Mechanochemical dechlorination of polyvinyl chloride with calcium sulfates

Polyvinyl chloride (PVC) was milled with hydrated or unhydrated calcium sulfates (CaSO₄·2H₂O or CaSO₄) in air by using a planetary mill to investigate mechanochemical dechlorination behavior. The milling process resulted in size reduction and in the breaking of bonds leading to mechanically induced solid state reaction, forming CaCl₂ and dechlorinated hydrocarbon with C=C double bonds in the product. Washing the milled mixtures with water at room temperature allowed removal of the chloride formed during milling, and more than 95% of the chlorine in PVC was removed from a mixture milled for 4 h. This process could offer a potential route for the handling and disposal of both PVC and gypsum wastes. H₂S gas was generated during milling; more H₂S was released from the unhydrated sample than from the hydrated sample.     

Effects of calcium hydroxide and calcium chloride addition to bentonite in iron ore pelletization.

Pyrite ash is created as waste from the roasting of pyrite ores during the production of sulphuric acid. These processes generate great amounts of pyrite ash waste that is generally land filled. This creates serious environmental pollution due to the release of acids and toxic substances. Pyrite ash waste can be utilized in the iron production industry as a blast furnace feed to process this waste and prevent environmental pollution. The essential parameters affecting the pelletization process of pyrite ash were studied using bentonite as a binder. Experiments were then carried out using bentonite and a mixture of bentonite with calcium hydroxide and calcium chloride in order to make the bentonite more effective. The metallurgical properties of pyrite ash, bentonite, calcium hydroxide, calcium chloride, a mixture of these and sintered pellets were studied using X-ray analysis. The crushing strength tests were carried out to investigate the strength of pyrite ash waste pellets. The results of these analyses showed that pyrite ash can be agglomerated to pellets and used in the iron production industry as a blast furnace feed. The crushing strength of the pellets containing calcium hydroxide and calcium chloride in addition to bentonite was better than the strength of pellets prepared using only bentonite binder.     

The effect of sodium chloride on the dissolution of calcium silicate hydrate gels

The use of cement based materials will be widespread in the long-term management of radioactive materials in the United Kingdom. One of the applications could be the Nirex reference vault backfill (NRVB) as an engineered barrier within a deep geological repository. NRVB confers alkaline conditions, which would provide a robust chemical barrier through the control of the solubility of some key radionuclides, enhanced sorption and minimised corrosion of steel containers. An understanding of the dissolution of C-S-H gels in cement under the appropriate conditions (e.g., saline groundwaters) is necessary to demonstrate the expected evolution of the chemistry over time and to provide sufficient cement to buffer the porewater conditions for the required time. A programme of experimental work has been undertaken to investigate C-S-H gel dissolution behaviour in sodium chloride solutions and the effect of calcium/silicon ratio (C/S), temperature and cation type on this behaviour. Reductions in calcium concentration and pH values were observed with samples equilibrated at 45 degrees C compared to those prepared at 25 degrees C. The effect of salt cation type on salt-concentration dependence of the dissolution of C-S-H gels was investigated by the addition of lithium or potassium chloride in place of sodium chloride for gels with a C/S of 1.0 and 1.8. With a C/S of 1.0, similar increases in dissolved calcium concentration with increasing ionic strength were recorded for the different salts. However, at a C/S of 1.8, anomalously high calcium concentrations were observed in the presence of lithium.     

Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration

In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C.     

高温烧结磷石膏钙渣制备轻质碳酸钙

以磷石膏钙渣为原料,通过高温煅烧,然后经消化、精制、碳化,制成轻质碳酸钙产品.研究结果表明:高温煅烧的最佳温度为 1 000 ℃,最佳煅烧时间为 1.0 h;沉淀反应的初始反应温度为 60 ℃,Ca(OH)2乳液质量浓度为 70 g/L,CO2流量为 1.8 L/h.制备的轻质碳酸钙产品各项指标均达到 HG/T2226...     

Removal of insoluble chloride from bottom ash for recycling

In order to recycle bottom ash and use it as raw material for cement production, the removal of insoluble chloride was investigated by testing various washing techniques. The present work is also focused on investigating the properties of insoluble chlorides and determining the conditions for dissolving these compounds in order to reduce the chlorine content to the required level, i.e., less than 0.1 wt%. Within this framework, the effect of washing with water and CO2 bubbling was investigated, because the main insoluble chloride found in bottom ash, i.e., Friedel's salt, can be dissolved by CO2. Then, in order to better understand the removal of Cl, Friedel's salt was artificially synthesized by hydration and then the effect of CO2 bubbling was investigated. If all chlorides in the ash are converted into Friedel's salt by hydration, all chlorides can then be dissolved by CO2 bubbling. In addition, the effect of pH on removing the remaining insoluble chlorides was investigated by washing the ash with sulfuric acid solution. It was found that the most effective technique to reduce the Cl content to less than 1000 ppm was washing with sulfuric acid solution, while keeping the pH value at less than 4. By using this method, Friedel's salt and other insoluble chlorides were dissolved.     

利用含铝废盐酸制备聚合氯化铝

以某医药企业产生的含铝废盐酸为原料制备了液体聚合氯化铝(PAC)。确定了适宜的有机物去除方法和碱化剂,考察了碱化剂投加量、废盐酸铝离子含量等合成条件对PAC产品指标的影响,并比较了自制PAC和市售PAC对该企业污水站二沉池出水的混凝效果。实验结果表明:采用活性炭吸附法去除废盐酸中有机物,选择固体Ca O作为碱化剂,在活性炭投加量1‰(w)、吸附时间1 h、铝离子含量9.5%(w,以Al_2O_3计)、CaO投加量80 g/L、反应时间24 h的条件下,制备的液体PAC达到行业标准HG/T 2677—2017《工业聚氯化铝》中的Ⅲ类标准;自制PAC对废水COD和SS的去除率均优于市售PAC,不仅可替代其使用,还可外售产生经济效益。     

用铝灰生产聚合氯化铝的工艺研究

以铝灰、废盐酸为原料,用酸溶法(一步法)生产液体聚合氯化铝,对投料比、反应温度、反应时间、搅拌速度、熟化温度、熟化时间等参数对产品性能的影响进行了试验,得到了最佳生产工艺条件,并对产品的净水效果进行了模拟试验,净水效果明显。     

Calcium phosphate stabilization of fly ash with chloride extraction

Municipal solid waste incinerator by products include fly ash and air pollution control residues. In order to transform these incinerator wastes into reusable mineral species, soluble alkali chlorides must be separated and toxic trace elements must be stabilized in insoluble form. We show that alkali chlorides can be extracted efficiently in an aqueous extraction step combining a calcium phosphate gel precipitation. In such a process, sodium and potassium chlorides are obtained free from calcium salts, and the trace metal ions are immobilized in the calcium phosphate matrix. Moderate calcination of the chemically treated fly ash leads to the formation of cristalline hydroxylapatite. Fly ash spiked with copper ions and treated by this process shows improved stability of metal ions. Leaching tests with water or EDTA reveal a significant drop in metal ion dissolution. Hydroxylapatite may trap toxic metals and also prevent their evaporation during thermal treatments. Incinerator fly ash together with air pollution control residues, treated by the combined chloride extraction and hydroxylapatite formation process may be considered safe to use as a mineral filler in value added products such as road base or cement blocks.     

新型二氯甲烷催化燃烧催化剂的性能

采用浸渍法制备了陶瓷负载型V2O5／Al2O3和Cr2O3／Al2O3催化剂,考察了两种催化剂对CH2Cl2的催化燃烧性能。实验结果表明,在进气CH2Cl2质量浓度为800—2400mg／m^3时,V2O3／Al2O3催化剂在400℃时可使CH2Cl2去除率达到95％以上,Cr2O3／Al2O3催化剂在340℃时可使CH2Cl2的去除率达到99％以上。Cr2O3／Al2O3催化剂的活性高于V2O3／Al2O3催化剂。催化剂的活性随温度的升高而提高,随进气CH2Cl2质量浓度的增加而降低。100h稳定性实验结果表明,这两种催化剂均具有较好的稳定性。     

Conversion of calcium sulphide to calcium carbonate during the process of recovery of elemental sulphur from gypsum waste

The production of elemental sulphur and calcium carbonate (CaCO₃) from gypsum waste can be achieved by thermally reducing the waste into calcium sulphide (CaS), which is then subjected to a direct aqueous carbonation step for the generation of hydrogen sulphide (H₂S) and CaCO₃. H₂S can subsequently be converted to elemental sulphur via the commercially available chemical catalytic Claus process. This study investigated the carbonation of CaS by examining both the solution chemistry of the process and the properties of the formed carbonated product. CaS was successfully converted into CaCO₃; however, the reaction yielded low-grade carbonate products (i.e. <90 mass% as CaCO₃) which comprised a mixture of two CaCO₃ polymorphs (calcite and vaterite), as well as trace minerals originating from the starting material. These products could replace the Sappi Enstra CaCO₃ (69 mass% CaCO₃), a by-product from the paper industry which is used in many full-scale AMD neutralisation plants but is becoming insufficient. The insight gained is now also being used to develop and optimize an indirect aqueous CaS carbonation process for the production of high-grade CaCO₃ (i.e. >99 mass% as CaCO₃) or precipitated calcium carbonate (PCC).     

高分子除氯剂对水中氯离子的吸附机理

采用高分子除氯剂吸附水中的氯离子,考察了除氯剂投加量、反应时间、反应温度、竞争离子等对氯离子去除率的影响。实验结果表明:随着除氯剂投加量增加,氯离子去除率不断提高;吸附动力学符合拟二级动力学模型,表明化学吸附可能是氯离子吸附过程的速率控制步骤;Elovich模型表明除氯剂表面吸附的氯离子存在非均相扩散的吸附-脱附过程;Freundlich等温吸附模型能更好地描述吸附过程,结合热力学计算表明该过程是一个自发进行的吸热熵增的化学吸附过程,温度越高自发程度越大。     

氯化铵浸取法回收盐泥中的镁

以盐泥为原料,采用氯化铵浸取回收盐泥中的Mg²⁺,以浸取液和回收的氨反应制取氢氧化镁产品。考察了盐泥浆液固含量、浸取时间、物料比（氯化铵与盐泥中氢氧化镁的摩尔比）等工艺条件对Mg²⁺浸取率的影响,并以比表面积为考察指标进行正交实验,确定氢氧化镁的最佳制备条件。实验结果表明：在盐泥浆液固含量为248 g/L、浸取时间为100 min、物料比为2.3的条件下,Mg²⁺浸取率为75.0%;在n（MgCl₂）:n（NH₄Cl）=0.5、氨水浓度3 mol/L、氨水滴加速率 0.8 mL/min、反应温度 90 ℃的最佳条件下,制备的氢氧化镁的比表面积为17.87 m²/g,粒径约为3 μm。该工艺简单可行,为盐泥的综合利用提供了新的思路。     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

次氯酸钙溶液的脱硫脱硝特性

采用Ca(ClO)2溶液在高效反应瓶中与模拟烟气进行脱硫脱硝实验,考察了模拟烟气中SO2和NOx的去除效果,以动力学为理论基础研究了Ca(ClO)2的脱硫脱硝性能。实验结果表明:在模拟烟气中SO2,NO,NO2的质量浓度分别为3700,1300,820 mg/m^3及Ca(ClO)2溶液浓度为0.35 mol/L的条件下,SO2去除率达到100%,NOx去除率达到67%。脱硫过程中吸收液中的ClO-是100%脱硫率的保障。Ca^2+吸收SO2的反应速率呈现一级反应的特征。得到的脱硫产物CaSO4·2H2O达到了工业石膏的品质要求。同时脱硫脱硝时NOx和SO2具有协同作用。     

Relation between mechanochemical dechlorination rate of polyvinyl chloride and mill power consumption

A sample of polyvinyl chloride (PVC) powder was milled with CaO powder in a planetary mill for various mill operational parameters. The milled product consisted of dechlorinated hydrocarbon and water-soluble CaOHCl. The dechlorination rate of PVC was determined by the concentration of Cl⁻ ions measured in solution after dispersing the milled product in water. To evaluate the power consumption during PVC dechlorination, the mill power consumption was measured during each experimental run. In addition, media motion during planetary milling was simulated using the discrete element method (DEM), enabling calculation of the mill power consumption. The power consumption calculated by the DEM simulation compared well with the power consumption measured experimentally. The dechlorination rate correlated well with the specific mill power consumption, regardless of the sample weight. The dechlorination rate of PVC when milled with oyster shells (CaCO₃) was observed to be faster than that of the PVC/CaO system, and oyster shells could be used as a reactant for the treatment of PVC wastes. This work should be useful for the design of a reactor for the dechlorination of PVC. Chemical Feedstock Recycling & Other Innovative Recycling Techniques 6     

Assessment and monitoring tools for aerobic bioremediation of vinyl chloride in groundwater

Direct aerobic biodegradation of vinyl chloride (VC) offers a remedial solution for persistent vinyl chloride plumes that are not amenable to the anaerobic process of reductive dechlorination because of either prevailing geochemical conditions or the absence of active Dehalococcoides ethenogenes. However, tools are needed to evaluate and optimize aerobic VC bioremediation. This article describes the development and testing of two techniques—a microbiological tool and a molecular tool—for this purpose. Both methods are based on detection of bacteria that can use vinyl chloride and ethene as growth substrates in the presence of oxygen. The microbiological tool is an activity assay that indicates whether bacteria capable of degrading ethene under aerobic conditions are present in a groundwater sample. This activity assay gave positive results in the area of active VC degradation of an aerobic VC bioremediation test site. A rapid semiquantitative genetic assay was also developed. This molecular tool, based on polymerase chain reaction (PCR) detection of a gene involved in the metabolism of both ethene and VC, revealed the presence of potential VC degraders in an enrichment culture and site groundwater. These tools could provide a basis for judging the potential of aerobic VC degradation by ethenotrophs at other sites in addition to offering a mechanism for treatment monitoring and system optimization. © 2009 Wiley Periodicals, Inc.     

烟气氯化氢分析中的干扰因素及消除

在火电厂烟气成分分析中，采用硝酸银容量法测定烟气氯化氢时发现主要干扰成分是二氧化硫，指出硫氰酸汞分光光度法不适用于火电厂烟气氯化氢的分析。     

Environmentally Friendly Oil-Modified Polyesters as Polymeric Plasticizers for Poly(vinyl chloride)

Oil-modified polyesters were synthesized to serve as polymeric plasticizers for PVC. A total of four polymeric plasticizers with different average molecular weights were prepared. Characterizations were done using Fourier-transformed infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Some of the tests conducted on PVC films include thermal stability test using thermogravimetric analyser, determination of glass transition temperature (T_g), plasticizer migration and leaching resistance test, morphology study of plasticized PVC films using field emission scanning microscope, toxicity test, and tensile test. Owing to the plasticizing effect of the palm oil-based compound, T_g of the plasticized PVC has decreased to an average of 65 °C at 20 wt% loading. The polymeric plasticizer is also able to contribute positively to the thermal stability and mechanical properties of the PVC films. Some of the advantages of incorporating polymeric plasticizer with high molecular weight includes lower rate of leaching from plastic, and improved tensile strength and elongation at break. Besides, thermal stability of the plastic studied using Kissinger’s and Flynn–Wall–Ozawa’s approaches shows that PVC blended with high molecular weight oil-modified polyester is more thermally stable, evidenced by the increase in the activation energy of decomposition, E_d. Toxicity test using brine shrimp egg shows encouraging results, where the oil-based plasticizer is considerably less toxic compared to some of the commercial plasticizers.