Research into Technology of Bao Steel's Pickling Tension Leveler

According to the survey of Bao Steel's pickling tenstion leveler,the technology of the tension leveler is analysed systematically.In order to solve the problem which hinders the production,the given technological parameters of this leveler have been improved and good results achieved.

Two-stage treatment process of pickling wastewater in the cold-rolling production of stainless steel

Based on the characteristics of pickling wastewater in the cold-rolling production of stainless steel, a new processing route, featuring source sludge reduction, wastewater two-stage treatment, heavy metal-contained sludge and calcium salt sludge separating recovery, was proposed. As shown by the research results, after the two-stage process treatment, the effluent water can steadily reach the emission standards, the sludge yield can be decreased by more than 8% ; within the heavy metal-contained sludge, the recovery rates of Fc,Cr and Ni can either reach or surpass 95% ,and the total content ofF and S can drop to around 3%. Therefore,the sludge in the front part can be used as ferric dust. In the calcium salt sludge ,the recovery rate of F can either reach or surpass 85% ,and the total contents of Fe,Cr and Ni can fall below 0.5%. So the sludge in the rear part can be used as fluorgypsum or fluorite. Meanwhile,the results of the analysis on heavy metals leaching toxicity and morphologic distribution indicate that the two kinds of sectionalized sludge are not classified as hazardous wastes, which have a stable behavior and better utilization values compared with the former mixed- sludge.

Synthesis of Fe_3O_4 Magnetic Powder from Spent Pickling Liquors

Spent pickling liquors pose a serious environmental problem in most industrialized countries, mainly owing to their corrosive properties and their ferrous iron and hydrochloric acid content. In this paper, spent pickling liquor was used as an inexpensive raw material to prepare Fe304 magnetic powder via an oxidation method. Being able to recover the dissolved iron from spent pickling liquors would not only salvage a valuable material but also render the effluent environmentally benign. The structure of the Fe_3O_4 magnetic powder was characterized by X-ray diffraction. The morphology and size were characterized by scanning electron microscopy and transmission electron microscopy. Their magnetic properties were tested at room temperature by a vibrating sample magnetometer. In addition, the saturation magnetization of Fe_3 O_4 products can be further enhanced to 96.1 emu/g after purification.

Does acid pickling of Mg-Ca alloy enhance biomineralization?

The mechanical and physical properties of biodegradable magnesium(Mg)alloys make them suitable for temporary orthopaedic implants.The success of these alloys depends on their performance in the physiological environment.In the present work,surface modification of Mg-Ca binary alloy by acid pickling for better biomineralization and controlled biodegradation is explored.The corrosion rates of nitric and phosphoric acid treated samples were analysed by conducting electrochemical corrosion tests.In vitro degradation behaviour was studied using immersion test in simulated body fluid(SBF).The sample surfaces were characterized using scanning electron microscope(SEM),energy dispersive X-ray spectroscopy(EDS),Fourier transform infrared spectroscopy(FTIR)and X-ray photoelectron spectroscopy(XPS).It is seen that acid pickling leads to significant improvement in biomineralization and develop in situ calcium phosphate(Ca P)coating on the sample surfaces.In addition,the treated samples recorded a reduced degradation rate in the SBF compared to untreated samples.Thus,acid pickling is suggested as an effective surface treatment method to tailor the biomineralization and degradation behaviour of the Mg-Ca alloy in the physiological environment.

Innovative surfactant of Gemini-type for dissolution mitigation of steel in pickling HCl medium

A new surfactant of Gemini-type,N,N'-((phthylbis(oxy))bis(ethane-2,1-diyl))bis(N,N-dimethyldodecan-1-aminium bromide)is prepped&confirmed.The dissolution suppression impact of the new compound on steel is performed in 1 mol·L^(-1)HCl environment by means of chemical and electrochemical methods.The prepared surfactant is an agreeable dissolution inhibitor for steel.The mitigation efficacy rises with the quantity of the compound.The surfactant belongs to inhibitors of mixed-type.The adsorption of the synthesized compound followed the Langmuir's model.The negative magnitudes of bothΔG_(ads)^(θ) andΔH^(adsθ)indicate that the adsorption process proceeds from its own accord and exothermic.The mechanism of adsorption is elucidated by scanning microscopy.It is established that the transfer resistance(R_(ct))value rose,where the value of the phase element(CPE)reduced with the amount of synthesized inhibitor.According to the experimental data arrived by surface tension measurements,the prepared compound is a powerful active agent at the air/water boundary.

Macroscopic,thermodynamic,kinetic and microscopic study of nitric acid pickling of Elektron 21(EV31A)magnesium alloy

The study of pickling of the EL21T6 substrate in a nitric acid bath firstly provided knowledge of the influence of the different experimental parameters(concentration of acid,temperature and stirring of the solution)in relation to the etching rate.This experimental part led to the choice of standard pickling(T_(bath)=25℃,moderate stirring(250 rpm),[HNO_(3)]=1.20 mol/L,duration of 2 min)so as to obtain constant removal of material,even after several uses of the pickling bath.SEM observations also confirmed that in these operating conditions,pickling concerns both the grains of the matrix and the precipitates of type Mg3(Nd,Gd),leading to uniform removal of material from the surface.Working from a number of assumptions,thermodynamic and chemical kinetic studies then allowed a pickling mechanism to be proposed and led to obtaining values for the corresponding kinetic parameters(order of reaction,constant of mean rate,activation energy)to be obtained.

Mechanism underlying the formation of cloud-shaped defects in 304 stainless steel after hot-rolled annealing and pickling

It is highly imperative to understand the mechanism underlying the formation of cloud-shaped defects in stainless steel to reduce the defect incidences. This study investigated the defect microstructure by SEM, simulated pickling in the laboratory, and performed structure analysis of oxide scales after hot rolling. Results show that the cloud-shaped defects in 304 No. 1 surface （after hot-rolled annealing and pickling） cause the pickling chromatic aberration between the honeycomb-shaped grains of the Cr-depleted layer and the smooth grains of the stainless steel matrix, which is formed in the case of insufficient pickling. The chromatic aberration is related to the uneven oxide scales formed before pickling. With the improvement of pickling capacity, it is possible to completely pickle the Cr-depleted layer and eliminate the cloud-shaped defects.

Study on the simulated pickling of 443NT medium chrome ferritic stainless steel

The oxide scale structure of 443NT hot-rolled strips was analyzed. The pickling of 443NT stainless steel was simulated via the 6σ experimental design. The results indicate that parabolic relations exist between the pickling scores and some of the pickling influencing factors, such as the nitric acid density, the hydrofluoric acid density and the pickling temperature. Effective pickling of 443NT can be achieved by controlling the pickling processing parameters with the HNO3 density ranging from 80 g/L to 180 g/L ,the HF density from 20 g/L to 40 g/L and the pickling temperature from 45 ℃ to60 ℃.

A new acid pickling process for copper alloys

The cleaning process of removing oxides on the surface of copper alloy sheetswas investigated systematically. Through optimizing, a perfect process was selected that is fit forremoving oxides on the surface. By acid pickling, all kinds of copper oxides are removedcompletely, furthermore, no poisonous gases are given out and a smooth and clean surface of copperalloys is obtained. At present, the process is applied successfully in the copper-processingindustry.

Study on the Corrosion inhibitor and Fog Suppressor for Chemical Pickling of Iron and Steel

A new type of corrosion inhibitor and fog suppressor composed of Nitrogen-containing alkaloid,water-soluble butadiene lower polymer, and inorganic electrolyte has been investigated by gravimetric and electrochemical method. Effects or this chemicals on pickling rate and hydrogen penetration into iron and steel material in 50～150 g/L HCI or/and H2SO4 solutions at 20～70℃ temperature were examined. The amount of acid fog escaping from the surface of air-liquid was determined by chemical titration. The results indicate that the efficiency of inhibition and suppression depends on film properties by which mean a barrier film on the interface of bare mild steel/solution or an unsolvable liquid membrane as hydrophibic effect.In present work the film-forming mechanism by in situ and chemistry-mechanics effect is also discussed.

Analytical Method to Monitor Industrial Pickling Baths Initially Constituted by HF, HNO₃

The present study couples the acid/basis titration and the ICP analysis in order to monitor the concentrations of nitric and hydrofluoric acids, and presents into baths used to pickle alloys of titanium or stainless steel, largely employed in the aeronautic industry. The pickling of the alloys releases various metallic cations able to react with HF in order to lead to metal-fluoride complexes and free H+, the last being able to react with the basis. In this study, it was determined: the most significant correlations providing the number of the protons released by the complexation of the metallic cation by the fluoride. The proposed method based on: 1) these correlations;2) the titration pH = f(VKOH) curves;and 3) the content of metallic cations determined by ICP, enables the monitoring of the content of HNO3 and HF into the pickling bath. Assuming that one bath was used for one type of alloy (alloys of Titanium for example, or alloys of stainless steel), then the proposed method appears providing reliable concentration values of both acids as well as metallic cations.

New Development of Acid Regeneration in Steel Pickling Plants

For acid pickling heat treated mild steel and steel products, up to the middle of the last century, sulfuric acid was primarily in use, which has been replaced stepwise by hydrochloric acid since the sixties. During this time, the pickling of high alloyed steel with hydrofluoric acid or mixtures for hydrofluoric acid together with nitric acid has also been applied on industrial scale. The technologies used by several plant contractors hereby show considerable differences in their engineering. The study provides a survey of the progress in the state of art of regeneration technology as well as the use of different pickl.ing media in the form of a review on existing technologies as well as improvements done within the recent years in the area.

Novel coprecipitation-oxidation method for recovering iron from steel waste pickling liquor

Waste pickling liquors （WPLs） containing high concentrations of iron and acid are hazardous waste products from the steel pickling processes. A novel combined coprecipitation-oxidation method for iron recovery by Fe304 nanoparhcle＇ production from the WPLs was developed in this study. 2＋All oxidation-reduction potential monitoring method was developed for real-time control of the Fe2＋/Fe3＋ molar ratio. The key coprecipitation-oxidation parameters were determined using the orthogonal experimental design method. The use of promoters greatly improved the Fe3O4 nanoparticle crystallinity, size, magnetization, and dispersion. X-ray diffraction patterns showed that the produced Fe3O4. nanoparticles were single phase. The Fe3O4 nan oparticles were approximately spherical and slightly aggtomerated. Vibrating sample magnetometry showed that the Fe3O4 nanopahicles produced from the WPLs had good magnetic properties, with a saturation magnetization of 80.206 emu. g-1 and a remanence of 10.500 emu. g-1. The results show that this novel coprecipitation-oxidation method has great potential for recycling iron in WPLs.

Pyrometallurgical recycling of stainless steel pickling sludge: a review

Stainless steel pickling sludge (SSPS), generated from the lime neutralization process of spent pickling liquor, is classified as a hazardous waste consisting of abundant metals like Fe, Cr and Ni, and other elements like F, S and Na, etc. Rather than a common disposal in landfill, recovering these metals and other valuable components from SSPS can not only create economic benefits, but also eliminate its adverse impacts on human health and the environment. A review of the formation mechanism and basic properties of SSPS was made, and the technical features, advantages and limitations of a series of pyrometallurgical treatment processes were summarized. Based on these, the main challenges for recycling of SSPS through the existing techniques are demonstrated. The traditional pelletizing/sintering-blast furnace process can only be used as a partial solution. Direct use of SSPS as flux in an argon-oxygen decarburization converter or electric arc furnace is a promising way, but low S sludges are preferred. The STAR process shows excellent recovery for metals, but it also has a low tolerance to the S and F contents in SSPS. And theINMETCO process is highly flexible in treatment of various wastes, whereas it exhibits relatively low Cr recovery and produces poor-quality pig iron. In addition, the feasibility of the rotary kiln-electric furnace, solid -state reduction of chromite and reduction-magnetic separation processes requires further studies. An urgent task at present is to develop a system for scientific classification and separate collection of SSPS in terms of chemical composition, notably S and F contents.

Treatment method of hazardous pickling sludge by reusing as glass–ceramics nucleation agent

Heavy metal containing pickling sludge（PS） is one of the by-products of the stainless-steel-making industry,which has been considered hazardous due to contained chromium and nickel.Traditional methods of PS disposing are landfill and cement solidification.This research is aimed at disposing PS by solidification/stabilization and reusing it as a nucleation agent of glass–ceramics.The crystallization behavior and the properties of a glass in the CaO–MgO–SiO2–Al2O3 system were studied by considering PS as the nucleation agent.Experimental results confirm that introducing 14 wt% PS as the nucleation agent of glass–ceramics can decrease crystallization temperature by 110.8 °C,refine the grain size by forming isometric crystals with size of 2 lm,enhance Vickers hardness by 2690 MPa and decrease water absorption from（1.21 ± 0.10） wt% to（0.04 ± 0.01） wt%.Therefore,it is reasonable to conclude that PS can be utilized as a nucleation agent to improve the crystallization and mechanical properties of the glass–ceramics.The testing results of US EPA toxicity characteristic leaching procedure（TCLP）confirm the safety of this reusing method.

Desulfurization thermodynamics experiment of stainless steel pickling sludge

A technical idea of returning stainless steel pickling sludge to smelting process so as to recycle valuable metals of Fe, Cr, and Ni was proposed, expecting to realize sludge detoxification and resource utilization. Thermodynamics calculation showed that not only most valuable elements including Fe, Cr and Ni, but also the harmful element of sulfur in pickling sludge can be enriched into molten metal. As a result, a theoretical study on desulfurization thermodynamics of sludge pretreatment was conducted, and results indicated that complete desulfurization temperature of pure pickling sludge was above 1400℃. When 0.5-0.8% carbon was added as reducing agent, the complete desulfurization temperature was reduced to 1000℃ or below. Desulfurization roasting experiment indicated that desulfurization rate at 1400℃ under inert environment was 78.74% and maximum desulfurization rate at 1000℃ under reducing environment was 91.62%.

Chemical fixation of toxic metals in stainless steel pickling residue by Na2S·xH2O,FeSO4·6H2O and phosphoric acid for beneficial uses

The leaching concentrations of different metals in stainless steel pickling residue(SSPR)were determined and the toxic metals were treated using Na2 S·xH2 O,FeSO4·6 H2 O,and phosphoric acid.A modified European Community Bureau of Reference(BCR)sequential extraction was used to identify the speciation of the concerned metals.Results showed that SSPR contains a large amount of Ca(58.41%),Fe(29.44%),Cr(3.83%),Ni(2.94%),Mn(2.82%)and some of Al,Cu,Mg,Zn.Among them,Cr and Ni were the most toxic metals in SSPR,thus the raw SSPR falls into hazardous waste category due to the leaching amount of Cr.In addition,the leached Cr was identified as Cr6+(MgCr04)in the waste.BCR test revealed that risk assessment code(RAC)of Cr and Ni were 33.29%and 61.7%,indicating they posed"high"and"very high"risk to the environment,respectively.After fixing by Na2 S·xH2 O and FeSO4·6 H2 O,the leaching concentrations of Cr and Ni were less than 1.5 and 0.5 mg/L,respectively.After fixing by Na2 S·xH2 O and FeSO4·6 H2 O the tre ated SSPR can be safely reused as roadbed materials,concrete and cement aggregates.This study provides a useful implication in treatment and beneficial reuse of heavy metal-containing hazardous wastes.

Sequential separation of Cu(Ⅱ)/Ni(Ⅱ)/Fe(Ⅱ)from strong-acidic pickling wastewater with a two-stage process based on a bi-pyridine chelating resin

A self-synthesized bi-pyridine chelating resin(PAPY)could separate Cu(Ⅱ)/Ni(Ⅱ)/Fe(Ⅱ)sequentially from strong-acidic pickling wastewater by a two-stage p H-adjusted process,in which Cu(Ⅱ),Ni(Ⅱ),and Fe(Ⅱ)were successively preferred by PAPY.In the first stage(p H 1.0),the separation factor of Cu(Ⅱ)over Ni(Ⅱ)reached 61.43 in Cu(Ⅱ)-Ni(Ⅱ)-Fe(Ⅱ)systems.In the second stage(p H 2.0),the separation factor of Ni(Ⅱ)over Fe(Ⅱ)reached 92.82 in Ni(Ⅱ)-Fe(Ⅱ)systems.Emphasis was placed on the selective separation of Cu(Ⅱ)and Ni(Ⅱ)in the first-stage.The adsorption amounts of Cu(Ⅱ)onto PAPY were 1.2 mmol/g in the first stage,while those of Ni(Ⅱ)and Fe(Ⅱ)were lower than 0.3 mmol/g.Cu(Ⅱ)adsorption was hardly affected by Ni(Ⅱ)with the presence of dense Fe(Ⅱ),but Cu(Ⅱ)inhibited Ni(Ⅱ)adsorption strongly.Part of preloaded Ni(Ⅱ)could be replaced by Cu(Ⅱ)based on the replacement effect.Compared with the absence of Fe(Ⅱ),dense Fe(Ⅱ)could obviously enhance the separation of Cu(Ⅱ)-Ni(Ⅱ).More than 95.0%of Cu(Ⅱ)could be removed in the former 240 BV(BV for bed volume of the adsorbent)in the fixed-bed adsorption column process with the flow rate of 2.5 BV/h.As proved by X-ray photoelectron spectrometry(XPS)and density functional theory(DFT)analyses,Cu(Ⅱ)exerted a much stronger deprotonation and chelation ability toward PAPY than Ni(Ⅱ)and Fe(Ⅱ).Thus,the work shows a great potential in the separation and purification of heavy metal resources from strong-acidic pickling wastewaters.

Effect of humic acid and metal ions on the debromination of BDE209 by nZVM prepared from steel pickling waste liquor

As a promising in situ remediation technology, nanoscale zero-valent iron （nZVI） can remove polybromi- nated diphenyl ethers such as decabromodiphenyl ether （BDE209） effectively, However its use is limited by its high production cost. Using steel pickling waste liquor as a raw material to prepare nanoscale zero-valent metal （nZVM） can overcome this deficiency. It has been shown that humic acid and metal ions have the greatest influence on remediation. The results showed that nZVM and nZVI both can effectively remove BDE209 with little difference in their removal efficiencies, and humic acid inhibited the removal efficiency, whereas metal ions promoted it. The promoting effects followed the order Ni2＋ 〉 Cu2＋ 〉 Co2＋ and the cumulative effect of the two factors was a combination of the promoting and inhibitory individual effects. The major difference between nZVM and nZVI lies in their crystal form, as nZVI was found to be amorphous while that of nZVM was crystal. However, it was found that both nZVM and nZVI removed BDE209 with similar removal efficiencies. The effects and cumu- lative effects of humic acid and metal ions on nZVM and nZVI were very similar in terms of the efficiency of the BDE209 removal.

Surface processing for iron-based degradable alloys:A preliminary study on the importance of acid pickling

The formation of a heterogeneous oxidized layer,also called scale,on metallic surfaces is widely recognized as a rapid manufacturing event for metals and their alloys.Partial or total removal of the scale represents a mandatory integrated step for the industrial fabrication processes of medical devices.For biodegradable metals,acid pickling has already been reported as a preliminary surface preparation given further processes,such as electropolishing.Unfortunately,biodegradable medical prototypes presented discrepancies concerning acid pickling studies based on samples with less complex geometry(e.g.,non-uniform scale removal and rougher surface).Indeed,this translational knowledge lacks a detailed investigation on this process,deep characterization of treated surfaces properties,as well as a comprehensive discussion of the involved mechanisms.In this study,the effects of different acidic media(HCl,HNO_(3),H_(3)PO_(4),CH_(3)COOH,H_(2)SO_(4) and HF),maintained at different temperatures(21 and 60℃)for various exposition time(15-240 s),on the chemical composition and surface properties of a Fe-13Mn-1.2C biodegradable alloy were investigated.Changes in mass loss,morphology and wettability evidenced the combined effect of temperature and time for all conditions.Pickling in HCl and HF solutions favor mass loss(0.03-0.1 g/cm^(2))and effectively remove the initial scale.