Effect of binder on the properties of iron oxide sorbent for hot gas desulfurization

The most difficult problem in hot gas desulfurization in Integrated Coal Gasification Combined Cycle （IGCC） is the pulverization of sulfur removal sorbents.Appropriate binders for hot gas sulfur removal sorbents can solve the pulverization problem.In this paper,six sorbents with binders of different argillaceous minerals were prepared by mechanical mixing method.Desulfurization behavior for hot gas desulfurization sorbents was investigated in a fixed-bed reactor.Result showed that sorbent NTKW2 with binder of clay had a better sulfidation performance.NTKW2 had a more stable performance than other sorbents in the continuous sulfidation-regeneration cycles.Sulfur capacity of sorbent remained the same in each cycle.The desulfurization efficiency and mechanical strength of NTKW2 were the best among the tested sorbents.The behavior of NTKW2 at different temperatures showed different performances,and the best reaction temperature was 550 ℃.Higher heat stability,sulfur capacity and desulfurization efficiency were found on NTKW2 in six continuous sulfidation-regeneration cycles.

Research on improvement in Zn-based sorbent for hot gas desulfurization

Two Zn-based sorbents, L-991 and L-992 used for hot gas desulfurization (HGD) were introduced. Zn/Ti ratio of the two sorbent was 1:1 and 2:3 resptively and a certain proportion of Cu and Mn metal oxide were added into L-992, which provided better performance than L-991 in aspects of suitable work temperature, sulfur capacity and agglomeration on the surface of sorbent particles. The evaluation tests were done on both sorbents include multi cycles tests. ARD and SEM analysis were done on fresh and post tests sorbent. During continuous sulfidation/regeneration, the H2S concentra- tion can be reduced from about 10 g/m3 to less than 20 mg/m3, the H2S removal effi- ciency >99 %.

Bench-Scale Testing of Zinc Ferrite Sorbent for Hot Gas Clean-up

Advanced integrated gasification combined cycle （IGCC） power generation systems require the development of high-temperature, regenerable desulfurization sorbents, which are capable of removing hydrogen sulfide from coal gasifier gas to very low levels. In this paper, zinc ferrites prepared by co-precipitation were identified as a novel coal gas desulfurization sorbent at high temperature. Preparation of zinc ferrite and effects of binders on pore volume, strength and desulfurization efficiency of zinc ferrite desulfurizer were studied. Moreover, the behavior of zinc ferrite sorbent during desulfurization and regeneration under the temperature range of 350-400 ℃ are investigated. Effects of binders on the pore volume, mechanical strength and desulfurization efficiency of zinc ferrite sorbents indicated that the addition of kaolinite to zinc ferrite desulfurizer seems to be superior to other binders under the experimental conditions.

Experimental study on SO_2 recovery using a sodium-zinc sorbent based flue gas desulfurization technology

A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.

DEVELOPMENT OF SMOVEN PROCESS FOR HOT GAS DESULFURIZATION

The Beijing Research lnstitute of Coal Chemistry (BRICC) is developing the SMOVEN process for hot gas desulfurization. The SMOVEN process features sulfidation in an entrained bed,regeneration in a low velocity fluid bed or a moving bed with oxygen and sorbent circuIation con-trolled by gas stream. A series of tests on the bench scale unit and the continuous process devel-opment unit were carried out. The regenerable metal oxide sorbents were adopted for the sulfur-related components removing from coal gas at the temperature of 550-650℃. A fluidized bed gasifier of 100 mm (id) generated coal gas for tests. The principle of SMOVEN process has been positively verified.

Desulfurization kinetics of ZnO sorbent loaded on semi-coke support for hot coal gas

Zn-based sorbent （Z20SC） prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp（-8.270×103/RgT） and Dep=1.262×10-4exp（1.522×104/RgT）.It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.

New nanostructured sorbents for desulfurization of natural gas

Desulfurization of natural gas is achieved commercially by absorption with liquid amine solutions. Adsorption technology could potentially replace the solvent extraction process, particularly for the emerging shale gas wells with production rates that are generally lower than that from the large conventional reservoirs, if a superior adsorbent （sorbent） is developed. In this review, we focus our discussion on three types of sorbents： metal- oxide based sorbents, Cu/Ag-based and other commercial sorbents, and amine-grafted silicas. The advantages and disadvantages of each type are analyzed. Possible approaches for future developments to further improve these sorbents are suggested, particularly for the most promising amine-grafted silicas.

Regeneration of Fe_(2)O_(3)-based high-temperature coal gas desulfurization sorbent in atmosphere with sulfur dioxide

Regeneration of a high-temperature coal gas desulfurization sorbent is a key technology in its industrial applications.A Fe_(2)O_(3)-based high-temperature coal gas desulfurizer was prepared using red mud from steel factory.The influences of regeneration temperature,space velocity and regeneration gas concentration in SO_(2) atmosphere on regeneration performances of the desulfurization sorbent were tested in a fixed bed reactor.The changes of phase and the composition of the Fe_(2)O_(3)-based high-temperature coal gas desulfurization sorbent before and after regeneration were examined by X-ray diffraction(XRD)and X-ray Photoelectron spectroscopy(XPS),and the changes of pore structure were characterized by the mercury intrusion method.The results show that the major products are Fe3O4 and elemental sulfur;the influences of regeneration temperature,space velocity and SO_(2) concentration in inlet on regeneration performances and the changes of pore structure of the desulfurization sorbent before and after regeneration are visible.The desulfurization sorbent cannot be regenerated at 500℃ in SO_(2) atmosphere.Within the range of 600℃-800℃,the time of regeneration becomes shorter,and the regeneration conversion increases as the temperature rises.The time of regeneration also becomes shorter,and the elemental sulfur content of tail gas increases as the SO_(2) concentration in inlet is increased.The increase in space velocity enhances the reactive course;the best VSP is 6000 h^(-1) for regeneration conversion.At 800℃,20 vol-%SO_(2) and 6000 h^(-1),the regeneration conversion can reach nearly to 90%.

Desulfurization performance of iron-manganese-based sorbent for hot coal gas

A series of iron-manganese-based sorbents were prepared by co-precipitation and physical mixing method,and used for H_(2)S removal from hot coal gas.The sulfidation tests were carried out in a fixed-bed reactor with space velocity of 2000 h^(-1)(STP).The results show that the suitable addition of manganese oxide in iron-based sorbent can decrease H_(2)S and COS concentration in exit before breakthrough due to its simultaneous reaction capability with H_(2)S and COS.Fe3O4 and MnO are the initial active components in iron-manganese-based sorbent,and FeO and Fe are active components formed by reduction during sulfidation.The crystal phases of iron affect obviously their desulfurization capacity.The reducibility of sorbent changes with the content of MnO in sorbent.S7F3M and S3F7M have bigger sulfur capacities(32.68 and 32.30 gS/100 g total active component),while S5F5M has smaller sulfur capacity(21.92 gS/100 g total active component).S7F3M sorbent has stable sulfidation performance in three sulfidation-regeneration cycles and no apparent structure degradation.The sulfidation performance of ironmanganese-based sorbent is also related with its specific surface area and pore volume.

A review on research and development of iron-based sorbents for removal of hydrogen sulfide from hot coal gases

In poly-generation and integrated gasificationcombined cycle(IGCC)systems for clean energy conversion,it is essential to remove impurities such as sulfur species from hot coal gases prior to entering the subsequent units.This paper provides a comprehensive review on previous studies on high temperature removal of hydrogen sulfide from high temperature coal gases using iron-based sorbents.A two-step desulphurization process for hot coal gas cleanup is highlighted,which is integrated with direct production of elemental sulfur during regeneration of ironbased sorbents in the primary desulphurization step.Different kinetic modeling approaches for sulfidation and regeneration were compared.Limited research on activated carbon supported sorbents was also briefly summarized.

Cold Model Study on Mg Desulfurization of Hot Metal Under Mechanical Stirring

The new method of in-situ desulfurization with mechanical stirring of new type impellers was introduced, in which the bubble＇s dispersion and disintegration of magnesium vapor were the key to boosting the desulfurization efficiency and increasing the utilization rate of magnesium. Effects of different new type of impellers on bubble dis persion and disintegration were studied through bubble image analysis, gas-liquid mass transfer, and power con- sumption levels of different impeller structures. The results showed that the sloped swept-back blade impeller-2 pro- duces optimal bubble＇s dispersion and disintegration, as well as higher volumetric mass transfer coefficient and CO2 gas utilization while consuming the least power. Numerical simulation result with Fluent software also showed that the sloped swept-back blade impeller-2 has higher turbulent kinetic energy and better velocity distribution than the other two impellers.

Kinetics of hot metal desulfurization by bottom blowing magnesium vapor

To solve the technical problems of hot metal desulfurization by injecting magnesium particulate,a new idea of hot metal desulfurization by bottom-blowing magnesium vapor was put forward.The reaction mechanism of hot metal desulfurization with magnesium vapor injection was analyzed,and the kinetic model of the desulfurization rate during the process of hot metal desulfurization with magnesium vapor injection was established.The dimensionless equation of the gas–liquid mass transfer coefficient under the injection conditions was obtained by the dimensional analysis method.And the theoretical calculation results were in good agreement with the experimental measurements.The results show that the diameter of the bubbles and the viscosity of the melt significantly affect the desulfurization rate of hot metal injected with magnesium vapor.When the temperature is 1573 K and the gas flow rate is 3 L/min,the desulfurization rate can reach 79%and the utilization rate of magnesium can reach 83%.

高温煤气脱硫 Ⅰ．铁锌基脱硫剂脱硫工艺条件及硫化动力学

用自制的铁酸锌高温煤气脱硫剂研究了硫化氢浓度、硫化温度、空速对脱硫反应及脱硫剂物理性质的影响。结果表明：铁酸锌脱硫剂的反应活性随着Ｈ２Ｓ浓度及硫化温度的升高而升高，脱硫温度为５５０℃时，脱硫剂的硫容量最高，脱硫剂的物理性质基本保持不变；硫化空速为８５０ｈ￣（－１）时，空速和反应时间同时达到最大值。硫化反应可用未反应核收缩模型描述，得到了转化率与时间之间的动力学方程。

钛酸锌高温煤气脱硫剂再生行为的研究

在热天平装置上研究了再生反应温度、反应气体中氧气体积分数、脱硫剂颗粒粒径对钛酸锌高温煤气脱硫剂再生行为的影响。实验结果表明,较高的反应温度和氧气体积分数,较小的颗粒粒径有利于提高脱硫剂的再生反应速率。由于二次反应的影响,脱硫剂再生过程中有硫酸盐生成,提高反应温度或降低反应气体的氧气体积分数可以减少硫酸盐的生成。利用收缩核模型对其动力学行为进行了分析,结果表明,脱硫剂的再生过程存在动力学控制步骤的转移。脱硫剂再生转化率较低(<65%)时,再生过程主要受化学反应控制;再生转化率较高(>75%)时,再生过程主要受颗粒内扩散控制。表观化学反应速率常数的指前因子为8.01×10-2m/s,活化能为19.11 kJ/mol;有效扩散系数的指前因子为3.12×10-4m2/s,扩散活化能为48.84 kJ/mol。

热煤气脱硫工艺基础特性研究

本文介绍了在加压流化床脱硫间歇试验装置上进行的热煤气脱硫工艺基础特性研究结果，利用美国ＵＣＩ公司制备的高温钛酸锌脱硫剂研究了反应温度、压力、气体速度等因素对煤气脱硫过程的影响；比较了不同再生介质以及不同再生条件下的脱硫剂再生行为；多循环试验验证了空气及纯氧直接再生的可行性；试验结果表明，当脱硫温度为５５０～６５０℃、进口煤气中Ｈ２Ｓ为０．５～１．５％时，脱硫出口气体中Ｈ２Ｓ为百万分之２０；低氧浓度气体可对高硫容量的脱硫剂进行再生，为获得高品质的再生尾气和提高再生速度，只要控制适当的硫容饱和度和采用相应的工艺参数，高氧浓度介质或纯氧直接再生是可行的。本研究工作为加压热煤气ＳＭＯＶＥＮ工艺开发研究的基础内容。

钛酸锌高温煤气脱硫剂的活性评价及表征

对钛酸锌高温煤气脱硫剂固定床的寿命进行61个循环的不间断评价试验,历时2 500 h;对不同工艺条件下脱硫剂脱硫活性、再生条件及使用寿命进行了试验研究.试验结果表明:脱硫温度600℃时脱硫剂的穿透硫容最高,表明脱硫剂的活性最好;进口H2S浓度对脱硫剂活性有一些影响,但不是很大;脱硫时空速加大可以有限地提高脱硫剂的穿透硫容.但空速过高时会使脱硫剂的脱硫效率下降;脱硫剂为700℃再生时效果最好;在61个循环的不间断地评价试验过程中,脱硫剂的穿透硫容呈缓慢下降趋势,最终仍能保持在初始硫容的70%左右.

高温煤气脱硫吸附剂的研制

叙述了用物理混合法制备高温煤气脱硫吸附剂的工艺研究及其参数的优化选择，并对所研制的锌铁、锌钛等几个吸附剂进行化学活性和物理特性的表征。从而求得吸附剂的某些物理特性与其脱硫性能的关系。

高温煤气金属脱硫剂的研究进展

煤的清洁转化利用符合中国的能源结构,高温煤气脱硫是提高能源利用率的关键技术。本文综述了单一金属氧化物和复合金属氧化物干法脱除H2S的研究进展,对比分析了单一金属氧化物在脱硫效率、使用温度和再生方面的优缺点,指出由于单一金属氧化物脱硫剂不能满足实际生产需要,因此兼有单一金属氧化物优点的复合金属脱硫剂成为未来研究方向。同时,论述了复合金属脱硫剂的制备原则、脱硫效率及再生等方面的研究状况。在此基础上,重点对铁酸锌和钛酸锌两种具有代表性的复合脱硫剂及其他复合金属脱硫剂进行了介绍。

铁锰高温煤气脱硫剂的程序升温还原(TPR)行为研究

考察了Fe-Mn复合氧化物脱硫剂的H2-TPR和CO-TPR还原行为,并与氧化铁和氧化锰脱硫剂的还原行为进行比较。结果表明:氧化锰脱硫剂较氧化铁脱硫剂更易被H2还原;焙烧温度从300℃升高到500℃,脱硫剂中氧化锰活性组分还原性变弱,但对氧化铁活性组分还原性影响不大;焙烧温度升高至750℃,脱硫剂还原性变弱。随着脱硫剂中锰相对含量的增大,脱硫剂的还原性变强,还原峰前移。铁锰摩尔比对脱硫剂中氧化铁活性组分的CO-TPR还原行为影响不大,但对活性组分氧化锰的还原行为有一定影响。

高温煤气脱硫剂铁酸锌的性能及再生研究

以共沉淀法制备的铁酸锌作为脱硫剂的活性组分制备了一种新型的高温煤气脱硫剂。对不同工艺条件下脱硫剂脱硫活性、再生条件及使用寿命进行了研究。结果表明,铁酸锌脱硫剂的脱硫效果显著,较高的温度下可得到高的硫容量;高的氧气含量可加快其再生速率,但硫容量会有所降低。