基于白碳黑的水化硅酸钙制备及其磷回收特性简

以白碳黑、硅灰、硅藻土和硅胶筛选硅质原料，并与钙质原料电石渣制备了水化硅酸钙。借助XRF、BET、FTIR等表征手段，通过多次重复除磷实验，研究了硅质原料特性对水化硅酸钙回收磷性能的影响。结果表明，白碳黑具有极高的反应活性，因此可作为制备具有磷回收特性的水化硅酸钙的硅质原料。结合XRD等表征发现，白碳黑的有效利用率是影响水化硅酸钙回收磷性能的关键，该利用率取决于白碳黑与电石渣的摩尔配比以及水热反应温度。当电石渣与白碳黑的摩尔比为1.6：1，反应温度为170℃时，白碳黑具有最佳的利用效率。该条件制备的水化硅酸钙可作为晶种，在其表面结晶形成羟基磷灰石，从而达到磷回收的目的，磷回收后固体物质中的磷含量为19.05%。     

粉煤灰、电石渣及其配合物碳酸化特性

为了促进粉煤灰和电石渣建材化高效利用和协同矿化CO_2减排,研究了粉煤灰、电石渣及其配合物的碳酸化特性。实验采用pH在线测试方法分别对粉煤灰、电石渣以及两者配合物的碳酸化过程的pH进行在线测试,并对原料和产物进行XRD、TGA和SEM表征。结果表明:相同条件下,粉煤灰碳酸化浆液pH降到7.0的平均速度约为电石渣的51倍;与等量电石渣单独碳酸化相比,粉煤灰与电石渣按照4:1(质量比)复配碳酸化pH降低到7.0的速度较纯电石渣提高了近5.6倍,且在相同电石渣配量的条件下,粉煤灰-电石渣复配料比碳酸钙-电石渣复配料的碳酸化反应完成时间缩短了31.6%,说明电石渣与粉煤灰复配后进行碳酸化反应具有明显协同促进作用。TGA分析表明,纯粉煤灰和纯电石渣的固碳率分别约为2%和61.3%,粉煤灰与电石渣复配料的固碳率较等量单一电石渣和粉煤灰的固碳率之和的计算值提高了19.6%。SEM分析表明,粉煤灰与电石渣复配料碳酸化产物碳酸钙颗粒在粉煤灰表面呈现异位分散附着形态,而单一电石渣碳酸化产物碳酸钙则在电石渣颗粒表面呈现原位聚集附着形态。这可能是复配料固碳率提高的主要原因。     

用电石渣、钢渣和煤矸石制备可控性低强度材料

可控性低强度材料(CLSM)是一种替代传统的回填材料,具有低强度、自流平、自我填充与自密实的特性,并在欧美地区得到广泛应用的一种材料。为了加强对可控低强度材料的研究,提出了以电石渣、钢渣、煤矸石为主要原料制备可控低强度材料,研究其不同温度、不同原料配比条件对其抗压强度的影响,通过X射线衍射分析了其物质发生的化学变化及变化规律。电石渣和钢渣的比例在1∶1附近时抗压强度达到最大,温度升高和氯化钙加入量的增加也有利于抗压强度的提高,氧化钙、二氧化硅等部分原料转变为复合硅酸盐晶体。     

锰磁活性炭的制备及其性能表征

以酶解提制烟碱后的烟渣和电解锰渣回收锰为原料，制备具备磁性和发达孔隙的活性炭。利用氮气吸附技术、红外光谱（FTIR）表征与分析了活性炭表面的孔隙结构和物化性质，考察了活性炭对亚甲基蓝的吸附性能和磁学性能。结果表明：以Mn／C基质废弃物为原料制得活性炭具有磁学性能；适量锰的添加有利于活性炭微孔的形成和发育；采用一步焙烧法有助于磁化物和活性炭基体相互作用形成化学键合，提高饱和磁化强度，实现废弃资源的充分利用。     

浅析电石渣固硫

研究了用电石渣作为固硫剂,探讨了最佳固硫的燃烧温度、电石渣用量和粒径,并掺入适量的 Ｆｅ_２Ｏ_３对电石渣进行改性,发现用电石渣固硫与其他钙基因硫剂相当,具有良好的应用前景。     

电石渣固硫性能的研究

研究采用电石渣作为固硫剂，探讨了最佳固硫的燃烧温度，电石渣用量和粒径，并掺入适量的Ｆｅ２Ｏ３对电石渣进行改性，发现用电石渣固硫能与其它钙基固硫剂人有很的应用前景。     

磷石膏基胶结材固结磷尾矿性能及浸出特征

以磷石膏基材料代替水泥作为磷尾矿充填胶结材,研究了磷尾矿固结浆体和硬化体性能、浸出液污染特性和固结机理。结果表明,在同样条件下,磷石膏基材料固结磷尾矿浆体比水泥泌水量要小、浆体流动性能更优;磷石膏基材料胶结磷尾矿硬化体除3 d抗压强度略低外,其他龄期的强度是水泥的1.21~1.95倍。3 d之后,磷石膏基材料和水泥胶结尾矿硬化体浸出液总磷含量基本相近,但pH明显远低于水泥,总磷也低于污水综合排放标准限值,对环境危害低。硬化体SEM和XRD分析发现,磷石膏基材料水化生成的水化硅酸钙凝胶、针状钙矾石晶体和磷尾矿中白云石、含磷矿物生成的透钙磷石等,是整个磷尾矿固结硬化体具有较高强度、较低总磷含量和pH值主要原因。该研究表明,磷石膏基材料固化磷尾矿比水泥更有应用前景。     

粉煤灰和电石渣对聚丙烯塑举裂解的影响研究

研究了粉煤灰和电石渣对聚丙烯塑料裂解的影响，讨论了加入量对裂解速度和裂解产物的影响。结果表明：粉煤灰和电石渣都使裂解产物中的轻质部分（汽油和裂解气）增加、重油降低；粉煤灰比电石渣更能加快反应的进行，而且加入量越多，反应越快，需时越短；粉煤灰比电石渣对聚丙烯塑料的裂解具有明显的催化促进效果。     

改良型湿法制备活性白土清洁生产及末端治理实验研究

传统湿法制备活性白土工艺中存在水耗、酸耗大等清洁水平较低的问题,本研究提出了在生产工艺流程中循环使用硫酸酸性废液、并从循环3次的硫酸废液中回收铝盐制备无铁硫酸铝的一种改良型湿法制备活性白土工艺,对末端治理采用电石渣替代石灰作为中和剂进行了探索性实验研究。实验结果表明,改良型湿法制备活性白土工艺对活性白土产品的理化性质无明显影响,产品质量符合行业标准,且酸的利用率从20%提高到约90%,水耗减少量为原工艺的1/3,无铁硫酸铝主要参数符合相关产品技术标准(HG/T2225-2001)。用电石渣作为中和剂处理酸性废液能够实现出水水质稳定达标,处理成本从255万元降低至210万元。本研究的实施使得活性白土的生产工艺清洁生产水平有较大提高。     

利用白云石回收污泥厌氧消化液中的磷

为经济有效地从污泥厌氧消化液中回收磷,构建了以白云石提供钙镁源的磷回收方法,探讨了磷回收的工艺条件与效果。通过盐酸酸化厌氧消化液以降低其碳酸盐含量,同时利用白云石溶于冷稀盐酸的特性使其钙镁缓慢释放到酸化的厌氧消化液中形成第一步磷回收体系,考察体系酸化pH、白云石与厌氧消化液的固液比以及反应pH对白云石的钙镁释放和磷回收效果的影响;第一步磷回收后的上清液为第二步厌氧消化液磷回收提供钙镁源,研究投加钙磷摩尔比对磷回收效果的影响。实验结果表明,当固液比为5.0时,在酸化pH为4.0～4.5且酸化溶出时间为10 h以及反应pH为9.0的条件下,第一步磷回收产物以磷酸钙盐沉淀为主,厌氧消化液磷回收率及回收产物含磷率（以P2O5计）分别达到99.43%和38.49%;第一步磷回收后的上清液按一定的钙磷摩尔比投加到酸化后的厌氧消化液中进行第二步磷回收,当投加钙磷摩尔比为0.20时,在反应pH为9.0的条件下,回收产物同时含有磷酸钙盐和磷酸铵镁,厌氧消化液中氮、磷回收率分别达到13.19%和90.90%,回收产物氮、磷含量（以P2O5计）分别为0.26%和39.58%;经XRD、XRF、ICP及SEM等分析表征,2步磷回收的产物以磷酸钙盐和磷酸铵镁为主要成分,杂质少。研究表明,利用白云石为钙镁源,通过分别构建不同的磷回收体系可以分步从污泥厌氧消化液中经济有效地回收磷,且磷回收率和回收产物含磷率高。     

Verification of the silica deficiency hypothesis based on biogeochemical trends in the aquatic continuum of Lake Biwa-Yodo River-Seto Inland Sea, Japan

The silica deficiency hypothesis holds that increases of still waters caused by hydraulic alterations and high nitrogen (N) and phosphorus (P) discharges enhance the growth of freshwater diatoms, which take up the dissolved silicate (DSi) supplied by natural weathering. The consequent decrease in the DSi supply to the sea is advantageous to flagellates (nonsiliceous and potentially harmful) but not to diatoms (siliceous and mostly benign) in coastal marine ecosystems. Verification of this hypothesis has been hampered by lack of relevant data, particularly in Asia. We investigated the aquatic continuum composed of Lake Biwa, the Yodo River, and the Seto Inland Sea, Japan, where the natural conditions make the silica deficiency less likely to emerge due to the inherently rich supply of DSi. The results showed that the silica was retained both in the lake and nearby the estuary. The relative dominance of diatom and flagellates could not be explained solely by the stoichiometric arguments but by the supportive discussion on the difference of their behavioral characteristics and the process nearby the estuary, where direct inputs of N and P and effluent Si enhanced diatom bloom, even though the Si/N ratio was lowered in the upstream reservoir. Thus the retention of DSi occurred in two places: in the lake and nearby the estuary, where the other N and P are loaded directly. The rate of DSi retention correlated with socio-economic changes, such as rapid economic growth in the 1960s and mitigations implemented after the 1980s. Sensitivity of this continuum to the Si processes suggests the global significance of this hypothesis.     

碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟的厌氧消化液为处理对象，通过小试实验，考察不同初始磷浓度Cp、Ca／P物质的量比、pH和温度下，碳酸根（CO3 2-）对磷酸钙沉淀反应回收磷的影响；利用扫描电镜（SEM）、x射线衍射仪（XRD）和傅里叶变换红外光谱（FT．IR）对沉淀产物进行表征。结果表明，高浓度的CO3 2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大；Cp相同时，CO3 2-浓度（CCO3^2-）越大，P的去除率越低，低C，（20mg／L）时尤为显著；当CCO3^2-相同时，随着Cp的增大，反应速率加快，P的去除率逐渐升高，但升高幅度越来越小；增大Ca／P比和pH能提高P的去除率，降低CO3 2-对磷酸钙沉淀反应的抑制作用，综合考虑实际效果，应选择Ca／P比为3．33，pH为9．0作为适宜的反应条件；升高温度对降低CO3 2-对磷酸钙沉淀反应的抑制作用贡献不大。在Cp为60ITIg／L，Ca／P比为1．67，pH为9．0，温度为20℃的条件下，当CCO3^2-为0时，得到的沉淀产物主要为羟基磷灰石HAP；当CCO3^2-为30mmol／L时，得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

Latent hydraulic reactivity of blended cement incorporating slag made from municipal solid waste incinerator fly ash

The reactivity of cement pastes made by blending Portland cement with slag from municipal solid waste incinerator (MSWI) fly ash was investigated to assess the potential of recycling MSWI fly ash slag. The slag, prepared by melting MSWI fly ash at 1400 degrees C for 30 min, was pulverized and ground, then blended with ordinary Portland cement (OPC), using various substitution levels to make slag-blended cement (SBC). The pozzolanic reactivity of the ecocement was then characterized by determining variations in the compressive strength, degree of hydration, microstructure, speciation, and mineralogical crystalline phases. The results suggest that the strength of the pastes at an early age decreased with increasing substitution levels, whereas the strength at a later age of the tested pastes (with substitution levels less than 10%) outperformed OPC paste because of typical SBC properties. The development of strength at a later age was also confirmed by X-ray diffraction and scanning electron microscopy techniques. This implies that active silica (Si) and alumina (Al) react with the hydration product, calcium hydroxide (Ca(OH)2), to form calcium silicate hydrate (C-S-H), which contributed to strength development at a later age by the filling up of pores in the SBC pastes. The pozzolanic activity of the SBC pastes indicates that it is suitable for use as a substitute for OPC in blended cement.     

A study of silicon carbide synthesis from waste serpentine

There are 60000 tons of serpentine wastes produced in year 2004 in Taiwan. This is due to the well-developed joints in the serpentine ore body as well as the stringent requirements of the particle size and chemical composition of serpentine by iron making company. The waste also creates considerable environmental problems. The purpose of this study is reutilization of waste serpentine to produce a high value silica powder after acid leaching. These siliceous microstructure products obtained from serpentine would be responsible for high reactivity and characteristic molecular sieving effect. In this study, the amorphous silica powder was then synthesized to silicon carbide with the C/SiO(2) molar ratio of 3. The experiment results show that silicon carbide can be synthesized in 1550 degrees C. The formed silicon carbide was whisker beta type SiC which can be used as raw materials for industry.     

Latent Hydraulic Reactivity of Blended Cement Incorporating Slag Made from Municipal Solid Waste Incinerator Fly Ash

Abstract

The reactivity of cement pastes made by blending Portland cement with slag from municipal solid waste incinerator (MSWI) fly ash was investigated to assess the potential of recycling MSWI fly ash slag. The slag, prepared by melting MSWI fly ash at 1400 °C for 30 min, was pulverized and ground, then blended with ordinary Portland cement (OPC), using various substitution levels to make slag-blended cement (SBC). The pozzolanic reactivity of the ecocement was then characterized by determining variations in the compressive strength, degree of hydration, microstructure, speciation, and mineralogical crystalline phases. The results suggest that the strength of the pastes at an early age decreased with increasing substitution levels, whereas the strength at a later age of the tested pastes (with substitution levels less than 10%) outperformed OPC paste because of typical SBC properties. The development of strength at a later age was also confirmed by X-ray diffraction and scanning electron microscopy techniques. This implies that active silica (Si) and alumina (Al) react with the hydration product, calcium hydroxide (Ca(OH)₂), to form calcium silicate hydrate (C-S-H), which contributed to strength development at a later age by the filling up of pores in the SBC pastes. The pozzolanic activity of the SBC pastes indicates that it is suitable for use as a substitute for OPC in blended cement.     

Biogenic cements from rice hull ash doped with aluminum and iron

This work describes the use of rice hull as starting material for the synthesis of cements doped with iron and aluminum. Rice hull contains about 10-20% of silica along with organic material. In many countries rice hull represents an environmental problem since this material is merely burned at rice fields, rendering suspended silica particles in the air. Dicalcium silicate (beta-Ca(2)SiO(4)) is the second most important component of Portland cement and presents many environmental advantages over commercial cement. It can be prepared at lower temperatures saving energy and raw-materials. In this work we describe the synthesis beta-Ca(2)SiO(4) using silica derived from rice hull ash. Silica was obtained from heating rice hull at 600 degrees C. Starting materials (silica, calcium oxide, barium chloride, iron or aluminum oxide) were weighed in stoichiometric proportions and aqueous dispersions having water:solid ratio of approximately 20:1 were prepared and treated in an ultrasonic bath for 60min. After this, an intermediate silicate and the excess of calcium hydroxide were obtained. Finally solids were dried, grounded and heated up to 800 degrees C. It was observed that beta-Ca(2)SiO(4) was obtained when dopant concentration was limited to 1%.     

中国炭黑工业大气污染控制

本文研究我国目前炭黑工业大气污染控制技术的状况及特点。近十年来，我国炭黑工业大气污染控制技术有了长足的进展，选择合理的工艺过程，采用袋滤器高效净化炭黑烟气，成功地开发了炭黑工业气体余热的回收及利用。为此，我国炭黑工业大气污染控制技术，实现了炭黑微粒和可燃气态污染物的高效净化，炭黑工业气体余热绝大部分得到了回收及利用，余热利用率达６０％以上。我国炭黑工业一跃成为低能耗、有效能高效利用，大气污染物高效净化的清洁生产的化工厂，和生产热力及电力的能源部门。     

Pore structure effects on Ca-based sorbent sulfation capacity at medium temperatures: activated carbon as sorbent/catalyst support

The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473-773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2 x g Ca(OH)2(-1), and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sulfated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/ activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/catalysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the desulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.     

Modelling reactions between cement pore fluids and rock: implications for porosity change

The migration of groundwater equilibrated with cement from a deep geological disposal facility for radioactive wastes will perturb the chemical, minerological and physical properties of the geosphere in advance of the migration of radionuclides. Preliminary modelling of a simplified scenario has been conducted to assess these changes using appropriate data for mineral dissolution kinetics, the chemical composition of cement pore fluids, and the hydrogeological characteristics of fractured crystalline rock. Chemical exchanges between rock immediately adjacent to the engineered barriers of a waste disposal facility and pore fluids were evaluated using the speciation-reaction path code. which revealed rapid loss of Ca, and gains in Na and Si of the evolved fluids, with little change in pH. Secondary minerals show a sequence of calcium silicate hydrates, and zeolites. Precise definition of the overall mass balance is uncertain due to the absence of both thermodynamic data for many zeolites and kinetic data for the precipitation of feldspars. Modelling has demonstrated that reaction kinetics will be important in governing chemical exchanges for length scales up to 20 m. Radionuclide retardation will be enhanced by the growth of zeolites and calcium silicate hydrates.