Synthesis Method of White Carbon Black Utilizing Water-Quenching

Oct 3, 2016 - Faculty of Environmental Studies, China University of Geosciences, Beijing 100085, People,s Republic of China. ABSTRACT: Blast furnace ...
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Synthesis Method of White Carbon Black Utilizing Water-Quenching Blast Furnace Slag Hongyu Gao,*,† Zhenzhen Song,‡ Lian Yang,† and Haolan Wu§ †

Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, Hubei 430074, People’s Republic of China Technology Center, ZhongYang Steel Company, Limited, Zhongyang, Shanxi 033400, People’s Republic of China § Faculty of Environmental Studies, China University of Geosciences, Beijing 100085, People’s Republic of China ‡

ABSTRACT: Blast furnace slag (BFS), a waste product of the iron manufacture process, contains a mass of silica obtained from gangue of the iron ores and ash content in fuels and fluxes. In recent years, large amounts of BFS have not been fully utilized, leading to the surrounding environmental pollution and the additional administration costs for steel enterprises in China. A simple method based on acid precipitation heated to 90−100 °C for 2 h was developed to produce white carbon black (WCB) from BFS. BFS and WCB washed by different concentrations of hydrochloric acid were characterized by X-ray fluorescence, scanning electron microscopy, X-ray diffraction (XRD), Brunauer−Emmett−Teller (BET) surface area, Fourier transform infrared spectroscopy (FTIR), and thermogravimetry and differential scanning calorimetry. White carbon black prepared by 5 mol/L acid (WCB5) contained 91.32% silica and 8.15% moisture. The major impurities of WCB produced from BFS were Ca, Mg, Al, and Ti. Acid washing resulted in impurities with a lower concentration. XRD revealed that WCB belonged to the amorphous material. FTIR data indicated the presence of siloxane and silanol groups. The BET surface area was 245 cm2/g. Moreover, the dibutyl phthalate (DBP) absorption value was controlled between 2.0 and 3.5. It showed that physical and chemical characteristics of WCB were up to the China industry standard (HG/T3061-1999). treatment,28−35 and application of BFS in flue gas desulfurization and denitration.36−40 The white carbon black (WCB), presenting the white color, is composed of SiO2·nH2O. WCB has properties similar to carbon black; therefore, WCB is used as a substitute for carbon black in certain applications, such as rubber, coating, plastic, medicine, pesticide, and papermaking. At present, WCB manufacturing ways include the vapor-phase method and precipitation method. In the vapor-phase method, silicon tetrachloride or methyl silicon chloroform is baking at 1000− 1800 °C to prepare WCB. The shortcomings of the vaporphase method are high energy consumption, expensive raw material, high-quality facility, complex technical control, and huge investment scale. In the precipitation method, sodium silicate is the raw material. The drawbacks of the precipitation method are high energy consumption (the production temperature of sodium silicate is 1400 °C), high environmental requirement, lower product activity, and uncontrollable granularity. Therefore, there are both high costs of production. On the basis of the preparation technology and the state of BFS treatment, we have proposed a new method for preparation of WCB using BFS in the study. In this paper, we have researched the synthesis method of WCB using WQBFS. WQBFS was chosen as a raw material as a result of its low price, high silicate content, and reuse of solid waste. Thus, the study of BFS has a magnitude of economic value and social significance.

1. INTRODUCTION Blast furnace slag (BFS) is the byproduct of the iron manufacture process. Briefly speaking, gangue of the iron ores and ash content in fuel, fluxes, and other materials staying outside of cast iron can produce the BFS, the actual production condition of which is approximately 300−700 kg/ton of pig iron. Generally, the initial temperature of BFS is 1450−1550 °C; therefore, molten BFS need to be handled to the normal temperature. According to the different cooling process system, there are water-quenching blast furnace slag (WQBFS) and aircooling blast furnace slag (ACBFS). WQBFS is the amorphous state, and ACBFS is the crystalline state, the chemical components of which are the same. The main components are silica−alumina mineral, including a few other metal oxides (i.e., Ti, Fe, and Mn). Because of the water-quenching technology with simple operations, less occupied area, low cost, and fast process time, there are more than 75% of iron and steel enterprises in China adopting water-quenching technology to deal with BFS.1 A lot of BFS not only needs large tracts of land to store and costs an enormous sum of money to manage but also pollutes the surrounding water and air. In 2014, the global pig iron output is 1.179 billion tons, with 0.712 billion ton produced by China. As a rule of thumb, the output of BFS is about 0.285 billion ton in China. Comprehensive utilization of BFS is a novel method to increase the economic benefits of steel enterprises. How to effectively achieve comprehensive utilization of BFS has been extensively concerned on a global scale.2−5 In 2014, the comprehensive utilization rate of BFS has been up to 100% in some developed countries, but it is only 82% in China.6 At present, the main utilization industry of BFS is landscaping and ordinary Portland cement,7−17 also including valuable metal recycles,18−27 harmful elements of wastewater © 2016 American Chemical Society

Received: August 25, 2016 Revised: October 2, 2016 Published: October 3, 2016 9645

DOI: 10.1021/acs.energyfuels.6b02154 Energy Fuels 2016, 30, 9645−9651

Article

Energy & Fuels Table 1. Chemical Composition of WQBFS (wt %) compound

SiO2

Al2O3

Fe2O3

MgO

CaO

Na2O

K2O

MnO

TiO2

P2O5

H2O

WQBFS

32.01

14.94

0.31

9.55

36.11

0.23

0.22

0.46

1.15

0.01

5.02

the typical nitrogen adsorption, and the N2 flow rate was 30 mL/min. The heating rate was 10 °C/min. According to the simultaneous thermal analyzer, the curve of TG spectra sharply reduced within the scope of 29−130 °C. 2.3.7. Oil Adsorption Value Measurement. The void volume was calculated with the dibutyl phthalate (DBP) volume absorbed by a certain amount of WCB (mL of DBP/1 g of WCB). The concrete measurement steps were as follows: First, 1 g of WCB samples (WCB1, WCB3, and WCB5) were weighed and put onto three glass panes. DBP was added to the WCB samples at a fixed speed. When the added volume was a third of the volume of the absorption value, the mixture was gently stirred by a glass rod to let DBP evenly infiltrate into the WCB sample. Second, the mixture was stirred until the granular sample was all broken. After that, DBP was continually added to the WCB samples at a slower speed with sitrring. When the sample was infiltrated completely by DBP, the mixture became strip or massive and had no dry powder. Finally, the mixture completely rolled onto the glass rod, or there was no oil stains on the glass pane.

2. MATERIALS AND METHODS 2.1. Materials. All chemicals used were analytical-grade and purchased from Sinopharm Chemical Reagent Co., Ltd. WQBFS was supplied by the ZhongYang Steel Co., Ltd., and its chemical composition was listed in Table 1. Deionized water (DIW) was used in the whole experiments. 2.2. Synthetic Method. WQBFS was ground by the ball mill until the particle size was less than 38 μm, which is defined as the superfine BFS acquisition. A total of 10.0 g of superfine BFS was mixed with 200 mL of 3 mol/L hydrochloric acid in a conical flask, and the mixture was kept for 2 h at 90−100 °C in the water bath after oscillating for 20−30 min in the oscillator. The mixture was filtered and washed several times using DIW. Finally, the solid was dried by vacuum freezing. The experimental process was shown in Figure 1.

3. RESULT AND DISCUSSION The physical structure and chemical characteristics of raw BFS and acid-treated BFS were all determined by SEM, XRD, BET surface area, FTIR, XRF, and TG−DSC. The silica in the BFS was not dissolved by hydrochloric acid. The WCB was obtained by the following reaction equation: M 2(SiO3)x + 2HCl + (n − 1)H 2O → 2M x + + 2Cl− + xSiO2 ·nH 2O

(1)

where M represents metal ions, including Ca, Mg, Al, K, Na, etc., x is the valence value, and n is the water content. 3.1. XRF of BFS and WCB. Each sample was well-analyzed 3 times. The results showed that the main chemical compositions of BFS were SiO2, CaO, MgO, and Al2O3. It also contained trace metal oxides, such as Fe2O3, Na2O, K2O, MnO, TiO2, and P2O5. After BFS was treated with acid, WCB5 was composed of 91.32% SiO2 and 8.155% H2O, indicating that the high concentration of hydrochloric acid is helpful to improve the purity of WCB (Table 2). 3.2. SEM of WCB. The morphology of WCB was investigated by SEM. As shown in Figure 2, the results indicated that superfine BFS exhibited an irregular-shape-like glassy structure, while the as-prepared WCB was a porous material with the loose structure. The water-quenched

Figure 1. Experimental process of WCB. 2.3. Analytical Method. 2.3.1. X-ray Fluorescence (XRF). The chemical compositions of the BFS and WCB were analyzed by XRF (Shimadzu EDX-800), utilizing a generator voltage of 50 kV and tube current of 40 mA. The diameter of the irradiation hole is 20 mm. 2.3.2. Scanning Electron Microscopy (SEM). The morphology of superfine BFS and WCB was observed with SEM (S-3000N, Hitachi, Japan). The resolution was 3.0 nm under the high-vacuum state, and the amplification factor was less than 300 000. The accelerating voltage was 3.0 kV. 2.3.3. X-ray Diffraction (XRD). XRD patterns of BFS and WCB were generated by an X-ray diffractometer (Holland, PANalytical) with Cu Kα radiation, utilizing a generator voltage of 40 kV and tube current of 40 mA. Divergence slit was fixed at 0.38 mm, and a diffraction angle of 5−90° was scanned at a rate of 5.48°/min. 2.3.4. Fourier Transform Infrared Spectroscopy (FTIR). FTIR spectra were recorded on a FTIR spectrometer (Nicolet Nexus 370) with a smart endurance single-bounce diamond attenuated total reflection (ATR) cell. Spectra were obtained from 4000 to 400 cm−1 by the co-addition of 64 scans with a resolution of 4 cm−1. A mirror velocity of 0.6 cm/s was used. 2.3.5. Brunauer−Emmett−Teller (BET) Surface Area. The BET surface area was determined as 57.84 ± 0.20 m2/g with ASAP 2000 (Micromeritics, Norcross, GA, U.S.A.). 2.3.6. Thermogravimetry and Differential Scanning Calorimetry (TG−DSC). TG−DSC was determined with STA409PG/PC (NETZSCH, Germany). The type of crucible was Al2O3 pan. It was

Table 2. Chemical Compositions of the BFS and WCB

9646

component

BFS (wt %)

WCB1 (wt %)

WCB3 (wt %)

WCB5 (wt %)

SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O MnO TiO2 P2O5 H2O

32.01 14.94 0.31 9.55 36.11 0.23 0.22 0.46 1.15 0.01 5.02

84.43 0.69 0.02 0.33 1.72 0.04 0.04 0.05 0.46 0.01 12.22

86.79 0.19 0.016 0.13 0.93 0.01 0.01 0.02 0.10 0.008 11.806

91.32 0.09 0.01 0.03 0.32 0.003 0.002 0.01 0.06 0.005 8.155

DOI: 10.1021/acs.energyfuels.6b02154 Energy Fuels 2016, 30, 9645−9651

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that a high concentration of hydrochloric acid was very conductive to decreasing the particle size of WCB. 3.4. FTIR of WCB. Figure 4 showed the infrared (IR) spectra of BSF and WCB. The results displayed that WCB had

Figure 2. (a) SEM of BFS and (b and c) SEM of WCB.

granulating process was the main reason why the glassy structure of superfine BFS was formed. As seen from panels b and c of Figure 2, the white parts were bumps on the surface of WCB and the black parts were pores in the WCB. 3.3. XRD of WCB. Judged by XRD, the shape peak position was crystal and the gentle peak position was the amorphous state. The WCB was washed with different concentrations of hydrochloric acid (1, 3, and 5 mol/L). In Figure 3, there was no

Figure 4. FTIR of raw BFS and different concentrations of hydrochloric acid washing of WCB.

a stronger absorption band at 1067.5 cm−1 compared to BFS, which resulted from the antisymmetric stretching vibration of Si−O−Si. According to the strength of the absorption spectrum, WCB5 was the largest and BFS was the worst. It showed that the acid strength stimulated the formation of Si− O−Si. In the reaction, some metal cations were dissolved in the acid solution from BFS, and these metal cations had a positive effect on the formation of Si−O−Si.41 Owing to the Si−O symmetric stretching vibration, some weak character peaks appeared at 430 and 796.25 cm−1. The weak character peak at 952 cm−1 corresponds to the Si−OH flexural vibration. At around 1640 and 3660 cm−1, there were weak absorption peaks, which were attributed the flexural vibration of water molecules, owing to hydroxyl antisymmetric stretching vibration and symmetric stretching vibration under the influence of water molecules, respectively. 3.5. BET Surface Area and Size Distribution of WCB. According to multilayer adsorption theory, the BET adsorption isotherm equation is shown as follows:

Figure 3. XRD of raw BFS and different concentrations of hydrochloric acid washing of WCB.

characteristic peak of the SiO2 crystal, but a wide peak appeared at 23.5°. It showed that different concentrations of hydrochloric acid washing had no obvious influence and hydrochloric acid (1 mol/L) was enough to deal with WCB. XRD of raw BFS and WCB indicated the relatively high disordered structure of silica. Therefore, the product was the amorphous structure of silica. However, the full width at half maximum increased with the increase of the concentration of hydrochloric acid, βWCB1 < βWCB3 < βWCB5. According to the Debye−Scherrer equation, D = 0.89λ/(β cos θ), the crystal particle size changed smaller when the full width at half maximum increased.46 The results showed

p /p0 V (1 − p /p0 )

=

C−1 p 1 + VmC p0 VmC

(2)

where V is the gas adsorption capacity, V m is the monomolecular layer saturation adsorption capacity (mL), p is the adsorbate pressure, p0 is the adsorbate saturated vapor pressure, and C is a constant. Then, setting Y = p/p0/V(1 − p/p0), X = p/p0, A = (C − 1)/ VmC, and B = 1/VmC, the BET fitting curve was shown in Figure 5. The equation was Y = 0.01785X − 0.000096, and R2 was 0.997. According to the Langmuir adsorption isothermal 9647

DOI: 10.1021/acs.energyfuels.6b02154 Energy Fuels 2016, 30, 9645−9651

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Figure 6. BET isotherm of WCB. Figure 5. BET surface area of WCB.

saturated extent of monolayer adsorption. After the B point, multilayer adsorption appeared. The curve increased quickly in the high p/p0 area because capillary condensation appeared. The desorption isotherm and the adsorption isotherm appeared to misalign, and the hysteresis loop was shown. The initial point of the hysteresis loop meant that condensation of the smallest capillary pore started when p/p0 was 0.35. The end point of the hysteresis loop meant that the biggest capillary pore was filled with condensate when p/p0 was 0.99. The reason was that the pore of WCB was filled with congealed N2 molecules under the below atmospheric pressure, capillary condensation effect results. When capillary condensation happened, cyclic annular appeared over the liquid level of the adsorption membrane. However, desorption happened from the spherical liquid level of the hole. Thus, the adsorption− desorption isotherm could not overlap, and the hysteresis loop appeared. In Figure 7, there was a ghost peak at 3.8 nm, which was caused by the tensile strength effect. WCB took generally the morphous hydrated silica. In comparison to Barrett−Joyner− Halenda (BJH) adsorption with BJH desorption, a shape peak appeared at 3.87 nm of the pore volume in the BJH desorption

equation, the specific surface area equation was shown as follows: 4.36Vm (3) W 2 where Sg is the specific surface area (cm /g) and W is the quality of adsorbate (g). From the adsorption characterization (Table 3), it obviously indicated that the adsorptive capacity of WCB was larger than Sg =

Table 3. BET Surface Area of BFS and WCB BFS WCB

BET surface area (m2/g)

Vpa (cm3/g)

Db (nm)

0.40 245

0.005 0.180

4.7 3.5

a

Vp is the pore volume of BFS and WCB. bD is the pore diameter of BFS and WCB.

that BFS. The WCB structure was successfully fabricated using an acidizing method and exhibited favorable textural parameters for adsorption in terms of the specific surface area (245 m2/g), pore size (3.5 nm), and pore volume (0.18 cm3/g). The BFS sample exhibited less favorable textural parameters in terms of the specific surface area (0.4 m2/g), pore size (4.7 nm), and pore volume (0.005 cm3/g). According to the BET classification method, the BET isotherm contains five types of the isotherm. The N 2 adsorption−desorption isotherms of WCB showed type IV isotherms with a H2 hysteresis loop, as judged from Figure 6. The type IV isotherm was a typical isotherm for mesopore materials, and the pore size was 2−50 nm. It had the characteristics of the drastic increase of adsorption capacity caused by capillary condensation after multilayer adsorption happened. It is also noted that the width of the hysteresis loop increased with an increasing pore volume. The mesopores had a regular framework with interparticle voids. In addition, the mesoporous material was prepared at acidic pH and a wellorganized mesostructure even in the bulk state. The N2 isotherm also showed that the porosity comprised uniform channels, such as the templated framework in silica monoliths.42−45 In Figure 6, the curve rose up in the low p/p0 area and an inflection point appeared when p/p0 was 0.08. It meant that monolayer absorption formed, and the B point was the

Figure 7. Pore diameter distribution diagram of BJH adsorption and desorption. 9648

DOI: 10.1021/acs.energyfuels.6b02154 Energy Fuels 2016, 30, 9645−9651

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Figure 8. TG, DSC, and DTG spectra of the WCB.

spectra. Since 91.1 °C, the TG curve was smooth, which showed weightlessness reduced slowly. Because adjacent Si− OH gradually appeared with the water condensation reaction and released heat, there was a large heat release area within the scope of 500−600 °C on the DSC spectra. Beginning from 600 °C, intermolecular Si−O−Si of the silica was broken and started to absorb heat. There was a small exothermic peak at 871.1 °C, and fracture of Si−O had been accomplished. Thus, crystal−amorphous silica began to absorb a lot of calories; there was an endothermic peak at 891.5 °C, as just the crystallization process without dehydration. Therefore, the curve of TG spectra was flat. 3.7. Determination of the DBP Absorption Value. As shown at Table 4, the DBP absorption value for WCB1 was the

curve. It had nothing to do with the adsorbent; on the contrary, it had a lot to do with the adsorbate. 3.6. TG−DSC of WCB. The type of WCB moisture content was divided into two kinds, including surface moisture and bound water. Surface moisture was also called moisture absorption. It came to dynamic balance after WCB absorbed water from the air in room temperature. With environmental change, with moist or drying regime, the moisture absorption obtained some characteristics: (a) it existed in the form of the molecule; (b) hydrogen bond and intermolecular forces were weak; (c) it changed with the environment changing; (d) it went against WCB with better reinforcing property; and (e) it could be changed by manmade control. The bound water was stabled and hard to remove. Generally speaking from essence and structure, it was the −OH group rather than water. There were some characteristics: (a) −OH interactions with Si, O, and H existing as a covalent bond in Si−OH groups and covalent bond energy were so great that the covalent bond was hard to destroy; (b) it had nothing to do with environmental change; and (c) it was conducive to WCB with a better reinforcing property. In Figure 8, there were masses of the Si−OH groups on the surface of WCB. Most of Si−OH groups were uncombined hydroxyl and had fairly high catalytic activity. Because of the uncombined hydroxyl, WCB was easily combined with the water molecule and adsorbed plenty of water. It was physical absorption and not stable. It also showed that the chemical property of WCB was associated with uncombined hydroxyl. Therefore, water adsorbed on the surface was lost after heating. De Boer et al. found that silica dried in air at 120 °C lost all physically adsorbed water.46 According to the study by Okkerse and Linsen, the removal of all physically adsorbed water at 120 °C was possible only if the silica sample was free of micropores.47 The curve of differential thermal spectra was a slippery slope and appeared as an endothermic peak at 91.1 °C. It could be seen that the water stripping rate was also the largest at 91.1 °C in the differential thermogravimetry (DTG)

Table 4. DBP Absorption Value of Different Concentrations of Hydrochloric Acid Washed WCB and HG/T3061-1999 (Chinese Index) WCB1 WCB3 WCB5 HG/T3061-1999 DBP absorption value (mL/g)

2.32

2.53

2.76

2.00−3.50

least, while that for WCB5 was the largest (WCB1 < WCB3 < WCB5). It showed that the concentration of hydrochloric acid had a great influence on the DBP adsorption value for WCB. The absorption value satisfied the standard range of HG/ T3061-1999 (Chinese index). It was because a high acid concentration contributed to increasing the surface area of WCB.

4. CONCLUSION According to the characterization, the results showed that SiO2 was amorphous in the WCB. The main chemical compositions of raw BFS were SiO2, CaO, MgO, and Al2O3. After BFS was treated with hydrochloric acid, the SiO2 quality fraction in the product was increased from 84.43 to 91.32%. Physical and chemical characteristics of WCB were up to the China industry 9649

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standard (HG/T3061-1999). In addition, treatment technology took low cost and low energy consumption and was operated easily. This investigation not only helps the comprehensive utilization of BFS but also effectively reduces the pollution of slag. Therefore, the method could be effectively applied in the practical production.



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS The authors gratefully acknowledge the support of the China University of Geosciences (Wuhan).



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DOI: 10.1021/acs.energyfuels.6b02154 Energy Fuels 2016, 30, 9645−9651