Efficacy of Ca/ZSM-5 zeolites derived from precipitated calcium carbonate in the methanol-to-olefin process

In the context of heightened environmental consciousness and the growing demand for light olefins,this study explores the promising future prospects for their sustainable production from renewable resources.Light olefins(especially propylene)are a pivotal constituent of the petrochemical industry,and their demand is poised for steady growth driven by various sectors(e.g.,electric mobility,consumer goods and packaging industries),which should not rely solely on traditional petroleum-led routes.Therefore,sustainable pathways,such as the methanol-to-olefin(MTO)process catalyzed by zeolites,are gaining attention.Intending to couple the future olefin demands with the concept of a"methanol economy",this study investigates the synthesis of hierarchical Ca/ZSM-5 zeolites using a cost-effective approach involving Precipitated Calcium Carbonate(PCC)as a hard template,leading to superior catalytic performance.Comprehensive characterization techniques are employed to elucidate the cata-lyst's properties,highlighting the dual importance of mesoporosity and calcium species in optimizing its per-formance.Operando spectroscopy provides in-depth insights into its enhanced anti-coking characteristics.This research contributes to expanding the catalyst toolkit for zeolite-catalyzed MTO processes,focusing on propylene production,thereby addressing the increasing demand for light olefins while promoting sustainability and circular economy principles.

Agglomeration Mechanisms and Kinetics during the Carbonation of a Suspension of Lime in a Pilot Batch Reactor

The reaction studied in this work is the synthesis of nanometric size calcium carbonate particles by carbonation of a suspension of lime, which represents the most common industrial route. It consists in bubbling carbon dioxide in a suspension of lime to obtain precipitated calcium carbonate (PCC). PCC is a mineral filler with various applications: sealants, paints, paper, ink, pharmacy, cosmetics, food etc. However, there is a challenge related to the synthesis and the use of this precipitate: the agglomeration of the monoparticles. The aim of this work is then to understand the mechanisms of this phenomenon and to study its kinetics to improve the run of the process and the control of its impact on the final product. Experiments realized with a high concentration in sodium chloride (2 M) showed that the modification of the electrostatic environment did not change the particle size distribution and the morphology of the agglomerates. This indicates that the electrostatic interactions are not responsible for the agglomeration but the formation of crystalline bridges induced by the crystal growth. Thus, thanks to an agglomeration model including the crystal growth rate, the agglomeration kernel β and the agglomeration constant β0 can be determined using a mathematical treatment of the experimental particle size distributions. Finally, by varying the experimental conditions, it appears that the agglomeration constant increases with the temperature whereas there is an optimal value regarding the shear rate.

Separation of manganese from calcium and magnesium in sulfate solutions via carbonate precipitation

The separation of manganese from sulfate solutions containing 14.59 g/L Mn2+, 1.89 g/L Mg2+ and 1.54 g/L Ca2+ was preformed successfully by carbonate precipitation. The results of thermodynamic analysis and tests indicate that carbonate precipitation holds better selectivity for manganese over magnesium than hydroxide precipitation and the feeding method is the most critical factor for minimizing the co-precipitation of calcium and magnesium. Furthermore, with adding MnSO4 solution to NH4HCO3 solution, the effects of the initial NH4HCO3 concentration, NH4HCO3 amount, solution pH value, reaction temperature and time on carbonate precipitation were evaluated and the optimum precipitation conditions were obtained. Under the optimum conditions, the precipitation rates of Mn2+, Ca2+ and Mg2+ are 99.75%, 5.62% and 1.43%, respectively. Moreover, the prepared manganese carbonate was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDX). The results demonstrate that the product can be indexed to the rhombohedral structure of MnCO3.

Experimental study on mitigating wind erosion of calcareous desert sand using spray method for microbially induced calcium carbonate precipitation

Wind erosion is one of the significant natural calamities worldwide, which degrades around one-third of global land. The eroded and suspended soil particles in the environment may cause health hazards, i.e.allergies and respiratory diseases, due to the presence of harmful contaminants, bacteria, and pollens.The present study evaluates the feasibility of microbially induced calcium carbonate precipitation(MICP)technique to mitigate wind-induced erosion of calcareous desert sand(Thar desert of Rajasthan province in India). The temperature during biotreatment was kept at 36℃ to stimulate the average temperature of the Thar desert. The spray method was used for bioaugmentation of Sporosarcina(S.) pasteurii and further treatment using chemical solutions. The chemical solution of 0.25 pore volume was sprayed continuously up to 5 d, 10 d, 15 d, and 20 d, using two different concentration ratios of urea and calcium chloride dihydrate viz 2:1 and 1:1. The biotreated samples were subjected to erosion testing(in the wind tunnel) at different wind speeds of 10 m/s, 20 m/s, and 30 m/s. The unconfined compressive strength of the biocemented crust was measured using a pocket penetrometer. The variation in calcite precipitation and microstructure(including the presence of crystalline minerals) of untreated as well as biotreated sand samples were determined through calcimeter, scanning electron microscope(SEM), and energydispersive X-ray spectroscope(EDX). The results demonstrated that the erosion of untreated sand increases with an increase in wind speeds. When compared to untreated sand, a lower erosion was observed in all biocemented sand samples, irrespective of treatment condition and wind speed. It was observed that the sample treated with 1:1 cementation solution for up to 5 d, was found to effectively resist erosion at a wind speed of 10 m/s. Moreover, a significant erosion resistance was ascertained in15 d and 20 d treated samples at higher wind speeds. The calcite content percentage, thickness of crust,bulk density, and surface strength of biocemented sand were enhanced with the increase in treatment duration. The 1:1 concentration ratio of cementation solution was found effective in improving crust thickness and surface strength as compared to 2:1 concentration ratio of cementation solution. The calcite crystals formation was observed in SEM analysis and calcium peaks were observed in EDX analysis for biotreated sand.

Preparation and Characterization of Three-dimensional Chrysanthemun Flower-like Calcium Carbonate

Calcium carbonate with three-dimensional chrysanthemun flower-like structure was successfully prepared from calcium chloride and sodium carbonate ethanol/water mixed solution by a simple precipitation method,using trisodium citrate as crystal modifier.The experimental results show that the three-dimensional structure of chrysanthemun flower-like calcium carbonate is built up with several symmetrical micrometer multi-layer petals arranged around the multi-layer pancake-liked center,and the micrometer center and petals are assemblied by a large number of nanometer spherical particles with size 10-20 nm.It is found that the amount of trisodium citrate,the ethanol volume content has an important influence on the formation of this morphology.A possible mechanism is proposed to explain the formation of three-dimensional chrysanthemun flower-like calcium carbonate according the results.Scanning electron microscopy（SEM）,X-ray powder diffraction（XRD）,flourier transform infrared spectroscopy（FT-IR）,thermogravimety analysis（TG）,transmission electron microscopy（TEM） equipped with energy-dispersive X-ray（EDX）,and selected area electron diffraction（SAED） were used to characterize the crystals.

The Thermal Decomposition of Calcium Carbonate

The thermogravimetry(TG) and derivative thermogravimetry(DTG) curves of the thermal decomposition reaction of calcium carbonate have been measured at five different heating rates. The kinetic parameters and the reaction mechanism of the reaction were evaluated from analysis of the TG and DTG curves by using the Ozawa method, the combined integral and differential methods and the reduced equations derived by us.

Field trial on use of soybean crude extract for carbonate precipitation and wind erosion control of sandy soil

Wind erosion is a major cause of land desertification and sandstorm formation in arid and semi-arid areas.The objective of this study was to evaluate the potential of soybeans crude extract induced calcium carbonate precipitation(SICP)on reducing wind erosion risk of sandy soil.Field tests were carried out in Ulan Buh Desert,Ningxia Hui Autonomous Region,China.Results showed that the SICP method could significantly enhance the surface strength and wind erosion resistance of the topsoil.The optimal cementation solution(urea-CaCl2)concentration and spraying volume,according to experiments conducted on sandy land,were 0.2 mol/L and 4 L/m^2,respectively.Under this condition,the CaCO3 content was approximately 0.45%,the surface strength of sandy soil could reach 306.2 kPa,and the depth of wind erosion was approximately zero,after 30 d completion of SICP treatment.Soil surface strength declined with the increase of time,and long-term sand fixation effects of SICP treatment varied depending on topography.Whereas wind erosion in the top area of the windward slope was remarkable,sandy soils on the bottom area of the windward slope still maintained a relatively high level of surface strength and a low degree of wind erosion 12 month after SICP treatment.Scanning electron microscopy(SEM)tests with energy dispersive X-ray(EDX)confirmed the precipitation of CaCO3 and its bridge effect.These findings suggested that the SICP method is a promising candidate to protect sandy soil from wind erosion in desert areas.

Stress sensitivity of permeability in high-permeability sandstone sealed with microbially-induced calcium carbonate precipitation

Microbially induced carbonate precipitation(MICP)catalyzed by S.pasteurii has attracted considerable attention as a bio-cement that can both strengthen and seal geomaterials.We investigate the stress sensitivity of permeability reduction for the initially high-permeability Berea sandstone(initial permeability∼110 mD)under various durations of MICP-grouting treatment.The results indicate that after 2,4,6,8 and 10 cycles of MICP-grouting,the permeabilities decrease incrementally by 87.9%,60.9%,38.8%,17.3%,and then 5.4%compared to the pre-grouting condition.With increasing the duration of MICP-grouting,the sensitivity of permeability to changes in stress gradually decreases and becomes less hysteretic.This stress sensitivity of permeability is well represented by a power-law relationship with the coefficients representing three contrasting phases:an initial slow reduction,followed by a rapid drop,culminating in an asymptotic response.This variation behavior is closely related to the movement and dislocation of the quartz framework,which is controlled by the intergranular bio-cementation strength.Imaging by scanning electron microscopy(SEM)reveals the evolution of the stress sensitivity to permeability associated with the evolving microstructures after MICP-grouting.The initial precipitates of CaCO3 are dispersed on the surfaces of the quartz framework and occupy the pore space,which is initially limited in controlling and reducing the displacement between particles.As the precipitates continuously accumulate,the intergranular slot-shaped pore spaces are initially bonded by bio-CaCO3,with the bonding strength progressively enhanced with the expanding volume of bio-cementation.At this stage,the intergranular movement and dislocation caused by compaction are reduced,and the stress sensitivity of the permeability is significantly reduced.As these slot-shaped pore spaces are progressively filled by the bio-cement,the movement and dislocation caused by compaction become negligible and thus the stress sensitivity of permeability is minimized.

不同钙源EICP溶液改良路基黄土动力特性研究

由于黄土地区路基基床强度低,在长期动态压力下黄土会发生不均匀沉降、滑坡或坍塌等工程问题。为了使动荷载作用下的黄土强度更符合实际工程需要,有必要进一步研究不同钙源EICP溶液对黄土动强度的改良效果。本工作以陕西某基坑黄土为研究对象,在胶凝液中引入环保型木钙代替传统钙源进行技术改进,结合室内动三轴试验在不同围压下比较三种钙源EICP溶液对黄土的固化效果。结果表明:EICP溶液能显著提高黄土的动强度;同一围压下,黄土试样动应力和阻尼比随应变的增大逐渐升高,而动剪切模量随应变的增大逐渐降低;围压较小时,乙酸钙源EICP溶液对黄土动强度的改良效果较好,而当围压较大时,木钙源EICP溶液对黄土动强度的改良效果较好;同一试样所受围压越大,动强度和动剪切模量越大,阻尼比越小。

EICP改良膨胀土的物理力学性质试验研究

为了探究脲酶诱导碳酸钙沉淀(EICP)技术改良弱膨胀土的物理力学特性,利用大豆脲酶开展EICP技术处理弱膨胀土的膨胀特性和力学特性试验研究。通过EICP多因素配比正交试验研究脲酶浓度、初始Ca^(2+)浓度、酶胶比、尿钙比、养护时间对膨胀土碳酸钙生成率、自由膨胀率的影响及其变化规律,确定了EICP反应液最佳配比。采用不同掺量EICP反应液改良膨胀土,通过无荷载膨胀率试验、无侧限抗压强度试验及三轴压缩试验验证改良效果。结果表明:EICP反应液掺量为20%时抑制膨胀土膨胀性效果最好,且此时土体力学强度和碳酸钙生成率最高。大豆脲酶诱导产生的沉淀物为方解石型碳酸钙,附着在土颗粒表面既填充了土颗粒孔隙,也胶结了土体骨架颗粒,阻碍土体与水分接触,提高了土体密实性和黏结强度,改善了膨胀土膨胀性和力学性能。

接触溶蚀条件下混凝土游离钙离子固化效果研究

为研究将硅灰和硅酸钠作为掺合料内掺后的喷射混凝土在接触溶蚀条件下析出钙离子的规律,在不同掺量下制备了单掺和复掺混凝土试块,开展30 d去离子水浸泡试验,测试溶液中的钙离子浓度、溶液pH值的变化情况,并结合SEM等微观检测对接触溶蚀过程进行研究。结果显示:单掺硅灰试块在不换水条件下的钙离子溶出量大大低于空白组,换水条件下30 d内3%、5%、7%掺量组较空白组平均溶出钙离子总重依次减少73.29%、69.65%、69.26%;单掺硅酸钠后,不换水条件下3%掺量的试块钙离子溶出量也能得到明显的降低,换水条件下30 d内1%、3%、5%掺量组较空白组平均溶出钙离子总重依次减少9.22%、20.53%、29.96%;将单掺组中固化效果良好的3%掺量硅灰和5%掺量硅酸钠复掺入混凝土后,不换水条件下浸泡溶液初始钙离子浓度仅为20~30 mg/L,从第18天左右溶液游离钙离子清零,换水条件下复掺试块较空白组平均溶出钙离子总重减少约85%。

微生物诱导碳酸钙沉淀技术的工程应用进展与评述

基于微生物诱导碳酸钙沉淀(Microbially Induced Calcium carbonate Precipitation,MICP)技术的土体胶结固化技术是21世纪以来岩土工程、地质工程领域研究的热点之一。本文系统阐述了MICP技术的加固机理,从MICP加固效果和应用实践的角度出发,对MICP技术工程应用的研究现状进行评述。结果表明:MICP固化后的场地强度呈现出不均匀性明显、碳酸钙含量分布随深度递减的趋势;沙漠环境中,原位提取的菌种诱导生成的碳酸钙覆膜较传统的巴氏芽孢杆菌,具有更好的强度表现和稳定性;新型MICP技术应用(如微生物水泥、微生物砖)在强度、耐久性上表现出良好的应用前景,有望为实现我国双碳目标注入新的活力。基于MICP技术碳酸钙沉淀特质的影响因素,现场尺度下如何提高碳酸钙分布的均匀性以及在季节性变化下的碳酸钙骨架的耐久性、不同环境下的固化效率改进方案应该成为日后研究的重中之重。

微生物岩土工程技术的过去、现在与未来

微生物岩土工程技术作为一种新兴的生态友好型岩土体改良加固技术,应用前景广阔。但限于理论水平和研究手段,该技术仍存在较多不足,难以实现高效固化,由此成为大规模现场应用的瓶颈。而提升固化效率的关键在于明确其作用原理和影响机制。文章梳理了微生物诱导碳酸钙沉积技术(MICP)的研究现状,系统归纳了固化原理和改良岩土体的物理力学特性,并分析得出固化效率主要受到反应物自身和外部环境两方面的影响。当前MICP技术已初步应用于土体固化、裂缝修复、防渗处理、污染修复及微生物水泥等领域,但由于矿化难以均匀、反应物不经济、微生物及脲酶活性期短且受环境干扰大、代谢产物附带毒性、现场应用性差,该技术目前主要限于实验室水平。作者分别提出了可能的突破与改进方向,并结合实验室成果指出豆粕进行菌体扩培和脲酶供给的碳源优势,以及将磷石膏作为现场钙源的环保性和经济性,以期为从事微生物岩土工程研究与技术开发的人员提供参考。

基于响应面法的PP-PAM复合改良微生物固化膨胀土优化研究

【目的】采用微生物诱导碳酸钙沉淀技术(MICP)加固膨胀土,可有效提高膨胀土的强度,降低胀缩性,但存在土体破坏时脆性明显,以及养护初期崩解量高等问题,为了进一步改善微生物固化膨胀土的脆性破坏和养护初期崩解量高的问题,【方法】在微生物固化膨胀土的基础上,研究掺入聚丙烯纤维(PP)和聚丙烯酰胺(PAM)对微生物固化膨胀土破坏模式和水稳性的影响。以纤维长度、纤维掺量和聚丙烯酰胺掺量为影响因素,以无侧限抗压强度和崩解量为响应值,采用Box-Behnken响应面法进行条件优化试验,建立了响应面回归模型,获得聚丙烯纤维长度、聚丙烯纤维和聚丙烯酰胺用量及其交互作用对微生物固化膨胀土强度和崩解性综合指标的影响。【结果】结果表明:聚丙烯纤维的掺入降低了微生物固化膨胀土破坏时的脆性、提高了土体强度、降低了膨胀土的崩解性,但随着纤维长度的增加,崩解量逐渐增加;聚丙烯酰胺的掺入降低了膨胀土的崩解量,但会降低土体强度。【结论】在影响因素试验范围内,以无侧限抗压强度最高和崩解量最低为原则,通过Box-Behnken响应面法获得最佳配比为:聚丙烯纤维长度为9 mm,掺量为0.5%,聚丙烯酰胺掺量为0.12%。在此配比下,复合固化土的无侧限抗压强度为1.24 MPa,相比优化前提高了29.57%,崩解量仅为0.34%,相比优化前降低了99.07%。

基于钙添加的海水无机碳移除的增汇潜力研究

本研究在实验室内模拟不同初始条件,通过改变海水初始pH值、Mg/Ca比值、施加晶核等方式,定期监测海水pH值、DIC和TA的变化,探讨向海水中添加Ca^(2+)移除溶解无机碳增加海洋碳汇的潜力.实验结果表明,向海水中引入Ca^(2+),可以有效降低当前自然海水的镁钙比值(5.2),并增加碳酸钙的过饱和度,从而促进海水体系中无机碳的移除.此外,含钙化合物的无机碳移除效果与海水初始pH值呈正相关,但单纯提升海水pH值并不足以诱导碳酸钙的生成,需通过额外引入Ca^(2+)来提升碳酸钙过饱和度以实现显著无机碳移除效果.同时,实验还发现通过添加特定晶核诱导非均相沉淀,能够进一步促进海水中碳酸钙的生成,从而提高海水的无机碳移除效果,研究结果表明在施加45mmol/L的Ca^(2+)和蒙脱土晶核、初始pH值达到8.5的条件下,碳酸钙生成量最高可达959μmol/L.海水无机碳移除后将在短期内吸收大气CO_(2)增加海洋碳汇,本文研究结果为探索海洋碳增汇技术提供了新的视角和理论基础.

利用脱碳气化渣矿化封存CO_(2)制备碳酸钙的影响研究

本实验研究了浸出剂种类、浓度、反应时间、温度和液固比等对脱碳气化渣中钙浸出率的影响,并讨论了CO_(2)流量、温度、碳酸化时间对碳酸化效率和生成的沉淀碳酸钙(PCC)晶型结构的影响规律。结果表明,在2 mol/L盐酸、液固比为20 mL/g、反应温度为50℃、反应时间为90 min的浸出条件下,钙浸出率最高,为98.79%。在碳酸化阶段,CO_(2)流量主要影响碳酸化效率,通过优化碳酸化反应条件,CO_(2)流量300 mL/min,反应温度60℃,反应120 min时,最高碳酸化效率可达99.59%。而反应温度和时间则会对碳酸钙晶型和形貌产生显著影响,降低反应温度和缩短反应时间更有利于球霰石型碳酸钙的生成。

钙源对微生物矿化胶结砂土材料均匀性的影响

微生物诱导碳酸钙沉积(MICP)技术可以改善砂土材料的力学性质,但MICP胶结砂土材料的均匀性问题是目前存在的重要问题,且严重影响了MICP技术的工程应用。进行小尺寸(直径3 cm、高度11 cm)和细长(直径5 cm、高度100 cm)砂柱试样的MICP一批次灌浆试验和溶液环境试验,探究氯化钙和乙酸钙两种钙源对MICP矿化反应过程和MICP胶结砂土材料均匀性的影响。MICP胶结砂土试样的碳酸钙含量和单轴抗压强度试验结果表明,与氯化钙作为钙源相比,乙酸钙作为钙源可以增加砂柱胶结长度,改善碳酸钙在灌浆方向的均匀性,减少MICP胶结砂土材料沿灌浆路径的强度差异;乙酸钙作为钙源可减缓MICP矿化反应过程,降低营养液中尿素的分解速率,进而提高营养液中未分解尿素和游离钙离子在MICP胶结砂土材料中的传输距离,有利于提高MICP胶结砂土材料的均匀性。

沸石增强砂土微生物固化效果研究

为提高砂土的微生物固化效果,考虑沸石作为吸附材料具有多孔的特性,通过宏观物理力学试验和微细观检测,系统分析了沸石对微生物固化砂土的增强效果。研究结果表明:沸石能够显著提高砂土微生物加固过程中的固菌率。与常规微生物固化相比,掺入沸石后,固菌率提升约5.5倍,抗压强度提升39.35%,渗透系数减小71.94%。掺入沸石,一方面能够增加碳酸钙沉淀生成量,并改善其分布均匀性;另一方面,沸石周围的碳酸钙沉淀对两侧砂颗粒起到良好的桥接作用,能够增强砂颗粒之间的结构性及试样的整体性。研究成果为进一步优化微生物诱导碳酸钙沉积技术提供参考。

基于高密度电阻率成像技术的MICP浆液入渗过程监测研究

微生物诱导碳酸钙沉淀(MICP)技术是一种生态环保、前景广阔的土体改性方法,其改性效果与浆液的入渗特征密切相关。为此,提出将高密度电阻率成像(ERT)技术用于MICP浆液入渗过程监测。文章通过开展模型试验,对石英砂试样进行混合一步注浆法MICP处理,同时对试样持续进行ERT监测及电导率分析,获取了试样的三维电阻率变化特征,处理完成后测定了试样中碳酸钙含量的空间分布。结果表明:(1)MICP反应过程中,砂土与注浆液电导率随尿素分解而逐渐升高;(2)注浆液的迁移分布对砂土内部低电阻区的分布规律起主导作用,而碳酸钙沉淀的影响较小;(3)在MICP处理过程中,碳酸钙沉淀的生成与注浆液的迁移渗透相互作用,共同影响改性效果;(4)ERT技术可有效监测MICP处理区电阻率的时空演化特征,准确反映注浆液渗透迁移情况,进而评价改性效果。研究结果表明,采用ERT技术监测MICP改性土体过程具有可行性,为评价和优化微生物矿化改性效果提供了新的技术思路和方向。

天然海水环境下离子浓度对MICP反应的影响

微生物岩土技术通过生物矿化过程改善基础材料的力学性质,使其更适用于建筑或解决多学科领域的环境问题。微生物矿化过程中产生的碳酸钙是改善基础材料力学性质的主要成分,但其生成量及形态等受多种因素的影响。通过离子计、pH计、SEM、EDS和XRD等手段探究天然海水和去离子水环境在矿化过程中氯化钙和尿素浓度、比例及菌液和胶结液(氯化钙、尿素)体积比等因素对沉淀物质形貌及晶体组成的影响。结果表明:钙离子和尿素浓度及比例低时,碳酸钙的产率较高,但当初始钙离子、尿素浓度超过1.0 mol/L时,离子浓度增大对细菌产脲酶有抑制作用,浓度越高对脲酶的抑制作用越明显,沉淀物产率也随之减小,海水环境总体沉淀量与沉淀效率均高于去离子水环境。菌胶结液体积比去离子水中为1∶4、海水中不高于1∶10时,碳酸钙生成量较高,去离子水环境晶型以方解石为主,海水环境晶型以球霰石为主且沉淀中含有镁盐。