Further Insight into the Formation and Oxidation of CaCr2

Further Insight into the Formation and Oxidation of CaCr2...
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Further insight into the formation and oxidation of CaCr2O4 during solid fuel combustion Hongyun Hu, Mengya Shi, Yuhan Yang, Huan Liu, Mian Xu, Junhao Shen, and Hong Yao Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b05538 • Publication Date (Web): 01 Feb 2018 Downloaded from http://pubs.acs.org on February 7, 2018

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Further insight into the formation and oxidation of CaCr2O4 during solid fuel

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combustion

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Hongyun Hua, Mengya Shia, Yuhan Yanga, Huan Liua,b, Mian Xua, Junhao Shena,

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Hong Yao a,b,*

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a

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Huazhong University of Science and Technology, Wuhan 430074, China

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b

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Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

State Key Laboratory of Coal Combustion, School of Energy and Power Engineering,

Department of New Energy Science and Engineering, School of Energy and Power

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*

Corresponding author. Tel & Fax: +86-27-87545526(O) E-mail: [email protected] (Prof. Hong Yao) 1

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Abstract

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The control of toxic chromate (Cr6+) formation is still a significant challenge in

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solid fuel combustion. In particular, the mechanism of chromium transformation from

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Cr3+ to chromate or other unoxidized forms remains unclear. The present study

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confirms the formation of a significant unoxidized Cr-containing compound

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CaCr2O4(Cr3+) during solid fuel combustion. Experiments were conducted, for the

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first time, to clarify the mechanism of CaCr2O4 oxidation, which is quite different

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from Cr2O3 oxidation. The findings demonstrate that CaCr2O4 was formed at

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temperatures above 1200 K, through rapid decomposition of CaCrO4 or slow and

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direct interaction between CaO and Cr2O3. Compared to Cr2O3, CaCr2O4 could be

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oxidized at lower temperatures under the influence of free CaO. In the absence of free

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CaO, the oxidation of CaCr2O4 was minimal; however, in the presence of CaSO4,

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calcium in the form of CaCr2O4 participated in the oxidation of CaCr2O4. Thus,

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chromium in the form of CaCr2O4 was more likely to be oxidized when

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CaCr2O4-containing fly ash was reheated. Fortunately, CaCr2O4 showed slight

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basicity on the surface, allowing it to react with acidic gases. Accordingly, measures

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were proposed to suppress the oxidation of CaCr2O4 by stimulating the reactions

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between CaCr2O4 and acidic substances, like SO2 and Si/Al-compounds. These

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compounds competed with chromium at high temperatures to react with calcium in

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the fly ash and in CaCr2O4. As a result, the unoxidized chromium was transformed

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into highly stable Cr2O3 or Ca3Cr2 (SiO4)3.

2

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TOC/Abstract Art

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Hated Ash

Cr2O3/Ca3Cr2 (SiO4)3

Cr5+/Cr6+

Reheating

+ Si/Al-compounds CaSO4

+ CaO

Oxidation Suppression (I)

Oxidation (II) Oxidation (I)

SO2

CaSO4 CaCr2O4

Ash Residues

Combustion

+ CaO

Decomposition CaCrO4

Cr2O3

+ CaO + CaO

Solid Fuel

CaSO4 Oxidation Suppression (II)

Organic-Cr / Cr2O3

32

3

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Introduction

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Chromium is widely distributed in coal, municipal solid waste, sewage sludge

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and other solid fuels 1, 2. In China, a large amount of chromium is released within flue

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gas into atmosphere during solid fuel combustion 3, which is a great threat to human

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health. Even so, most of the chromium is transferred into ash residues, predominantly

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as trivalent chromium (Cr3+) 2. More importantly, trivalent chromium can partly

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oxidize to form more toxic hexavalent chromium (Cr6+), which is classified as a group

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A inhalation carcinogen 4. Compared with Cr3+, Cr6+ is more easily leached from ash

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residues, leading to serious water and/or soil pollution 5. Therefore, a series of

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stringent policies were implemented by the Chinese government for emission control

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of Cr6+ 6.

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Generally, the predominant form of chromium in solid fuels is Cr3+, and it is

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difficult to oxidize during fuel combustion 7, 8. However, a large fraction of Cr6+ was

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found in the fly ash during the combustion of solid fuels that contained high contents

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of alkali and/or alkaline earth metal compounds 1, 9. Among these substances, CaO is

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confirmed to facilitate Cr3+ oxidation over a wide temperature range 10, 11. Conversely,

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CaO is widely used as a sorbent for the capture of acid gases, such as SO2, and toxic

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trace elements, such as As2O3, from flue gas

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conditioner for dewatering of sewage sludge

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ubiquitous use, CaO is frequently introduced into solid fuels, and it is essential to

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understand the oxidation of Cr3+ in the presence of CaO.

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12, 13

. CaO is also commonly used as a

14

. Because of its prevalence and

To date, several studies have been conducted to understand the mechanisms 4

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involved in Cr3+ oxidation in the presence of CaO. The oxidation of Cr3+ was found to

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be a slow process, and most chromium still existed as Cr3+ in the ash produced in the

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combustion of coal and waste sludge 8, 11. Nevertheless, the unoxidized Cr3+ may

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transfer into various species

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distinguished these unoxidized species or examined their potential oxidizing capacity.

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When ash residues containing unoxidized Cr3+ are reheated at high temperature, the

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oxidation of unoxidized Cr3+ compounds likely determines the Cr6+ concentration in

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the products, such as in the case of fuel combustion in a circulating fluidized bed or in

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the case of ash thermal treatment for the production of building materials.

5, 15

, and to our knowledge, few studies have

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Our previous study found that CaCr2O4 was an important intermediate in

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chromium oxidation in the presence of CaO 16. Unlike Cr2O3, CaCr2O4 is composed

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of both chromium and calcium. The details regarding the oxidation performance of

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chromium in CaCr2O4 are still unclear and are surely different from that of Cr2O3,

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according to our former experiments. On the other hand, it is possible that the calcium

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in CaCr2O4 participated in chromium oxidation, and its behavior might differ from

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that of free CaO. In addition, free CaO could react with acid gases and/or acidic

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inorganic components, such as Si/Al-compounds, in the ash

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compete with chromium oxides to react with free CaO. As a result, the amount of free

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CaO available for chromium oxidation decreases. Based on these theories, Mao et al.

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limited the potential of CaO to promote Cr2O3 oxidation by converting free CaO into

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phosphate minerals 18. Similarly, Low et al. suppressed the oxidation of Cr2O3 through

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scavenging of free lime by reaction with kaolinite

19

17

. These substances

. Therefore, the fate of calcium

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likely determined the oxidation of CaCr2O4, and measures could be taken to inhibit

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CaCr2O4 oxidation based on our understanding of calcium behavior in the process.

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The aim of this work is to investigate the formation of CaCr2O4 in the Ca-Cr-O

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system and to evaluate the oxidation of CaCr2O4 in simulated flue gas. In this study,

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CaCr2O4 was synthesized and well characterized. Then, the oxidation mechanism of

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CaCr2O4 was determined, considering the effects of free CaO and CaSO4. The fate of

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calcium in CaCr2O4 was also explored, especially in reactions with SO2 and

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Si/Al-compounds. Based on our findings, several measures were proposed to suppress

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the oxidation of CaCr2O4 during reheating of CaCr2O4-containing fly ash.

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Experimental Procedures

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Materials. Analytical grade reactants, including CaO, Cr2O3, and CaSO4, were

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used as raw materials for the investigation of chromium oxidation and for the

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preparation of test samples: CaCrO4 (Cr6+), Ca3(CrO4)2 (Cr5+) and CaCr2O4 (Cr3+)).

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To determine the fate of CaCr2O4 during the thermal treatment of fly ash, ash residues

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were collected from a municipal solid waste incineration plant. Water-washed ash and

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acid-washed ash samples were obtained after washing the raw fly ash with deionized

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water and dilute acid solution, respectively. The properties of the ash samples are

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given in Table S1 and Figure S1 (shown in the Supporting Information). To prepare

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the mixed samples, all reactants were thoroughly mixed and finely ground prior to the

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reaction.

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Oxidation of Chromium Oxides. The oxidation of chromium oxides was

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conducted in a horizontal tube furnace, and a thermogravimetric analyzer and in situ 6

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high temperature X-ray powder diffraction (XRD) instrument were used to

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characterize the oxides. The testing temperature, heating rate and atmosphere were

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well controlled, and the detailed conditions for chromium oxidation in each sample

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are summarized in Table S2.

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After the reactions, some Cr-products, like CaCrO4, were directly obtained after

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cooling. However, for CaCr2O4, some by-products were removed to obtain high purity

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CaCr2O4. As stated in the following discussion section, CaCr2O4 was formed either

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through the decomposition of oxidized CaCrO4 (labeled as CaCr2O4-I) or through the

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interaction between CaO and Cr2O3 (labeled as CaCr2O4-II). Based on the leaching

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abilities of various Cr-products

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CaCrO4 by dissolving the formed Ca3(CrO4)2 with deionized water. Similarly,

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CaCr2O4, formed through the interaction between CaO and Cr2O3, was purified by

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removing excessive CaO from the products with diluted HCl solution.

20

, CaCr2O4 was separated from the decomposed

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Characterization of Cr-products. To determine the crystalline structures of the

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Cr-products, both traditional and in situ high temperature XRD were employed. The

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microstructure and surface basicity of the samples were determined by scanning

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electron microscope (SEM) and CO2 temperature-programmed desorption (CO2-TPD)

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techniques, respectively. To get more details of the Cr-samples, transmission electron

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microscope (TEM) observations were conducted. Before analysis, the samples were

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thoroughly dispersed over a standard glass slide and pressed by a copper grid coated

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with amorphous carbon film.

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After CaCr2O4 reacted with CaSO4, the formed chromate was leached out of the 7

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products with deionized water, due to the high leaching ability of chromate. The

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oxidation of CaCr2O4 was evaluated by measuring the concentration of chromium

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using microwave plasma-atomic emission spectroscopy (MP-AES). However, after

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the reaction of Cr2O3 with CaO in N2, the distribution of the formed CaCr2O4 and

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unreacted Cr2O3 in the product could not be distinguished because of their similar

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leaching abilities. The transformation of Cr2O3 into CaCr2O4 was evaluated according

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to the contents of Ca and Cr in the products, as detected by X-ray fluorescence (XRF).

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Specifically, the fraction of chromium in the form of CaCr2O4 was calculated based

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on the content of Ca in the sample, and the remaining chromium was in the form of

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Cr2O3.

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Results and Discussion

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Formation of CaCr2O4. Thermogravimetric experiments on the decomposition

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of CaCrO4 were conducted in carrier gas containing various concentrations of oxygen,

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and the TG/DTG curves are shown in Figure 1. The concentration of oxygen played

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an important role in the decomposition of CaCrO4. The initial temperature of CaCrO4

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decomposition decreased with decreasing O2 concentration. In an oxygen-depleted

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atmosphere (pure N2), the initial decomposition temperature was as low as 1186 K.

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Figure S2 presents the in situ XRD patterns of the products formed during the

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decomposition of CaCrO4 in air. It was clear that CaCrO4 decomposed to form

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Ca3(CrO4)2(Cr5+) and CaCr2O4 (CaCr2O4-I, Eq. (1)). According to Eq. (1), 50% of

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chromium was transformed into CaCr2O4 in the decomposition of CaCrO4.

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4CaCrO4 → Ca3(CrO4)2 + CaCr2O4 + 2O2 8

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Alternatively, the formation of CaCr2O4 might occur through the direct

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interaction between CaO and Cr2O3. From TG-DSC curves (not shown here), a weak

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endothermic peak was observed between 1250 K and 1350 K, which was assigned to

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the formation of CaCr2O4 (CaCr2O4-II, Eq. (2)). To obtain more detailed information,

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the crystalline structures of the CaO/Cr2O3 mixtures were recorded via in situ high

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temperature XRD during the heating process under vacuum. The heating program is

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given in Figure S3. Figure 2 shows the patterns of the products formed at each

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temperature. The results suggest that the formation of CaCr2O4 through direct

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interaction between CaO and Cr2O3 was more difficult than via decomposition of

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CaCrO4. The direct formation of CaCr2O4 began at higher temperature (around 1300

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K), and the process was quite slow, as evident by the lack of peaks for CaCr2O4 even

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after heating at 1323 K for 10 min.

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CaO + Cr2O3 → CaCr2O4

(2)

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To limit the effect of physical contact between the reactants on CaCr2O4

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formation, the interactions between CaO and Cr2O3 were conducted with excess CaO.

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Figure 3 shows the fractions of formed CaCr2O4 as a ratio of total chromium after

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thermal treatment at temperatures ranging from 1223 K to 1423 K. A similar

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phenomenon for the slow formation of CaCr2O4 was observed. Additionally, the

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formation of CaCr2O4 generally took place at higher temperature. At each temperature,

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limited amounts of CaCr2O4 formed in a short reaction time, and the formation of

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CaCr2O4 was remarkably stimulated by increasing the reaction time from 1 to 5 min.

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Further increasing the reaction time from 5 to 10 min resulted in a continuous increase 9

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in the CaCr2O4 fraction in the products obtained at 1223 and 1323 K. However, few

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changes were found for CaCr2O4 formation at 1423 K. After heating at 1423 K for 10

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min, about 10% of chromium still remained unreacted, which was mainly caused by

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insufficient contact between CaO and Cr2O3 or other unknown factors.

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According to the results, the formation of CaCr2O4 occurred in the combustion of

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solid fuel either through the rapid decomposition of CaCrO4 or through the slow and

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direct interaction between CaO and Cr2O3. Several studies also stated the formation of

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CaCr2O4 in solid fuel combustion fly ash

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regarding CaCr2O4 formation, CaCr2O4 was separated from each product by

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dissolving chromate and excess CaO. After purification, CaCr2O4 was characterized.

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Although the samples showed similar XRD patterns, the microstructures differed in

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various CaCr2O4 products (shown in Figure S4). More specifically, CaCr2O4-I was

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needle/rod-shaped, while CaCr2O4-II was granular. As shown in Figure 4, Cr2O3,

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CaCr2O4-I and CaCr2O4-II had interplanar distances of 2.52, 2.96 and 2.45 Å,

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corresponding to the crystal planes (110), (130) and (021), respectively. Different

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microstructure characteristics of CaCr2O4 might lead to various oxidation

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performances.

15, 21

. To get more detailed information

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Oxidation of CaCr2O4. Figure S5 depicts the TG/DTG curves for the oxidation

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of three Ca-Cr mixtures: CaO with Cr2O3, CaCr2O4-I or CaCr2O4-II. The initial

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oxidation temperatures progressed in the following order, Cr2O3 (973 K) > CaCr2O4-I

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(823 K) > CaCr2O4-II (773 K), indicating that the oxidation of CaCr2O4 could take

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place at lower temperatures than the oxidation of Cr2O3. However, the oxidation of 10

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CaCr2O4 was slower, and this was likely due to the various forms of calcium in the

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reactants. It is assumed that calcium in free CaO and CaCr2O4 play different roles in

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the oxidation of chromium. However, the oxidation of CaCr2O4-I and CaCr2O4-II had

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slight difference in the oxidation capacities. In addition, a sharp mass-loss peak

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(centered at approximately 1323 K) was recorded in each curve, which was attributed

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to the decomposition of oxidized chromate.

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To further clarify the mechanism involved in the oxidation of CaCr2O4, the XRD

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patterns of the oxidized products, in terms of heating temperature and Ca/Cr molar

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ratio, were obtained, and the results are displayed in Figure S6. At a molar ratio of 1:1

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Ca (including calcium from CaCr2O4 and added free CaO) to Cr, most chromium

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remained unoxidized, especially at 1373 K. The results suggest that calcium in the

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form of CaCr2O4 could not play the same role as free CaO in the promotion of

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chromium oxidation. Additionally, the oxidation of CaCr2O4 was mainly determined

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by free CaO, which was further confirmed by evaluating the oxidation of CaCr2O4

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mixed with varied free CaO content at 1373 K. From the TG results, shown in Figure

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5, few changes were found regarding the mass of the sample in the absence of free

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CaO, demonstrating that calcium in CaCr2O4 did not promote the oxidation of

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chromium under these experimental conditions. The oxidation of CaCr2O4 was

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observed upon the addition of free CaO in the sample, which was significantly

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enhanced by increasing the free CaO content. Apart from the contents of free CaO, the

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oxidation of CaCr2O4 was strongly affected by temperature. The forms of oxidized

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chromium differed at various temperatures. As demonstrated by Figure S6, CaCr2O4 11

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was oxidized to CaCrO4 (Cr6+) at 1173 K (Eq. (3)) while at 1373 K CaCr2O4 formed

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thermally stable Ca3(CrO4)2 (Cr5+) (Eq. (4)). Compared to the formation of CaCrO4,

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higher free CaO content was needed for the formation of Ca3(CrO4)2.

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CaCr2O4 + CaO + 1.5O2 → 2CaCrO4

(3)

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CaCr2O4 + 2CaO + O2 → Ca3(CrO4)2

(4)

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In the fuel combustion process, free CaO probably reacted with acid gases and

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was rapidly transformed into corresponding Ca-salts 22. CaSO4 was widely distributed

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in solid fuels and was also the dominant Ca-compound in the fuel combustion.

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Therefore, chromium oxides were more likely to interact with CaSO4 rather than free

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CaO, and the oxidation of CaCr2O4 under the influence of CaSO4 should be further

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investigated. Figure 6 compares the TG/DTG curves for the oxidation of Cr2O3 or

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CaCr2O4 affected by CaSO4. For the mixture of CaCr2O4 and CaSO4, one mass-gain

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peak was observed between 1000 K and 1200 K, which was probably related to the

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oxidation of chromium. In addition, the mass-loss peak around 1350 K was attributed

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to the decomposition of oxidized products. In contrast, the oxidation of Cr2O3 was

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minimal, and the mass of the Cr2O3-containing sample slowly decreased with

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increasing heating temperature. A significant mass-loss peak was observed at 1323 K,

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and this was likely caused by the release of chromium in the form of Cr2(SO4)3 23, due

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to the interactions between Cr2O3 and CaSO4 at this high temperature.

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To further confirm the oxidation of CaCr2O4 in the presence of CaSO4, CaCr2O4

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was heated under air in a horizontal tube furnace after mixing with various contents of

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CaSO4 to obtain certain Ca/Cr ratios. The oxidation of CaCr2O4 was evaluated by 12

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measuring highly soluble chromate and the percentage of oxidized chromium at

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different temperatures, and these results are presented in Figure 7. Without the

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addition of CaSO4, the oxidation of CaCr2O4 was minimal. After CaSO4 addition, a

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small fraction of CaCr2O4 was oxidized at 873 K, and the oxidation of CaCr2O4 was

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strongly stimulated by increasing temperature. About 40% of the chromium in

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CaCr2O4 was oxidized after heating at 1173 K at a molar ratio of 1:1 Ca to Cr.

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Interestingly, an increase in the CaSO4 content slightly affected the amount of

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oxidized CaCr2O4. The XRD patterns of the products (given in Figure S7) show that

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CaCrO4 was the main oxidized compound, and the unoxidized chromium was

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transformed into Cr2O3. It is worth noting that CaSO4 remained the predominant

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crystalline structure in the products. Therefore, CaSO4 was not instrumental in the

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oxidation of CaCr2O4, but CaSO4 played a significant role in this process, which

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promoted the transformation of CaCr2O4 into CaCrO4 and Cr2O3 (Eq. (5))

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2CaCr2O4 + 1.5O2 → 2CaCrO4 + Cr2O3

(5)

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Inhibition of CaCr2O4 Oxidation. As stated before, CaCr2O4 was more easily

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oxidized than Cr2O3, even in the absence of free CaO. Therefore, conversion of

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CaCr2O4 into Cr2O3 is a promising way to lower the oxidation capacity of chromium.

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However, the problem lies in the removal of calcium from CaCr2O4. It is well known

249

that free CaO is a strong alkaline substance that tends to react with acid gases and

250

other acidic compounds at high temperature

251

might have a similar reaction performance to free CaO, which is mostly determined

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by the surface basicity of CaCr2O4.

13, 17

. Calcium in the form of CaCr2O4

13

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For comparison, the basic sites on the surface of CaCr2O4, Cr2O3 and CaO/Cr2O3

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mixtures (molar ratio 1:1) were determined by CO2-TPD, and the resulting profiles

255

are given in Figure S8. A broad desorbed peak of CO2 was clearly observed for Cr2O3

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in the temperature range of 573 to 1073 K, which was mainly assigned to strong basic

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sites (related to unsaturated O2- ions) 24, 25. The strong basic sites stimulated reactions

258

with acidic compounds at high temperature. After the addition of free CaO, a large

259

amount of CO2 evolution was found at temperatures between 673 and 873 K, which

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was related to great moderate basic sites (corresponding to M-O pairs)

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contrast, apart from the strong basic sites, CaCr2O4 contained some moderate basic

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sites on the surface, as evident by the several weak desorption peaks at low

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temperatures. As a result, CaCr2O4 might show similar performance to CaO in a

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reaction with acidic compounds.

25, 26

. In

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Figure S9 shows the XRD patterns of CaCr2O4 after reaction with SO2. It was

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found that CaCr2O4 could react with SO2 by forming Cr2O3 and CaSO4 at 1173 K and

267

1373 K (Eq. (6)). However, the reaction was strongly suppressed at 973 K.

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Furthermore, the oxidation of CaCr2O4 was hardly observed, even in the presence of

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formed CaSO4, demonstrating that the sulphonation of CaCr2O4 occurred more easily

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than the oxidation of CaCr2O4.

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CaCr2O4 + SO2 + 0.5O2 → CaSO4 + Cr2O3

(6)

272

Similarly, the heating temperatures had an obvious effect on the interactions

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between CaCr2O4 and Si/Al-compounds. Figure 8 displays the XRD patterns of

274

thermally treated mixtures containing CaCr2O4 and Si/Al-rich fly ash. At 973 K and 14

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1173 K, Si/Al-compounds hardly reacted with calcium compounds including CaCr2O4.

276

Meanwhile, calcium compounds in ash, such as calcite, stimulated the oxidation of

277

CaCr2O4 by forming CaCrO4, especially in the Ca-rich water-washed fly ash (shown

278

in Table S1). In the acid-washed fly ash, calcite was removed and the remaining

279

calcium was mainly in the form of CaSO4. The formation of CaCrO4 in the

280

acid-washed fly ash further confirmed the promotion of CaCr2O4 oxidation under the

281

influence of CaSO4. Nevertheless, most chromium remained unoxidized in the form

282

of CaCr2O4 after thermal treatment with acid-washed fly ash.

283

In most cases, increasing heating temperature strongly enhanced the interactions 27, 28

284

between Si/Al-compounds and calcium

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CaCr2O4 was transformed into calcium aluminosilicates (Eq. (7)), and unoxidized

286

chromium was in the form of Cr2O3 in the acid-washed fly ash. In the Ca-rich

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water-washed fly ash, CaCr2O4 reacted with Si/Al-compounds, and some intermediate

288

products formed in the heating process (Eq. (8)). As a result, a fraction of the

289

chromium

290

Si/Al-compounds in fly ash competed with CaCr2O4 to react with Ca-compounds at

291

1373 K, which effectively suppressed the oxidation of CaCr2O4.

292 293 294

was

transformed

into

. After the reaction, calcium from

Ca3Cr2

(SiO4)3

(Eq.

CaCr2O4 + Si/Al-compounds → CaAl2SiO2 + Cr2O3 Ca-compounds +SiO2 → CaSiO3 CaCr2O4 + 2CaSiO3 +SiO2 → Ca3Cr2(SiO4)3

(9)).

Therefore,

(7) (8) (9)

295

Environmental Implications. Few studies have reported on the formation and

296

oxidation of CaCr2O4 in ash residues during solid fuel combustion. This is largely 15

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because of the low concentration of chromium in ash samples and limited analytical

298

methods. The findings in this study demonstrate that CaCr2O4 was probably formed

299

through the decomposition of CaCrO4 and/or the direct interaction between CaO and

300

Cr2O3. Compared to Cr2O3, CaCr2O4 was more easily oxidized to form more toxic

301

chromate species (Cr6+ or Cr5+), and this reaction could take place at low temperature,

302

around 773 K. Therefore, measures should be taken to suppress the formation of

303

CaCr2O4 during fuel combustion.

304

In solid fuel samples containing low free CaO content, the reaction between CaO

305

and Cr2O3 predominantly generated CaCr2O4. However, the reaction was very slow,

306

and decreasing the reaction time could effectively inhibit the formation of CaCr2O4.

307

Furthermore, considering the increased CaCr2O4 formation at high temperatures,

308

another promising way for the control of CaCr2O4 formation is to perform fuel

309

combustion at temperatures below 1200 K.

310

In Ca-rich fuel, chromium was probably oxidized to form calcium chromate

311

during combustion 1, 29. An effective method to suppress the oxidation of chromium is

312

to decrease the free CaO content, by separating Ca-rich components from the fuel or

313

enhancing the interactions of Si/Al- or P-compounds with free CaO 18, 19. In addition,

314

increasing the operating temperature could partly decrease the fraction of chromate in

315

ash residues. This effect was attributed to the rapid decomposition of oxidized

316

CaCrO4. As a result, a large fraction of unoxidized chromium was transformed to

317

CaCr2O4. Then, control of CaCr2O4 oxidation was the key issue, especially for ash

318

residue treatment via heating. When ash samples were reheated, CaCr2O4 showed 16

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great oxidation capacity for the formation of toxic chromate. Even in the absence of

320

free CaO, the oxidation of CaCr2O4 could occur in the presence of CaSO4, which was

321

widely prevalent in the fly ash during fuel combustion and/or desulfurization of flue

322

gas.

323

According to the results in this study, CaCr2O4 contained some basic sites on its

324

surface to support the reactions with acid gases or other acidic compounds. The

325

addition of sulfur-rich materials into the CaCr2O4-containing ash residue enhanced the

326

transformation of CaCr2O4 to CaSO4 and Cr2O3 at high temperature. In this way, SO2

327

produced in the heating process was captured in situ, and the oxidation of chromium

328

was suppressed. Another practical approach was to mix CaCr2O4-containing ash with

329

Si/Al-rich ash before thermal treatment. In this case, calcium from CaCr2O4 was

330

transformed into aluminosilicates, and the chromium remained unoxidized. However,

331

it is worth noting that Ca-compounds in ash might stimulate the oxidation of CaCr2O4,

332

especially at low temperatures like 973 K and 1173 K. Therefore, the operating

333

temperature should be well controlled to suppress CaCr2O4 oxidation by enhancing

334

the interactions between CaCr2O4 and Si/Al-compounds.

335

In summary, in order to control Ca-chromate formation in fuel combustion,

336

attention should be paid to the ash forming process as well as the ash treatment

337

process. The findings from this study broaden our understanding of the formation of

338

CaCr2O4 as well as its thermal behavior. Moreover, the control strategies for

339

chromium oxidation during fuel combustion could be optimized based on these

340

findings. 17

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341

Acknowledgments

342

The present work was supported by the National Natural Science Foundation of

343

China (51606075, 51406062, 51506064) and the General Financial Grant from the

344

China Postdoctoral Science Foundation (Grant, 2016M592330). We appreciate the

345

experimental measurements provided by the Analytical and Testing Center of

346

Huazhong University of Science and Technology.

347

References

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Figure captions

438

Figure 1. TG-DSC curves for the decomposition of CaCrO4 in terms of various

439

concentration of oxygen in the carrier gas

440

Figure 2. In situ high temperature XRD patterns of the mixture of CaO and Cr2O3

441

during thermal treatment under vacuum

442

Figure 3. The formation of CaCr2O4 during reactions between CaO and Cr2O3 in N2

443

at a molar ratio of Ca and Cr 4:1

444

Figure 4. TEM images and crystallites size measurements of Cr3+-compounds

445

Figure 5. Thermogravimetric analysis of CaCr2O4 oxidation at 1373 K with the

446

addition of various contents of free CaO

447

Figure 6. TG curves for the oxidation of Cr2O3 and CaCr2O4 under the influence of

448

CaSO4

449

Figure 7. Percentages of oxidized chromium in the heated mixtures of CaCr2O4 and

450

CaSO4 at various mole ratios of Ca and Cr (ND, not detected)

451

Figure 8. XRD patterns of the products from the reactions between CaCr2O4 and (a)

452

water-washed ash, (b) acid-washed ash

453

23

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TG / %

100 98

16 1337 K

TG curve

12

96

8

94

4

-1

20

In N2 with 20% O2

DSC / mW mg

102

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DSC curve

TG curve

96

6

94

4

92 2

90

DSC curve 0

In pure N2

6 1186 K

TG curve

4

TG / %

88 100 98 96 94 92 90 88 86 84

454

-1

8

DSC / mW mg

TG / %

98

1304 K

2

-1

100

0

In N2 with 5% O2

DSC / mW mg

92

DSC curve 0 373 473 573 673 773 873 973 1073 1173 1273 1373

Temperature / K

455

Figure 1. TG-DSC curves for the decomposition of CaCrO4 in terms of various

456

concentration of oxygen in the carrier gas

24

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2 2 1 2

2

Intensity / A.U.

1 3

1.CaO 2.Cr2O3 3.CaCr2O4

4

2

2

4. Experimental carrier

2 1

11

1323 K- 10min 1323 K-1min 1273K-1min 1223 K-1min 1173 K-1min

10 457

20

30

40

50 60 2-Theta / °

70

80

90

458

Figure 2. In situ high temperature XRD patterns of the mixture of CaO and Cr2O3

459

during thermal treatment under vacuum

460

25

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Cr(CaCr2O4)/Total Cr (%)

100 1223 K 1323 K 1423 K

80 60 40 20 0 1

461

3 5 Heating time / min

10

462

Figure 3. The formation of CaCr2O4 during reactions between CaO and Cr2O3 in N2

463

at a molar ratio of Ca and Cr 4:1

26

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Cr2O3 464

CaCr2O3-I

CaCr2O3-II

Figure 4. TEM images and crystallites size measurements of Cr3+-compounds

465

27

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108 CaCr2O4 without CaO

106

CaCr2O4 with CaO n(Ca/Cr) 1:1 CaCr2O4 with CaO n(Ca/Cr) 1.2:1

104 TG / %

CaCr2O4 with CaO n(Ca/Cr) 1.5:1

102 100 98 96

Heating to 1373 K in Argon

Adding 20 % O2

94 0 466

10

20

30 40 50 60 Retention time / min

70

80

90

467

Figure 5. Thermogravimetric analysis of CaCr2O4 oxidation at 1373 K with the

468

addition of various contents of free CaO

469

28

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100.5

TG / %

99.0

TG curve for the mixture of CaSO4 and CaCr2O4

97.5 96.0 94.5 93.0 373

470

TG curve for the mixture of CaSO4 and Cr2O3

573

773 973 Temperature / K

1173

1373

471

Figure 6. TG curves for the oxidation of Cr2O3 and CaCr2O4 under the influence of

472

CaSO4

473

29

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Percentages of oxidized chromium / %

Environmental Science & Technology

474

50 Without CaSO4 addition n(Ca):n(Cr) 1:1 n(Ca):n(Cr) 2:1

40 30 20 10 0

ND 873

ND 1023 Temperature / K

ND 1173

475

Figure 7. Percentages of oxidized chromium in the heated mixtures of CaCr2O4 and

476

CaSO4 at various mole ratios of Ca and Cr (ND, not detected)

30

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(a)

1.CaCrO4 2.CaCr2O4 3.Ca3Cr2(SiO4)3 4.Quartz SiO2

63 55 4 3 5 4 36

5 56

5.Cr2O3 6.Gehlenite CaAl2SiO7

3

55

1373 K

1 4

1

Intensity / A. U.

1 1

4 5

4

1

4 1 41

41 1

1173 K

1 4 1 4

4 2

10

20

1

1 41 5

30

1

40

(b)

Intensity / A. U.

50 60 2-Theta /°

70

80

90

4.Quartz SiO2 5.Cr2O3

4 5 3 4

24 1 4

4 2 1 20

973 K

1.CaCrO4 2.CaCr2O4 3.Anorthite CaAl2Si2O8

4

10

4

30

32 5

5

4

22

2

22 1

2

40

4

4

1373K

4

4

4

1173K

4

4

4

973K

50 60 2-Theta /°

70

80

90

477

Figure 8. XRD patterns of the products from the reactions between CaCr2O4 and (a)

478

water-washed ash, (b) acid-washed ash

31

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