Production Practice of Solid Waste Desulfurizer Disposal in European Metallurgical Furnace

In order to realize the OY Smelting Furnace disposal of solid waste,municipal waste,form a model of steel enterprises and urban integration,through the production practice of smelting furnace,analyzes the mechanism of solid waste disposal,and proposed the disposal of solid waste desulfurization agent and disposal method:According to the theory to guide the actual production process,the test ton of iron with 10-15kg of desulfurizer in the production process does not affect the quality of molten iron and slag quality.

Efficient Absorptive Oxidation of H_(2)S Using a Fe(Ⅲ)-Cu(Ⅱ) Coupled DES (ChCl/EG) Desulfurizer

In this experiment,an EG/ChCl deep eutectic solvent(DES)was synthesized using choline chloride(ChCl)and ethylene glycol(EG)as the raw materials.The synthesized DES was characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis.The results demonstrate the successful synthesis of DES.A certain amount of FeCl_(3) and CuSO_(4) was added to the DES to promote the absorption of H_(2)S;thus,a Fe(Ⅲ)-Cu(Ⅱ)coupled DES desulfurization system was obtained.The effects of DES raw materials’ratio,FeCl_(3) concentration,water content,CuSO_(4) concentration,and reaction temperature on the desulfurization efficiency and the regeneration conditions were studied.The results show that ChCl/EG DES with a molar ratio of 1:2 has a better desulfurization effect,and the addition of an appropriate amount of water can effectively promote the dissolution of CuSO_(4) and the absorption of H_(2)S.An appropriate increase in reaction temperature and CuSO_(4) concentration would also promote the absorption of H_(2)S.When the concentration of CuSO_(4) in DES desulfurizer was 0.15 mol/L,the gas speed was 20 mL/min,and the sulfur capacity could reach 10.23 g/L.The desulfurizer could be regenerated by passing O_(2),and the desulfurization efficiency did not change much after repeated use of desulfurization-regeneration many times.The desulfurization product was characterized by XRD as rhombohedral sulfur.

Study on Desulfurization Efficiency and Products of Ce-Doped Nanosized ZnO Desulfurizer at Ambient Temperature

Ce-doped nanosized ZnO desulfurizer was prepared by homogeneous precipitation,and its desulfurization efficiency at ambient temperature was investigated through dynamic experiments.The results showed that the desulfurization activity of nanosized Ce-ZnO had improved greatly,compared to nanosized ZnO desulfurizer.Nanosized Ce-ZnO desulfurizer was characterized by XRD,TPD-MS,XPS,and TEM.The research results indicated that doping Ce decreased the particle size of the nanosized ZnO desulfurizer and ZnS was the principal desulfurization product.There were adsorption complexes of HS and S on the surface of desulfurizer as well.Only a small amount of vapor appeared in the tail gas on the condition of meeting the precision of desulfurization.

Preparation and Characterization of a New Desulfurizer and Its Performance on Removal of SO₂

Sulfur dioxide is one of the major pollutants resulting from fuel combustion. In this study, CaO and attapulgite were utilized as raw material for synthesizing CaO/attapulgite (CaO/ATP) desulfurizer. The physicochemical characteristics of CaO/ATP desulfurizer were evaluated by various techniques such as XRD, SEM, FT-IR. The performance of samples was studied in dynamic conditions. Major factors affecting on desulfurization such as weight ratio of CaO to total, types of modifiers, roasting time and temperature were investigated. The desulfurization agent synthesized under optimal synthesis conditions with CaO content of 30 wt% and NaOH modifier, and the desulfurization roasting time of 2 hours and roasting temperature of 600°C, exhibit sulfur tolerance of 10.15 wt%. This desulfurizer with excellent absorbency and catalysis of desulfurization, economical and?environment-friendly, could be especially useful in industrial applications.

Effect of relative humidity on the desulfurization performance of calcium-based desulfurizer

Low desulfurization efficiency impedes the wide application of dry desulfurization technology,which is a low-cost and simple process,and one significant solution is the development and manufacture of high-performance desulfurizers.In this study,firstly,a steam jet mill was used to digest quicklime;then,we utilized numerical simulation to study the flow field distribution and analyze the driving factors of quicklime digestion;and lastly,the desulfurization performance of the desulfurizer was evaluated under different relative humidities.The results show that the desulfurizer prepared via the steam jet mill had better apparent activity than traditional desulfurizers.Also,the entire jet flow field of the steam jet mill is in a supersonic and highly turbulent flow state,with high crushing intensity and good particle acceleration performance.Sufficient contact with the nascent surface maximizes the formation of slaked lime.The experiments demonstrated that the operating time with 100%desulfurization efficiency and the“break-through”time for the desulfurizer prepared via the steam jet mill is longer than that of traditional desulfurizers,and has significant advantages,especially at low flue gas relative humidity.Compared with traditional desulfurizers,the desulfurizer prepared via steam jet mill expands the range of acceptable flue gas temperature,and the failure temperature is 1.625 times that of traditional desulfurizers.This work breaks through the technical bottleneck of low dry desulfurization efficiency,which is an important step in pushing forward the application of dry desulfurization.

Synergistic catalysis of the N-hydroxyphthalimide on flower-like bimetallic metal-organic frameworks for boosting oxidative desulfurization

Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.

Few-layered hexagonal boron nitride nanosheets stabilized Pt NPs for oxidation promoted adsorptive desulfurization of fuel oil

A few-layered hexagonal boron nitride nanosheets stabilized platinum nanoparticles(Pt/h-BNNS)is engineered for oxidation-promoted adsorptive desulfurization(OPADS)of fuel oil.It was found that the few-layered structure and the defective sites of h-BNNS not only are beneficial to the stabilization of Pt NPs but also favor the adsorption of aromatic sulfides.By employing Pt/h-BNNS with a Pt loading amount of 1.19 wt%as the active adsorbent and air as an oxidant,a 98.0%sulfur removal over dibenzothiophene(DBT)is achieved along with a total conversion of the DBT to the corresponding sulfones(DBTO_(2)).Detailed experiments show that the excellent desulfurization activity originates from the few-layered structure of h-BNNS and the high catalytic activity of Pt NPs.In addition,the OPADS system with Pt/h-BNNS as the active adsorbent shows remarkable stability in desulfurization performance with the existence of different interferents such as olefin,and aromatic hydrocarbons.Besides,the Pt/h-BNNS can be recycled 12 times without a significant decrease in desulfurization performance.Also,a process flow diagram is proposed for deep desulfurization of fuel oil and recovery of high value-added products,which would promote the industrial application of such OPADS strategy.

Fabrication of Silane and Desulfurization Ash Composite Modified Polyurethane and Its Interfacial Binding Mechanism

Polyurethane/desulfurization ash(PU/DA)composites were synthesized using"one-pot method",with the incorporation of a silane coupling agent(KH550)as a"molecular bridge"to facilitate the integration of DA as hard segments into the PU molecular chain.The effects of DA content(φ)on the mechanical properties,thermal stability,and hydrophobicity of PU,both before and after the addition of KH550,were thoroughly examined.The results of microscopic mechanism analysis confirmed that KH550 chemically modified the surface of DA,facilitating its incorporation into the polyurethane molecular chain,thereby significantly enhancing the compatibility and dispersion of DA within the PU matrix.When the mass fraction of modified DA(MDA)reached 12%,the mechanical properties,thermal stability,and hydrophobicity of the composites were substantially improved,with the tensile strength reaching 14.9 MPa,and the contact angle measuring 100.6°.

Synthesis of boron nitride nanorod and its performance as a metalfree catalyst for oxidative desulfurization of diesel fuel

In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal efree catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by heating treatment at 900℃in nitrogen atmosphere that the characteristics of the sample were identified by the X-ray diffraction,Fourier-transform infrared spectroscopy,Raman spectroscopy,field emission scanning electron microscopy,transmission electron microscopy,atomic force microscopy,and N2 adsorptionedesorption isotherms.The results of structural and morphological analysis represented that BN has been successfully synthesized.The efficacy of the main operating parameters on the process was studied by using response surface methodology based on the BoxeBehnken design method.The prepared catalyst showed high efficiency in oxidative desulfurization of diesel fuel with initial sulfur content of 8040 mg·kg^(-1)S.From statistical analysis,a significant quadratic model was obtained to predict the sulfur removal as a function of efficient parameters.The maximum efficiency of 72.4%was achieved under optimized conditions at oxidant/sulfur molar ratio of 10.2,temperature of 71℃,reaction time of 113 min,and catalyst dosage of 0.36 g.Also,the reusability of the BN was studied,and the result showed little reduction in activity of the catalyst after 10 times regeneration.Moreover,a plausible mechanism was proposed for oxidation of sulfur compounds on the surface of the catalyst.The present study shows that BN materials can be selected as promising metal-free catalysts for desulfurization process.

Experimental Study on Deep Desulfurizer in LF Process

CaO-Al2O3-SiO2-CaF2-MgO was selected as the slag system for desulfurization in LF process.The reaction between steel and slag during desulfurization has been simulated by using Factsage software to study the influence of component on the sulfur distribution ratio.In order to research the influence of CaO content,aluminum powder content and its granularity on desulfurization,laboratory experiments have been carried out in a 200 kg inductive furnace.Results showed that the optimal composition of deep desulfurizer is wCaO=64% and aluminium powder 10% with a granularity of 30 μm.Industrial trials showed that the main composition range of final slag in LF process is wCaO=53.0%-57.0%,wAl2O3=23.4%-25.1%,wSiO2=8.1%-10.0%,and wCaF2=3.2%-4.7%.The sulfur mass percent in steel is lower than 0.0008% with a desulfurization rate above 89%.According to the result of industrial production,this desulfurizer could meet the production requirement for ultra-low sulfur steel,of which sulfur mass percent is under 0.0015%

Study of MgO-Based Desulfurizer in Hot Metal Desulfurization

This paper has investigated a new desulfurizer for iron and steel industry to make up the lackness of magnesium-based desulfurizer. In order to explore the desulfurization process of hot metal by the new desulfurizer, both the thermodynamics and experiments have been studied.. The results of thermodynamics indicated that, under the standard condition,the lowest reaction temperatures of MgO + C and MgO +Si were 1846℃ and 2132℃ and the pressure of Mg vapor at the hot metal temperature were 0.2-0.5kPa and 0.005-0.01kPa, respectively. In the case of reaction between MgO and Al, the calculated starting reaction temperature under standard condition was 1475 ℃, and the pressure of Mg vapor was distributed from 27 kPa to 45kPa at the hot metal temperature, showing that it was easy to happen the reaction of MgO+Al. The experimental results displayed that the desulfurization efficiency was only 42.31% by the desulfurizer of MgO and C, while the effect of MgO+ Al and MgO+ Al-Si was good, since the desulfurization efficiencies were above 85%, and the lowest sulfur content was below 40×10-6.

Integration of Desulfurization and Lithium-Sulfur Batteries Enabled by Amino-Functionalized Porous Carbon Nanofibers

Hydrogen sulfide(H_(2)S)is an industrial exhausted gas that is highly toxic to humans and the environment.Combining desulfurization and fabrication of cathode materials for lithium-sulfur batteries(LSBs)can solve this issue with a double benefit.Herein,the amino-functionalized lotus root-like carbon nanofibers(NH_(2)-PLCNFs)are prepared by the amination of electrospinning carbon nanofibers under dielectric barrier discharge plasma.Selective catalytic oxidation of H_(2)S to elemental sulfur(S)is achieved over the metalfree NH_(2)-PLCNFs catalyst,and the obtained composite S@NH_(2)-PLCNFs is further used as cathode in LSBs.NH_(2)-PLCNFs enable efficient desulfurization(removal capacity as high as 3.46 g H_(2)S g^(−1) catalyst)and strongly covalent stabilization of S on modified carbon nanofibers.LSBs equipped with S@NH_(2)-PLCNFs deliver a high specific capacity of 705.8 mA h g^(−1) at 1 C after 1000 cycles based on the spatial confinement and the covalent stabilization of electroactive materials on amino-functionalized porous carbon matrix.It is revealed that S@NH_(2)-PLCNFs obtained by this kind of chemical vapor deposition leads to a more homogeneous S distribution and superior electrochemical performance to the sample S/NH_(2)-PLCNF-M prepared by the traditional molten infusion.This work opens a new avenue for the combination of environment protection and energy storage.

Facile synthesis of efficient pentaethylenehexamine-phosphotungstic acid heterogeneous catalysts for oxidative desulfurization

The ultra-deep desulfurization of oil needs to be solved urgently due to various problems,including environmental pollution and environmental protection requirements.Oxidative desulfurization(ODS)was considered to be the most promising technology.The facile synthesis of highly efficient and stable HPW-based heterogeneous catalysts for oxidative desulfurization is still a challenging task.In this paper,pentamethylene hexamine(PEHA)and phosphotungstic acid(HPW)were combined by a simple one-step method to prepare a heterogeneous catalyst of PEHA-HPW for the production of ultra-deep desulfurization fuel oil.The composite material exhibited excellent catalytic activity and high recyclability,which could reach a 100% dibenzothiophene(DBT)removal rate in 30 min and be recycled at least 5 times.Experiments and DFT simulations were used to better examine the ODS mechanism of PEHA-HPW.It was proved that the rich amino groups on the surface of PEHA-HPW play a crucial role.This work provides a simple and feasible way for the manufacture of efficient HPW-based catalysts.

Progress in research of process intensification of spouted beds:A comprehensive review

The development of intensification technology for spouted beds has become a current research focus,and an effective way to improve the efficiency of spouted beds is to reform their structure.Although numerous studies have been conducted on conventional beds,there are few reviews on the comprehensive application of intensification technology for spouted beds.In this paper,we comprehensively review the role of intensification technology in spouted beds for use in hydrodynamics,drying,desulfurization,pyrolysis,coating,biomass and waste gasification,and biomass drying from the perspective of experiment and simulation.Finally,potential problems and challenges in current spouted-bed research are summarized.

Research on process modeling and simulation of spent lead paste desulfurization enhanced reactor

In the reaction process of carbonate desulfurization lead paste,the produced PbCO_(3) is easily wrapped in the outer periphery of PbSO_(4) to form a product layer,hindering the mass transfer process.Therefore,it is necessary to break the PbCO_(3) product layer.In this work,the rotor stator-reinforced reactor was selected as the enhanced desulfurization reactor for the purpose of breaking the PbCO_(3) product layer and promoting mass transfer.The breakage process of the PbCO_(3) product layer generated during the PbSO_(4) desulfurization was modeled.Computational fluid dynamics simulation to the rotation conditions was carried out to theoretically analyze the fluid flow characteristics of PbSO_(4) slurry and the wall shear stress affecting the breakage of PbCO_(3) product layer.By optimizing the rotation conditions,the distribution ratio of effective rotor wall shear stress range achieved 96.1%,and the stator wall shear stress range reached 99.15%under a rotation of 2000 r·min^(-1).The research work provides a reference for analysis of the mechanism of product layer breakage in the PbSO_(4) desulfurization process,and gives a clear and intuitive systematic study on the fluid flow characteristics and wall shear stress of the desulfurization reactor.

Encapsulation of ionic liquid, phosphotungstic acid inside the nanocages of MIL-101(Cr): Effective and reusable catalyst for efficient solvent-free oxidative desulfurization from fuel oil

Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.

Titanium-rich TS-1 zeolite for highly efficient oxidative desulfurization

The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.

New insights into the mechanism of reactive adsorption desulfurization on Ni/ZnO catalysts:Theoretical evidence showing the existence of interfacial sulfur transfer pathway and the essential role of hydrogen

As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.

Design and Development of Highly Efficient Ni/ZnO Catalysts Based on Semiconductor Metal Oxide Catalysis Theory

In the context of reactive adsorption desulfurization,the development of an efficient Ni/ZnO desulfurizer has attracted increasing attention.In the work reported here,a novel Ni/Mn-ZnO composite nanowire desulfurizer is designed on the basis of the catalytic theory of semiconductor metal oxides and the characteristics of one-dimensional nanomaterials.X-ray diffraction,scanning electron microscopy,N_(2) adsorption-desorption,and X-ray photoemission spectroscopy demonstrate that Mn doping changes the crystal structure and morphology of the Ni/ZnO desulfurizer,increases the number of quasi-free electrons in the ZnO,and promotes H_(2)S adsorption.The Ni/Mn-ZnO composite nanowire desulfurizer exhibits good desulfurization performance when used with gasoline as the raw material.

Fabrication of adsorbents with enhanced CuⅠ stability: Creating a superhydrophobic microenvironment through grafting octadecylamine

In atmospheric conditions, CuⅠis easily oxidized to CuⅡdue to the coexistence of moisture and oxygen.The poor oxidation inhibition of CuⅠrestricts the practical application of CuⅠ-containing materials.Herein we introduce an approach to construct a superhydrophobic microenvironment in CuⅠfunctionalized metal–organic frameworks by coordinatedly grafting organic amine compounds onto open metal sites(OMSs), which can hinder the accessibility of moisture to pores thereby enhancing the stability of CuⅠ. As a proof of concept, MIL-101(Cr) with abundant OMSs and octadecylamine(OA)with long hydrophobic alkyl groups are used as carrier and surface coating. As superhydrophobic porous materials, the resultant CuⅠM-OA exhibits improved CuⅠstability in addition to retaining high crystallinity and intact porosity while almost all CuⅠis oxidized in hydrophilic CuⅠM upon exposure in a humid atmosphere for 30 h. CuⅠM-OA owns excellent adsorption desulfurization performance(ADS) with regard to thiophene, benzothiophene, and 4,6-dimethyl dibenzothiophene. Even from hydrated fuel, the adsorption performance of CuⅠM-OA maintains well while the adsorption capacity of CuⅠM decreases to 7% after4 cycles. The remarkable moisture resistance, CuⅠstability, and high porosity make the current adsorbent CuⅠM-OA highly promising for the practical ADS process.