Metagenomic Insight Reveals the Microbial Structure and Function of the Full-Scale Coking Wastewater Treatment System:Gene-Based Nitrogen Removal

Microbial communities play crucial roles in pollutant removal and system stability in biological systems for coking wastewater(CWW)treatment,but a comprehensive understanding of their structure and functions is still lacking.A five month survey of four sequential bioreactors,anoxic 1/oxic 1/anoxic 2/oxic 2(A1/O1/A2/O2),was carried out in a full-scale CWW treatment system in China to elucidate operational performance and microbial ecology.The results showed that A1/O1/A2/O2 had excellent and stable performance for nitrogen removal.Both total nitrogen(TN;(17.38±6.89)mgL1)and ammonium-nitrogen(NH4 t-N;(2.10±1.34)mg·L^(-1))in the final biological effluent satisfied the Chinese national standards for CWW.Integrated analysis of 16S ribosome RNA(rRNA)sequencing and metagenomic sequencing showed that the bacterial communities and metagenomic function profiles of A1 and O1 shared similar functional structures,while those of A2 significantly varied from those of other bioreactors(p<0.05).The results indicated that microbial activity was strongly connected with activated sludge function.Nitrosospira,Nitrosomonas,and SM1A02 were responsible for nitrification during the primary anoxic-oxic(AO)stage and Azoarcus and Thauera acted as important denitrifiers in A2.Nitrogen cycling-related enzymes and genes work in the A1/O1/A2/O2 system.Moreover,the hao genes catalyzing hydroxylamine dehydrogenase(EC 1.7.2.6)and the napA and napB genes catalyzing nitrate reductase(EC 1.9.6.1)played important roles in the nitrification and denitrification processes in the primary and secondary AO stages,respectively.The mixed liquor suspended solids(MLSS)/total solids(TS),TN removal rate(RR),total organic carbon(TOC)(RR),and NH_(4)^(+)t-N(RR)were the most important environmental factors for regulating the structure of core bacterial genera and nitrogen-cycling genes.Proteobacteria were the potential main participants in nitrogen metabolism in the A1/O1/A2/O2 system for CWW treatment.This study provides an original and comprehensive understanding of the microbial community and functions at the gene level,which is crucial for the efficient and stable operation of the full-scale biological process for CWW treatment.

Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model

Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al_(2)O_(3) catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH_(4)/CO_(2) molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible.The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.

Combination of hydrotreating and delayed coking technologies for conversion of residue

Residue conversion by combining catalytic hydrotreating and delayed coking has been evaluated comparatively with both processes alone.Optimal operating conditions are defined to achieve the greatest economic benefit for upgrading an atmospheric residue from a heavy crude oil.A literature model was adapted to simulate the hydrotreating reactor,and for delayed coking,correlations reported in the literature were used.The results with both approaches were employed to calculate the techno-economic feasibility of the combined process scheme.The combination of hydrotreating and delayed coking presented an increase in light fractions of 29% and a reduction in coke production of 47.8%.Based on the calculated net benefit values,it was demonstrated that the combination of hydrotreating and delayed coking is technically and economically better than using each process alone,with highest benefit of 57.7 USD·m^(-3).

Coking of Pt/γ-Al_(2)O_(3) catalyst in landfill gas deoxygen and its effects on catalytic performance

Catalytic oxidation of CH_(4) has been proved to be an attractive option for landfill gas(LFG) upgrading.However, coking of catalysts in catalytic LFG deoxygen has been clearly observed in industrial applications. In this regard, it is necessary to investigate whether coke deposition originates from CH_(4) or volatile organic compounds present in LFG, and the influence of coke deposition on catalytic performance. Herein,we evaluate the LFG deoxygen on Pt/γ-Al_(2)O_(3) catalyst in simulated LFG(CH_(4), CO_(2), O_(2), N_(2)) and its co-feed with representative volatile organic compounds, ethylbenzene, toluene, benzene and cyclohexane. The results show that the coking of the catalyst is originated from volatile organic compounds rather than CH_(4). The Pt/γ-Al_(2)O_(3) catalyst does not deactivate during LFG deoxygen process, even significant amount of coke deposited, up to 18.15%(mass). Characterization analyses reveal that although coke deposition overall covers the catalyst surface, resulting in mesopores blockage and a reduced number of accessible Pt sites, however, the coke formed, H-rich carbonaceous components, behaves as counterpart for O_(2) elimination. Besides, the coke deposited is mainly filamentous. Thus, coke formation has little negative effect on the overall catalytic performance of Pt/γ-Al_(2)O_(3) catalyst ultimately. The results obtained in this work are helpful for the rational design of robust Pt based catalysts for LFG deoxygen without undue attention to their coking properties, and also favor the innovation of more attractive purification scheme configurations.

RESEARCH ON THE QUALITY PRICE RATIO OF COKING COAL

If assortment priee parity of Clase coking coal and its qtalty price danrcnee is nonreasonable, it deren't gulde in Anprotrig tbe quallry metaliurgical coking coal and may be influence theeconomic benefit of metallurgical enterprises. This paper propose the principles and mathematicmodel for determination aseortment party of clean cokingcoal and its quality difference of ash content in clean coking coal in order to urge wasbenes into producing superior clean coking cleal whichis under condition of consideration both interest waskeries and interest metallurgicai industry. It canbe used as a method in theory to make price strategies under condition of socialism maket economicfor washeries of clean coking coal

Adaptive State Feedback Predictive Control and Expert Control for a Delayed Coking Furnace

An adaptive state feedback predictive control （SFPC） scheme and an expert control scheme are presented and applied to the temperature control of a 1200 kt·a^-1 delayed coking furnace, which is the key equipment for the delayed coking process. Adaptive SFPC is used to improve the performance of temperature control in normal operation. A simplified nonlinear model on the basis of first principles of the furnace is developed to obtain a state space model by linearization. Taking advantage of the nonlinear model, an online model adapting method is presented to accommodate the dynamic change of process characteristics because of tube coking and load changes. To compensate the large inverse response of outlet temperature resulting from the sudden increase of injected steam of a particular velocity to tubes, a monitoring method and an expert control scheme based on heat balance calculation are proposed. Industrial implementation shows the effectiveness and feasibility of the proposed control strategy.

Confined Ni-In intermetallic alloy nanocatalyst with excellent coking resistance for methane dry reforming

Carbon dioxide and methane are two main greenhouse gases which are contributed to serious global warming.Fortunately,dry reforming of methane(DRM),a very important reaction developed decades ago,can convert these two major greenhouse gases into value-added syngas or hydrogen.The main problem retarding its industrialization is the seriously coking formation upon the nickel-based catalysts.Herein,a series of confined indium-nickel(In-Ni)intermetallic alloy nanocatalysts(In_(x)Ni@SiO_(2))have been prepared and displayed superior coking resistance for DRM reaction.The sample containing 0.5 wt.%of In loading(In_(0.5)Ni@SiO_(2))shows the best balance of carbon deposition resistance and DRM reactivity even after 430 h long term stability test.The boosted carbon resistance can be ascribed to the confinement of core–shell structure and to the transfer of electrons from Indium to Nickel in In-Ni intermetallic alloys due to the smaller electronegativity of In.Both the silica shell and the increase of electron cloud density on metallic Ni can weaken the ability of Ni to activate C–H bond and decrease the deep cracking process of methane.The reaction over the confined InNi intermetallic alloy nanocatalyst was conformed to the Langmuir-Hinshelwood(L-H)mechanism revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS).This work provides a guidance to design high performance coking resistance catalysts for methane dry reforming to efficiently utilize these two main greenhouse gases.

Steam reforming of acetic acid over Ni-Ba/Al2O3 catalysts:Impacts of barium addition on coking behaviors and formation of reaction intermediates

The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).

Pretreatment of coking wastewater using anaerobic sequencing batch reactor (ASBR)

A laboratory-scale anaerobic sequencing batch reactor (ASBR) was used to pretreat coking wastewater. Inoculated anaerobic granular biomass was acclimated for 225 d to the coking wastewater, and then the biochemical methane potential (BMP)of the coking wastewater in the acclimated granular biomass was measured. At the same time, some fundamental technological factors, such as the filling time and the reacting time ratio (tf/tr), the mixing intensity and the intermittent mixing mode, that affect anaerobic pretreatment of coking wastewater with ASBR, were evaluated through orthogonal tests. The COD removal efficiency reached 38％～50％ in the stable operation period with the organic loading rate of 0.37～0.54 kg COD/(m3.d) at the optimum conditions of tf/tr, the mixing intensity and the intermittent mixing mode. In addition, the biodegradability of coking wastewater distinctly increased after the pretreatment using ASBR. At the end of the experiment, the microorganism forms on the granulated sludge in the ASBR were observed using SEM (scanning electron microscope) and fluoroscope. The results showed that the dominant microorganism on the granular sludge was Methanosaeta instead of Methanosarcina dominated on the inoculated sludge.

Speciation and thermal transformation of sulfur forms in high-sulfur coal and its utilization in coal-blending coking process:A review

The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.

The Kinetics for Electrochemical Removal of Ammonia in Coking Wastewater

Electrochemical removal of ammonia is a new and effective method in coking wastewater.The reaction mechanism of ammonia removal was proved by stable polarization curve in this paper.First,the supposing of reaction steps of the electrode were proposed.And then reaction parameter of the electrode was measured by Tafel curve.Finally,the reaction mechanism was determined by quasi-equilibrium approach.The results showed that Cl2+H2O→HOCl+H++Cl was the rate-determining step,the calculated apparent transfer coefficient was uniform to the experimental value.

Advanced treatment of biologically pretreated coking wastewater by intensified zero-valent iron process(IZVI) combined with anaerobic filter and biological aerated filter(AF/BAF)

Experiments were conducted to investigate the behavior of the sequential system of intensified zero-valent iron process(IZVI) and anaerobic filter and biological aerated filter(AF/BAF) reactors for advanced treatment of biologically pretreated coking wastewater. Particular attention was paid to the performance of the integrated system for the removal of chemical oxygen demand(COD), ammonia nitrogen(NH3-N) and total nitrogen(TN). The average removal efficiencies of COD, NH3-N and TN were 76.28%, 96.76% and 59.97%, with the average effluent mass concentrations of 56, 0.53 and 18.83 mg/L, respectively, reaching the first grade of the national discharge standard. Moreover, the results of gas chromatography/mass spectrum(GC/MS) and gel permeation chromatography(GPC) analysis demonstrated that the refractory organic compounds with high relative molecular mass were partly removed in IZVI process by the function of oxidation-reduction, flocculation and adsorption which could also enhance the biodegradability of the system effluent. The removal efficiencies of NH3-N and TN were achieved mainly in the subsequent AF/BAF reactors by nitrification and denitrification. Overall, the results obtained show that the application of IZVI in combination with AF/BAF is a promising technology for advanced treatment of biologically pretreated coking wastewater.

Analysis and calculation model of energy consumption and product yields of delayed coking units

Delayed coking is an important process consumption and light oil yield are important factors used to convert heavy oils to light products. Energy for evaluating the delayed coking process. This paper analyzes the energy consumption and product yields of delayed coking units in China. The average energy consumption shows a decreasing trend in recent years. The energy consumption of different refineries varies greatly, with the average value of the highest energy consumption approximately twice that of the lowest energy consumption. The factors affecting both energy consumption and product yields were analyzed, and correlation models of energy consumption and product yields were established using a quadratic polynomial. The model coefficients were calculated through least square regression of collected industrial data of delayed coking units. Both models showed good calculation accuracy. The average absolute error of the energy consumption model was approximately 85 MJ/t, and that of the product yield model ranged from 1 wt% to 2.3 wt%. The model prediction showed that a large annual processing capacity and high load rate will result in a reduction in energy consumption.

Technology for Coking of Heavy Crude Oil with High Acid Number

Sudan Khartoum Refinery Co. has selected a unique route featuring delayed coking of crude in connection with the highly sour and high-calcium heavy crude extracted from Sudanese oil block No. 6.The crude oil after pretreatment for calcium removal is subjected to coking for removal of acids and metals with the coker products being further processed. The crude oil extracted from Sudanese oil block No. 6contains as high as 13 mg KOH/g of crude in addition to a calcium content of 1600 ppm. This article makes an analysis on problems related with the operation of commercial delayed coking unit for processing of highly sour crude and bring forth measures to solve these problems. The liquid yield resulted from coking of crude oil can reach 82m%, and the petroleum coke can meet the quality requirement for class 3B petroleum coke.

Degradation analysis of A^2/O combined with AgNO3 + K2FeO4 on coking wastewater

In this work, a coking wastewater was selected and a biochemical Az/O treatment device for fractional degradation was designed and employed. After each stage of the treatment, the products were analyzed through gas chromatography-mass spectroscopy （GC-MS） to determine their composition. Finally, AgNO3 ＋ K2FeO4 was used as an advanced deep catalytic oxidation treatment. It was concluded from the analysis that cyclic organics could be degraded and the chemical oxygen demand （COD） was controlled within 50 mg. L-1, in line with the target value, Meanwhile, the spectra obtained from the GC-MS were in accordance with the conclusions reached based on the COD. The research results showed that all hard-degradable organics in coking wastewater could be eliminated through the A2/O bio-membrane treatment and the advanced treatment of making use of K2FeO4 as an oxidant and Ag＋ as a catalyst, the catalytic efficiency with Ag＋ as a catalyst of K2FeO4 was very high. Ag＋ could evidently improve the oxidation capacity of K2FeO4 to wastewater in its short stability time, and this is an important innovation.

Preparation of CaO-containing carbon pellets from coking coal and calcium oxide:Effects of temperature,pore distribution and carbon structure on compressive strength in pyrolysis furnace

CaO-containing carbon pellets(CCCP)were successfully prepared from well-mixed coking coal(CC)and calcium oxide(CaO)and roasted at different pyrolysis temperatures.The effects of temperature,pore distribution,and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace(350-750℃).The results showed that as the roasting temperature increased,the compressive strength also increased and furthermore,structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures,thus forming high-ordered CC.Notably,the CCCP preheated at 750℃exhibited the highest compressive strength.A positive relationship between the compressive strength and pore-size homogeneity was established.A linear relationship between the com-pressive strength of the CCCP and the average stack height of CC was observed.Additionally,a four-stage caking mechanism was developed.

Preparation and coking properties of coal maceral concentrates

The concentrates with different maceral contents were obtained from Kailuan coking coals with different coal ranks(Ro;ranvarying from 0.88%to 1.73%)by float–sink separation in lab.Then these concentrates were characterized by proximate analysis,ultimate analysis,petrography analysis and coking index determination.The results show that the vitrinite is characterized as nature of lower carbon content,higher hydrogen content,higher volatile matter and stronger caking property compared to inertinite.The relationships between variation rate of volatile matter and maximum volatile matter and coal ranks are identified,and a linear model is developed for fast determination of the maceral contents.Compared to inertinite-rich concentrate,the blending ratio of vitrinite-rich concentrate is increased by 13%,which is considered to be a potential technique based on maceral separation for expanding the coking coal resources.

Performance and mechanism of solid waste coking sulfur paste modified asphalt mixture before and after curing

For the resource utilization of the solid waste coking sulfur paste and the improvement of performance of the asphalt mixture,a method for preparing modified asphalt mixture with coking sulfur paste modifier(CSPM)is herein proposed.Compared with the matrix asphalt mixture,the Marshall stability of the 30%CSPM modified asphalt mixture increased by 38.3%,the dynamic stability increased by nearly one time(reaching 1847.5 times/mm),the splitting strength ratio increased by 39.3%while the splitting tensile strength decreased by 11.7%.After curing,the performance of the CSPM modified asphalt mixture was further improved.The results show that CSPM improved the high temperature stability and water damage resistance of the asphalt mixture,and the low-temperature anti-cracking performance of that was slightly reduced.Chemical analysis of asphalt binders shows that a little sulfur reacted with asphalt to produce polysulfide compounds(R-Sx-R′),and a part of sulfur existed in the form of crystalline sulfur which was further increased after curing.The presence of crystalline sulfur as an inorganic filler is the key point for improving the high temperature stability and water resistance performance of modified asphalt mixture.

Effect of Hydrothermal Treatment on Suppressing Coking of ZSM-5 Zeolite during Methanol-to-Propylene Reaction

Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a temperature of 480 ℃; a methanol WHSV of 3 h-1; a methanol partial pressure of 30 k Pa; and a time on stream of 12 h, 24 h and 48 h, respectively. The BET parameters of catalysts and diffusion coefficients of toluene showed that there were two types of mesopores generated under different hydrothermal conditions. Mild temperature and moderate CAWF conditions led to external open mesopores which could be entered from the external surface of the zeolite, while a high temperature or a high CAWF condition resulted in the generation of macropores or internal isolated mesopores, which were occluded in the microporous matrix. The TGA results showed that catalyst with external open mesopores had good ability to resist coke accumulation and good performance on propylene selectivity, while the internal isolated mesopores did no contribute to the increased diffusivity of reactants and products.

Electrochemical treatment of COD in biologically pretreated coking wastewater using Ti/RuO2-IrO2 electrodes combined with modified coke

The electrochemical treatment of COD contained in biologically pretreated coking wastewater treated by a three-dimensional electrode system with modified coke as the particle electrode was investigated. And the electrochemical perromance of the coke modified with various active components was studied. The results show that the coke modified with Fe（NO3）2 has the lowest energy consumption and higher COD removal rate under the same condition, and the modified coke has better surface characteristics for the purpose of this study. In addition, the kinetic constant was also calculated. The study shows that the three-dimensional electrode system with Fe （NO3）z-modified coke can give a satisfactory solution in biologically pretreated coking wastewater.