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Synthesis Of Reagent Based ß Cyclodextrin For The Beneficiation Of Low Quality Iron Ore

Abstract: A method of developing a modified ß-cyclodextrin (ß-CD) based flocculant to be used for separation of iron oxide in the blast furnace comprises: formation of ß-cyclodextrin (ß-CD) methacrylate synthesis of methacrylate ß-cyclodextrin grafted Polyacrylamide polyacrylic acid; wherein the preparation of ß-cyclodextrin methacrylate comprises: i) taking ß-cyclodextrin dissolved in MiliQ water in a round bottom flask; ii) triethylamine (TEA) was added dropwise and left for 15 minutes with continuous stirring; iii) addition of methacrylic anhydride with continuous stirring and the reaction continued for 2-3 hours at 35-50deg. C; iv) cooling down the reaction mixture to room temperature to obtain a white precipitate (CD-Meth) with acetone, which is subjected to separation, washing and drying; and the synthesis ß-cyclodextrin methacrylate grafted polyacrylamide polyacrylic acid comprises: i) dissolving of the CD-Meth in miliQ water in a round bottom flask fitted with magnetic stirrer at a temperature of 60-80°C with nitrogen purging; ii) addition of potassium per sulphate (KPS) to the reaction mixture after suitable duration of Nitrogen purging and continued the reaction till completion; iii) subjected to polymerization reaction by addition of the aqueous solution of acrylamide followed by addition of catalytic amount of tetramethyl ethylene diamine (TEMED) and Acrylic acid; iv) termination of polymerization reaction; v) isolation of the final product which is precipitated, dried and subjected to various characterization and beneficiation procedure of iron ores.

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Patent Information

Application #
Filing Date
27 December 2018
Publication Number
27/2020
Publication Type
INA
Invention Field
POLYMER TECHNOLOGY
Status
Email
Parent Application
Patent Number
Legal Status
Grant Date
2022-11-23
Renewal Date

Applicants

TATA STEEL LIMITED
A public limited company within meaning of the Companies act, 2013, having its registered office at Bombay house, 24, Homi Mody street, Mumbai- 400001, India, having its works address as tata steel limited, Bistupur, Jamshedpur- 831 001, India

Inventors

1. ABHAY SHANKAR PATRA
C/o.TATA STEEL LIMITED, having its registered office at Bombay house, 24, Homi Mody street, Mumbai- 400001, India, having its works address as tata steel limited, Bistupur, Jamshedpur- 831 001, India
2. ASIM KUMAR MUKHERJEE
C/o. TATA STEEL LIMITED, having its registered office at Bombay house, 24, Homi Mody street, Mumbai- 400001, India, having its works address as tata steel limited, Bistupur, Jamshedpur- 831 001, India
3. SAGAR PAL
DEPT. OF APPLIED CHEMISTRY, IIT DANBAD, DHANBAD-826004, INDIA
4. PRIYAPRATIM PATRA
DEPT. OF APPLIED CHEMISTRY, IIT DANBAD, DHANBAD-826004, INDIA

Specification

FIELD OF INVENTION [0001]. The present invention relates to a methodology for producing of novel reagent for enhanced iron ore gangue separation, or more particularly developing a flocculation reagent named as modified β-cyclodextrin (β-CD) used for separating iron oxide from a slurry containing alumina and silica. BACKGROUND OF INVENTION: [0002]. Iron ores containing high A12O3/SiO2 gangue are detrimental to blast furnace and sinter plant operations. Therefore, they must be beneficiated before being fed to the blast furnace for optimum production of steel. Kaolinite is a common gangue mineral frequently found in iron ore deposits. Therefore, the gangue minerals have to be separated from the iron oxide by different beneficiation techniques. In the ultra-fine size range one of the most effective beneficiation process is selective flocculation, where the iron oxide particles are settled (flocculated) selectively from a mixture of iron oxide, alumina and silica particles. In selective flocculation process, initially all the minerals are dispersed so that the selective flocculant can attach to the target mineral and flocculate only the wanted mineral particles together leaving beside the gangue mineral particles. The selectivity of the flocculant is determined by the characteristic of the functional group and the nature of the hydrocarbon chain and the matrix. [0003]. PRIOR ARTS: [0004]. The use of starch (potato, corn) and guar gum have been well established for the selective flocculation of iron oxide from the gangue minerals. Several research studies have also predicted the reason for the selectivity of natural polymers with iron oxide. [0005]. Pradip P and his team has carried out a lot of work in this area of selective flocculation of iron ore slime by starch and guar gum. [0006]. One of the article published recently by them is: Guar gum as a selective flocculant for the beneficiation of alumina rich iron ore slimes: Density functional theory and experimental studies. Vinay Jain, Venugopal Tammishetti, Kaustubh Joshi, Dharmendr Kumar, Pradip, Beena Rai, Tata Research Development and Design Centre, Tata Consultancy Services, 54-B, Hadapsar Industrial Estate, Pune, Maharashtra 411 013, India. Minerals Engineering 109 (2017) 144–152. [0007]. CN108394976 discloses a floating type flocculant. The floating type flocculant is characterized by being prepared from the following raw materials in percentage by mass: 17 to 60 percent of slow release aerofloat reagent and 40 to 83 percent of the flocculant, wherein the flocculant is any one or more of flocculants such as an inorganic flocculant, an organic flocculant and an inorganic-organic compound flocculant; the slow release aerofloat reagent is one or more of sodium percarbonate, sodium carbonate and oxygenates such as oxygen capsules or an aerogenesis reagent. The floating type flocculant disclosed by the invention has better floatation effect and flocculation effect; a floc is enable to float up, so that pollutants such as suspended matters and phosphorus in the water are completely removed; in addition, small amount of the slow release aerofloat reagent can achieve better floatation effects and the floc continuously floats for a long time. [0008]. The capacity of a mineral to adsorb selectively a particular reagent molecule depends on a wide range of chemical, thermodynamic and steric factors. Iron ore bearing minerals like hematite can be selectively flocculated by natural polymers like starch, guar gum etc. But the process is generally very slow due to the nature of the natural polymers which is they are not very high in molecular weight and the adsorbing sites are limited. Therefore, it is an important task to design and synthesize reagents which can improve the selectivity as well as improve the settling speed of the particles to make the process more cost effective and feasible. [0009]. The present invention meets the above-mentioned need. OBJECTS OF THE INVENTION [00010]. It is therefore the principal object of the present invention to provide a modified β-Cyclodextrin for selective flocculation of iron oxide from a slurry having alumina and silica. [00011]. Another object of the present invention to provide a modified β-Cyclodextrin, which substantially enhance iron ore- gangue separation from low grade iron ore. [00012]. Yet another object of the present invention to provide a modified β-Cyclodextrin, which can improve the selection as well as enhance the settling speed of the particles. [00013]. Further another object of the present invention to provide a modified β-Cyclodextrin, which is cost effective and feasible. [00014]. These and other objects and advantages of the present invention will be apparent to those skilled in the art after a consideration of the following detailed description taken in conjunction with the accompanying drawings in which a preferred form of the present invention is illustrated. SUMMARY OF INVENTION [00015]. One or more drawbacks of conventional process for producing a modified β-cyclodextrin are overcome, and additional advantages are provided through the method as claimed in the present disclosure, Additional features and advantages are realized through the technicalities of the present disclosure. Other embodiments and aspects of the disclosure are described in detail herein and are considered to be part of the claimed disclosure. [00016]. A method of developing a modified β-cyclodextrin (β-CD) based flocculant to be used for separation of iron oxide in the blast furnace comprises: formation of β-cyclodextrin (β-CD) methacrylate synthesis of methacrylate β-cyclodextrin grafted Polyacrylamide polyacrylic acid; wherein the preparation of β-cyclodextrin methacrylate comprises: i) taking β-cyclodextrin dissolved in MiliQ water in a round bottom flask; ii) triethylamine (TEA) was added dropwise and left for 15 minutes with continuous stirring; iii) addition of methacrylic anhydride with continuous stirring and the reaction continued for 2-3 hours at 35-50deg. C; iv) cooling down the reaction mixture to room temperature to obtain a white precipitate (CD-Meth) with acetone, which is subjected to separation, washing and drying; and the synthesis β-cyclodextrin methacrylate grafted polyacrylamide polyacrylic acid comprises: i) dissolving of the CD-Meth in miliQ water in a round bottom flask fitted with magnetic stirrer at a temperature of 60-80°C with nitrogen purging; ii) addition of potassium per sulphate (KPS) to the reaction mixture after suitable duration of Nitrogen purging and continued the reaction till completion; iii) subjected to polymerization reaction by addition of the aqueous solution of acrylamide followed by addition of catalytic amount of tetramethyl ethylene diamine (TEMED) and Acrylic acid; iv) termination of polymerization reaction; v) isolation of the final product which is precipitated, dried and subjected to various characterization and beneficiation procedure of iron ores. [00017]. Various objects, features, aspects, and advantages of the inventive subject matter will more apparent from the following detailed of preferred embodiments, alongwith the accompanying drawing figures. [00018]. It is to be understood that the aspects and embodiments of the disclosure described above may be used in any combination with each other. Several of the aspects and may be combined to form a further embodiment of the disclosure. [00019]. The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and will become apparent by reference to the drawings and the following detailed description. BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS: [00020]. The illustrated embodiments of the subject matter be best understood by reference to the drawings. The following description is intended only by way of example, and simply illustrates certain selected embodiments of method, systems, that are consistent with the subject matter as claimed herein, wherein: [00021]. Figure 1 the general scheme of synthesis. [00022]. Figure 2 illustrates 13C NMR spectrum of the polymer. [00023]. Figure 3a illustrates FESEM morphology of CD-Meth. [00024]. Figure 3b illustrates FESEM morphology of graft copolymer. [00025]. The figures depict embodiments of the disclosure for purposes of only. One skilled in the art will readily from the following description that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles of the disclosure described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS: [00026].While the embodiments of the disclosure are subject to various modifications and alternative forms, specific embodiment thereof have been shown by way of the figures and will be described below. It should be understood, however, that it is not intended to limit the disclosure to the particular forms disclosed, but on the contrary, the disclosure is to cover all modifications, equivalents, and alternative falling within the scope of the disclosure. [00027]. It is to be noted that a person skilled in the art would be motivated from the present disclosure to arrive at a method of developing modified β-cyclodextrin (β-CD) based flocculant. Such method of producing β-cyclodextrin may vary based on configuration of one or more workpieces. However, such modifications should be construed within the scope of the disclosure. Accordingly, the drawings illustrate only those specific details that are pertinent to understand the embodiments of the present disclosure, so as not to obscure the disclosure with details that will be clear to those of ordinary skill in the art having benefit of the description herein. [00028]. As used in the description herein and throughout the claims that follow, the meaning of “a”, “an”, and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise. [00029]. The terms “comprises”, “comprising”, or any other variations thereof used in the disclosure, are intended to cover a non-exclusive inclusion, such that a system, coal tar pitch, method, carbon foam, assembly that comprises a list of components does not include only those components but may include other components not expressly listed or inherent to such method. In other words, one or more elements in a system or device proceeded by “comprises…..a” does not, without more constraints, preclude the existence of other elements or additional elements in the system, apparatus or device. [00030]. The present subject matter directed towards a method of developing a modified β-cyclodextrin (β-CD) based flocculant, used in selective flocculation of iron oxide from a slurry or mixture having iron oxide with alumina and silica. [00031].Reagents containing nitrogen, oxygen have strong hydrogen bonding capabilities and this phenomenon is utilized to bind with different mineral surfaces in the froth flotation process. In an effective flotation process, mineral-reagent interaction should be as good as the air bubble reagent interaction. Then only the reagent (collector) can carry the gangue mineral to the top of the flotation cell in the form of froth. [00032].The name of the different reagents and their source are given below: [00033]. i) β-CD - Alfa Aesar, England, ii) methacryl anhydride - Alfa Aesar, England, iii) Triethylamine - Avra Synthesis Private Ltd, India, iv) Potassium persulphate - KPS, Glaxo Smith Kline Pharmaceuticals Ltd., Mumbai, India, v) Acrylamide - Merck, India), vi) Acrylic acid - TCI Chemicals, Japan), vii) TEMED - Sigma-Aldrich, USA), viii) Acetone - Merck, India and MiliQ water. [00034]. In this method, β-CD was modified by meth acylation with triethylamine (TEA) and methacrylic anhydride (MAH) and then methacrylate β-CD subjected to polymerization through free radical polymerization using potassium per sulphate as initiator with subsequent purging of nitrogen gas to crate an inert atmosphere. β-CD methacrylate formed a three-dimensional network like structure which comprises more than one polymerizable methacrylate groups. After that, acrylamide and acrylic acid was added to generate a co-polymeric chain of poly acrylamide (PAM) and poly-acrylic acid (PAA). [00035].Figure 1 illustrates the general scheme of the synthesis of modified β-cyclodextrin. [00036].The methodology of producing β-cyclodextrin (β-CD) is given below in detail: [00037]. The procure is broadly divided in two steps i) Preparation of β- cyclodextrin methacrylate and ii) Preparation of β- Cyclodextrin Methacrylate grafted Polyacrylamide Polyacrylic acid [00038]. i) Preparation of β- cyclodextrin methacrylate [00039].β-CD (500 mg/4.4×10-4 mol) was dissolved in MiliQ water (30 mL) at room temperature i.e 25 ° -30°C in a round bottom (RB) flask and triethylamine (TEA) was added (3.52×10-3 mol) dropwise and left the reaction mixture for 15 min. Then the RB flask containing reaction mixture was transferred on another magnetic stirrer which is equipped with oil-bath and coil heater remained in pre-maintained temperature of 40°C. After that, methacrylic anhydride (1.76×10-3 mol) was added very slowly with continuous starring and the reaction was continued for two to three hours at 35 to 50°C. Afterward the reaction mixture was cooled down to room temperature to precipitate very slowly and the obtained white precipitate was separated by centrifugation and washed by acetone for several times i.e., for 3 to 5 times. The product (CD-Meth) was dried in vacuum oven at 50 °C. Finally, the dried product was used for polymerization step. [00040]. ii) Synthesis of β- Cyclodextrin Methacrylate grafted Polyacrylamide Polyacrylic acid: - the obtained product CD-Meth from the previous steps was further modified to synthesize the desired polymer β-Cyclodextrin Methacrylate grafted Polyacrylamide Polyacrylic acid. [00041].CD-Meth (500 mg) was dissolved in 40 mL of MiliQ water in a two-necked round bottom flask fitted on a magnetic stirrer with the temperature of the solution was kept at 60° to 80°C along with subsequently purging of N2 gas to create an inert atmosphere. Aqueous solution of potassium per sulphate (KPS) (5.54×10-5 mol in 5 mL water) was added to the reaction mixture after 15 min N2 purging and the reaction was continued for next 20 min. After that, an aqueous solution of acrylamide (2.81×10-2 mol in 10 mL water) was added to the reaction mixture followed by addition of catalytic amount of Tetramethyl ethylenediamine (TEMED) (6.66×10-4 mol) and subsequently Acrylic acid (1.45×10-2 mol). [00042].The polymerization reaction was continued for next 2 to 3 hour with continuous N2 purging. The polymerization reaction was terminated by exposing the reaction mixture to open atmosphere and then cool down to room temperature. Afterward, the product was isolated by precipitation in excess amount of acetone i..,e 250 to 600 ml and dried in vacuum oven at 40 °C. Finally, the product was used for various characterization and beneficiation of iron ore. [00043].Characterization tests [00044].13C NMR Spectra were recorded in a 400 MHz NMR spectroscopy instrument (JEOL, Japan). The exterior morphology of starch and St-g-(PAAm-co-PMETAC) were assessed using field emission scanning electron microscope (Supra 55, Zeiss, Germany). [00045]. Fig. 2 represents the 13C NMR spectrum of the developed polymer. The chemical shifts arises at 104.5, 81.1 and 61.5 ppm are responsible for anomeric carbon (C1), C5 ring carbon and the carbon of -CH2OH group (C6) of CD Meth. The other ring carbons (C2-C4) of CD Meth exhibits the chemical shift at 73.5 ppm. The carbonyl carbons (C=O) of methacrylate group, PAM and PAA moieties (C7, C8 and C9) exhibits chemical shift at 179.2 ppm. The carbon of methyl group present in the methacrylate group of CD Meth demonstrates the chemical shift at 8.6 ppm. Chemical shifts arise at 41.8 and 31.6 ppm represents methylene carbons (C12, C13, C15 and C11, C14, C16 respectively) generated by the polymerization of vinylic groups of CD Meth, acrylamide and acrylic acid. Moreover, the no chemical shift at region of vinylic carbon (i.e at 120-130 ppm) confirms the successful polymerization of CD Meth, acrylamide and acrylic acid. [00046].β CD demonstrates a smooth surface in FESEM analysis (Fig. 3a and 3b), whereas after methacrylation of β CD the morphology of CD-Meth appears like small three dimensional quadrilateral plates (Fig. 3a). This change in morphology suggests the successful modification of β CD. Again, the final copolymer () exhibits excellent rhombohedral shape (Fig. 3b) quite bigger compere to its starting material CD-Meth. This is may be due to the attachment of copolymeric chain of PAM and PAA on to the three-dimensional CD-Meth structure. [00047].Experiment 1: [00048]. Selective flocculation experiments [00049]. Selective Flocculation Procedure for Iron Ore slimes Conditioning solids: 5% pH: 8.5

Documents

Application Documents

# Name Date
1 201831049337-STATEMENT OF UNDERTAKING (FORM 3) [27-12-2018(online)].pdf 2018-12-27
2 201831049337-FORM 1 [27-12-2018(online)].pdf 2018-12-27
3 201831049337-FIGURE OF ABSTRACT [27-12-2018(online)].pdf 2018-12-27
4 201831049337-DRAWINGS [27-12-2018(online)].pdf 2018-12-27
5 201831049337-DECLARATION OF INVENTORSHIP (FORM 5) [27-12-2018(online)].pdf 2018-12-27
6 201831049337-COMPLETE SPECIFICATION [27-12-2018(online)].pdf 2018-12-27
7 201831049337-FORM 18 [14-01-2019(online)].pdf 2019-01-14
8 201831049337-Proof of Right (MANDATORY) [06-02-2019(online)].pdf 2019-02-06
9 201831049337-OTHERS [20-11-2020(online)].pdf 2020-11-20
10 201831049337-FER_SER_REPLY [20-11-2020(online)].pdf 2020-11-20
11 201831049337-DRAWING [20-11-2020(online)].pdf 2020-11-20
12 201831049337-COMPLETE SPECIFICATION [20-11-2020(online)].pdf 2020-11-20
13 201831049337-FER.pdf 2021-10-18
14 201831049337-US(14)-HearingNotice-(HearingDate-21-10-2022).pdf 2022-09-30
15 201831049337-FORM-26 [06-10-2022(online)].pdf 2022-10-06
16 201831049337-FORM-26 [20-10-2022(online)].pdf 2022-10-20
17 201831049337-Correspondence to notify the Controller [20-10-2022(online)].pdf 2022-10-20
18 201831049337-Written submissions and relevant documents [01-11-2022(online)].pdf 2022-11-01
19 201831049337-PatentCertificate23-11-2022.pdf 2022-11-23
20 201831049337-IntimationOfGrant23-11-2022.pdf 2022-11-23
21 201831049337-PROOF OF ALTERATION [06-03-2023(online)].pdf 2023-03-06
22 201831049337-Response to office action [18-06-2023(online)].pdf 2023-06-18

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