活性炭催化剂上甲基叔丁基醚裂解反应动力学的研究

常压下,在265～295℃温度范围内,用内循环无梯度反应器对甲基叔丁基醚(MTBE)在CRN型活性炭催化剂上裂解制异丁烯的反应动力学进行了研究。研究结果表明,裂解反应由吸附的MTBE生成非吸附产物的不可逆表面反应所控制,其本征动力学方程为 (-r_A)=κP_A/(1+κ_AP_A)式中κ=2.6167×10~9 exp(-1.4730×10~2/RT) κ_A=8.6829×10~6 exp(-1.1661×10~2/RT)     

Cu-K/Al_2O_3催化剂上溴甲烷合成二甲醚的失活动力学研究

采用Cu-K/Al2O3催化剂,在固定床积分反应器上进行溴甲烷合成二甲醚的动力学实验,反应温度(463.15~523.15)K条件下,得出主反应的宏观动力学方程:r=1.1+2.8×10-3T-4.4exp(-21.5/RT)pCH3Br,主反应的活化能约为21.5 k J·mol-1。对主反应宏观动力学方程进行统计检验,结果表明,在给定99%的置信度下,方程显著、可信。失活前后的XRD表征结果表明,催化剂晶相由Cu O转变为Cu Br2是导致催化剂失活的主要原因。采用独立失活机理描述催化剂失活速率方程,通过回归得到各项参数,建立了适用于Cu-K/Al2O3催化剂上溴甲烷合成二甲醚的失活动力学方程:r=[-1.1+2.8×10-3T-4.4exp(-21.5/RT)pCH3Br]×exp(-2.1×10-3t)。     

对氯甲苯催化氯化反应动力学研究

在温度为298.15～348.15 K,采用SbCl3(质量分数为1.5% )为催化剂,将对氯甲苯(p-CT)催化氯化合成2,4-DCT和3,4-DCT.实验结果得出p-CT催化氯化的反应动力学方程式为:(d[p-CT]/dt =k[p-CT], k = 8.969×10exp ((1575.451/T);并得出2,4-DCT和3,4-DCT的反应动力学方程,可分别表示为:d[2,4-DCT]/dt=[p-CT]0×[ka/(ka-kc)]×[ka exp((kat)(kc exp((kct)],d[3,4-DCT]/dt=[p-CT]0×[kb/(kb(kd)]×[kb exp((kbt) (kd exp((kdt)],其中:ka = 9.558×10 exp ((1687.561/T), kb = 9.757×exp((1298.839/T),kc = 1.687×102exp((2378.880/T),kd=8.189×102exp((2184.041/T),结果表明p-CT催化氯化反应过程为一级平行反应.还考察了催化剂浓度对p-CT催化氯化合成DCT过程的反应速率常数的影响.     

正庚烷在镍系水蒸汽转化催化剂上的恒速积碳和随即恒速消碳的动力学研究

本文研究了460—550℃,一个大气压下,正庚烷在国产RKN催化剂上,水蒸汽转化过程中的积碳和随即的水蒸汽消碳动力学.得到了无水蒸汽下恒速积碳速率γ_0=1.99×10~7exp[-16100/RT]P_(Hep)~(0.97)kg(C)/kg(cat.)h,有水蒸汽下的恒速积碳速率γ_c=4.71×10~6exp[-18600/RT]P_(Hep)~(0.94)P_(H_2O)~(-0.96)kg(C)/kg(cat.)h;以及无水蒸汽下积碳累积量约40mg后,用水蒸汽消碳的恒速消碳速率γ_0~’=3.75×10~8exp[-30000/RT]kg(C)/kg(cat)h,和有水蒸汽时积碳约40mg后,即用水蒸汽消碳的恒速消碳速率γ_c~’=4.52×10~8exp[-29600/RT]×[1十0.27×ln(P_(Hep)/P_(H_2O))]kg(C)/kg(cat)h的动力学方程式.讨论了反应级数、反应活化能和指前因子以及水蒸汽的作用.提出了水蒸汽的作用不单是气化已生成的积碳,其更本质的作用是抑制和消除碳须核(Carbon fibre nuclei)的形成和生长的观点.     

合成己二腈宏观反应动力学的研究

本文对于以磷酸为催化剂,用熔融(液相)已二酸与气相氨作用生成己二腈的反应过程,研究了中和与脱水反应的宏观动力学。实验考察了温度、时间和催化剂浓度等对反应的影响,结果表明中和反应是受传质和化学反应动力学共同影响的快速反应。在 C_B≥3.5%时,反应对己二酸浓度为一级,在 C_B<3.5%时,属于动力学控制的二级反应,其速率常数为:k_1=3.31×10~4exp[-(13.8-158C_P)×10~3/RT]k_2=3.07×10~4exp[-(23.4-420C_P)×10~3/RT]同时提出了总脱水为一级反应,其速率常数为:k=1.03×10~8exp{-[23.6+2.07exp(-644C_P)]×10~3/RT}     

活性炭负载硫酸氢钠催化合成乙酸丁酯动力学

在间歇反应釜中以活性炭负载硫酸氢钠为催化剂,丁醇和乙酸为原料催化合成乙酸丁酯。在消除内外扩散影响的前提下,以初始速率法回归动力学方程。结果表明:在催化剂粒径小于0.075 mm,实验转速为200 r/min条件下,反应内外扩散可以消除。在实验范围内获得了本征动力学方程,反应动力学方程表达式为:-r_A=f(w)k_0exp(-E_a/RT)(C_AC_D-C_EC_W/K)=(0.028w+0.0135)×4.31×10~5×exp(-4.39×10~4/RT)×(C_AC_D-C_EC_W/2.78)。其中,反应活化能为43.99 kJ·moL~(-1),指前因子k0=4.31×10~5 moL~(-1)·L·min~(-1)。     

半水煤气甲烷化耐硫催化剂的研制及其本征动力学的测试

本文叙述了所研制的半水煤气甲烷化耐硫催化剂所具有的物化特征.活性温度范围400～550℃,压力不小于0.6MPa,原料气中硫含量500～5000ppm(mol),空速1000h~(-1)左右,一氧化碳转化率约为40%,其本征动力学方程dN_(CH_4)/dw=1.120×10~(-6)exp(-7.788×10~4/RT)P~(1.13)y_(H_2O)~(0.4)y_(CO)~(0.73)dN_(CO_2)/dw=1.767×10~(-7)exp(-7.423×10~4/RT)P~(1.39)y_(CO)~(0.16)y_(H_2O)~(1.23)(1-β)     

钾长石焙烧熟料的浸出动力学

以钾长石和Na2CO3焙烧熟料为原料,研究其在NaOH溶液中的浸出动力学. 考察了在不同温度和搅拌强度条件下SiO2浸出率与时间的关系. 结果表明,SiO2浸出的优化工艺条件为：浸出温度95℃、搅拌强度400 r/min、熟料粒度74~89 mm、NaOH溶液浓度0.2 mol/L和浸出时间80 min. 在该条件下,SiO2浸出率可达99%. 熟料浸出过程受无固体膜生成的化学反应和外扩散混合控制. 浸出过程分为两个阶段：0~10 min为反应前期,10~80 min为反应后期,表观活化能分别为15.24和29.94 kJ/mol. 前期和后期的浸出动力学方程分别为1-(1-a)1/3=7.074exp[-15239/(RT)]t和1-(1-a)1/3=45.85exp[-29940/(RT)]t.     

活性炭负载硫酸氢钠催化合成乙酸苯甲酯研究

通过浸渍法制备了负载型催化剂(NaHSO4/C),并将其应用于乙酸苯甲酯的合成,考察了催化剂用量、反应温度、酸醇物质的量比对反应酯化率的影响,并获得了动力学方程,结果表明:在乙酸与苯甲醇的物质的量比为1∶3,催化剂用量为1.8g/0.15mol乙酸,反应温度80℃,带水剂用量20mL的条件下酯化率达到92.9%。动力学方程表达式为:-rA=-dcAdt=1.366×107exp(-76070/RT)cAcB,反应活化能为76.07kJ/moL,指前因子为1.366×107 L/(moL·s)。     

骨架锌Zn-HZSM-5分子筛催化剂上甲醇制汽油反应动力学（英文）

通过水热晶化法,合成含有骨架杂原子Zn的Zn-HZSM-5分子筛催化剂,采用XRD、BET、NH3-TPD表征催化剂结构和物化性能,在微型固定床反应器中测定催化剂的甲醇制汽油反应性能和反应动力学数据,研究Zn-HZSM-5分子筛催化剂的甲醇制汽油本征反应动力学。结果表明,杂原子Zn引入ZSM-5分子筛骨架后增加对产物汽油选择性有利的弱酸量。采用Chen and Reagan建立的甲醇制汽油三集总动力学模型,通过四阶龙格库塔法和最小二乘法对实验数据的回归,计算反应速率常数为k_1=1. 154×10~(12)exp (-97600/RT),k_2=0. 687×10~(12)exp (-105200/RT)和k_3=1. 739×10~7exp (-84700/RT)。以目标残差函数OF参数值为检验模型的标准,模拟值和实验值的相关系数R~2均在0. 993以上。因此Chen and Reagan建立的甲醇制汽油三集总动力学模型可以准确描述Zn-HZSM-5分子筛催化剂的甲醇制汽油反应动力学行为。     

A model for coke oxidation from catalyst pellets in the initial burning period

A model for predicting the transient temperatures during the initial period of regeneration of a coked catalyst has been developed. The model considers the reaction of both hydrogen and carbon in the coke. The hydrogen is assumed to react at a sharp interface and the carbon is assumed to react in the diffusion zone between the hydrogen interface and the surface. The maximum temperature profiles predicted by the model give better agreement with the experimental data reported in the literature especially in the lower temperature range of regeneration.     

The correlation between nitrogen species in coke and NOx formation during regeneration☆

Nitrogen oxides(NO x)emission during the regeneration of coked fluid catalytic cracking(FCC)catalysts is an environmental issue.In order to identify the correlations between nitrogen species in coke and different nitrogencontaining products in tail gas,three coked catalysts with multilayer structural coke molecules were prepared in a fixed bed with model compounds(o-xylene and quinoline)at first.A series of characterization methods were used to analyze coke,including elemental analysis,FT-IR,XPS,and TG–MS.XPS characterization indicates all coked catalysts present two types of nitrogen species and the type with a higher binding energy is related with the inner part nitrogen atoms interacting with acid sites.Due to the stronger adsorption ability on acid sites for basic nitrogen compounds,the multilayer structural coke has unbalanced distribution of carbon and nitrogen atoms between the inner part and the outer edge,which strongly affects gas product formation.At the early stage of regeneration,oxidation starts from the outer edge and the product NO can be reduced to N_2 in high CO concentration.At the later stage,the inner part rich in nitrogen begins to be exposed to O_2.At this period,the formation of CO decreases due to lack of carbon atoms,which is not bene ficial to the reduction of NO.Therefore,nitrogen species in the inner part of multilayer structural coke contributes more to NO X formation.Based on the multilayer structure model of coke molecule and its oxidation behavior,a possible strategy to control NO X emission was discussed merely from concept.     

苯与乙烯在ZSM－5上的烷基化反应（Ⅲ）固定床反应器行为的化较

给出了低浓度乙烯和苯在ＺＳＭ－５型分子筛催化剂上的宏观动力学方程。建立了中试固定床反应器模型。模型值与中试结果相一致。化较了单段绝热床、等温床和多段绝热床反应器行为。结果表明：在达到乙烯９５％转化率时，苯生成乙苯和乙烯生成乙苯的选择性为等温床要化单段绝热床好；四段绝热床可达到与等温床相当的指标。考虑到绝热床投资少，操作简单，可变性强，四段绝热床反应器应该是首选的反应装置。     

催化剂烧炭再生模拟和分析

催化剂烧炭再生是非定态过程。本文建立了绝热反应器内催化剂烧炭模型,利用移动边界正交配置法求解。以结炭的BO2催化剂再生为工作反应,模拟预测与实验值吻合良好。模拟计算表明,用递升进口温度序列烧炭,使再生时间明显缩短。     

粒径变化对沸腾床渣油加氢催化剂的影响

采用抚顺石油化工研究院(FRIPP)自主研发的微球形催化剂,以伊朗常压渣油(IRAR)为原料油,在间歇式高压反应釜内考察了粒径变化对沸腾床渣油加氢催化剂性能和加氢反应后催化剂性质影响.结果表明:减小催化剂粒径可以提高脱金属率、脱硫率、残炭转化率.生焦后催化剂的比表面积、孔容损失严重.     

EFFECT OF DIFFUSIONAL RESISTANCE ON THE REGENERATION OF COKE-DEACTIVATED SUPPORTED METAL CATALYST

This paper presents the solution of the model of the simultaneous diffusion and reaction of the uniformly coked catalyst undergoing regeneration with gaseous reaction with the solid coke. The reaction is assumed to be catalytic hence it obeys Langmuir-Hinshelwood kinetics. The resulting -gas and coke mass balance non-linear coupled equations were solved by finite difference technique. Profiles of coke and gas consumption within the pellet are presented and the effect of diffusional resistances are evaluated by the effect of a sufficient variation in Biot number.     

催化裂化催化剂再生过程中的氮化学进展

从流化催化裂化待生催化剂中含氮化合物的主要类型和生成机制、再生过程中含氮化合物的转化途径以及降低再生过程中氮氧化物排放的相应控制措施等几个方面,综述了流化催化裂化催化剂再生过程中的氮化学研究进展。     

活性炭用于柴油深度脱硫研究进展

综述了活性炭作为吸附剂和催化剂在柴油深度脱硫方面应用的新进展。通过表面热氧化和负载金属离子对活性炭表面进行化学性能改性,有效提高对柴油中噻吩类硫化物的吸附性能。活性炭作为催化剂,能有效催化过氧化氢和氧化柴油中的噻吩类硫化物而达到催化氧化脱硫。活性炭在柴油深度脱硫方面具有广阔的应用前景,但要真正实现其在脱硫上的工业化应用,尚需加强其表面化学性能改性、再生、吸附和催化氧化机理等方面的研究。     

高纯氯化氢对电石法PVC失活低固汞催化剂的原位再生

以电石法乙炔氢氯化失活低固汞催化剂为基础,在等温固定床反应器中模拟实际生产转换器单管装置,对失活催化剂通入高纯无水氯化氢气体,研究在氯化氢气体作用下,失活低固汞催化剂的再生效果,并考察再生温度、再生压力、空速以及再生时间对低固汞催化剂再生后汞含量、碘吸附值、四氯化碳吸附值、载体BET比表面积以及催化性能的影响。结果表明,在再生温度220℃、再生压力100 k Pa、空速500 h~(-1)和再生时间60 h条件下,失活低固汞催化剂再生性能最好,再生后乙炔转化率达到99.8%。     

REGENERATION PROTOCOLS FOR FIXED BED REACTORS DEACTIVATED BY COKE

Coked catalyst in fixed bed reactors is regenerated by passing hot air mixed with a non-reacting diluent (like steam(. The concentration of oxygen in the regenerating stream is increased from the beginning of the regeneration following a so called regeneration protocol, in order to minimize the regeneration time but still maintaining the maximum temperature within the reactor below permissible level. In this paper, we have modelled the low temperature regeneration in fixed bed reactors and have suggested general regeneration protocols, suitable for wide range of process conditions

A pseudo-homogeneous model is developed to simulate regeneration of fixed bed reactors. The model accounts for major industrially important issues like, non-uniform coke deposition along the reactor length, hydrogen content (with faster burning of hydrogen) of coke and incomplete combustion of coke. Detailed qualitative understanding of the regeneration process and the role of protocol is developed. Specific guidelines were evolved and discussed to aid process engineers to select better regeneration protocol. One worked example of regeneration of fixed bed reactors is included