Effect of sulfation during carbonation on CO_2 capture in calcium looping cycle

Abstract： Two Canadian limestones with different properties were tested to determine the effect of SO2 during the carbonation of sorbent on the CO2 capture performance in Ca- looping. When the reaction gas is mixed with SO2, the carbonation ratio of the sorbent is always lower than that without SO2 for each cycle under the same conditions, and the sulfation ratio increases almost linearly with the increase in the cycle times. At 650 ℃, there is little difference in the carbonation ratio of the sorbent during the first four cycles for the two carbonation time, 5 and 10 rain at 0. 18% SO2. The indirect sulfation reaction that occurs simultaneously with the carbonation of CaO is responsible for the degradation of the sorbent for CO2 capture, and the carbonation duration is not the main factor that affects the ability of the sorbent. 680℃ is the best carbonation temperature among the three tested temperatures and the highest carbonation ratio can be obtained. Also, the sulfation ratio is the highest. The probable cause is the different effects of temperature on the carbonation rate and sulfation rate. A higher SO2 concentration will decrease the carbonation ratio clearly, but the decrease in the carbonation capability of the sorbent is not proportional to the increase of the SO2 concentration in flue gases.

Model of limestone calcination / sulfation under oxy-fuel fluidized bed combustion

The characteristics of the simultaneous calcination/ sulfation of limestone under oxy-fuel fluidized bed combustion were studied and compared with those of the sulfation of precalcined CaO. During the calcination stage, SO2 can react with product CaO and slow down the CaCO3 decomposition rate by the covering effect of the CaSO4 product. The sulfation rate of simultaneous calcinatiort/sulfation is slower than that of precalcined CaO, but with a long enough sulfation time, the calcium conversion of simultaneous calcination/sulfation is higher than that of the precalcined CaO. A grain-micrograin model is established to describe the simultaneous calcination, sintering and sulfation of limestone. The graln-micrograln model can reflect the true reaction process of the calcination and sulfation of limestone in oxy-fuel fluidized bed combustion.

Influence of sulfation on CeO_2-ZrO_2 catalysts for NO reduction with NH_3

CeO2‐ZrO2 (CeZr) and sulfated CeO2‐ZrO2 (S‐CeZr) catalysts were prepared for the selective catalytic reduction of NO with NH3. The CeZr catalysts exhibited higher activity at low temperatures (< 200°C) and lower activity at high temperatures (> 200 °C) than the S‐CeZr catalysts. The sulfation ofCeZr was studied in terms of surface acidity, redox properties and NO adsorption‐desorption bytemperature‐dependent experiments and in situ infrared spectroscopy. S‐CeZr displayed high concentrationsof acidic sites and increased surface acidities, but poor reducibility compared with CeZr.The high acidity of S‐CeZr was attributed to the presence of Br?nsted acid sites, arising mainly fromthe surface sulfates. Because the surface was covered with sulfate species, S‐CeZr showed lower NOadsorption and weaker oxidation ability than CeZr. The adsorption of NH3 on the Br?nsted acid sites restricted the reaction with NO at low temperatures, but the selective catalytic reduction cycle occurred easily at relatively low temperatures (150 °C), and the weakly bound nitrite was partially activated on the S‐CeZr catalyst at relatively high temperatures (300 °C). The catalytic mechanisms for the CeZr and S‐CeZr catalysts at 150 and 300 °C were also studied.

Application of response surface methodology in optimizaing thesulfation-roasting-leaching process of nickel laterite

Nickel was recovered from nickel laterite using a sulfation-roasting-leaching process and the effects of operation parameters in- cluding acid addition, roasting temperature, and roasting time on nickel extraction and iron dissolution were investigated using response sur- face methodology （RSM）. Two second-order polynomial models of high significance were presented to show the relationship between the responses and the variables. The analysis of variance （ANOVA） showed high coefficients of determination （R2） of 0.894 and 0.980 for the two models, respectively. Optimum areas of 〉-80% Ni extraction and 〈5% Fe dissolution were obtained by the overlaid contours. Verification experiments in the optimum areas were conducted and the results indicate a close agreement with the predicted values obtained from the models.

Formation of arsenic−copper-containing particles and their sulfation decomposition mechanism in copper smelting flue gas

The heat recovery steam generator(HRSG)of copper smelting generates a large number of arsenic−coppercontaining particles,and the in-situ separation of arsenic and copper is of importance for cutting off environmental risk and realizing resource recovery.The formation of arsenic−copper-containing particles was simulated,the method of in-situ decomposition of arsenic−copper-containing particles by pyrite was proposed,and the decomposition mechanism was confirmed.It was found that particles with high arsenic content were formed in the simulated HRSG,and copper arsenate was liable for the high arsenic content.Pyrite promoted the sulfation of copper,leading to the in-situ decomposition of copper arsenate.In this process,gaseous arsenic was released,and thus the separation of arsenic and copper was realized.

Recovery of lead and silver from zinc acid-leaching residue via a sulfation roasting and oxygen-rich chlorination leaching method

A large amount of acid-leaching residue is produced during the conventional Zn hydrometallurgy process,and this residue has a large concentration of a variety of valuable metals.The purpose of this study was to evaluate the ability of a procedure that entails the use of sulfation roasting,water leaching,and chlorination leaching(blowing oxygen technique)to recover Pb and Ag,followed by cooling crystallization and the replacement of Ag with lead sheet,to realize the full recovery of all valuable metals from zinc acid-leaching residue;consequently,good results were achieved.The best results were obtained under the following conditions:a sulfuric acid at 70%of the raw material quality,roasting temperature of 300°C and roasting time of 2 h,followed by the process of leaching the roasted residue for 1 h by applying a water-to-solid ratio of 5꞉1 at room temperature.The recovery rates of Zn and Fe were 98.69%and 92.36%,respectively.The main parameters of the chlorine salt leaching system were as follows:Cl−concentration of 300 g/L,Fe3+concentration of 25 g/L,acid concentration of 2 mol/L,liquid-to-solid ratio of 9 mL:1 g,temperature of 90℃,and leaching time of 0.5 h;this leaching process was followed by filtration separation.These conditions resulted in high extents of leaching for Pb and Ag(i.e.,98.87%and 96.74%,respectively).Finally,the kinetics of the process of Ag leaching using Cl−ions in an oxygen-rich medium was investigated.It was found that the leaching process was controlled by the diffusion of the product layers,and the activation energy was 19.82 kJ/mol.

Influence of Sulfation on the Catalytic Activity of Ni-ZrO_2 for NO Reduction with Propane in Excess Oxygen

Selective catalytic reduction （SCR） of nitric oxide with propane in excess oxygen was investigated on Ni-ZrO2 （NZ） and sulfated Ni-ZrO2 （SNZ）, prepared by coprecipitation from a mixture of nickel nitrate-zirconium oxychloride followed by modifying with （NH4）2SO4. It was found that sulfated Ni-ZrO2 catalyst showed higher activity for the SCR of NO with propane than that of Ni-ZrO2. The structural and surface properties of catalysts were studied by XRD, BET, SEM and FT-IR of pyridine adsorption. The experimental results indicated that the modification of （NH4）2SO4 resulted in the generation of strong BrOnsted and Lewis acid sites and promoted the dispersion of the Ni species, which could lead to higher NO conversion and propane efficiency in NO reduction.

Preparation of supported nano-copper oxide and its sulfation kinetics

CuO/γ-Al2O3 sorbents were prepared by means of impregnation. Thermogravimetric technique was used to study the sulfation of CuO/γ-Al2O3 sorbents. The sulfation tests were performed using gas containing 0.1%-0.9% SO2, 5% O2, 3% H2O steam, and N2 as the balance. Experimental conditions including temperature, SO2 concentration and pore structure were studied. The sulfation experiment results show that the sulfation reaction rate increases with increasing temperature and SO2 concentration, and the surface and pore volume decrease after sulfation. Sulfation kinetics analysis shows that the reaction between CuO/γ-Al2O3 and SO2 obeys pore-blocking model well. Proportionality (pore-blocking constant) 1/λ decreases with increasing temperature. The activation energy and reaction order with respect to SO2 obtained are 37.9 kJ/mol and the first order, respectively. The existing state of CuO exerts an influence on activation energy.

Sulfation behavior of CuO/γ-Al_2O_3 sorbent for the removal of SO_2 from flue gas

CuO/γ-Al2O3 has been considered as a promising and recycling sorbent to remove sulfur dioxide from flue gas. In this study, a series of CuO/γ-Al2O3 sorbents with different CuO loadings were prepared by impregnation. The monolayer coverage of CuO supported on γ-Al2O3 determined by X-ray quantitative analysis was 0.275 g CuO/g （γ-Al2O3）. Below the monolayer coverage, CuO was found highly dispersed on γ-Al2O3. Thermogravimetric technique was used to study sulfation kinetics and sulfation recycling. It was found that the Langmuir kinetic adsorption model described well the experimental data at the rapid sulfation region of the CuO/γ-Al2O3 sorbent. The adsorption activation energy was 19.98 kJ/mol and the pre-exponential factor was 9.97× 10^-5 s^-1.Pa^-1. The CuO/γ-Al2O3 sorbent has shown good performance on regeneration, but long sulfation time might cause the deactivation of the CuO/γ-Al2O3 sorbent. It was also seen that the sulfated γ-Al2O3 support could not be reduced at 400℃.

Recovery of Copper from Copper Sulfide Concentrate by Sulfation Roasting

Sulfation roasting was studied to extract copper from the copper sulfide concentrate. Sodium sulfite was added as sulfation agent to the copper sulfide concentrate during roasting in this study. Sulfur removal rate at different roasting temperatures was investigated, and the effects of roasting temperature, roasting time, and the amount of sodium sulfite on copper extraction were studied. Copper extraction higher than 96% was achieved at optimum roasting conditions.

Preparation of synthetic rutile via selective sulfation of ilmenite with(NH4)2SO4 followed by targeted removal of impurities

This paper describes a novel, facile chemical pathway for preparing synthetic rutile from ilmenite. The pathway consists of two primary units, i.e., selectively sulfating ilmenite, which was realized via roasting ilmenite with(NH_4)_2SO_4followed by selective thermal decomposition of the sulfated ilmenite, and targeted leaching of the impurities. The effects of the process parameters were systematically investigated. The results showed that the optimum sulfation conditions were a mass ratio of(NH_4)_2SO_4to ilmenite of 14, temperature of 360 °C, and time of 120 min with a sulfation ratio of ~ 95%. The optimum thermal decomposition conditions were480 °C in N_2 atmosphere, and nearly all Ti OSO_4 were decomposed with co-decomposition of Fe SO_4 of 23%. For acid leaching, the optimum conditions were 2.5 wt% HCl, 98 °C and 120 min. Under those conditions, 94.2% iron was removed with a Ti O_2 dissolution loss b 1%. For alkali leaching, 67% Si O_2 was removed in 5 wt% Na OH at102 °C for 1 h. A synthetic rutile with a Ti O_2 content N 92 wt% and total Mg O + Ca O b 1.5 wt% was obtained.Based on these results, a schematic flowsheet was proposed. Additionally, it was found that the decomposition of Fe SO_4 mixed with Ti OSO_4 under N_2was inhibited due to its oxidation to a higher thermal stability Fe_2(SO_4)_3by oxygen emitted from the decomposition of Ti OSO_4. At the same time, Ti OSO_4 decomposition was promoted due to the immediate in situ consumption of oxygen by Fe SO_4. The synergetic effect might be responsible for the enhanced selectivity of sulfated ilmenite thermal decomposition.

SULFATION OF PACHYMAN WITH CHLOROSULFONIC ACID USING THE IMPROVED WOLFROM METHOD

High purity polysaccharide of pachyman was isolated from the powder of Poria cocos sclerotium with an yield of 77.8%. The intrinsic viscosity of polysaccharide was found to be 78.95 mL/g in DMSO solution at 25℃. The isolated polysaccharide was reacted with chlorosulfonic acid to obtain pachyman sulfate using the improved Wolfrom method. The results of the orthogonality experiment on the sulfation reaction identified that the effectiveness of the reaction conditions on the degree of sulfation and the value of intrinsic viscosity is in the following order： molar ratio of chlorosulfonic acid to glucoside （3-5） 〉 reaction temperature （60-80℃） 〉 reaction time （1 2 h）, The kinetic studies of the pachyman sulfation indicated that the hydrolysis is accompanied with the sulfation process. The decrease in intrinsic viscosity of the sulfated pachyman is proportional to the increase in the degree of sulfation under the mild reaction conditions of 〈 80℃, chlorosulfonic acid/glucoside mole ratio 〈 5, and reaction time 〈 2 h. Beyond the above reaction conditions, excessive loss of --OH group occurs during hydrolysis. The NMR results indicated a complete sulfation on C-6 and a partial sulfation on the C-2 and C-4 of glucoside.

Sulfation Kinetics in the Preparation of Cellulose Sulfate

In the established apparatus, the conversion ratios of cellulose sulfation (X) under different sulfation conditions were measured. The range of temperature was from -5℃ to +5℃, and the H2SO4 concentration was from 3.1 mol·L-1 to 4.5mol·L-1. The experimental results were used for the establishment of the kinetic model for cellulose sulfation. With the model, X values and the yield of NaCS (Y) can be calculated, thus the reaction with respect to H2SO4 concentration is determined to be third order.

Sulfation of chondroitin and bile acids converges to antagonize Wnt/β-catenin signaling and inhibit APC deficiency-induced gut tumorigenesis

Sulfation is a crucial and prevalent conjugation reaction involved in cellular processes and mammalian physiology.3’-Phosphoadenosine 5’-phosphosulfate(PAPS)synthase 2(PAPSS2)is the primary enzyme to generate the universal sulfonate donor PAPS.The involvement of PAPSS2-mediated sulfation in adenomatous polyposis coli(APC)mutation-promoted colonic carcinogenesis has not been reported.Here,we showed that the expression of PAPSS2 was decreased in human colon tumors along with cancer stages,and the lower expression of PAPSS2 was correlated with poor prognosis in advanced colon cancer.Gut epithelial-specific heterozygous Apc deficient and Papss2-knockout(Apc^(Δgut-Het)Papss2^(Δgut))mice were created,and the phenotypes were compared to the spontaneous intestinal tumorigenesis of Apc^(Δgut-Het)mice.Apc^(Δgut-Het)Papss2^(Δgutmice) were more sensitive to gut tumorigenesis,which was mechanistically accounted for by the activation of Wnt/β-catenin signaling pathway due to the suppression of chondroitin sulfation and inhibition of the farnesoid X receptor(FXR)-transducin-like enhancer of split 3(TLE3)gene regulatory axis.Chondroitin sulfate supplementation in Apc^(Δgut-Het)Papss2^(Δgutmice) alleviated intestinal tumorigenesis.In summary,we have uncovered the protective role of PAPSS2-mediated chondroitin sulfation and bile acids-FXR-TLE3 activation in the prevention of gut carcinogenesis via the antagonization of Wnt/β-catenin signaling.Chondroitin sulfate may be explored as a therapeutic agent for Papss2 deficiency-associated colonic carcinogenesis.

Selective lithium recovery from black powder of spent lithiumion batteries via sulfation reaction:phase conversion and impurities influence

The aim of this study is to present a new understanding for the selective lithium recovery from spent lithium-ion batteries(LIBs)via sulfation roasting.The composition of roasting products and reaction behavior of impurity elements were analyzed through thermodynamic calculations.Then,the effects of sulfuric acid dosage,roasting temperature,roasting time,and impurity elements were assessed on the leaching efficiency of valuable metals.Characterization methods such as X-ray diffraction(XRD),scanning electron microscopy-energy dispersive spectroscopy(SEM-EDS),and X-ray photoelectron spectroscopy(XPS)were employed to analyze the phase transformation mechanism during roasting process.The results indicate that after sulfation roasting(n(H_(2)SO_(4)):n(Li)=0.5,550℃,2 h),94%lithium can be selectively recovered by water leaching and more than 95%Ni,Co,and Mn can be leached through acid leaching without the addition of reduction agent.During the sulfation roasting process,the lithium in LiNi_(x)Mn_(y)Co_zO_(2)is mainly converted to Li_(2)SO_(4),while the Ni,Co and Mn are first transformed to sulfate and then converted into oxide form.In addition,impurity elements such as Al and F will combine with lithium to form LiF and LiAlO_(2),which will reduce the leaching rate of lithium.These results provide a new understanding on the mechanisms of phase conversion during sulfation roasting and reveal the influence of impurity elements for the lithium recovery from spent LIBs.

Getting insights into gas-phase sulfation effect on catalytic performance of praseodymium oxides in NH_(3)-SCR of NO

Sulfation treatment has been widely used to promote the catalytic performance of ceria(CeO_(2))based catalysts for the selective catalytic reduction of NO by NH_(3)(NH_(3)-SCR of NO).Praseodymium oxide(PrO_(x)),another commonly used rare earth material with similar structural properties as CeO_(2),also shows satistactory redox properties due to the facile redox cycle of Pr^(3+)■Pr^(4+).In this work,gas phase sulfation treatment with varied duration was performed on PrO_(x) at 200℃,and the NH_(3)-SCR activity of sulfated PrO_(x) was evaluated.Based on the results of systematic characterizations(e.g.,N_(2)-physisorption,NH_(3) oxidation,NO oxidation,in situ diffuse Fourier transform infrared spectroscopy),it is revealed that the catalytic performance of sulfated PrO_(x)is highly dependent on the sulfation time(or the amount of sulfate species deposited on PrO_(x)),which has a significant impact on the competitive reaction between NH_(3) oxidation and NH_(3)-SCR of NO,thus determining the NH_(3)-SCR activity of PrO_(x).This work provides new insight into tuning the interaction between PrO_(x) surface and reactants(NO,NH_(3))via sulfation treatment,which cam guide the design and application of PrO_(x)based catalysts for NH_(3)-SCR of NO in the future.

Tyrosylprotein sulfotransferase suppresses ABA signaling via sulfation of SnRK2.2/2.3/2.6

Phytohormone abscisic acid(ABA)plays vital roles in stress tolerance,while long-term overactivation of ABA signaling suppresses plant growth and development.However,the braking mechanism of ABA responses is not clear.Protein tyrosine sulfation catalyzed by tyrosylprotein sulfotransferase(TPST)is a critical post-translational modification.Through genetic screening,we identified a tpst mutant in Arabidopsis that was hypersensitive to ABA.In-depth analysis revealed that TPST could interact with and sulfate SnRK2.2/2.3/2.6,which accelerated their degradation and weakened the ABA signaling.Taken together,these findings uncovered a novel mechanism of desensitizing ABA responses via protein sulfation.

Chemical protein synthesis elucidates key modulation mechanism of the tyrosine-O-sulfation in inducing strengthened inhibitory activity of hirudin

Tyrosine sulfation is an important post-translational modification that enhances the inhibitory activity of hirudin.Herein,we developed a facile synthetic strategy to afford the sulfated hirudins with up to three modifications and in multi-milligram scales,after a single HPLC purification step.Through these synthetic proteins,a novel type of modulation mechanism exhibited by tyrosine sulfation was proposed,which would help to delineate the structure-function relationships in other sulfated proteins and more importantly,to serve as a basis for the development of related antithrombotic agents.

Sulfation of the extracellular polysaccharide from the edible fungus Stropharia rugosoannulata with its antioxidant activity

An acidic extracellular polysaccharide(EPS)was gained from Stropharia rugosoannulata fermentation broth by the alcohol precipitate method.Sulfated derivative of EPS(S-EPS)was gained by chlorosulfonic acid-pyridine method and the conditions were as follows:pyridine as the reaction solvent,temperature 80°C,and reaction time 90 min.The chemical structure and chain conformation of EPS and S-EPS were characterized by FT-IR,NMR and size exclusion chromatography(SEC)coupled with multi-angle laser light scattering(MALLS)detection.FT-IR spectra indicated the sulfated group was linked to the polymer.The EPS mainly consists of mannose,glucose and glucuronic acid,and the glycosidic bond type is mainly(1→4)-linked and(1→6)-linked.C6 and C2 were substituted by sulfate groups.The EPS was degraded into smaller molecular weight(Mw)polysaccharides with the larger molecular size(Rg)after sulfation and S-EPS has better hydrophilicity.Moreover,the sulfated derivative S-EPS was found to have a better scavenging ability on hydroxyl radicals than EPS.It proved that the chemical modification of S.rugosoannulata polysaccharides by sulfation effectively enhanced their antioxidant activity.

Photobiomodulation inhibits the expression of chondroitin sulfate proteoglycans after spinal cord injury via the Sox9 pathway

Both glial cells and glia scar greatly affect the development of spinal cord injury and have become hot spots in research on spinal cord injury treatment.The cellular deposition of dense extracellular matrix proteins such as chondroitin sulfate proteoglycans inside and around the glial scar is known to affect axonal growth and be a major obstacle to autogenous repair.These proteins are thus candidate targets for spinal cord injury therapy.Our previous studies demonstrated that 810 nm photo biomodulation inhibited the formation of chondroitin sulfate proteoglycans after spinal cord injury and greatly improved motor function in model animals.However,the specific mechanism and potential targets involved remain to be clarified.In this study,to investigate the therapeutic effect of photo biomodulation,we established a mouse model of spinal cord injury by T9 clamping and irradiated the injury site at a power density of 50 mW/cm~2 for 50 minutes once a day for 7 consecutive days.We found that photobiomodulation greatly restored motor function in mice and down regulated chondroitin sulfate proteoglycan expression in the injured spinal cord.Bioinformatics analysis revealed that photobiomodulation inhibited the expression of proteoglycan-related genes induced by spinal cord injury,and versican,a type of proteoglycan,was one of the most markedly changed molecules.Immunofluorescence staining showed that after spinal cord injury,versican was present in astrocytes in spinal cord tissue.The expression of versican in primary astrocytes cultured in vitro increased after inflammation induction,whereas photobiomodulation inhibited the expression of ve rsican.Furthermore,we found that the increased levels of p-Smad3,p-P38 and p-Erk in inflammatory astrocytes were reduced after photobiomodulation treatment and after delivery of inhibitors including FR 180204,(E)-SIS3,and SB 202190.This suggests that Sma d 3/Sox9 and MAP K/Sox9 pathways may be involved in the effects of photobiomodulation.In summary,our findings show that photobiomodulation modulates the expression of chondroitin sulfate proteoglycans,and versican is one of the key target molecules of photo biomodulation.MAPK/Sox9 and Smad3/Sox9 pathways may play a role in the effects of photo biomodulation on chondroitin sulfate proteoglycan accumulation after spinal cord injury.