Kinetic mechanism on elemental mercury adsorption by brominated petroleum coke in simulated flue gas

A waste byproduct of petroleum coke was obtained as a precursor modified with bromine for elemental mercury capture from simulated flue gas on a bench scale fixed-bed reactor. The reaction temperature, the initial inlet elemental mercury concentration and the individual flue gas components of O2, NO, SO2 and HCl were determined to explore their influence on elemental mercury capture by the brominated petroleum coke. Results indicate that high initial inlet mercury concentration can enhance initial mercury accumulation and the optimal temperature for elemental mercury capture by brominated petroleum coke is about 150 °C. Kinetic models reveal that the pseudo-second order and Elovich models are best fitted to the mercury adsorption process, indicating that chemisorption is the control step with the intra-particle diffusion and external mass transfer taking place simultaneously. The kinetic parameters demonstrate that the initial mercury adsorption rate (h or a) and the equilibrium adsorption quantity (Qe) increase remarkably, when higher concentrations of O2 or NO exist in N2 atmosphere. On the contrary, Qe decreases with the presence of high SO2 or HCl, which indicates a two-sided effect on the performance of mercury adsorption owing to their concentrations.


Introduction
Elemental mercury emitted from coal combustion has increasingly become a global threat and injecting a carbon based adsorbent upstream of coal-red ue gas to control elemental mercury has been proved a relatively effective technology. 1 However, the cost of injecting activated carbon is high, and replaceable low-cost adsorbents, especially bromine and sulfur modied carbon based materials, have received more and more attention. [2][3][4][5][6] Petroleum coke, produced from the exploitation of oil or the extraction of traditional oil all over the world, is considered as an industrial waste due to the high content of organic sulfur.
In our previous studies, petroleum coke was modied by a chemical-mechanical bromination procedure 7 to remove elemental mercury from coal-red ue gas, in order to replace the expensive activated carbon adsorbent, which showed better performance than commercial activated carbon in ideal argon gas. The adsorption mechanism conrmed that more active mercury binding sites were created on the surface of brominated petroleum coke aer the special bromination process, the inherent thiophene S and the loading Br in petroleum coke played a dominant role on mercury removal. 8,9 Further Density Functional Theory conrmed that the mercury adsorption capacity directly correlated with the inherent organic S and the binding Br from chemical-mechanical bromination procedure, HgBr and Hg(Br)Br were the main forms chemisorbed on the surface of brominated petroleum coke and appeared approaching to bind on the carbon site next to the sulfur atom. 10 The synergetic effect of the inherent thiophene sulfur and loading bromine enhanced the elemental mercury removal efficiency of the adsorbent in ideal argon gas. However, the environment in real ue gas of coal-red power plant is complex, and the intrinsic reaction rate, the adsorption strength and quantity of solid surface active sites of the sorbent are affected by ue gas components including O 2 , NO, SO 2 , HCl, et al., [11][12][13][14][15][16] it is necessary to nd out the inuences of the components on mercury removal by the brominated petroleum coke for its further application in the plant.
Some researchers discussed the effect of ue gas component on mercury oxidation/adsorption and the atomic interaction between elemental mercury and the ue gas component using the rst-principles calculation. 17,18 However, kinetic studies are also widely used on understanding the adsorption process of carbon based adsorbents. [19][20][21][22][23][24][25][26][27] Zhou 24 revealed that the mercury adsorption process for activated carbon could be divided into two stages: external diffusion and intraparticle diffusion adsorption. Johari 25 conrmed that pseudo-second order kinetic model could accurately describe the adsorption mechanism of mercury on the surface of modied coconut shell adsorbent. Khunphonoi 26 found that pseudo-second order kinetic equation accurately described the mechanism on the surface of silver loaded activated carbon. Zhang 27 found that the pseudo-rst order and pseudo-second order kinetic models could better describe the adsorption process of mercury on the surface through the study of the kinetic models before and aer the modication of activated carbon, indicating that the external mass transfer and chemical adsorption were dominant.
Since the inuence of ue gas components on mercury removal by brominated petroleum coke have not been discussed in bench scale xed-bed experimental system before, the apparent reaction rate of brominated petroleum coke will be affected by the internal and external diffusion process, and the relevant parameters involved are difficult to be obtained directly through experiments. It is necessary to use mathematical models to describe the kinetic adsorption mechanism, so as to further understand the mercury removal by the adsorbent in the simulated coal-red ue gases. Thus in this study, the bench scale xed-bed reactor is used as an experimental system to better understand the novel brominated petroleum coke on elemental mercury removal in ue gas. The xed-bed reaction temperature, the initial elemental mercury concentration and the possible ue gas components of O 2 , NO, SO 2 and HCl are investigated. Mathematic kinetic adsorption models are chosen to nd out the adsorption mechanism on elemental mercury by brominated petroleum coke in simulated ue gas.

Material preparation
The raw petroleum coke obtained from the upgrading of oil sands deposits in Alberta, Canada was grounded with ball mill and sieved through 100-mesh. Aer dried at 110 C for 24 h, 2 g of which was put in a ball with certain amount of small glass beads and 20 mg liquid bromine to shake for 30 min. Then, the ball was put in a fume hood for 1 h and set in a vacuum drying oven at 200 C for 30 min to let the non-binding bromine evaporate completely. The received sample was cooled naturally and then kept in a sealed container for further experiments. The novel chemical-mechanical bromination procedure and the tested brominated petroleum coke were described in detail and well characterized in our previous studies. 7,8 2.2 Bench scale xed-bed experimental system The schematic diagram of bench scale xed-bed experimental system for elemental mercury adsorption by brominated petroleum coke is shown in Fig. 1. The setup includes ve parts as ue gas distribution part, elemental mercury permeation device, xed-bed adsorption reactor, gas washing device and online mercury analyzer. Elemental mercury is volatilized by adjusting the temperature of the circulating water bath. The high-purity N 2 with the rate of 30 mL min À1 as carrier gas passes through elemental mercury permeation device and enters the gas premix tank. The rate of carrier ow and balancer ow is controlled by D07-19B mass ow-meter, so as to keep the inlet mercury content constant in the simulated ue gases. The ow rate of ue gas component (O 2 , NO, SO 2 , HCl) is controlled by the rote-meter to keep 2 L min À1 in the pipeline. Aer fully mixed in the gas premix tank, the mixed gas is divided into two paths, part of which discharges through the tail gas and the rest enters the temperature controlled xed-bed reactor, where a quartz glass tube is set inside.
During the experiment, 50 mg brominated petroleum coke was evenly laid on the glass wool in the quartz tube reactor. The mixed gas containing a certain amount of elemental mercury passed through the adsorbent, which rst came into the gas washing device to remove the possible acid gas in the gas path, and then entered the VM3000 mercury analyzer (Mercury Instruments, German) for online monitoring, of which the accuracy of which was 0.1 mg m À3 . The mixed gas was divided into two air ows, the main ow was set passing the brominated petroleum coke and the VM3000 mercury analyzer, the bypass ow was set not passing the adsorbent but the VM3000 mercury analyzer. Before each test, the main ow was closed and the initial elemental mercury passed through the bypass ow and kept for 30 min for inlet mercury stable. Aer that, the setup was changed to the main ow and the outlet mercury concentration was recorded continuously. The initial inlet mercury concentration and the outlet mercury concentration were expressed as Hg in 0 and Hg out 0 separately. At the end of each pipeline, an adsorption box equipped with activated carbon lter was used to treat the tail gas before discharging it into the atmosphere.
The unit cumulative mercury quantity at a certain time was used to evaluate the adsorption performance of mercury, which could be expressed by (1): where Q t : the unit cumulative mercury adsorption quantity, mg g À1 ; Q: the unit ow rate, m 3 min À1 ; t: the cumulated time, min; m: the total amount of brominated petroleum coke, g.

Kinetic models
The changes of mercury mass, based on the principle of mass balance in axial microelements inside the xed-bed reactor during the adsorption process by brominated petroleum coke was shown in Fig. 2 and the reaction formula was obtained as (2): dM Hg;gas dt ¼ M Hg;gas;in À M Hg;gas;out À G where M Hg,adsorb expresses mercury mass adsorbed in microelement of brominated petroleum coke in unit time; M Hg,gas,in expresses the inlet mercury mass to microelement in unit time; M Hg,desorb expresses mercury mass desorbed from microelement of brominated petroleum coke in unit time; M Hg,gas,out expresses the outlet mercury mass from microelement in unit time; M Hg,gas expresses accumulative mercury gas mass in microelement of brominated petroleum coke in unit time; G expresses mercury adsorption efficiency of brominated petroleum coke in unit time.
Because of the complex situation of the mercury adsorption in coal red ue gas, the reaction rate is affected by various environmental factors and is difficult to obtain from the experiments, appropriate kinetic models were needed to t the mercury adsorption data, the relevant parameters are obtained to predict the control steps and the adsorption mechanism. 28 Based on the mass balance principle, Langmuir adsorption isotherm and Temkin adsorption isotherm, 29-31 four simplied kinetic models 9 were obtained to evaluate the elemental mercury adsorption from ue gas by brominated petroleum coke. The xed-bed temperature, initial inlet mercury concentration and individual ue gas components of O 2 , NO, SO 2 and HCl were conducted on the xed-bed reactor. Intra-particle diffusion model is to describe the process of elemental mercury diffusing to brominated petroleum coke through the action of concentration gradient and the role of van der Waals force, and the mathematical expression is shown as: Q t ¼ k p t 1/2 + C; Pseudo-rst order kinetic model is originated from Lagergren equation, which is to describe the process of external mass transfer, and the mathematical expression is shown as: dQ t /dt ¼ k 1 (Q e À Q t ); Pseudo-second order kinetic model is based on Langmuir adsorption isotherm, which is to describe the process of chemical adsorption, and the mathematical expression is shown as: dQ t /dt ¼ k 2 (Q e À Q t ) 2 ; Elovich kinetic model is based on Temkin adsorption isotherm, which is the other equation to describe the process of chemical adsorption in more complex situation, and the mathematical expression is shown as: where Q t : the unit cumulative mercury adsorption quantity, mg g À1 ; K p : the intra-particle diffusion rate constant, mg (g À1 min À1/ 2 ); C: the constant related to the boundary layer, mg g À1 ; Q e : the mercury equilibrium adsorption quantity, mg g À1 ; k 1 : the pseudo-rst order adsorption rate constant (min À1 ); k 2 : the pseudo-second order adsorption rate constant, g (mg À1 min À1 ); a: the Elovich initial adsorption rate, mg (g À1 min À1 ); b: the Elovich desorption constant, g mg À1 .

Results and discussion
3.1 Effect of reaction temperature and Hg in 0 concentration 3.1.1 Temperature and Hg in 0 concentration. The temperature of xed-bed reactor which is one of the key factors can affect the elemental mercury removal performance of brominated petroleum coke. As shown in Fig. 3a, the elemental mercury cumulative quantity was greatly different when the reaction temperature from 50 to 200 C, and 150 C was found as the best reaction temperature. The main reason was that high temperature provided sufficient activation energy for the occurrence of chemisorption, 32 with the increase of reaction temperature, molecules accelerated moving, resulting in the increase of effective collision of mercury molecules on the surface of brominated petroleum coke, which improved the reaction rate of substances, while the amount of mercury adsorbed by adsorbent also increased. However, when the temperature reached 200 C, the mercury cumulative quantity decreased because of the loss of effective bromine breaking away from the sorbent. 8 Another, the amount of mercury adsorbed at 50 C was higher than that at 100 C, because the activation energy provided by temperature was limited at low temperatures, with the physisorption played a leading role with small amount mercury could be chemically adsorbed. 33 The ue gas temperature of upstream of the electrostatic precipitator in coal-red power plant was about 140 C, 33 indicating that the optimal temperature for mercury removal by brominated petroleum coke was consistent with the ue gas temperature in actual coal-red power plant. The initial elemental mercury concentration is the other important factor affecting elemental mercury accumulation on the brominated petroleum coke. The inlet mercury concentration of (29.5 AE 0.5) mg m À3 and (57.5 AE 0.5) mg m À3 were set to compare the different cumulative mercury adsorption quantity at 150 C with the data acquisition time of 120 min as shown in Fig. 3b. The amount of mercury adsorbed by brominated petroleum coke increased when the initial inlet mercury concentration increased, it is mainly because the increase of inlet Hg 0 concentration can increase the driving force towards the surface of activated carbon and improve the efficiency external mass transfer rate and internal diffusion rate. 24 3.1.2 Kinetic analysis. Four kinetic models of intra-particle diffusion, pseudo-rst order, pseudo-second order and Elovich were used in order to nd out the elemental mercury adsorption mechanism of brominated petroleum coke with the inlet elemental mercury concentration of (29.5 AE 0.5) mg m À3 at 150 C in 120 min as shown in Table 1. Elovich kinetic model demonstrated the highest related coefficient R 2 of 0.9999, which indicated that chemical adsorption was the dominant step on elemental mercury removal for brominated petroleum coke in pure N 2 atmosphere. Meanwhile, R 2 of intra-particle diffusion and pseudo-rst order were 0.9957 and 0.9997 separately, which showed that intra-particle diffusion and external mass transfer carried out simultaneously as well in the complex process. The intra-particle diffusion rate k p was higher than that the initial mercury adsorption rate a from Elovich kinetic model, which indicated that the adsorption process could be divided into two stages: chemical adsorption and internal diffusion adsorption. The chemical adsorption was dominant in the initial adsorption stage, because a large number of adsorption active sites with loading bromine 8 existed on the surface of the adsorbent promoting the adsorption rate. The surface adsorption rate decreased and the internal diffusion rate increased when the active sites were occupied gradually. Although the external mass transfer and internal diffusion limited the whole adsorption process, the chemisorption at the active sites on the surface of brominated petroleum coke was the rate control step because of the initial lower chemisorption rate.
The adsorption equilibrium state of the xed bed system was considered as that the mercury concentration at the outlet was equal to the inlet concentration. Thus, the saturated adsorption capacity of the adsorbent was dened as the equilibrium adsorption quantity, which could be calculated by the kinetic models and accurately predicted from the adsorption parameters. 23,24 As pseudo-second order kinetic model was better tted the adsorption process than pseudo-rst order kinetic model, the obtained equilibrium adsorption quantity was 273.49 mg g À1 of the system with the inlet elemental mercury concentration of (29.5 AE 0.5) mg m À3 at 150 C.

Effect of individual ue gas components
The volume percentages for main components in the ue gas of coal-red power plants are about 12% CO 2 , 6% O 2 , 75% N 2 , 5% H 2 O and the other possible components include SO 2 , HCl and NO x . 33 Among them, SO 2 , HCl, NO and O 2 can oxidize elemental mercury so then affect the mercury adsorption process by the adsorbent. Thus, the effects of individual ue gas component of SO 2 , HCl, NO and O 2 on mercury removal by brominated petroleum coke was investigated, in order to understand their promotion or inhibition mechanism.
3.2.1 Effect of O 2 . The effect of O 2 on elemental mercury adsorption by brominated petroleum coke was explored under 5% and 10% O 2 in N 2 atmosphere on the xed-bed reactor. As shown in Fig. 4, a certain amount of O 2 could promote the unit mercury accumulation on the brominated petroleum coke obviously. The unit accumulation enhanced via increasing O 2 composition, indicating that oxygen promoted mercury adsorption by brominated petroleum coke in simulated ue gas compared with that under pure N 2 atmosphere.
The mechanism was explored mainly as the following possibilities: (1) oxygen were adsorbed by brominated petroleum coke to form new oxygen-containing functional groups, such as carbonyl and lactone groups, which were proved to promote mercury adsorption 34,35 when oxygen was in contact with the surface of the brominated petroleum coke. (2) Oxygen were adsorbed on the active sites of the brominated petroleum coke, which could form carbon oxygen compounds, and then reacted with elemental mercury to form new substances. 36 (3) Oxygen reacted with mercury in simulated ue gas in the form of mercuric oxide, and then adsorbed on the surface of the brominated petroleum coke. 37 3.2.2 Effect of HCl. HCl was one of the important factors on mercury removal by brominated petroleum coke. It was reported that HCl in ue gas reacted with the active sites on the surface of the adsorbent to form active Cl reaction group and then undergo heterogeneous oxidation in the form of electron exchange to form HgCl x , 32 which was competitive with HgBr x (ref. 8) on active sites of the brominated petroleum coke. The adsorption mechanism might be that they promoted simultaneously or competed for active sites on the surface of the sorbents. As shown in Fig. 5, the unit cumulative adsorption mercury quantity on brominated petroleum coke sample increased compared with that in pure N 2 atmosphere, when adding HCl to the simulated ue gas, and the results had not

Kinetic models Kinetic parameters
Intra-particle diffusion model K p (mg (g À1 min À1/2 )) C (mg g À1 ) R 2 1.0269 2.9605 0.9959 Pseudo-rst order kinetic model Q e (mg g À1 ) k 1 (min À1 ) R 2 152.85 0.0044 0.9997 Pseudo-second order kinetic model Q e (mg g À1 ) k 2 (g (mg À1 min À1 )) R 2 273. 49 8.9718 Â 10 À6 0.9998 Elovich kinetic model a (mg (g À1 min À1 )) b (g mg À1 ) R 2 0.6668 0.0078 0.9999 a R 2 : tting correlation coefficient; K p : intra-particle diffusion rate constant, mg (g À1 min À1/2 ); C: the constant related to the boundary layer, mg g À1 ; Q e : mercury equilibrium adsorption quantity, mg g À1 ; k 1 : pseudo-rst order adsorption rate constant (min À1 ); k 2 : pseudo-second order adsorption rate constant, g (mg À1 min À1 ); a: Elovich initial adsorption rate, mg (g À1 min À1 ); b: Elovich desorption constant, g mg À1 .  changed a lot with the concentration between 50 and 100 ppm HCl in the ue gas. Therefore, continuing increasing the concentration of HCl would not improve mercury adsorption quantity on the surface of brominated petroleum coke. The result was consistent with other researchers reported. 38 Krishnakumar 39 explored that Cl atom was reacted much faster than Cl 2 , and HCl got the highest reaction barrier as to cause the lowest reaction process. That was conrmed in our previous inlet mercury stable test, when a certain amount of HCl owing through the bypass pipeline, the concentration of outlet elemental mercury got a sudden decrease of 3 mg m À3 , indicating a partial homogeneous oxidation occurred possibly. 40 In conclusion, a proper certain amount of HCl was benet for elemental mercury removal by brominated petroleum coke, but it would cause mercury adsorption decrease in the high HCl concentration.

Effect of NO.
In order to explore the effect of NO on elemental mercury removal by brominated petroleum coke, the test was conducted under N 2 atmosphere with 250 and 800 ppm NO for comparison on xed-bed reactor. As shown in Fig. 6, the unit mercury cumulative quantity increased compared with that in pure N 2 atmosphere and the higher the NO concentration in N 2 atmosphere, the higher the mercury cumulative quantity, which indicated NO in simulated ue gas promoted mercury removal by brominated petroleum coke obviously. The results conrmed that NO in ue gas played an important role in promoting the unit mercury cumulative adsorption quantity.
The chemical adsorption mechanism was mainly that NO was easily adsorbed by the active sites on the surface of carbon based adsorbent to form NO-C n reaction groups. 41 When NO-C n groups increased, more stable (NO) 2 -C n reaction group could be easily formed with two NO-C n groups on the adjacent adsorption sites. The reaction formula was shown as follows: C n + NO / NO-C n NO-C n + NO / (NO) 2 -C n NO-C n + Hg 0 + 2NO / HgNO 3 -C n + N 2 (NO) 2 -C n + Hg 0 + NO / HgNO 3 -C n + N 2 HgNO 3 -C n + 3NO / Hg(NO 3 ) 2 -C n + N 2 3.2.4 Effect of SO 2 . The effect of SO 2 was conducted in N 2 atmosphere with 450 and 1500 ppm separately for comparison. As shown in Fig. 7, a certain amount of SO 2 adding in the pipeline accelerated mercury adsorption rate by brominated petroleum coke. When the amount increased to 1500 ppm, the mercury adsorption rate decreased. The results were consistent with the research results reported by other researchers, An et al. reported that the promotion of 800 ppm SO 2 was reduced on elemental mercury adsorption by active coke, 42 Chiu reported that mercury removal changed from promotion to inhibition with SO 2 concentration of 500 ppm by MnO x /SCR catalyst. 43 SO 2 mainly played a role in promoting the mercury removal process by brominated petroleum coke, and the promotion level was greatly affected by the concentration of SO 2 in ue gas, which had a two-sided effect on the performance of mercury removal by adsorbents, oxidation and activated adjacent sites were considered to be the main reasons for the promotion effect. It was conrmed that more complex structure with sulfur functional groups was formed on the surface of brominated petroleum coke for elemental mercury adsorption, because the free orbit of the outer layer of the sulfur atom could accept two electrons in the outer layer of the elemental mercury to form oxidized mercury. On the other side, SO 2 was easy to combine with oxygen-containing functional groups on the surface of the adsorbent, which was compete with elemental mercury adsorption, so then lead to the reduction of adsorption capacity of brominated petroleum coke in high SO 2 concentration. [44][45][46][47][48][49] 3.2.5 Comparison among ue gas components. It was secured from Fig. 8 that the nal mercury cumulative quantity was 35 mg g À1 in pure N 2 environment within 60 min, and all other ue gas components improved the unit mercury  accumulative quantity on the surface of brominated petroleum coke. With the existence of 800 ppm NO in N 2 atmosphere, the mercury accumulative quantity reached 85 mg g À1 , which was increased signicantly compared to that under other ue gas components. The presence of 250 ppm NO, 100 and 500 ppm HCl increased the mercury accumulative quantity by about twofold quantity compared to that under N 2 atmosphere. But to SO 2 , the situation was different, the quantity increased with the concentration 450 ppm, but decreased with 1500 ppm, which inhibited the nal mercury cumulative quantity, so as to lower the mercury accumulative quantity of brominated petroleum coke in 60 min.
3.2.6 Kinetic mechanism. In elemental mercury adsorption by brominated petroleum coke, it was conrmed that chemical adsorption played the dominant place in pure N 2 atmosphere, which revealed from kinetic analysis at various xed-bed temperature and initial mercury concentration. To further investigate the effect of ue gas components on mercury adsorption by brominated petroleum coke, kinetics analysis was also used to conduct the inuence of O 2 , HCl, NO and SO 2 with pseudo-second order kinetic model and Elovich kinetic model describing chemical adsorption. The experimental data was obtained with the inlet mercury concentration (29.5 AE 0.5) mg m À3 and the xed-bed reaction temperature 150 C in 60 min. The relevant kinetic parameters like the tting correlation coefficient R 2 , pseudo-second order adsorption rate h(k 2 Q e 2 ), the initial mercury adsorption rate a and the equilibrium adsorption quantity Q e were obtained and compared as shown in Table 2. It could be seen from the table that the correlation coefficient R 2 in pseudo-second order kinetic equation and the Elovich equation were basically reached to above 0.999, indicating that both equations could be used to describe the adsorption process of mercury removal by brominated petroleum coke and chemisorption was still dominant under the condition of participation of ue gas components. The difference of initial mercury adsorption rates h and a from both models were not statistically signicant, which illustrated that h and a both could be used to describe the reaction process.
The initial mercury adsorption rate (h/a) in each ue gas component improved compared with that in pure nitrogen, indicating that the participation of oxidizing gas could accelerate the chemical adsorption process of mercury removal by brominated petroleum coke. 800 ppm NO existence in ue gas demonstrated the highest acceleration, more than double rate than in pure N 2 atmosphere, with the initial mercury adsorption rate of 1.5082 mg (g À1 min À1 ) obtained from the Elovich kinetic model. Almost the same initial mercury adsorption rate was obtained for the other components' concentration of 50 ppm HCl, 100 ppm HCl and 250 ppm NO, which enhanced positively as well. However, when the concentration of SO 2 reached to 1500 ppm, the initial mercury adsorption rate decreased more than that for 450 ppm, indicating that there was a maximum limit for the concentration of SO 2 in ue gas. Aer reaching to a high concentration, the promotion effect was weakened. This result was consistent with the conclusion that high content of sulfur oxides could reduce the mercury capture ability of activated carbon as reported by other researchers. 45,46 Regarding the equilibrium adsorption quantity Q e , found from pseudo-second order, applying oxidized gas could increase the mercury adsorption quantity, the mercury adsorption amount came to 4074.85 mg g À1 with the existence of 800 ppm NO in the ue gas. As to O 2 , the equilibrium adsorption quantity increased almost fourfold when double concentration applied in N 2 atmosphere. As to HCl and SO 2 , the equilibrium adsorption quantity decreased sharply in higher concentration, that meant high HCl and SO 2 in ue gas was negative for elemental adsorption on brominated petroleum coke.
It was interesting to nd that, 800 ppm NO in ue gas showed the highest rate, more than twofold the rate in pure atmosphere; increasing HCl concentration from 50 to 100 ppm, the equilibrium adsorption quantity decreased evidently but the initial mercury adsorption rate increased; increasing SO 2 concentration from 450 to 1500 ppm, the equilibrium adsorption quantity decreased obviously but the initial mercury adsorption rate remained almost the same; increasing O 2 concentration from 5 to 10%, and NO concentration from 250 to 800 ppm, the equilibrium adsorption quantity increased remarkably while the initial mercury adsorption rate increased concurrently, it might be the new oxygen-containing functional groups formed and more active sites created on the surface of the brominated petroleum coke. Since the mercury removal behavior of the different brominated carbon-based sorbents such as brominated biomass based, brominated coal based and commercial brominated activated carbon in coal-red ue gas 50 are quite different from those in the simulated ue gas, mainly as a result of large proportion of Hg 2+ and Hg p , the effect of components on mercury removal of brominated petroleum coke might be different, further comparison should be conducted in the coal-red ue gas.

Conclusions
The effect of temperature, initial elemental mercury concentration and ue gas components of O 2 , HCl, NO and SO 2 were compared on mercury capture by brominated petroleum coke, and then the kinetic mechanism was investigated with the data of unit accumulative mercury quantity on a bench scale xedbed reactor. The initial inlet mercury concentration could enhance the adsorption by brominated petroleum coke and the optimal temperature for elemental mercury removal was about 150 C. Another, all the ue gas components including O 2 , HCl, NO and SO 2 showed a certain promoting effect on the mercury adsorption, but demonstrated promotion or competition on mercury removal by brominated petroleum coke according to the concentration of each ue gas component.
The tting correlation coefficients R 2 of pseudo-second order kinetic model and Elovich kinetic model were slightly higher than those of the intra particle diffusion model and pseudo-rst order kinetic model, indicating that the chemical adsorption was accelerated and taken the role, while intra-particle diffusion and external mass transfer taking place simultaneously in the complex adsorption process as well. Kinetic parameters indicated that the initial mercury adsorption rate h and the equilibrium adsorption quantity Q e increased, when supplying higher concentration of O 2 or NO in N 2 atmosphere as new oxygen-containing functional groups formed and more active sites created on the surface of the brominated petroleum coke. On the contrary, the concentration of SO 2 or HCl was too high, the mercury equilibrium adsorption quantity decreased as heterogeneous reaction occurred simultaneously. The adsorption kinetic mechanism can be concluded that chemical adsorption process is dominant and accelerated while intraparticle diffusion and external mass transfer taking place concurrently in simulated ue gas. Further effects of these gas mixtures and inter-reaction should be conducted between ue gas components and S/Br on the surface of brominated petroleum coke in simulated ue gas; the reusable possibility and adsorption performance of the adsorbent for elemental mercury aer regenerating the brominated petroleum coke at elevated temperatures were expected to study in the future.

Conflicts of interest
There are no conicts to declare.