一种新的芒硝制碱法实验室研究

The purpose of this work is to find a new way for utilizing the rich sodium sulfate resource to produce soda ash. A novel process is proposed which uses aqueous dichromate solution as working medium through decomposition of calcium carbonate in aqueous sodium dichromate, complex decomposition of aqueous sodium sulfate and calcium chromate, regeneration of sodium dichromate and production of sodium bicarbonate from carbonation of aqueous sodium chromate solution, processing and utilization of byproduct calcium sulfate, and production of sodium carbonate from sodium bicarbonate. The process has the features of less corrosion and pollution and low energy consumption.     

Production of glycerol carbonate via reactive distillation and extractive distillation:An experimental study☆

A process for the production of glycerol carbonate (GC) is proposed with the transesterification of glycerol (GL) and dimethyl carbonate (DMC) with CaO as catalyst by reactive distil ation and extractive distil ation. The perfor-mance of solvents in separating DMC-methanol azeotrope and the effects of operation parameters on the reactive distillation process are investigated experimental y. The results indicate that both the GL conversion and GC yield increase with the DMC/GL molar ratio, reflux ratio, final temperature of tower bottom, and CaO/GL molar ratio and decrease as the recycle number of CaO increases. The calcium concentration in the residual reaction mixture also decreases remarkably as the DMC/GL molar ratio increases. At DMC/GL molar ratio 4.0, reflux ratio 1.0, final temperature of tower bottom 358 K, and CaO/GL molar ratio 0.05, both the GL conversion and GC yield can reach above 99.0%, and the mass concentration of calcium in the product is less than 0.08%.     

微通道内乙醇胺吸收CO2的过程特征（英文）

Process characteristics of CO2 absorption using aqueous monoethanolamine(MEA) in a microchannel reactor were investigated experimentally in this work.A T-type rectangular microchannel with a hydraulic diameter of 408 μm was used.Operating parameters,i.e.temperature,pressure and molar ratio of MEA to CO2 were studied.Under 3 MPa pressure,the mole fraction of CO2 in gas phase could decrease from 32.3% to 300×10?6 at least when gas hourly space velocity ranged from 14400 to 68600 h?1 and molar ratio of MEA to CO2 was kept at 2.2.In particular,the effects of temperature on CO2 absorption flux,mass transfer driving force,gas-liquid contact time and en-hancement factor were analyzed in detail and found that mass transfer enhancement by chemical reaction was a crucial factor for the process of CO2 absorption.     

Enhancement of CO2 capture and microstructure evolution of the spent calcium-based sorbent by the self-reactivation process

The effect of self-reactivation on the CO_2 capture capacity of the spent calcium based sorbent was investigated in a dual-fixed bed reactor.The sampled sorbents from the dual-fixed bed reactor were sent for XRD,SEM and N_2 adsorption analysis to explain the self-reactivation mechanism.The results show that the CaO in the spent sorbent discharged from the calciner absorbs the vapor in the air to form Ca(OH)_2 and further Ca(OH)_2·2 H_2 O under environmental conditions,during which process the CO_2 capture capacity of the spent sorbent can be self-reactivated.The microstructure of the spent sorbent is improved by the self-reactivation process,resulting in more porous microstructure,higher BET surface area and pore volume.Compared with the calcined spent sorbent that has experienced 20 cycles,the pore volume and BET surface area are increased by 6.69 times and 56.3% after self-reactivation when φ=170%.The improved microstructure makes it easier for the CO_2 diffusion and carbonation reaction in the sorbent.Therefore,the CO_2 capture capacity of the spent sorbent is enhanced by self-reactivation process.A self-reactivation process coupled with calcium looping process was proposed to reuse the discharged spent calcium based sorbent from the calciner.Higher average carbonation conversion and CO_2 capture efficiency can be achieved when self-reactivated spent sorbent is used as supplementary sorbent in the calciner rather than fresh CaCO_3 under the same conditions.     

Leaching calcium from phosphogypsum desulfurization slag by using ammonium chloride solution: Thermodynamics and kinetics study

Phosphogypsum(PG) desulfurization slag is a calcium-rich residue from reductive decomposition of PG using sulfur as the reductant. We proposed a technology of preparation light calcium carbonate with PG desulfurization slag, which mainly contains two steps: leaching and carbonizing. In this work, we concentrated on the former, in which ammonium chloride aqueous solution was utilized as leaching agent to extract calcium from the slag, and conducted thermodynamics and kinetics study on it. Fact Sage software was employed to do thermodynamic and phase equilibrium diagram calculations. The influence of leaching conditions including agitation speed, initial concentration of leaching solution, reaction temperature, and liquid/solid ratio on the calcium leaching rate was discussed in detail by means of experiment optimal design. A kinetic model developed from the shrinking core model was given to describe the leaching process. The apparent kinetic activation energy(Ea) of the leaching reaction was calculated to be 10.58 k J·mol~(-1).     

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.     

膜电解法再生碳酸钾脱碳溶液(英文)

In this work, the regeneration mechanism of potassium carbonate solution after absorption of CO2 using ion-exchange membrane electrolysis was presented. The solutions of potassium carbonate (K2CO3) and potassium bicarbonate (KHCO3) were used to simulate the solution after absorbing CO2. Experiments were carried out at various electrodes, temperatures and current densities. The results indicate that the membrane electrolysis can increase concentration ratio of K2CO3 and KHCO3, and achieve 100% conversion. In this process, not only CO2 is desorbed from carbonate solution, but also hydrogen, as a byproduct, is generated at the cathode, which is the main contributor to reduce energy consumption. Thus, the membrane electrolysis is valuable in the regeneration of the K2CO3 absorbent.     

高温下改性钙基吸附剂固定床反应器从烟气中捕捉二氧化碳(英文)

Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors: calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption capacity of those sorbents was investigated in a fixed-bed reactor in the temperature range of 350-650℃. It was found that all of those sorbents showed higher capacity for CO2 absorption when the operating temperature higher than 450℃. The CaAc2-CaO sorbent showed the highest CO2 absorption capacity of 299mg·g-1. The morphology of those sorbents was examined by scanning electron microscope (SEM), and the changes of composition before and after carbonation were also determined by X-ray diffraction (XRD). Results indicated that those sorbents have the similar chemical compositions and crystalline phases before carbonation reaction [mainly Ca(OH)2], and CaCO3 is the main component after carbonation reaction. The SEM morphology shows clearly that the sorbent pores were filled with reaction products after carbonation reaction, and became much denser than before. The N2 adsorption-desorption isotherms indicated that the CaAc2-CaO and CaCO3-CaO sorbents have higher specific surface area, larger pore volume and appropriate pore size distribution than that of CaO-CaO and Ca(OH)2-CaO.     

Synthesis of hierarchical dendritic micro–nano structure ZnFe_2O_4 and photocatalytic activities for water splitting

Hierarchical dendritic micro–nano structure Zn Fe_2O_4 have been prepared by electrochemical reduction and thermal oxidation method in this work. X-ray diffractometry, Raman spectra and field-emission scanning electron microscopy were used to characterize the crystal structure, size and morphology. The results show that the sample(S-2) is composed of pure ZnFe_2O_4 when the molar ratio of Zn~(2+)/Fe~(2+)in the electrolyte is 0.35. Decreasing the molar ratio of Zn~(2+)/Fe~(2+), the sample(S-1) is composed of ZnFe_2O_4 and α-Fe_2O_3, whereas increasing the molar ratio of Zn~(2+)/Fe~(2+), the sample(S-3) is composed of ZnFe_2O_4 and Zn O. The lattice parameters of ZnFe_2O_4 are influenced by the molar ratio of Zn~(2+)/Fe: Zn at excess decreases the cell volume whereas Fe at excess increases the cell volume of Zn Fe_2O_4. All the samples have the dendritic structure, of which S-2 has micron-sized lush branches with nano-sized leaves. UV–Vis diffuse reflectance spectra were acquired by a spectrophotometer. The absorption edges gradually blue shift with the increase of the molar ratio of Zn~(2+)/Fe~(2+). Photocatalytic activities for water splitting were investigated under Xe light irradiation in an aqueous olution containing 0.1 mol·L~(-1)Na_2S/0.02 mol·L~(-1)Na_2SO_3 in a glass reactor. The relatively highest photocatalytic activity with 1.41 μmol·h-1· 0.02 g~(-1)was achieved by pure ZnFe_2O_4sample(S-2). The photocatalytic activity of the mixture phase of Zn Fe_2O_4 and α-Fe_2O_3(S-1) is better than ZnF e_2O_4 and ZnO(S-3).     

Indirect mineral carbonation of titanium-bearing blast furnace slag coupled with recovery of TiO2 and Al2O3

Large quantities of CO_2 and blast furnace slag are discharged in the iron and steel industry. Mineral carbonation of blast furnace slag can offer substantial CO_2 emission reduction and comprehensive utilization of the solid waste.This paper describes a novel route for indirect mineral carbonation of titanium-bearing blast furnace(TBBF) slag,in which the TBBF slag is roasted with recyclable(NH_4)_2SO_4(AS) at low temperatures and converted into the sulphates of various valuable metals, including calcium, magnesium, aluminium and titanium. High value added Ti-and Al-rich products can be obtained through stepwise precipitation of the leaching solution from the roasted slag. The NH_3 produced during the roasting is used to capture CO_2 from flue gases. The NH_4HCO_3 and(NH_4)_2CO_3 thus obtained are used to carbonate the CaSO_4-containing leaching residue and MgSO_4-rich leaching solution, respectively. In this study, the process parameters and efficiency for the roasting, carbonation and Ti and Al recovery were investigated in detail. The results showed that the sulfation ratios of calcium,magnesium, titanium and aluminium reached 92.6%, 87% and 84.4%, respectively, after roasting at an AS-to-TBBF slag mass ratio of 2:1 and 350 °C for 2 h. The leaching solution was subjected to hydrolysis at 102 °C for 4 h with a Ti hydrolysis ratio of 95.7% and the purity of TiO_2 in the calcined hydrolysate reached 98 wt%.99.7% of aluminium in the Ti-depleted leaching solution was precipitated by using NH_3. The carbonation products of Ca and Mg were CaCO_3 and(NH_4)_2 Mg(CO_3)_2·4H_2O, respectively. The latter can be decomposed into MgCO_3 at 100–200 °C with simultaneous recovery of the NH_3 for reuse. In this process, approximately 82.1% of Ca and 84.2%of Mg in the TBBF slag were transformed into stable carbonates and the total CO_2 sequestration capacity per ton of TBBF slag reached up to 239.7 kg. The TiO_2 obtained can be used directly as an end product, while the Al-rich precipitate and the two carbonation products can act, respectively, as raw materials for electrolytic aluminium,cement and light magnesium carbonate production for the replacement of natural resources.     

深井降温系统管道结垢微观机理

以深部矿井降温系统管道内壁出现的结垢问题为研究对象,首先采集管道水样进行水质全分析测试,确定管道内成垢性离子并建立化学及数学模型,其次采用第一性原理计算方法研究得到了深部矿井降温系统管道结垢微观机理。结果表明,深井降温系统管道内壁结垢过程包括Ca²⁺和CO₃²⁺的结合结晶及MgCo₃、CaSO₄转化为CaCO₃的转化;理论分析及第一性原理计算结果表明,深井降温系统管道内壁结垢的主要影响因素为成垢性离子（Ca²⁺、HCO^-、Mg²⁺和SO₄^2-）,且和的存在会抑制碳酸钙结垢的产生。该研究对于深部高温热害矿井的降温系统的结垢产生机制以及采取合理的防、除垢措施,保障良好的矿井降温效果和安全生产具有理论指导意义。     

二氧化碳在双极膜电渗析系统中溶解吸收过程的研究

在二氧化碳捕集、利用和封存（CCUS）技术中,海水固碳技术绿色环保、安全可靠,具有很好的发展前景。其中,双极膜电渗析法海水固碳技术的关键之处在于二氧化碳在系统中的溶解吸收。考察了结晶器中添加晶种、通气体系成分、模拟烟道气流量、双极膜电渗析装置的电流密度对海水固碳过程中二氧化碳溶解吸收效果的影响,结果表明：系统外加晶种、模拟烟道气作为通气体系时更有利于二氧化碳在双极膜电渗析系统中的溶解吸收,促进碳酸钙生成。在上述基础上,随着模拟烟道气流量的增加,二氧化碳的比吸收速率降低,二氧化碳在溶液中大部分转化成碳酸氢根,碳酸根和碳酸钙的生成速率则会降低;随着电渗析装置电流密度的提高,碳酸氢根、碳酸根和碳酸钙的生成速率均会随之提高。该研究为酸性气体在双极膜电渗析系统中溶解吸收和矿化利用提供了指导。     

Desorption of Cl- from Mg-Al layered double hydroxide intercalated with Cl- using CO2 gas and water

Mg-Al layered double hydroxide intercalated with CO_3~(2-)(CO_3·Mg-Al LDH) is effective for treating HCl exhaust gas.HCl reacts with CO_3~(2-) in CO_3·Mg-Al LDH, resulting in the formation of Cl·Mg-Al LDH.We propose that CO_2 can be used for the desorption of Cl~-from Cl·Mg-Al LDH to regenerate CO_3·Mg-Al LDH.Herein,we studied the desorption of a from CI-Mg-Al LDH by adding water to Cl·Mg-Al LDH and blowing CO_2 into it.We also analyzed the effects of temperature and water addition speed on the desorption of CI~-from Cl·Mg-Al LDH.Our results show that the added water adhered to CI·Mg-Al LDH and that CO_2 in the gaseous phase was dissolved in this adhered water,thus generating CO_3~(2-).Therefore,anion exchange occurred between CO_3~(2-) and Cl~-in the Cl·Mg-Al LDH,thus desorbing Cl~-.     

真空制盐两碱净化过程成垢离子的脱除及控制

通过研究卤水两碱法净化过程成垢离子(Ca2+,Mg2+和CO32-)的行为,揭示卤水净化成垢离子脱除与控制的基本规律.研究了"NaOH-Na2CO3"两碱用量对卤水中钙镁离子净化效果及精卤中残留碳酸根离子浓度的影响.研究结果表明,通过优化两碱用量,调控卤水pH值,可以在脱除钙镁离子的同时,实现碳酸根离子的高效利用,控制...     

富钙溶液中萃取与反应耦合强化CO2矿化过程

提出一种溶剂萃取与Ca²⁺碳酸化的耦合反应过程,以三丁胺为萃取剂将HCl从水相萃取到有机相,在固定CO₂的同时实现CaCl₂的碳酸化,副产碳酸钙与氯化铵。实验结果显示,超过98%的Ca²⁺在1400s内沉淀为碳酸钙,反应后有机相迅速与水相实现分层,并通过与氨水反应再生,三丁胺回收率约为98%。采用粒径分布与显微镜观察证明了Ca²⁺沉淀过程发生在油包水结构中。以15%浓度的CO₂作为碳源,反应时间为2700 s时,Ca²⁺沉淀率达到98.31%,显示该工艺将高成本的CO₂捕集过程和封存过程集成,可处理低浓度烟气中的CO₂。过程无须CO₂捕集费用以及热量输入,同时副产碳酸钙和氯化铵产品,有望缓解常规CO₂捕集封存技术高成本的难题。     

Influence of anode current density on carbon parasitic reactions during electrolysis

In the electro-deoxidation process, carbon parasitic reaction (CO₃^2- + 4e^-=C + 3O^2-) usually occurs when using carbon materials as the anode, which leads to increase of the carbon content in the final metal and decrease of the current efficiency of the process. The aim of this work is to reduce the negative effect of carbon parasitic reaction on the electrolysis process by adjusting anode current density. The results indicate that lower graphite anode area can achieve higher current density, which is helpful to increase the nucleation site of CO₂ bubbles. Most of CO₂ would be released from the anode instead of dissolution in the molten CaCl₂ and reacting with O^2- to form CO₃^2-, thus decreasing the carbon parasitic reaction of the process. Furthermore, the results of the compared experiments show that when the anode area decreases from 172.78 to 4.99 cm², CO₂ concentration in the released gases increases significantly, the carbon mass content in the final metal product decreased from 1.09% to 0.13%, and the current efficiency increased from 6.65% to 36.50%. This study determined a suitable anode current density range for reducing carbon parasitic reaction and provides a valuable reference for the selection of the anode in the electrolysis process.     

交变电磁场与超声波对硬水溶液及其结晶的影响

实验研究了交变电磁场、超声波及二者协同作用对硬水溶液pH及电导率的影响,并对实验过程中溶液内析出的碳酸钙晶体表面形态及晶体组成进行了观测与研究。研究结果表明：交变电磁场与超声波都能影响Ca（HCO₃）₂溶液内的离子水解平衡;交变电磁场能提升正、负离子的碰撞概率,促进CaCO₃晶体成核并抑制其体积增长;超声波能够促使CaCO₃沉淀的生成,同时增大溶液内离子的迁移速率,破坏晶体内碳酸根排列的有序性,诱导CaCO₃晶体缺陷性生长;通过SEM对最终生成的晶体形态观测可知,交变电磁场与超声波协同作用能够增加CaCO₃小尺寸晶体的数量,并抑制晶体体积生长,且能增加霰石在沉淀中的比例。     

氨碱废液溶采二层盐制备优级液体盐工艺研究

针对内蒙古吉兰泰盐湖补水困难、二层盐硫酸根含量高、氨碱废液排量大后处理困难等技术难题,分别探究了二层盐饱和卤水混配氨碱废液制备液体盐工艺,以及氨碱废液混兑蒸馏水后溶采二层盐制备液体盐工艺。通过在线拉曼实验,测得该反应达到平衡需要1 h以上;探究了机械搅拌速率、化学反应时间、氨碱废液与蒸馏水混配比例等因素对液体盐氯化钠、硫酸根、钙离子含量的影响。结果表明：在硫酸根和钙离子物质的量比为1∶1、25 ℃、300 r/min条件下,氯化钙和硫酸钠的反应过程是二水硫酸钙结晶过程的速率控制步骤;二层盐饱和卤水混配氨碱废液制备液体盐工艺中,在相同条件下,反应120 min后分离可获得优级液体盐;氨碱废液混配蒸馏水后直接溶采二层盐制备液体盐工艺中,氨碱废液与蒸馏水体积混配比例为1∶（5.55~6.36）、25 ℃、300 r/min条件下,反应120 min后分离可获得优级液体盐。     

DBU/甘油/CO2反应过程及动力学

1,8-二氮朵双环[5.4.0]十一碳-7-烯（DBU）-甘油溶液作为一种新型溶剂,具有低热容、高沸点等优点,目前被广泛研究应用于化学合成和产物分离等。本文考察了不同摩尔比的DBU-甘油溶液吸收CO₂效果,测定了不同摩尔比的DBU-甘油溶液吸收CO₂反应过程中体系的黏度变化,研究了DBU-甘油溶液吸收CO₂反应的动力学。结果表明,在反应温度25℃、CO₂气体流速为238mL/min的条件下,DBU与甘油摩尔比为0.49~1的溶液对CO₂的吸收量可在120min的反应时间内达到10.88g/100g溶液;DBU与甘油摩尔比为0.49∶1和1.12∶1的溶液在吸收CO₂后体系的黏度显著增大,而DBU与甘油摩尔比为0.11∶1和3.43∶1的溶液在吸收CO₂后体系的黏度变化较小。25℃、常压下,在消除扩散影响,甘油大大过量时,DBU/甘油/CO₂反应的速率方程为r=0.22C_DBUP_CO2^0.5,反应的活化能为40.44kJ/mol。     

CO2 mineralization of carbide slag for the production of light calcium carbonates

The production of polyvinyl chloride by calcium carbide method is a typical chemical process with high coal consumption, leading to massive flue gas and carbide slag emissions. Currently, the carbide slag with high CaO content is usually stacked in residue field, easily draining away with the rain and corroding the soil. In this work, we coupled the treatment of flue gas and carbide slag to propose a facile CO₂ mineralization route to prepare light calcium carbonate. And the route feasibility was comprehensively evaluated via experiments and simulation. Through experimental investigation, the Ca²⁺ leaching and mineralization reaction parameters were determined. Based on the experiment, a process was built and optimized through Aspen Plus, and the energy was integrated to obtain the overall process energy and material consumption. Finally, the net CO₂ emission reduction rate of the entire process through the life-cycle assessment method was analyzed. Moreover, the relationship between the parameters and the CO₂ emission life-cycle assessment was established. The final optimization results showed that the mineralization process required 1154.69 kW·h·(t CO₂)^-1 of energy (including heat energy of 979.32 kW·h·(t CO₂)^-1 and electrical energy of 175.37 kW·h·(t CO₂)^-1), and the net CO₂ emission reduction rate was 35.8%. The light CaCO₃ product can be sold as a high value-added product. According to preliminary economic analysis, the profit of mineralizing can reach more than 2,100 CNY·(t CO₂)^-1.