白云石的硫化氢高温脱除性能研究

用天然白云石制备了半焙烧白云石和全焙烧白云石，并在固定床上对这些白云石进行硫化氢的高温脱除性能研究，同时考察了反应温度、空速、粒子粒径对白云石脱硫性能的影响。用X射线衍射（XRD）、热重分析（TG）和气体吸附等测试手段，对脱硫剂的物相组成、结构、比表面积和孔容进行了表征。结果表明，白云石是一种很好的吸硫剂。在同样条件下，3种白云石中半焙烧白云石具有最好的脱硫效果；而对于同一种白云石，反应条件的差异也会导致其脱硫效果的变化。白云石的脱硫性能与其微观结构有密切关系。     

改性凹凸棒黏土脱除120~#溶剂油硫化物的研究

以甘肃临泽产凹凸棒黏土(以下简称凹土)为原料制备吸附剂,对120#溶剂油进行脱硫实验,同时采用脱硫率、X射线衍射(XRD)和红外光谱(IR)对吸附剂进行了表征.结果表明:(1)以临泽凹土为原料制备吸附剂的最佳条件为焙烧时间3.0h、焙烧温度350℃、未精制吸附剂质量和溶剂油体积的比值1∶5 g/mL、脱硫时间75 min.按此最佳条件制备吸附剂,可将120#溶剂油含硫量由424 μg/g降至213 μg/g.脱硫率可以达到49.8％.(2)经过XRD及IR分析,120 #溶剂油中的硫被脱除后在吸附剂中以硫醚和CaS的形式存在.用浸渍法制备的吸附剂达到了一定的脱硫效果.     

焙烧条件对CuO/ZSM-5催化剂脱硫脱硝性能的影响

以ZSM-5分子筛为载体,通过浸渍法制备10％ CuO/ZSM-5(金属氧化物质量占载体质量)催化剂,以CH4为还原气,考察不同焙烧温度和焙烧时间对催化剂脱硫脱硝性能的影响.XRD和TPR的表征结果显示,最佳焙烧条件为550℃下焙烧4h,在此焙烧条件下,10％ CuO/ZSM-5催化剂达到的最高脱硝脱硫率分别为90.6％和98.8％.     

金属负载型催化剂对烟气脱硫性能的影响

介绍了国内外烟气脱硫催化剂的研究现状,研究了金属氧化物负载型催化剂对烟气脱硫性能的影响。以活性炭(AC)为载体,选用8种不同的金属硝酸盐作为浸渍液,采用等体积浸渍法制备金属氧化物负载型催化剂。以脱硫效果较好的Fe2O3/AC为例,研究了不同焙烧温度、金属负载量以及焙烧时间对催化剂脱硫性能的影响。实验结果表明,Fe2O3/AC催化剂脱硫率随着金属负载量的增加呈递增趋势,最优金属负载量为10.0%(质量分数);脱硫率随着焙烧温度的增加显著提高,最优焙烧温度为350℃;脱硫率随着焙烧时间的增加而提高,最优焙烧时间为3.0h。     

石灰石高温煤气脱硫的试验研究

采用天然石灰石做脱硫剂,在固定床上进行硫化氢高温脱除的试验研究,考察了脱硫剂粒径、反应温度、气速及高温煤气中H2对石灰石脱硫性能的影响,同时还用热重分析(TG)、扫描电镜(SEM)、X-射线衍射(XRD)等测试手段对脱硫剂的物相组成和结构等进行了表征。结果表明,脱硫剂的粒径对脱硫效果的影响很大,0.38～0.83 mm的石灰石脱硫效果最佳;温度对脱硫效果的影响比较复杂,最佳的操作温度为850℃;气速对脱硫效果的影响较明显,脱硫剂的穿透时间随气速的减小而加长;H₂对脱硫过程起阻碍作用,气速越小,这种阻碍作用越明显。     

含钒钢渣低温钠化焙烧钒浸出效果及其焙砂湿法脱硫作用

含钒钢渣钠化焙烧过程中添加CaF_2等助剂以降低提钒工艺的能耗,分析了不同因素对低温钠化焙烧后钒浸出效果的影响,并将含钒钢渣焙砂配制成吸收浆液以净化烟气中的SO_2。在浸出钒实现其资源化利用的同时,也探索出一种高效烟气脱硫的新方法。添加3.0%CaF_2作为助剂,温度为700℃、焙烧时间为1 h的条件下,所得焙砂中钒浸出率可达68.1%。X射线衍射(XRD)与热重(TG)分析表明,混合物料中添加CaF_2助剂能促进焙烧过程物相的改变,白云母、钛铁矿等衍射峰明显减弱,含钒钢渣混合料在700℃条件下便呈现明显的热失重,在较低温度条件下即可实现钠化焙烧。以此含钒焙砂配制脱硫吸收浆液,脱硫率不低于95%的穿透时间可达125 min,而同样条件下磷矿浆脱硫系统仅为35 min。     

Fe_2O_3/TiO_2/γ-Al_2O_3催化剂同时脱硫脱硝性能

以溶胶凝胶法制备的15%TiO_2/γ-Al_2O_3为载体,通过浸渍法制备12%Fe_2O_3/15%TiO_2/γ-A_l2O_3催化剂,采用XRD和TPR对催化剂结构和性质进行表征,并考察不同焙烧温度、焙烧时间和载体对催化剂脱硫脱硝性能的影响。结果显示,最佳焙烧条件为500℃下焙烧3 h,12%Fe_2O_3/15%TiO_2/γ-Al_2O_3催化剂达到的最高脱硝脱硫率分别为98.2%和95.4%。     

均匀设计法处理含硫废水的研究

对钠盐型和铵盐型含硫工业废水进行脱硫处理,采用均匀设计法设计试验,得到定量描述试验内在规律的多元非线性回归方程.用该回归方程计算的预测值与试验结果一致.对影响脱硫效果和脱硫效率的影响因素--絮凝剂投加量、pH以及废水含硫量进行了考察.利用回归方程,对反应体系进行了模拟优化处理.研究表明,在试验条件下,用聚合氯化铝作为絮凝剂、pH=7的条件下,采用两段工艺,可以使脱硫后废水含硫量降至40 mg/L以下,满足下游污水处理装置对含硫量的要求.     

微波辐照糠醛渣制备活性炭及其性能研究

以糠醛渣及废炭粉为原料,通过掺合活化剂K2CO3成形后,在微波辐照下活化制备活性炭.研究K2CO3掺合比、辐照功率、活化气体CO2流量、辐照时间对活性炭结构与脱硫性能的影响,并设计正交实验优化工艺条件.结果表明,在最佳工艺条件下,即K2CO3掺合比为1.0:2.0(质量比)、辐照功率为640 W、CO2流量为200 mL/min、辐照时间为10 min时,活性炭的吸附和脱硫性能较佳.扫描电镜和脱硫实验表明,后处理前后的活性炭在结构和脱硫性能以及脱硫机制上差异较大.     

气升式反应器中微生物烟气脱硫研究

基于微生物酸性铁溶液烟气脱硫特性,实验构建了一套内循环气升式反应器.在反应器中,利用处于对数生长期的氧化亚铁硫杆菌(Thiobacillus ferrooxidans)酸性铁溶液进行了模拟烟道气SO2脱除实验研究.为寻求高脱硫率,实验研究了铁离子浓度、入口氧含量、细菌数和pH值的变化对脱硫率的影响.考察了反应液中Fe(Ⅱ)离子浓度的变化规律.实验表明,含T.f菌酸性铁溶液的脱硫效果较高;Fe离子浓度在7.67 g/L左右时脱硫率最佳;入口气中氧含量、反应液中细菌数和pH值越高,反应液的脱硫率也就越高.反应液中的Fe(Ⅱ)离子浓度是一先扬后抑的变化过程.     

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.     

On the Intrinsic High Temperature Calcium Oxide-Sulfur Dioxide Reaction Using the Vacuum Thermogravimetric Analysis Technique

Abstract

The high temperature CaO/SO2 reaction was studied using four Swedish limestones and one dolomite as sorbents. The measurements were carried out in a vacuum thermogravimetric analysis (TGA) apparatus in order to investigate the intrinsic reaction mechanism. The reaction was found to be fast at the beginning due to the surface reaction, while the subsequent stage was controlled by the product layer diffusion, showing a lower reaction rate. The reaction rate increased as temperature increased up to 1000 °C in the range tested. SO2 partial pressure weakly affected the reaction. The fine sorbent particles used in the study resulted in the high CaO conversion. Further grinding of the sorbents gave a small increase in CaO conversion. Sintering generally decreased the initial reactivity but might not affect the ultimate CaO capacity. The larger pores in nascent CaO particles were valuable for the initial reaction conversion.     

共沉淀法制备铁锌基中高温煤气脱硫剂

采用共沉淀法制备Cu—Zn—Fe脱硫剂,优化共沉淀制备工艺。固定床实验结果表明,共沉淀溶液中金属离子总浓度为0．6mol／L,焙烧温度600℃,添加10％活性助剂Cu时所得Cu—Zn—Fe脱硫剂循环脱硫性能最佳,此时ZFDCu10脱硫剂的硫容可达到41．2gS／100g脱硫剂。XRD和SEM对铁锌基脱硫剂的表征结果表明,加入Cu助剂后少量的ZnO、CuO可阻碍ZnFe2O4晶粒聚集,增强铁锌基脱硫剂活性组分的分散性,避免大晶粒的ZnFe2O4硫化时形成较多的产物层而降低脱硫剂的利用率。实验结果为制备脱硫性能较好的Cu-Zn-Fe脱硫剂提供了理论依据。     

钙基吸附剂捕集生物质燃气中的二氧化碳

生物质热解燃气中CO2的捕集,是提高燃气热值和实现碳减排的关键问题之一。为利用生物质热解燃气温度偏高的特点,拟通过化学吸附方法,捕集燃气中高浓度的CO2。为此,利用不同钙基前驱物制备了系列钙基固体吸附剂,系列钙基固体吸附剂对CO2的单次吸附和循环吸附实验结果表明,含钙和镁氧化物混合物的吸附剂具有较稳定的循环吸附特性以及较大的吸附负荷。孔结构特性分析表明,适宜于CO2吸附的有效孔径范围可能为小于4 nm。因此,可以通过对天然白云石的改性获得合适孔径的钙镁基固体吸附剂,达到有效捕集生物质燃气中CO2的目的。     

Pore Structure Effects on Ca-Based Sorbent Sulfation Capacity at Medium Temperatures: Activated Carbon as Sorbent/Catalyst Support

Abstract

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?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 sul-fated 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/cata-lysts 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 des-ulfurization 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.     

The utilization of catalyst sorbent in scrubbing acid gases from incineration flue gas

Catalyst sorbents based on alumina-supported CuO, CeO2, and CuO-CeO2 were applied to a dry scrubber to clean up the SO2/HCl/NO simultaneously from pilot-scale fluidized-bed incineration flue gas. In the presence of organic compounds, CO and the submicron particles SO2 and HCI removed by the fresh catalyst sorbents and NO reduced to N2 by NH3 under the catalysis of fresh and spent desulfurization/dechloridization (DeSO2/DeHCl) catalyst sorbents (copper compounds, Cu, CuO, and CuSO4) were evaluated in this paper. The fresh and spent catalyst sorbents were characterized by the Brunner-Emmett-Teller method (BET), X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), inductively coupled plasma-mass spectrometry (ICP-MS), and the elemental analyzer (EA). The study showed that the performances of CuO, CeO2, and CuO-CeO2/gamma-Al2O3 were better than that of Ca(OH)2. The removal efficiency of SO2 and HCl was 80-95% in the dry scrubber system. Under NH3/NO = 1, NO could not be reduced to N2 because it was difficult to control the ratio of air/fuel in the flue gas. For estimating the feasibility of regenerating the spent catalyst sorbents, BET and EA analyses were used. They indicated that the pore structures were nearly maintained and a small amount of carbon accumulated on their surface.     

NiOγ／-Al2O3反应吸附苯并噻吩

以等体积浸渍法制备了负载型NiOγ／-Al2O3吸附剂,在固定床反应装置上对含苯并噻吩的模型化合物进行反应吸附脱硫实验,考察了NiO负载量、模型化合物硫含量及活性组分的形态对吸附剂脱硫性能的影响,并用XRD、SEM—EDS分析、XPS分析对载体和吸附剂进行了表征。实验结果表明：NiOγ／-Al2O3吸附剂具有较高的穿透硫容,能有效脱除模型化合物中的苯并噻吩;反应过程中生成了NiS;C的沉积以及Ni的硫化物的生成导致了吸附剂的失活。     

Laboratory study on the high-temperature capture of HCl gas by dry-injection of calcium-based sorbents

This is a laboratory study on the reduction of combustion-generated hydrochloric acid (HCl) emissions by in-furnace dry-injection of calcium-based sorbents. HCl is a hazardous gaseous pollutant emitted in significant quantities by municipal and hazardous waste incinerators, coal-fired power plants, and other industrial furnaces. Experiments were conducted in a laboratory furnace at gas temperatures of 600-1000 degrees C. HCl gas diluted with N2, and sorbent powders fluidized in a stream of air were introduced into the furnace concurrently. Chlorination of the sorbents occurred in the hot zone of the furnace at gas residence times approximately 1 s. The sorbents chosen for these experiments were calcium formate (CF), calcium magnesium acetate (CMA), calcium propionate (CP), calcium oxide (CX), and calcium carbonate (CC). Upon release of organic volatiles, sorbents calcine to CaO at approximately 700 degrees C, and react with the HCl according to the reaction CaO + 2HCl <=> CaCl2 + H2O. At the lowest temperature case examined herein, 600 degrees C, direct reaction of HCl with CaCO3 may also be expected. The effectiveness of the sorbents to capture HCl was interpreted using the "pore tree" mathematical model for heterogeneous diffusion reactions. Results show that the thin-walled, highly porous cenospheres formed from the pyrolysis and calcination of CF, CMA, and CP exhibited high relative calcium utilization at the upper temperatures of this study. Relative utilizations under these conditions reached 80%. The less costly low-porosity sorbents, calcium carbonate and calcium oxide also performed well. Calcium carbonate reached a relative utilization of 54% in the mid-temperature range, while the calcium oxide reached an 80% relative utilization at the lowest temperature examined. The data matched theoretical predictions of sorbent utilization using the mathematical model, with activation energy and pre-exponential factors for the calcination reaction of 17,000 K and 300,000 (g gas/cm2/s/atm gas), respectively. Thus, the kinetics of the calcination reaction were found to be much faster (approximately 500 times) than those of the sulfation reaction examined previously in this laboratory.     

Optimizing the specific surface area of fly ash-based sorbents for flue gas desulfurization

High performance sorbents for flue gas desulfurization can be synthesized by hydration of coal fly ash, calcium sulfate, and calcium oxide. In general, higher desulfurization activity correlates with higher sorbent surface area. Consequently, a major aim in sorbent synthesis is to maximize the sorbent surface area by optimizing the hydration conditions. This work presents an integrated modeling and optimization approach to sorbent synthesis based on statistical experimental design and two artificial intelligence techniques: neural network and genetic algorithm. In the first step of the approach, the main and interactive effects of three hydration variables on sorbent surface area were evaluated using a full factorial design. The hydration variables of interest to this study were hydration time, amount of coal fly ash, and amount of calcium sulfate and the levels investigated were 4-32 h, 5-15 g, and 0-12 g, respectively. In the second step, a neural network was used to model the relationship between the three hydration variables and the sorbent surface area. A genetic algorithm was used in the last step to optimize the input space of the resulting neural network model. According to this integrated modeling and optimization approach, an optimum sorbent surface area of 62.2m(2)g(-1) could be obtained by mixing 13.1g of coal fly ash and 5.5 g of calcium sulfate in a hydration process containing 100ml of water and 5 g of calcium oxide for a fixed hydration time of 10 h.