obvious environmental protection benefit.
2. According to the invention, the pH sensitive composite collector is designed, the intermediate and tail chain molecules are fully mixed under alkaline conditions and form a Gemini-like structure under the action of static electricity, the polar groups of the intermediate structure part are combined with hydrophilic sites on the surface of coal, so that the two tail chain molecules are promoted to better play a hydrophobic role, the floatability of the coal is enhanced, and particularly, the intermediate structure is disulfide bonds, sulfoxy groups and the like, compared with other traditional collectors, the intermediate structure has strong surface activity, the affinity is improved, the collecting performance is further improved, and the yield of clean coal is greatly improved;
Under the acidic condition, depolymerizing is carried out between the intermediate and tail chain molecules, only the tail chain molecules play a role, the tail chain molecules exist in the form of hydrocarbon oil and are selectively adsorbed on the surface of coal, so that the selectivity of the collector is improved, the ash content of the flotation clean coal is reduced, and the grade of the clean coal is improved;
the composite collector designed by the invention can enhance the hydrophobicity of the coal surface through the strong hydrophobicity of tail chain molecules in the assembled or depolymerized state, thereby ensuring the flotation separation effect.
3. The pH sensitive composite collector is matched with a two-stage flotation and continuous dissociation reselection process, the collecting capacity of the collector is timely adjusted according to the physical property change of ore pulp, and the ash content of the clean coal is reduced while the yield of the clean coal is ensured;
The pH value of the ore pulp is regulated to be weak alkaline in the first-stage flotation, so that the collector forms a Gemini-like structure for roughing, and more clean coal products are ensured to be obtained;
Aiming at the secondary flotation tail coal, the invention adopts an ore grinding process to release the clean coal in the middling intergrowth, furthest recovers and utilizes coal resources, combines with a pH sensitive medicament flotation process, forms a high-ash refractory coal flotation recovery technical system based on selective dissociation-interface regulation and control, and realizes the accurate separation of coal gangue.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to designate like parts throughout the drawings;
FIG. 1 is a schematic diagram of the high ash refractory coal deep flotation process equipment of the present invention;
FIG. 2 is a flow chart of the high ash refractory coal deep flotation process of the invention;
FIG. 3 is a schematic diagram of the assembled state of the composite collector of the present invention;
FIG. 4 is a schematic diagram of the depolymerization state operation of the composite collector of the present invention;
FIG. 5 is a working principle diagram of the invention for preparing the composite collector by taking kitchen waste oil as a raw material.
Reference numerals:
1-feeding pool, 2-feeding pump, 3-collector stirring barrel, 4-collector dosing pump, 5-foaming agent barrel, 6-foaming agent dosing pump, 7-alkaline solution barrel, 8-alkaline solution dosing pump, 9-acid solution barrel, 10-acid solution dosing pump, 11-one-stage automatic dosing machine, 12-two-stage automatic dosing machine, 13-ore pulp preprocessor, 14-ore pulp pump, 15-one-stage flotation machine, 16-two-stage flotation machine and 17-ball mill.
Detailed Description
The following detailed description of preferred embodiments of the application is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the application, are used to explain the principles of the application and are not intended to limit the scope of the application.
The high-ash refractory coal has the characteristics of higher ash content and more fine-particle-grade coal slime, pollutants such as fine-particle clay minerals are easy to adsorb and cover on the surface of the coal, the hydrophobicity of the surface of the coal is reduced, the adhesion efficiency of particles and bubbles is reduced, the adsorption of a collector is hindered, the separation efficiency of the high-ash fine-particle coal slime in a conventional washing and separating process is lower, flotation indexes are influenced by the existence of a plurality of middlings, and the high-yield and low-ash clean coal is difficult to obtain simultaneously.
In one embodiment of the invention, a method for applying kitchen waste oil to flotation of high ash refractory coal is disclosed, as shown in fig. 2, and comprises the following steps:
(1) Preparing a flotation reagent, namely preparing a composite collector solution by taking kitchen waste oil as a raw material;
Inputting the composite collector into a one-stage automatic dosing machine through a collector dosing pump, respectively inputting the foaming agent in a foaming agent barrel and the alkaline solution in an alkaline solution barrel into the one-stage automatic dosing machine through the foaming agent dosing pump and the alkaline solution dosing pump, and adding the medicament in the one-stage flotation process by the one-stage automatic dosing machine and automatically regulating and controlling the dosage;
Adding the acid solution in the acid solution barrel into a two-stage automatic dosing machine through an acid dosing pump, adding the medicament in the two-stage flotation process by the two-stage automatic dosing machine, and automatically regulating and controlling the dosage;
the foaming agent is an alcohol foaming agent, the consumption of the primary flotation collector is 500-1500 g/t, and the consumption of the foaming agent is 100-250 g/t;
(2) The ore pulp in the feeding pool is conveyed to an ore pulp preprocessor by a feeding pump, after the ore pulp and the medicament from the first-stage automatic medicament adding machine are fully mixed, alkaline ore pulp is pumped into the first-stage flotation machine for flotation by the ore pulp pump, the flotation clean coal is scraped out by a scraper of the flotation machine, the clean coal a and the tail coal b of primary flotation are obtained through rough flotation, the clean coal a of flotation continues to enter a second-stage flotation machine for concentration, and the tail coal b of flotation enters a dewatering system as a final tail coal product;
(3) Feeding the flotation clean coal a generated by the first-stage flotation machine into a second-stage flotation machine, adding an acid solution through a second-stage automatic dosing machine to adjust the pH value of ore pulp to be slightly acidic, performing flotation through the second-stage flotation machine to generate clean coal d and middlings c, and enabling the second-stage flotation clean coal d to enter a dehydration link to become a clean coal product;
(4) The continuous body dissociation recleaning, namely, the secondary flotation machine picks middling coal c and enters a ball mill for selective grinding and dissociation, so that the middling continuous body is fully dissociated, the coal slurry is returned to the primary flotation machine to be mixed with feeding for floatation, and the grinding time in the ball mill is 2-3 min
Further, in the step (1), the kitchen waste oil is used as a molecular substance of a tail chain of the composite collector, and the preparation method of the composite collector solution comprises the following steps:
Step 1, removing impurities and dehydrating kitchen waste oil, mixing with an intermediate aqueous solution according to a molar ratio, and adjusting the pH of the mixed solution to 7.5-8.5;
And2, stirring the mixed solution in the step 1 to obtain the composite collector solution with the solute molecules of the Gemini-like structure.
The simulated Gemini structure is formed by 1 intermediate and 2 tail chain molecules under the action of static electricity, and is a composite collector in an assembled state.
The concentration of the intermediate aqueous solution is less than 0.05 mM, the intermediate aqueous solution is controlled to be proper, the intermediate is better dissolved and dispersed, tail chain molecules are added to form the composite collector, if the concentration of the intermediate aqueous solution is too high, the added tail chain molecules are correspondingly increased, the tail chain molecules are mainly hydrocarbon oil, so that the dissolution and dispersion are difficult, kitchen waste oil and fat are mixed in the intermediate aqueous solution, the mixed solution is required to be fully stirred, dispersed and uniformly mixed, the intermediate and tail chain substances are fully contacted, the adsorption assembly effect is realized, and the composite collector in an assembled state is obtained, wherein the molar concentration of the collector solution is equal to that of the intermediate aqueous solution.
The kitchen waste oil is subjected to pretreatment before use, and for the use of coal slime flotation, the kitchen waste oil is subjected to filtering and impurity removal by a physical method according to the density difference, and then is subjected to heating precipitation, further dehydration and impurity removal to be used as tail chain molecular substances to be mixed with an intermediate solution;
The kitchen waste oil is mainly composed of vegetable oil, is rich in carboxylic acid substances, mainly oleic acid, linoleic acid, linolenic acid and the like, has certain economical efficiency and obvious environmental protection benefit, and unsaturated acids such as oleic acid, linoleic acid, linolenic acid and the like have stronger adsorption effect on the surface of coal, thus being more beneficial to flotation separation;
The kitchen waste oil is used as tail chain molecule, which accords with the general structural formula The Gemini-like structure accords with the general formula:;
preferably, when the kitchen waste oil is used as the tail chain molecular substance, the 2 tail chain molecules are the same or different, and the tail chain molecular structure is one or more of the following combinations:
。
illustratively, the Gemini-structure-imitated composite collector comprises:
,
,
。
Further, in the step (3), the pH value of the weak acid ore pulp is 5.5-6.0 in the second-stage flotation.
Specifically, in the weak acid pulp, the intermediate and tail chain molecules of the composite collector are in a depolymerized state.
When kitchen waste oil is used as a tail chain molecular substance, the working principle of the composite collector is shown in figure 5.
Under alkaline conditions, the intermediate of the composite collector and two tail chain molecules are assembled through electrostatic action to form a Gemini-like structure, the Gemini-like structure has strong collecting performance, can be efficiently adsorbed on the surface of coal, and further improves the flotation recovery rate, under acidic conditions, when the composite collector is not assembled or depolymerized, only tail chain molecules play a role, and because the tail chain molecules exist in the form of hydrocarbon oil, the tail chain molecules can be selectively adsorbed on the surface of the coal, have strong selectivity, and are beneficial to reducing the ash content of the flotation clean coal, and in an assembled state or a depolymerized state, the hydrophobicity of the surface of the coal can be enhanced through the strong hydrophobicity of the tail chain molecules, so that the flotation separation effect is ensured.
On the other hand, the embodiment of the invention also provides a high-ash refractory coal composite collector which is used for flotation of the high-ash refractory coal and comprises 1 intermediate and 2 tail chain molecules, wherein the chemical structural general formula of the high-ash refractory coal composite collector is as follows: The general structural formula of the intermediate is R1 in the intermediate structure contains part of atoms in N, S, O, C atoms, the total number of non-hydrogen atoms in R1 is 2-8, R2 contains N atoms or N, C atoms, the total number of atoms is 1-3, and the molecular structural formula of the tail chain is as follows: The 2 tail chain molecules are the same or different, wherein R3 is a polar group of the tail chain molecule, and is deprotonated-COOH or-SO 3H, n is the carbon chain length of the tail chain molecule, and the numerical value is 6-18.
The intermediate and the tail chain molecule are assembled or depolymerized by adjusting the pH.
The pH sensitive composite collector is matched with a two-stage flotation and continuous dissociation recleaning process, the collecting capacity of the collector is timely adjusted according to the physical property change of ore pulp, and the ash content of the clean coal is reduced while the yield of the clean coal is ensured;
The pH value of the ore pulp is regulated to be weak alkaline in the first-stage flotation, so that the collector forms a Gemini-like structure for roughing, and more clean coal products are ensured to be obtained;
Aiming at the secondary flotation tail coal, a grinding process is adopted to release clean coal in the middling intergrowth, coal resources are recovered and utilized to the maximum extent, and a high-ash refractory coal flotation recovery technology system based on selective dissociation-interface regulation is formed by combining a pH sensitive agent flotation process, so that coal gangue accurate separation is realized.
Preferably, R1 in the intermediate structure is one of the structures- (CH 2) 2-, -CH2C (O) CH2-, -S-, - (CH 2) 2NH (CH 2) 2-, -ch=ch-, -n=n-;
When R1 in the intermediate structure is a strong polar group such as a disulfide bond, a sulfoxy group and the like, sulfur or oxygen atoms can generate a hydrogen bond and other adsorption effects with polar sites on the coal surface or the middling intergrowth surface, and compared with other traditional collectors, the collector has strong surface activity, improved affinity and higher collecting performance.
Preferably, R2 in the intermediate structure is two end groups of the intermediate and is one of protonated-NH 2 and-C (NH) NH2 structures.
Preferably, the intermediate structure comprises:。
In one possible design, the tail chain molecular structure of the composite collector has the general formula: The two tail chain molecules are the same or different, wherein R3 is a polar group of the tail chain molecule, and is deprotonated-COOH or-SO 3H, n is the carbon chain length of the tail chain molecule, the numerical value is 6-18, the C-C bond in the tail chain is a single bond or an unsaturated bond, R2 is a cationic group, R3 is an anionic group, and the common tail chain molecular structure is The working principle of the composite collector taking the structure as the tail chain molecules is shown in fig. 3 and 4, the intermediate of the composite collector and the two tail chain molecules are assembled under the alkaline condition through the electrostatic action to form the Gemini-like structure, the intelligent composite collector can be depolymerized under the acidic condition, the intermediate with cationic groups at the two ends has less influence on flotation, and the tail chain molecules form micro-oil drops in ore pulp to spread on the surfaces of coal particles.
The high-ash refractory coal flotation system is shown in figure 1, and comprises a flotation dosing system, a feeding system, a primary flotation machine 15, a secondary flotation machine 16 and a ball mill 17 which are sequentially connected through pipelines;
The outlet of the feeding system is connected with the inlet of the first-stage flotation machine 15, the first outlet of the first-stage flotation machine is connected with the inlet of the second-stage flotation machine, the first outlet of the second-stage flotation machine 16 is connected with the inlet of the ball mill 17, the outlet of the ball mill 17 is connected with the inlet of the first-stage flotation machine 15, and the second outlets of the first-stage flotation machine and the second-stage flotation machine are both product outlets;
The feeding system comprises a feeding pool 1, a feeding pump 2, an ore pulp preprocessor 13 and an ore pulp pump 14 which are sequentially connected through pipelines, wherein an outlet of the feeding pool is connected with an inlet of the feeding pump, an inlet of the ore pulp preprocessor is connected with an outlet of the feeding pump, and an inlet of the ore pulp pump is connected with an outlet of the ore pulp preprocessor;
the flotation dosing system comprises a first-stage flotation dosing system and a second-stage flotation dosing system, wherein an outlet of the first-stage flotation dosing system is connected with the ore pulp preprocessor through a pipeline, and the second-stage flotation dosing system is connected with the second-stage flotation machine through a pipeline;
the primary flotation dosing system comprises a primary automatic dosing machine 11, a collector stirring barrel 3, a foaming agent stirring barrel 5 and an alkaline solution barrel 7, wherein the collector stirring barrel 3, the foaming agent stirring barrel 5 and the alkaline solution barrel 7 are respectively connected into the primary automatic dosing machine 11 through a collector dosing pump 4, a foaming agent dosing pump 6, an alkaline solution dosing pump 8 and a pipeline;
The two-stage flotation dosing system comprises an acid solution barrel 9, an acid solution dosing pump 10 and a two-stage automatic dosing machine 12 which are connected in sequence through pipelines.
In conclusion, the pH sensitive composite collector is matched with the two-stage flotation and continuous dissociation recleaning process, the collecting capacity of the collector is timely adjusted according to the physical property change of ore pulp, the yield of clean coal is ensured, the ash content of the clean coal is reduced, aiming at the characteristics of high ash content and complex components of high ash content difficult coal, kitchen waste oil is adopted to prepare tail chain molecular substances for obtaining the composite collector, mainly oleic acid, linoleic acid and linolenic acid with unsaturated bonds, the adsorption effect of the unsaturated carboxylic acids and the coal surface is stronger, the dosage of the agent is reduced, the adsorption strength and the spreading rate of the collector are greatly improved, and the tail chain molecular substances prepared from the kitchen waste oil have certain economical efficiency and obvious environmental protection benefit.
The composite collector and the deep flotation process of the present invention will be described below with reference to specific examples.
Example 1
The first-stage roughing-second-stage concentrating process is adopted to carry out floatation and ash reduction on coking coal in some coal preparation plant in Shanxi, and the ash content of raw coal is 23%.
The first-stage roughing-second-stage refining process flow is as follows:
(1) Preparing a section of flotation reagent, namely carrying out filtration, impurity removal and dehydration pretreatment on kitchen waste oil until no water and impurities are visible to naked eyes, and for the use of coal slime flotation, carrying out physical filtration and impurity removal on the kitchen waste oil according to the density difference, and then carrying out heating precipitation, further dehydration and impurity removal to obtain tail chain molecular substances which are mixed with an intermediate solution;
preparation of intermediate at normal temperature A solution with a concentration of 0.04 mM;
Adding the pretreated kitchen grease into an intermediate solution to prepare a pH sensitive composite collector, wherein the molar concentration ratio of the kitchen grease to the intermediate is 2:1 (the kitchen grease adopts average molecular weight according to the specific composition analysis of the kitchen grease);
The average molecular weight of the kitchen grease in the preparation process is calculated as 278;
The tail chain molecules of the composite collector in an assembled state can be linoleic acid or linolenic acid in kitchen waste oil or 2 combinations of oleic acid, linoleic acid and linolenic acid;
One possible structural formula is:
。
Respectively inputting the composite collector, the foaming agent and the alkaline solution in the assembled state into a section of automatic dosing machine, and adding and automatically regulating the dosage of the agents in the flotation process of the section of automatic dosing machine;
The consumption of the first-stage flotation collector is 500 g/t, the consumption of the foaming agent is 150 g/t, and the consumption of the alkaline solution is adjusted according to the pH value requirement of ore pulp;
adopting terpineol as a foaming agent and sodium hydroxide to prepare an alkaline solution;
(2) The first-stage flotation, namely conveying ore pulp in a feeding pool to an ore pulp preprocessor by a feeding pump, fully mixing the ore pulp and a medicament from a first-stage automatic dosing machine, keeping the pH value of the ore pulp to be 7.5-8.5, pumping alkaline ore pulp into a first-stage flotation machine by an ore pulp pump for flotation, scraping out flotation clean coal by a scraper of the flotation machine, obtaining primary flotation clean coal a and tail coal b through rough flotation, continuously feeding the flotation clean coal a into a second-stage flotation machine for concentration, and feeding the flotation tail coal b as a final tail coal product into a dewatering system;
(3) Feeding the flotation clean coal a generated by the first-stage flotation machine into a second-stage flotation machine, adding an acid solution (prepared by sulfuric acid) through a second-stage automatic dosing machine to adjust the pH value of ore pulp to be 5.5-6.0, performing flotation through the second-stage flotation machine to generate clean coal d and middlings c, and enabling the second-stage flotation clean coal d to enter a dehydration link to become a clean coal product;
(4) And (3) disjunction recleaning, namely selecting middlings c by a two-stage flotation machine, selectively grinding and disjunction in a ball mill for 2-3 min, fully dissociating middlings, and returning coal slurry to the one-stage flotation machine for mixing with a feed for flotation.
The product index obtained is shown in Table 1.
Example 2
The anthracite coal of a certain coal preparation plant in Henan is subjected to flotation and ash reduction by adopting a one-stage roughing-two-stage refining process, and the ash content of raw coal is 26%.
The first-stage roughing-second-stage refining process flow is as follows:
(1) Preparing a section of flotation reagent, namely carrying out filtration, impurity removal and dehydration pretreatment on kitchen waste oil until no water and impurities are visible to naked eyes, and for the use of coal slime flotation, carrying out physical filtration and impurity removal on the kitchen waste oil according to the density difference, and then carrying out heating precipitation, further dehydration and impurity removal to obtain tail chain molecular substances which are mixed with an intermediate solution;
preparing an intermediate triethylenetetramine solution at normal temperature, wherein the concentration of the solution is 0.04 mM;
Adding the pretreated kitchen grease into an intermediate solution to prepare a pH sensitive composite collector, wherein the molar concentration ratio of the kitchen grease to the intermediate is 2:1 (the kitchen grease adopts average molecular weight according to the specific composition analysis of the kitchen grease);
The average molecular weight of the kitchen grease in the preparation process is calculated as 278;
The tail chain molecules of the composite collector in an assembled state can be linoleic acid or linolenic acid in kitchen waste oil or 2 combinations of oleic acid, linoleic acid and linolenic acid;
One possible structural formula is:
。
Respectively inputting the composite collector, the foaming agent and the alkaline solution in the assembled state into a section of automatic dosing machine, and adding and automatically regulating the dosage of the agents in the flotation process of the section of automatic dosing machine;
The consumption of the first-stage flotation collector is 500 g/t, the consumption of the foaming agent is 150 g/t, and the consumption of the alkaline solution is adjusted according to the pH value requirement of ore pulp;
adopting terpineol as a foaming agent and sodium hydroxide to prepare an alkaline solution;
(2) The first-stage flotation, namely conveying ore pulp in a feeding pool to an ore pulp preprocessor by a feeding pump, fully mixing the ore pulp and a medicament from a first-stage automatic dosing machine, keeping the pH value of the ore pulp to be 7.5-8.5, pumping alkaline ore pulp into a first-stage flotation machine by an ore pulp pump for flotation, scraping out flotation clean coal by a scraper of the flotation machine, obtaining primary flotation clean coal a and tail coal b through rough flotation, continuously feeding the flotation clean coal a into a second-stage flotation machine for concentration, and feeding the flotation tail coal b as a final tail coal product into a dewatering system;
(3) Feeding the flotation clean coal a generated by the first-stage flotation machine into a second-stage flotation machine, adding an acid solution (prepared by sulfuric acid) through a second-stage automatic dosing machine to adjust the pH value of ore pulp to be 5.5-6.0, performing flotation through the second-stage flotation machine to generate clean coal d and middlings c, and enabling the second-stage flotation clean coal d to enter a dehydration link to become a clean coal product;
(4) And (3) disjunction recleaning, namely selecting middlings c by a two-stage flotation machine, selectively grinding and disjunction in a ball mill for 2-3 min, fully dissociating middlings, and returning coal slurry to the one-stage flotation machine for mixing with a feed for flotation.
The product index obtained is shown in Table 1.
Example 3
The anthracite coal of a certain coal preparation plant in Henan is subjected to flotation and ash reduction by adopting a one-stage roughing-two-stage refining process, and the ash content of raw coal is 26%.
The first-stage roughing-second-stage refining process flow is as follows:
(1) Preparing a section of flotation reagent, namely carrying out filtration, impurity removal and dehydration pretreatment on kitchen waste oil until no water and impurities are visible to naked eyes, and for the use of coal slime flotation, carrying out physical filtration and impurity removal on the kitchen waste oil according to the density difference, and then carrying out heating precipitation, further dehydration and impurity removal to obtain tail chain molecular substances which are mixed with an intermediate solution;
Preparing an intermediate ethylenediamine solution at normal temperature, wherein the concentration of the solution is 0.04 mM;
Adding the pretreated kitchen grease into an intermediate solution to prepare a pH sensitive composite collector, wherein the molar concentration ratio of the kitchen grease to the intermediate is 2:1 (the kitchen grease adopts average molecular weight according to the specific composition analysis of the kitchen grease);
The average molecular weight of the kitchen grease in the preparation process is calculated as 278;
The tail chain molecules of the composite collector in an assembled state can be linoleic acid or linolenic acid in kitchen waste oil or 2 combinations of oleic acid, linoleic acid and linolenic acid;
One possible structural formula is:
。
Respectively inputting the composite collector, the foaming agent and the alkaline solution in the assembled state into a section of automatic dosing machine, and adding and automatically regulating the dosage of the agents in the flotation process of the section of automatic dosing machine;
The consumption of the first-stage flotation collector is 500 g/t, the consumption of the foaming agent is 150 g/t, and the consumption of the alkaline solution is adjusted according to the pH value requirement of ore pulp;
adopting terpineol as a foaming agent and sodium hydroxide to prepare an alkaline solution;
(2) The first-stage flotation, namely conveying ore pulp in a feeding pool to an ore pulp preprocessor by a feeding pump, fully mixing the ore pulp and a medicament from a first-stage automatic dosing machine, keeping the pH value of the ore pulp to be 7.5-8.5, pumping alkaline ore pulp into a first-stage flotation machine by an ore pulp pump for flotation, scraping out flotation clean coal by a scraper of the flotation machine, obtaining primary flotation clean coal a and tail coal b through rough flotation, continuously feeding the flotation clean coal a into a second-stage flotation machine for concentration, and feeding the flotation tail coal b as a final tail coal product into a dewatering system;
(3) Feeding the flotation clean coal a generated by the first-stage flotation machine into a second-stage flotation machine, adding an acid solution (prepared by sulfuric acid) through a second-stage automatic dosing machine to adjust the pH value of ore pulp to be 5.5-6.0, performing flotation through the second-stage flotation machine to generate clean coal d and middlings c, and enabling the second-stage flotation clean coal d to enter a dehydration link to become a clean coal product;
(4) And (3) disjunction recleaning, namely selecting middlings c by a two-stage flotation machine, selectively grinding and disjunction in a ball mill for 2-3 min, fully dissociating middlings, and returning coal slurry to the one-stage flotation machine for mixing with a feed for flotation.
The product index obtained is shown in Table 1.
Comparative example 1
The anthracite coal of a certain coal preparation plant in Henan is subjected to flotation and ash reduction by adopting a one-stage roughing-two-stage refining process, and the ash content of raw coal is 26%.
The first-stage roughing-second-stage refining process flow is as follows:
(1) Preparing a first-stage flotation reagent, namely respectively inputting the composite collector in an assembled state, a foaming agent and an alkaline solution into a first-stage automatic dosing machine, adding the reagent in the first-stage flotation process by the first-stage automatic dosing machine, automatically regulating and controlling the dosage, wherein the dosage of the first-stage flotation collector is 600 g/t, the dosage of the foaming agent is 150 g/t, and the dosage of the alkaline solution is regulated according to the pH value requirement of ore pulp;
adopting terpineol as a foaming agent and sodium hydroxide to prepare an alkaline solution;
wherein the preparation steps of the composite collector in an assembled state are as follows:
(1-1) preparing an intermediate triethylenetetramine solution at normal temperature, wherein the concentration of the solution is 0.04 mM;
(1-2) adding linolenic acid into an intermediate solution to prepare a pH sensitive composite collector, wherein the molar concentration ratio of the linolenic acid to triethylenetetramine is 2:1;
and (1-3) adjusting the pH of the solution by using sodium hydroxide, wherein the pH=7.5-8.5, and fully stirring and uniformly mixing the mixed solution to obtain the composite collector in an assembled state.
(2) The ore pulp in the feeding pool is conveyed to an ore pulp preprocessor by a feeding pump, after the ore pulp and the medicament from the first-stage automatic medicament adding machine are fully mixed, alkaline ore pulp is pumped into the first-stage flotation machine for flotation by the ore pulp pump, the flotation clean coal is scraped out by a scraper of the flotation machine, the clean coal a and the tail coal b of primary flotation are obtained through rough flotation, the clean coal a of flotation continues to enter a second-stage flotation machine for concentration, and the tail coal b of flotation enters a dewatering system as a final tail coal product;
(3) Feeding the flotation clean coal a generated by the first-stage flotation machine into a second-stage flotation machine, adding an acid solution (prepared by sulfuric acid) through a second-stage automatic dosing machine to adjust the pH value of ore pulp to be 5.5-6.0, performing flotation through the second-stage flotation machine to generate clean coal d and middlings c, and enabling the second-stage flotation clean coal d to enter a dehydration link to become a clean coal product;
(4) And (3) disjunction recleaning, namely selecting middlings c by a two-stage flotation machine, selectively grinding and disjunction in a ball mill for 2-3 min, fully dissociating middlings, and returning coal slurry to the one-stage flotation machine for mixing with a feed for flotation.
The product index obtained is shown in Table 1.
Comparative example 2
The anthracite coal of a certain coal preparation plant in Henan is subjected to flotation and ash reduction by adopting a one-stage roughing-two-stage refining process, and the ash content of raw coal is 26%.
The first-stage roughing-second-stage refining process flow is as follows:
(1) Preparing a first-stage flotation reagent, namely respectively inputting the composite collector in an assembled state, a foaming agent and an alkaline solution into a first-stage automatic dosing machine, adding the reagent in the first-stage flotation process by the first-stage automatic dosing machine, automatically regulating and controlling the dosage, wherein the dosage of the first-stage flotation collector is 600 g/t, the dosage of the foaming agent is 150 g/t, and the dosage of the alkaline solution is regulated according to the pH value requirement of ore pulp;
adopting terpineol as a foaming agent and sodium hydroxide to prepare an alkaline solution;
wherein the preparation steps of the composite collector in an assembled state are as follows:
(1-1) preparation of intermediate at Normal temperature A solution with a concentration of 0.04 mM;
(1-2) adding linolenic acid to the intermediate solution to prepare a pH-sensitive composite collector, linolenic acid and The molar concentration ratio of (2) to (1);
(1-3) adjusting the pH of the solution by using sodium hydroxide, wherein the pH=7.5-8.5, and fully stirring and uniformly mixing the mixed solution to obtain the composite collector in an assembled state;
(2) The ore pulp in the feeding pool is conveyed to an ore pulp preprocessor by a feeding pump, after the ore pulp and the medicament from the first-stage automatic medicament adding machine are fully mixed, alkaline ore pulp is pumped into the first-stage flotation machine for flotation by the ore pulp pump, the flotation clean coal is scraped out by a scraper of the flotation machine, the clean coal a and the tail coal b of primary flotation are obtained through rough flotation, the clean coal a of flotation continues to enter a second-stage flotation machine for concentration, and the tail coal b of flotation enters a dewatering system as a final tail coal product;
(3) Feeding the flotation clean coal a generated by the first-stage flotation machine into a second-stage flotation machine, adding an acid solution (prepared by sulfuric acid) through a second-stage automatic dosing machine to adjust the pH value of ore pulp to be 5.5-6.0, performing flotation through the second-stage flotation machine to generate clean coal d and middlings c, and enabling the second-stage flotation clean coal d to enter a dehydration link to become a clean coal product;
(4) And (3) disjunction recleaning, namely selecting middlings c by a two-stage flotation machine, selectively grinding and disjunction in a ball mill for 2-3 min, fully dissociating middlings, and returning coal slurry to the one-stage flotation machine for mixing with a feed for flotation.
As can be seen from table 1, examples 1, 2 and 3 achieve better separation effects, wherein the yield of primary roughing clean coal is higher than 85.7%, the collecting performance of the collecting agent is higher than that of comparative examples 1 and 2, the yield of primary clean coal is improved, the ash content of secondary clean coal is lower than 9.7%, the yield of clean coal is higher than 73.5%, and the collecting agent has higher selectivity than that of comparative examples 1 and 2, so that the floating clean coal ash content is reduced, and the clean coal grade is improved;
on the other hand, the yields of the two sections of refined coals in examples 1, 2 and 3 are obviously higher than those in comparative examples 1 and 2 under the condition of using fewer collecting agents, and the hydrophobic modification effect of the unsaturated carboxylic acid in the kitchen waste oil is obvious, so that the dosage of the agent can be reduced.
In conclusion, the pH sensitive composite collector is designed to be matched with a two-stage flotation and continuous dissociation recleaning process, the collecting capacity of the collector is timely adjusted according to the change of physical properties of ore pulp, the yield of clean coal is ensured, meanwhile, the ash content of the clean coal is reduced, aiming at the characteristics of high ash content and complex components of high-ash refractory coal, kitchen waste oil is adopted to prepare and obtain tail chain molecular substances of the composite collector, the adsorption effect on the surface of the coal is stronger, the dosage of the agent is reduced, the adsorption strength and the spreading rate of the collector are greatly improved, and the preparation of the tail chain molecular substances from the kitchen waste oil has certain economical efficiency and obvious environmental protection benefit.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.

Claims (10)

1. The method for applying the kitchen waste oil to the flotation of the high-ash refractory coal is characterized by comprising the following steps of:
(1) Preparing a flotation reagent, namely preparing a composite collector solution by taking kitchen waste oil as a raw material;
(2) The primary flotation, namely mixing ore pulp with a composite collector solution, fully mixing the ore pulp, keeping the pH value of the ore pulp to be weak alkaline, pumping the alkaline ore pulp into a primary flotation machine for flotation, and obtaining refined coal and tailing coal subjected to primary flotation through roughing;
(3) The second-stage flotation, namely sending the flotation clean coal generated by the first-stage flotation machine into the second-stage flotation machine, adjusting the pH value of ore pulp to be weak acid, generating clean coal and middling through the second-stage flotation machine, and enabling the second-stage flotation clean coal to enter a dehydration link to become a clean coal product;
(4) And the continuous body dissociation recleaning, namely, the secondary flotation machine picks middlings, enters a ball mill for selective grinding and dissociation, so that the middlings are fully dissociated, and the coal slurry is returned to the primary flotation machine to be mixed with the feed for flotation.
2. The method according to claim 1, wherein the kitchen waste oil and fat is used as a tail chain molecular substance of the composite collector in the step (1), and the preparation method of the composite collector solution comprises the following steps:
Step 1, removing impurities and dehydrating kitchen waste oil, mixing with an intermediate aqueous solution, and regulating the pH of the mixed solution to 7.5-8.5, wherein the intermediate has a structural general formula of R 1 in the intermediate structure contains partial atoms in N, S, O, C atoms, the total number of non-hydrogen atoms in R 1 is 2-8, R 2 contains N atoms or N, C atoms, and the total number of the atoms is 1-3;
And2, stirring the mixed solution in the step 1 to obtain the composite collector solution with the solute molecules of the Gemini-like structure.
3. The method of claim 2, wherein the molar ratio of the kitchen waste oil to the intermediate aqueous solution is 2:1.
4. The method of claim 2, wherein the Gemini-like structure is formed from 1 intermediate and 2 tail molecules under electrostatic action as a composite collector in an assembled state.
5. The method of claim 1, wherein the weak acid pulp in the second stage flotation in step (3) has a pH of 5.5 to 6.0.
6. The method of claim 5, wherein in the weak acid pulp, the intermediate and tail molecules of the composite collector are in a disaggregated state.
7. The method of claim 4, wherein the 2 tail molecules are the same or different.
8. The method of claim 2, wherein a high ash refractory coal composite collector for high ash refractory coal flotation comprises 1 intermediate and 2 tail chain molecules, and has a chemical structural formula: The general structural formula of the intermediate is R 1 in the intermediate structure contains partial atoms in N, S, O, C atoms, the total number of non-hydrogen atoms in R 1 is 2-8, R 2 contains N atoms or N, C atoms, the total number of atoms is 1-3, and the intermediate and the tail chain molecules are assembled or depolymerized by adjusting pH.
9. The method of claim 8, wherein the tail chain has a general structural formula: The 2 tail chain molecules are the same or different, wherein R 3 is a polar group of the tail chain molecule, and is deprotonated-COOH or-SO 3 H, n is the carbon chain length of the tail chain molecule, and the numerical value is 6-18.
10. The method of claim 8, wherein the Gemini structure-imitated composite collector comprises:
,,。
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