Effect of integration of mechanical ball milling and flue gas desulfurization gypsum on dealkalization of bauxite residue

The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and microtopography.The results showed a significant decrease in Na_(2)O content(>30 wt.%)of FGD gypsum-treated bauxite residue after 30 min of mechanical ball milling.Mechanical ball milling resulted in differentiation of the elemental distribution,modification of the minerals in crystalline structure,and promotion in the dissolution of alkaline minerals,thus enhancing the acid neutralization capacity of bauxite residue.5 wt.%FGD gypsum combined with 30 min mechanical ball milling was optimal for the dealkalization of bauxite residue.

Experimental Studies on a Circulating Fluidized Bed for Flue Gas Desulfurization

The tests of flue gas desulfurization were carried out on a circulating fluidized bed reactor in which the flue gas had different velocities at different sections. The SO 2 removal efficiency could be as high as 80% when Ca/S molar ratio was 1 1 and a small amount of water was sprayed into the reactor by a two phase (gas liquid) system nozzle.

Experimental and mechanism studies on seawater flue gas desulfurization

Seawater flue gas desulfurization (Seawater FGD) process has a number of advantages, but the study on mechanism of seawater FGD is little. The effects of absorbing efficiency of SO 2 by the constant component and part of trace transition elements in seawater are studied by the experiment. The results indicate that the effect factors of absorption of SO 2 by seawater are alkaline, ion intensity, catalysis of Cl - and transition metal ions Fe 2+ , Mn 2+ . The degree of effect is alkaline > the catalysis of Cl -, Fe 2+ and Mn 2+ >ion intensity. The mechanisms of catalysis oxidation for S(IV) by Cl -, Fe 2+ and Mn 2+ are discussed. According to the results, some measures can be used to improve the capability of desulfurization.

Transformation of Flue-Gas-Desulfurization Gypsum to α-Hemihydrated Gypsum in Salt Solution at Atmospheric Pressure

Direct phase transformation of flue gas desulfurization gypsum in hot salt solution at atmospheric pres-sure was investigated.The effects of temperature,salt species,salt concentration,solids content,pH and modifier were examined.The crystals obtained under different conditions and solubility of calcium sulfate in contact with solid gypsum were also determined.α-Calcium sulfate hemihydrate crystals of stubby columnar shape and regular pentahedral sides were obtained under the following conditions：salt concentration 20%-30%,operation tempera-ture 95-100 °C,solids mass content in the slurry 10%-30% and neutral pH.Thermodynamic analysis revealed that phase transformation of calcium sulfate dihydrate to α-calcium sulfate hemihydrate occurs because of the difference in solubilities between the two solid gypsum phases in this system.

Calcium sulfate whisker prepared by flue gas desulfurization gypsum:A physical–chemical coupling production process

In this paper,the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects.Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution.A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed.Through the comparison of product morphology,the best grinding time was determined to be 3.5 h.The mechanism of desulfurization gypsum through physical–chemical coupling to reduce energy consumption was clarified.The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate.By calculating the conversion and crystallization rate of calcium sulfate whiskers,it was found that there were obvious"autocatalytic"kinetic characteristics during the crystallization process.

Promotion of conversion activity of flue gas desulfurization gypsum into α-hemihydrate gypsum by calcination-hydration treatment

The massive accumulation of flue gas desulfurization(FGD)gypsum produced in the wet limestone-gypsum flue gas desulfurization process not only encroaches on lands but also causes serious environmental pollution.The preparation ofα-hemihydrate gypsum(α-HH)is an important way to achieve high-value utilization of FGD gypsum.Although the glycerol-water solution approach can be used to produceα-HH from FGD gypsum under mild conditions,the transition is kinetically unfavorable in the mixed solution.Here,an easy pretreatment was used to activate FGD gypsum by calcination and hydration to readily complete the transition.The pretreatment deteriorated the crystallinity of FGD gypsum and caused it to form small irregular flaky crystals,which dramatically increased the specific surface area.Additionally,most of the organics adsorbed onto FGD gypsum surfaces were removed after pretreatment.The poor crystallinity,increased specific surface area,and elimination of organics adsorbed onto crystal surfaces effectively improved the conversion activity of FGD gypsum,thereby promoting dihydrate gypsum(DH)dissolution andα-HH nucleation.Overall,the phase transition of FGD gypsum toα-HH is facilitated.

Ternary System of Fe-based Ionic Liquid,Ethanol and Water for Wet Flue Gas Desulfurization

Fe-based ionic liquid （Fe-IL） was synthesized by mixing FeCl3·6H2O and 1-butyl-3-methylimidazolium chloride [Bmim]C1 in this paper. The phase diagram of a ternary Fe-IL, ethanol and water system was investigated to construct a ternary desulfurization solution for wet flue gas desulfurization. The effects of flow rate and concentration of SO2, reaction temperature, pH and Fe-IL fraction in aqueous desulfurization solution on the desulfiariza- tion efficiency were investigated. The results shows that the best composition of ternary desulfurization solution of Fe-IL, ethanol and water is 1 ： 1.5 ： 3 by volume ratio, and pH should be controlled at 2.0. Under such conditions, a desulfurization rate greater than 90% could be obtained. The product of sulfuric acid had inhibition effect on the wet desulfurization process. With applying this new ternary desulfurization solution, not only the catalyst Fe-IL can be recycled and reused, but also the product sulfuric acid can be separated directly from the ternary desulfurization system.

Applying ACF to Desulfurization Process from Flue Gas

Inasmuch as the status of environmental pollution caused by SO2 is more and more serious and the policy of environmental protection is executed more and more strictly, desulfu-rization from flue gas (FGD) is introduced to a wide-spread field of national economy. By a comparison with lime-limestone method, the application of adsorption method in FGD is more effective in desulfurization and more adapted to the situation of our country in respect of its more valuable byproduct. However, the technique of adsorption method is limited by the large amount of adsorbent used. In this paper, activated carbon fiber (ACF) is proposed as a new type of adsorbent to apply in FGD. A series of experiments have been made in order to compare the performances between ACF and granular activated carbon (GAC) which has been mostly used. Experiments show that under the same working conditions ACF's adsorption capacity is 16.6 times as high as that of GAC, mass loss rate is 1/12 of GAC's, desorption effciency of ACF can reach 99.9%. The theory of micropore adsorption dynamics is adopted to analyze the characteristics of both adsorbents. It is indicated that adsorbability and perfectibility of desorption are tightly related to the distribution of pores and the surface micromechanism of adsorbent surface. The accessibility of pores for specified adsorptive and the effects of capillary condensation are crucial factors to influence the process of FGD. According to the research of different adsorbents, conclu-sion can be drawn that ACF is a kind of good material with a strong selectivity for SO2. Compared with the traditional methods of FGD, the use of ACF can greatly economize the consumption of adsorbent and obviously reduce the introduction of new adsorbent, and at the same time keep down the equipment investment and operating cost.

Experimental Study on Refinery Gas Desulfurization Using Gas-Liquid Membrane Contactor

Gas-liquid contactors equipped with polytetrafluoroethylene （PTFE） or polypropylene （PP） hydrophobic membranes were applied for removal of sulfur dioxide from refinery gas. Pure water, NaOH solution and MDEA were adopted as the absorbents. The performance of the two kinds of membranes for separation of SO2 was evaluated in terms of the concentration of absorbent solution, the concentration of SO2, and the feed flow rate. The efficiency for removal of SO2 increased with an increasing absorbent concentration. Upon increasing the concentration of SO2 and the feed flow rate, the desulfurization efficiency was decreased.

Wet flue gas desulfurization performance of 330 MW coal-fired power unit based on computational fluid dynamics region identification of flow pattern and transfer process

Wet Flue Gas Desulfurization(WFGD)unit based upon spray scrubber has beenwidely employed to control SO_(2) emissions from flue gas in coal-fired power plant.To clarify the dependence of desulfurization performance on inter-phase transfer behaviors with non-ideal contacting patterns of flue gas and slurry droplets,three regions in spray scrubber are distinguished in terms of gas-slurry flow structures using CFD method in the Eulerian-Lagrangian framework.A comprehensive model is established by involving the transfer process between two phases and chemical reactions in aqueous phase,which is validatedwith the measured data froma WFGD scrubber of 330 MW coal-fired power unit.Numerical results show that the overall uniformity degree of flue gas in whole scrubber is largely determined by the force-balanced droplets in the middle part of scrubber,which is dominated by counter-current mode.Both momentum transfer behavior and SO_(2) chemical absorption process present the synchronicity with the evolution of gas-slurry flow pattern,whilst the heat transfer together with H_(2)O evaporation has little effect on overall absorption process.Three regions are firstly defined as Gas Inlet Region(GIR),Dominant Absorption Region(DAR)and Slurry Dispersed Region(SDR)from the bottom to top of scrubber.SO_(2) is mainly scrubbed in DAR,which provides much more intensive interaction between two phases compared to GIR or SDR.A better understanding of the desulfurization process is obtained from the fundamental relationship between transport phenomena and chemical reactions based upon the complicated hydrodynamics of gas-slurry two-phase flow,which should be useful for designing and optimizing the scrubber in coal-fired power unit.

Influence of Thermally Treated Flue Gas Desulfurization(FGD) Gypsum on Performance of the Slag Powder Concrete

The feasibility of flue gas desulphurization （FGD） as concrete admixture was studied. A combined concrete admixture of the thermally-treated FGD gypsum and slag powder was explored. The FGD gypsum was roasted at 200℃ for 60 min and then mixed with the slag powder to form FGD gypsum-slag powder combined admixture in which the SO3 content was 3.5wt%. Cement was partially and equivalently replaced by slag powder alone or FGD gypsum-slag powder, at concentration of 25wt%, 40wt%, and 50wt%, respectively. The setting times, hydration products, total porosity and pore size distributions of the paste were determined. The compressive strength and drying shrinkage of cement mortar and concrete were also tested. The experimental results show that, in the presence of FGD gypsum, the setting times are much slower than those of pastes in the absence of FGD gypsum. The combination of FGD gypsum and slag powder provides synergistic benefits above that of slag powder alone. The addition of FGD gypsum provides benefit by promoting ettringite formation and forms a compact microstructure, increasing the compressive strength and reduces the drying shrinkage of cement mortar and concrete.

Effect of binder on the properties of iron oxide sorbent for hot gas desulfurization

The most difficult problem in hot gas desulfurization in Integrated Coal Gasification Combined Cycle （IGCC） is the pulverization of sulfur removal sorbents.Appropriate binders for hot gas sulfur removal sorbents can solve the pulverization problem.In this paper,six sorbents with binders of different argillaceous minerals were prepared by mechanical mixing method.Desulfurization behavior for hot gas desulfurization sorbents was investigated in a fixed-bed reactor.Result showed that sorbent NTKW2 with binder of clay had a better sulfidation performance.NTKW2 had a more stable performance than other sorbents in the continuous sulfidation-regeneration cycles.Sulfur capacity of sorbent remained the same in each cycle.The desulfurization efficiency and mechanical strength of NTKW2 were the best among the tested sorbents.The behavior of NTKW2 at different temperatures showed different performances,and the best reaction temperature was 550 ℃.Higher heat stability,sulfur capacity and desulfurization efficiency were found on NTKW2 in six continuous sulfidation-regeneration cycles.

Practice of flue gas desulfurization application technology in Baosteel No.3 Sinter Plant

With the enhancement of domestic steel production capacity ,iron and steel enterprises have become one major source of SO2 emissions especially in the sintering process. Based on its own characteristics and combined with the experience of desulfurization, Baosteel No. 3 Sinter Plant has independently developed the gas spout-swriling limestonegypsum desulfurization technology, which includes processes, controls and equipments. The theory, process and control of the sintering desulfurization systems are described in this study. Through process monitoring, control and adjustment of operating parameters, the new desulfurization system fit in with the original sintering system. And the quality of the gypsum products is stable, which can be reused as by-product. This method can not only significantly reduce SO2 emissions,but also effectively reduce the cost of desulfurization.

DEVELOPMENT OF SMOVEN PROCESS FOR HOT GAS DESULFURIZATION

The Beijing Research lnstitute of Coal Chemistry (BRICC) is developing the SMOVEN process for hot gas desulfurization. The SMOVEN process features sulfidation in an entrained bed,regeneration in a low velocity fluid bed or a moving bed with oxygen and sorbent circuIation con-trolled by gas stream. A series of tests on the bench scale unit and the continuous process devel-opment unit were carried out. The regenerable metal oxide sorbents were adopted for the sulfur-related components removing from coal gas at the temperature of 550-650℃. A fluidized bed gasifier of 100 mm (id) generated coal gas for tests. The principle of SMOVEN process has been positively verified.

Experimental study on SO_2 recovery using a sodium-zinc sorbent based flue gas desulfurization technology

A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.

Cold-modeling study of a circulating fluidized bed reactor for flue gas desulfurization (FGD)

Short residence time of the sorbent in the gas stream and formation of a dense layer of reaction product surrounding its surface influence the sulfur removal efficiency. A practical means of improving the process performance is to employ fluidized bed reaction in replacement of entrained bed reaction on normally used in cool side desulfurizaiton. This paper describes cold modeling study of a circulating fluidized bed reactor. Several aspects of the problem are discussed: fluidization behavior of CaO, attrition of the sorbent and solids entrainment from the fluidized bed. Mechanisms and key controlling parameters are identified, and an integral model based on rate of attrition and mass balance is developed for predicting steady state mass flows and particle size distributions of the system. A process flow scheme is finally presented for conducting desulfurization tests in the second stage of the study.

Research on improvement in Zn-based sorbent for hot gas desulfurization

Two Zn-based sorbents, L-991 and L-992 used for hot gas desulfurization (HGD) were introduced. Zn/Ti ratio of the two sorbent was 1:1 and 2:3 resptively and a certain proportion of Cu and Mn metal oxide were added into L-992, which provided better performance than L-991 in aspects of suitable work temperature, sulfur capacity and agglomeration on the surface of sorbent particles. The evaluation tests were done on both sorbents include multi cycles tests. ARD and SEM analysis were done on fresh and post tests sorbent. During continuous sulfidation/regeneration, the H2S concentra- tion can be reduced from about 10 g/m3 to less than 20 mg/m3, the H2S removal effi- ciency >99 %.

Liming Characteristics of a High-Calcium Dry Flue Gas Desulfurization By-Product and a Class-C Fly Ash

Due to coal’s availability and low cost, coal combustion continues to be the United States’ primary energy source. However, coal combustion produces large quantities of waste material. Some coal combustion by-products (CCBs) have chemical and physical characteristics that make them potentially useful as soil amendments. The objectives of this study were to characterize a relatively new, high-calcium dry flue gas desulfurization (DFGD) by-product and compare its agronomic liming potential to a Class-C fly ash (FA) and reagent-grade calcium carbonate (CaCO3). Calcium car-bonate equivalence (CCE), degree of fineness (DOF), and effective neutralizing value (ENV) for each CCB were determined using standard methods. The CCBs and CaCO3 were also incubated with an acidic (~4.5) clay sub-soil at application rates equiva-lent to 0, 0.5, 1, and 2 times the soil’s lime requirement and compared to an una-mended control. Soil pH was then measured periodically during a 40-day incubation. The ENV of 79.4% for the DFGD by-product and 57.3% for the FA were comparable to those of commercially available liming materials, but were significantly lower (P < 0.05) than that of reagent-grade CaCO3. After 40 days of incubation at the 0.5× ap-plication rate, both CCBs raised the pH of the clay soil to only 5.0, while the CaCO3 raised the pH to 6.5. After 40 days at the 1× rate, all three materials had raised the soil pH to between 6.5 and 7.0, although the FA increased the soil pH more slowly than did the other two materials. At the 2× rate, both CCBs increased the soil pH to between 7.5 and 8.0, while the CaCO3 increased the soil pH to only 7.0. Both CCBs appear to be useful as soil liming materials, although care should be taken to avoid over-application, as this may make the soil too alkaline for optimum plant growth.

Fluoride Ion Adsorption Effect and Adsorption Mechanism of Self-Supported Adsorbent Materials Based on Desulfurization Gypsum-Aluminate Cement

The adsorption method has the advantages of low cost,high efficiency,and environmental friendliness in treating fluorinated wastewater,and the adsorbent material is the key.This study combines the inherent anion-exchange adsorption properties of layered double hydroxides(LDHs).Self-supported porous adsorbent materials loaded with AFm and AFt were prepared from a composite cementitious system consisting of calcium aluminate cement(CAC)and flue gas desulfurization gypsum(FGDG)by chemical foaming technique.The mineral composition of the adsorbent material was characterized by X-ray diffraction(XRD)and Scanning electron microscopy(SEM).Through the static adsorption experiment,the adsorption effect of the mineral composition of the adsorbent on fluoride ions was deeply analyzed,and the adsorption mechanism was revealed.XRD and SEM showed that the main hydration phases of the composite cementitious system consisting of CAC and FGDG are AFm,AFt,AH_(3),and CaSO_(4)·2H_(2)O.FGDG accelerates the hydration process of CAC and inhibits the transformation of AFt to AFm.The AFt content increased,and the AFm content decreased or even disappeared as the amount of FGDG increased.Static adsorption experiment results showed that AFm and AFt in adsorbent materials could significantly enhance the adsorption of fluoride ions.The adsorption of F^(−)in aqueous solution by PAG tends more towards monolayer adsorption with a theoretical maximum capacity of 108.70 mg/g and is similar to the measured value of 112.77 mg/g.