Advanced green refractory technologies for coke ovens at Baosteel

To construct world-class iron and steel enterprises, Baosteel has adopted a strategy of environmental management that emphasizes environmental protection in the low-carbon and ecological manufacturing of steel products. In recent years, Baosteel has developed a series of advanced green refractory technologies （including composite refractory precast blocks with a unique ceramic glaze, and high-thermal-conductivity/high-density silica brick） for use in Baosteel coke ovens. The results of these applications not only reduce production costs and increase production efficiency, but also facilitate clean production by coke ovens. Baosteel＇ s coke oven has become China＇ s leading example of the application of green refractories.

Damage Mechanism and Structure Analysis of Used Clay Checker Bricks for Regenerators of Coke Ovens

During long-term use,the clay checker bricks for regenerators of coke ovens on gas side react with the impurities containing Fe and K20,causing foaming,softening and deformation,which is not only related with the impurity content and properties of the clay checker bricks,but also related with the type and the composition of the dust in the gas.After long term use,the clay checker bricks of coke ovens on air side have relative lower impurities containing Fe and K20.The inferior clay checker bricks,with high impurity content and high porosity,are easy to pulverize and deteriorate due to the oxidationreduction reaction with the iron oxide and the gas.The gas quality shall be concerned for long service life of the coke oven regenerators.

On-site raw gas cut-off during the shut down of Baosteel phaseⅠcoke ovens

The preparation and implementation of raw coke oven gas cut-off, which was the key process involved with shutting down the Baosteel phase I coke ovens, were investigated, and the main technical points and countermeasures are presented.

Research and Application of Wear Resistant Refractories for Cooling Zone of Large Scale Coke Dry Quenching Ovens

In order to prolong the service life of the cooling zone of large scale coke dry quenching ovens,six kinds possible refractories for the cooling zone of large scale coke dry quenching ovens： SiC containing brick A,SiC containing brick B,mullite-andalusite brick,spinel containing brick,zirconia containing brick,corundum-mullite brick and grade B mullite brick,were analyzed in properties. It is found that the cooling zone lining adopting SiC containing bricks or mullite-andalusite bricks has much longer service life. Based on this,a new type of wear resistant brick was developed. The brick has a compressive strength of 135 MPa,a wear loss of 2. 10cm^3（only a quarter of that of the grade B mullite brick）,and a higher bulk density than the grade B mullite brick. The application of the brick in a 140t·h^（-1）coke dry quenching oven showed that it performed better than the grade B mullite brick. The cooling zone adopting the new bricks has a lower coke discharging temperature,which is beneficial to the enhancement of heat recovery efficiency and steam power generation.

Benchmark Dose Assessment for Coke Oven Emissions-Induced Mitochondrial DNA Copy Number Damage Effects

Objective The study aimed to estimate the benchmark dose(BMD)of coke oven emissions(COEs)exposure based on mitochondrial damage with the mitochondrial DNA copy number(mtDNAcn)as a biomarker.Methods A total of 782 subjects were recruited,including 238 controls and 544 exposed workers.The mtDNAcn of peripheral leukocytes was detected through the real-time fluorescence-based quantitative polymerase chain reaction.Three BMD approaches were used to calculate the BMD of COEs exposure based on the mitochondrial damage and its 95%confidence lower limit(BMDL).Results The mtDNAcn of the exposure group was lower than that of the control group(0.60±0.29 vs.1.03±0.31;P<0.001).A dose-response relationship was shown between the mtDNAcn damage and COEs.Using the Benchmark Dose Software,the occupational exposure limits(OELs)for COEs exposure in males was 0.00190 mg/m^(3).The OELs for COEs exposure using the BBMD were 0.00170 mg/m^(3)for the total population,0.00158 mg/m^(3)for males,and 0.00174 mg/m^(3)for females.In possible risk obtained from animal studies(PROAST),the OELs of the total population,males,and females were 0.00184,0.00178,and 0.00192 mg/m^(3),respectively.Conclusion Based on our conservative estimate,the BMDL of mitochondrial damage caused by COEs is0.002 mg/m^(3).This value will provide a benchmark for determining possible OELs.

Partial oxidation of simulated hot coke oven gas to syngas over Ru-Ni/Mg(Al)O catalyst in a ceramic membrane reactor

Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.

Perovskite-type oxygen-permeable membrane BaCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ) for partial oxidation of methane in coke oven gas to hydrogen

Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.

Performance of a tubular oxygen-permeable membrane reactor for partial oxidation of CH_4 in coke oven gas to syngas

A gas-tight BaCo 0.7 Fe 0.2 Nb 0.1 O 3-δ（BCFNO） tubular membrane was fabricated by hot pressure casting.And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to partial oxidation of CH4 in coke oven gas.At 875 ℃,95% of methane conversion,91% of H 2 and as high as 10 ml cm-2·min-1 of oxygen permeation flux were obtained.There was a good match in the coefficient of thermal expansion between Ag-based alloy and BCFNO membrane materials.The tubular BCFNO membrane reactor packed with Ni-based catalysts exhibited not only high activity but also good stability in hydrogen-enriched coke oven gas（COG） atmosphere.

Hydrogen production via chemical looping reforming of coke oven gas

Coke oven gas(COG)is one of the most important by-products in steel industry,and the conversion of COG to value-added products has attracted much attention from both economic and environmental views.In this work,we use the chemical looping reforming technology to produce pure H_(2) from COG.A series of La1-xSrxFeO_(3)(x?0,0.2,0.3,0.4,0.5,0.6)perovskite oxides were prepared as oxygen carriers for this purpose.The reduction behaviors of La1-xSrxFeO_(3) perovskite by different reducing gases(H_(2),CO,CH4 and the mixed gases)are investigated to discuss the competition effect of different components in COG for reacting with the oxygen carriers.The results show that reduction temperatures of H_(2) and CO are much lower than that of CH4,and high temperatures(>800℃)are requested for selective oxidation of methane to syngas.The co-existence of CO and H_(2) shows weak effect on the equilibrium of methane conversion at high temperatures,but the oxidation of methane to syngas can inhibit the consumption of CO and H_(2).The doping of suitable amounts of Sr in LaFeO_(3) perovskite(e.g.,La0.5Sr0.5FeO_(3))significantly promotes the activity for selective oxidation of methane to syngas and inhibits the formation of carbon deposition,obtaining both high methane conversion in the COG oxidation step and high hydrogen yield in the water splitting step.The La0.5Sr0.5FeO_(3) shows the highest methane conversion(67.82%),hydrogen yield(3.34 mmol g^(-1))and hydrogen purity(99.85%).The hydrogen yield in water splitting step is treble as high as the hydrogen consumption in reduction step.These results reveal that chemical looping reforming of COG to produce pure H_(2) is feasible,and an O_(2)-assistant chemical looping reforming process can further improves the redox stability of oxygen carrier.

Hydrogen production from simulated hot coke oven gas by catalytic reforming over Ni/Mg(Al)O catalysts

Hydrogen production by catalytic reforming of simulated hot coke oven gas （HCOG） with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg（Al）O catalysts. The catalysts were prepared by a homogeneous precipitation method using urea hydrolysis and characterized by ICE BET, XRD, TPR, TEM and TG. XRD showed that the hydrotalcite type precursor after calcination formed （Ni, Mg）Al2O4 spinel and Ni-Mg-O solid solution structure. TPR results suggested that the increase in Ni/Mg molar ratio gave rise to the decrease in the reduction temperature of Ni^2＋ to Ni^0 on Ni/Mg（Al）O catalysts. The reaction results indicated that toluene and CH4 could completely be converted to H2 and CO in the catalytic reforming of the simulated HCOG under atmospheric pressure and the amount of H2 in the reaction effluent gas was about 4 times more than that in original HCOG. The catalysts with lower Ni/Mg molar ratio showed better catalytic activity and resistance to coking, which may become promising catalysts in the catalytic reforming of HCOG.

Chinese Standard on Refractories——Silica Brick for Coke Oven

This standard specifies the classification,specification, test method, quality appraisal procedure,labeling, packing, transportation, storage and quality certification of silica brick for coke oven.

Microstructure Analysis of Used Silica Brick in Coke Oven of Meisteel

Microstructure analysis shows quartz remains more or less in used silica brick for coking chamber of coke oven, and quartz gradually becomes metastable cristobalite and then translates into tridymite in used brick for high temperature combustion chamber. Phase change of silica brick only limits to transformation of quartz and metastahie cristobalite. When finished, structure of silica brick tends to stable. Carbon sedimentates and graphitize. helping to protect the silica brick and improve heat conductivity of silica brick for coking chamber.

Development and Application of Zero Expansion Silica Brick for Hot Repairing of Coke Oven

In order to meet the needs of hot repairing technology of coke oven, the zero expansion, silica brick with super properties has been developed, and the problem of poor thermal stability of common silica brick has been over-comed . This product can be directly used after being rapidly heated after construction. At present, it has been applied in coke ovens in Italy and Baosteel.

Survey on State of Baosteel Phase One M-type Coke Oven and Practices

The phase one M-type coke oven in Baosteel was a large coke oven imported from Nippon Steel&Sumitomo Metal,which played an important role in the development of large-scaled coke ovens in China.By investigating the shutting down process and the damage process of M-type coke oven body in Baosteel,the damage of used refractories in different parts,including carbonation chamber,combustion chamber,oven top,regenerative chamber,rising pipe,flue pipe and so on,was investigated and analyzed,which laid a good foundation for further damage analysis of coke oven body and improvement of maintenance in daily production.

Feedback control strategy of longitudinal temperature and finished carbonization time for coke oven and its application

Based on the detailed analysis of the third coke oven in BaoSteel, a feedbackcontrol strategy of longitudinal temperature and finished carbonization time of coke ovens wasproposed and it was applied to the third coke oven in BaoSteel. As a result, the ratio of theinstance that the absolute deviation of the longitudinal temperature is within +- 7 deg C and thefinished carbonization time within +- 10 min is more than 80 percent, having acquired the patentsaving effect of an energy consumption lowered by 2.92 percent. At the same time, it can provide anexample for the same coke ovens inside and outside the nation.

Optimization and Simulation of Inclined Channel Area Lining for CDQ Ovens

The mechanical force borne by the lintel and“brackets”in the inclined channel area of CDQ and the thermal stress generated by the top-down temperature gradient were simulated by ANSYS software.The following conclusions are drawn.(1)The mechanical force has very mild effect on the damage of the“brackets”.(2)The temperature gradient caused by the uneven temperature distribution of CDQ oven is the key factor affecting the“bracket”damage.The different expansion of refractory materials in various parts results in the thermal stress concentration which tears the“brackets”.(3)The structure adjustment of the“brackets”has very little effect on the thermal stress distribution.(4)The multi-phase nitride bonded silicon carbide for CDQ can effectively alleviate the stress concentration at the“brackets”,realizing the long-life and stable operation.

Fireclay Brick and Semi-silica Brick for Coke Oven

1 Scope This standard specifies the technical requirements, test methods, quality appraisal procedure, packing, transportation, storage, and quality certificate of fireclay brick and semi-silica brick for coke oven.

Fluorite Ce_(0.8)Sm_(0.2)O_(2-δ) porous layer coating to enhance the oxygen permeation behavior of a BaCo_(0.7)Fe_(0.2)Nb_(0.1)O_(3-δ) mixed conductor

Fluorite Ce0.8Sm0.2O2-δ（SDC） nanopowder with a crystallite size of 15 nm was synthesized by a co-precipitation method. An SDC porous layer was coated onto a BaCo0.7Fe0.2Nb0.1O3-δ（BCFN） mixed conductor to improve its oxygen transport behavior. The results show that the SDC-coated BCFN membrane exhibits a remarkably higher oxygen permeation flux（JO2） than the uncoated BCFN in the partial oxidation of coke oven gas（COG）. The maximum JO2 value of the SDC-coated BCFN is 18.28 mL ·min^-1·cm^-2 under a COG/air flux of 177 mL ·min^-1/353 mL ·min^-1 at 875℃ when the thickness of the BCFN membrane is 1 mm; this JO2 value is 23% higher than that of the uncoated BCFN membrane. This enhancement is likely because of the higher oxygen ionic conductivity of SDC, which supplies oxygen vacancies and accelerates oxygen exchange on the membrane/coating layer/gas three-phase boundary.

Technology Progress of Refractories for Iron Making in China

This paper reviews the present development situation of refractories for iron making system in China, which includes blast furnace, hot blast stove and coke dry quenching, etc. Varieties and performances of refractories used by the top steel and iron groups such as Baosteel, Wuhan I＆S Group and Anshan I＆S Group for iron making were exemplified and concerned problems were analyzed, together with solutions and suggestions for future refractories R＆D work.