Minimum tank volumes for CFST bioreactors in series

The primary reactor type currently used in the production of microorganisms or microbial products is the stirred tank reactor (STR). If operated on a continuous flow basis (CFSTR) they become similar in performance to the primary reactor configuration used in most of the chemical industry. In this work, microbial kinetics are considered in the design of CFSTRs in series. An equation is derived to predict the minimum possible total residence time to achieve any desired substrate conversion. The equation permits the use of a wide variety of growth kinetic models and is applied here to Monod, substrate inhibition and product inhibition cases. For the majority of cases, it is found that three optimally designed CFSTRs in series provide close to the minimum possible residence time for any desired substrate conversion. A comparison to the use of a PFR is made for cases of both no-recycle and biomass recycle to the CFSTR train. It is found that three CFSTRs, which are not equi-volume, provide the same required total mean residence time as a PFR for Monod kinetics, but are significantly superior (i.e., less total volume required) to a PFR for substrate-inhibited growth.     

氯苯反应器数学模型的研究

通过对氯苯反应器中气、液两相传质及反应特征的分析,提出了按照CSTR串联PFR模型设计氯苯反应器的观点。其中CSTR为主要反应区域,约占全塔反应体积的80%。进一步的计算表明,用模型预测的反应器出口转化率与反应器的实际转化率一致。     

Membrane Reactor/Separator: A Design for Bimolecular Reactant Addition

Abstract

A membrane reactor (MBR) is used to investigate the effect of selective reactant addition on series-parallel reaction networks, such as the oxidative dehydrogenation of ethane to ethylene. Ethylene is favored in an oxygen-lean environment, while excess oxygen favors the formation of combustion products. Control of the reactant ratio (ethane to oxygen) is crucial to both the overall selectivity and the hydrocarbon conversion. Traditional reactor designs co-feed the bimolecular reactants at the top of the reactor at some preset feed ratio. The MBR uses a tube (porous alumina membrane) and shell configuration. One reactant is fed at the top of a catalyst bed packed within the membrane core. The other reactant permeates into the tube along the length of the reactor via an imposed pressure drop. The reactant ratio is large at the top of the MBR, which leads to high selectivities; as the oxygen is consumed, it is replenished via downstream permeation to improve the ethane conversion. The MBR and a plug flow reactor (PFR) are evaluated at 600 [ddot]C, with identical space velocities, and using a magnesium oxide catalyst doped with samarium oxide. At low to moderate reactant feed ratios, the ethylene yield in the MBR exceeds the PFR by a factor of three, under some conditions. At higher feed ratios, the performance of the PFR nears or exceeds the performance of the MBR.     

Application of a carbon membrane reactor for dehydrogenation reactions

This research tests a membrane reactor, equipped with a molecular-sieve carbon membrane, using isobutane dehydrogenation on a chromia alumina catalyst as a model reaction. Most pores of the carbon membrane employed are 6- in size and previous independent transport studies show that the permeability ratio of hydrogen to isobutene is larger than 100. These features make the membrane an excellent highly selective low-cost candidate for application in a membrane reactor. The novelty of this study is in the proposed application at relatively high temperatures (450°C and 500°C); only a few studies have tested carbon membrane reactors.Two types of operation modes were studied, using either nitrogen as a sweeping gas in counter current flow or using vacuum as a driving force for membrane transport. As expected, higher conversions were achieved with decreasing feed flow rate. The conversion achieved in the counter-current flow operation method was higher than in all other modes achieving a maximum of 85% at 500°C. While this result is much higher than in the corresponding PFR, the obtained improvement is a result of nitrogen transport and dilution. The conversions obtained in the vacuum mode show modest gains above the ones received in the PFR (40% vs. 30% at 500°C). These results were compared with simulations that used the experimentally determined transport parameters.     

Simulation of nylon 6 polymerization in tubular reactors with recycle

In the hydrolytic polymerization of ?-caprolactam, the ring opening of the monomer is much slower than the polyaddition reaction. Hence, the mixing of aminocaproic acid to the feed results in a faster conversion of the monomer. Industrially, this fact is exploited by using a recycle stream. An isothermal plug flow reactor (PFR) with a recycle is simulated in this study, using two techniques: the method of successive substitutions and Wegstein's method. It is found that, under certain operating conditions, the use of a recycle stream gives higher monomer conversions and lower cyclic dimer concentrations than either a PFR or a homogeneous continuous-flow stirred-tank reactor (HCSTR), with the degree of polymerization almost the same as that obtained in an HCSTR, and thus offers a considerable advantage. However, when a recycle reactor is coupled with a subsequent flashing operation and a finishing reactor, these advantages are considerably reduced.     

Energy-dense liquid fuel intermediates by pyrolysis of guayule (Parthenium argentatum) shrub and bagasse

Guayule is a perennial shrub grown in the southwestern United States that is used to produce high quality, natural rubber latex. However, only about 10% of the plant material is used for latex production; the remaining biomass, called bagasse, can be used for renewable fuel production. Fast pyrolysis of guayule, both whole shrub and bagasse was performed. From both feedstocks a very viscous, high energy content (∼30 MJ/kg) pyrolysis liquid (bio-oil) was produced in yields averaging over 60% without any catalyst. The properties and compositions of the bio-oils were found to be similar in the two feedstocks. Co-products, charcoal (20-30 wt%) and non-condensable gas (5-15%), were also dense and had a high energy content. Of the two feedstocks, the whole shrub yielded higher quantities of charcoal that also had a higher energy content than the charcoal produced from bagasse. As a result, the energy recovery, estimated as the percentage of the energy products, to energy input into the reactor was lower (60%) for guayule bagasse than for the whole shrub (73%). This notwithstanding, the bagasse is a more attractive feedstock for thermochemical conversion, not only because it is a residue from a primary process (latex extraction) that is on-site, but also because it has a high energy content. Moreover, it produces high quality pyrolysis products. Co-production of latex rubber from the whole shrub and renewable fuels from the residual bagasse by pyrolysis should improve the already positive economics of the guayule latex rubber industry.     

Differentiation criteria study for continuous stirred tank reactor and plug flow reactor

All reactors in reality are not ideal plug flow reactor (PFR) or ideal continuous stirred tank reactor (CSTR). They are difficult to differentiate. This study was to investigate the reactor analysis of PFR and CSTR through tracer response curves, residence time distributions (RTD) and several hydraulic performance indexes. We set up the differentiated value of each index. The tracer response curve showed that our lab-scale CSTR was close to ideal CSTR and got 99.9% recovery. In the RTD curves, the results could significantly recognize the PFR nature of high rate pond (HRP). With hydraulic performance indexes study, every selected index demonstrated that the studied HRP was closer to PFR than the studied CSTR. Based on the lab-scale study results, this study established the cutting point between the PFR and CSTR in each index; we were looking through the different types of reactors in literature and we confirmed the criteria with all literature reactors with the “graphic method”. The method helped us to establish those important values to help us to differentiate the reactor types in practice and to understand the designs better.     

分段导数分析法用于苯胺甲醛缩合反应过程综合

苯胺甲醛缩合制多胺的反应是典型的第Ⅲ类反应体系,反应过程复杂。针对反应的阶段性特征,采用分段导数分析法对其进行反应器网络综合,第一阶段应采用DSR或PFR;第二阶段应采用PFR。采用不同的流程结构进行试验,结果为：采用DSR+PFR的流程结构,最终产品中二氨基二苯甲烷（MDA）含量最高;采用PFR+PFR的流程结构,最终产品中二氨基二苯甲烷（MDA）含量次之。试验结果与导数分析法分析结果一致,表明本文所用方法是有效的。     

State multiplicity in PFR-separator-recycle polymerization systems

This article explores the non-linear behaviour of isothermal and non-isothermal plug-flow reactor (PFR)-separator-recycle systems, with reference to radical polymerization. The steady-state behaviour of six reaction systems of increasing complexity, from one-reactant first-order reaction to chain-growth polymerization, is investigated. In PFR-separator-recycle systems feasible steady states exist only if the reactor volume exceeds a critical value. For one-reaction systems, one stable steady state is born at a transcritical bifurcation. In case of consecutive-reaction systems, including polymerization, a fold bifurcation can lead to two feasible steady states. The transcritical bifurcation is destroyed when two reactants are involved. In addition, the thermal effects also introduce state multiplicity. When multiple steady states exist, the instability of the low-conversion branch sets a lower limit on the conversion achievable at a stable operating point. A low-density polyethylene process is presented as a real plant example.The results obtained in this study are similar to CSTR-separator-recycle systems. This suggests that the behaviour is dictated by the chemical reaction and flowsheet structure, rather than by the reactor type.     

Steady state multiplicity behavior of an isothermal axial dispersion fixed-bed reactor with nonuniformly active catalyst

An isothermal, heterogeneous fixed-bed reactor packed with nonuniformly active catalyst pellets where a biomolecular Langmuir-Hinshelwood reaction occurs, is studied using an axial dispersion model. A catalyst activity distribution given by a Dirac delta function, where the active catalyst is deposited at a specific location within the pellet, is considered. This includes the common case of externally coated pellets with external mass transfer resistance. The steady state multiplicity behavior of this reactor, and its limiting cases: CSTR, PFR and pseudohomogeneous axial dispersion, are examined in detail. The nonlinearity of the reaction kinetics provides two sources of multiplicity, through the heterogeneous nature of the reactor and the presence of axial dispersion in the fluid phase. Their roles in determining reactor multiplicity behavior are fully explored. It is shown that this system can admit at most nine steady state solutions. The limiting behavior of the heterogeneous axial dispersion model as Pe → 0 or ∞ is not represented fully by the CSTR or PFR models because of ignition phenomenon. Finally, the effects of mixing on reactor conversion are discussed.     

Reduced power consumption compared to a traditional stirred tank reactor (STR) for enzymatic saccharification of alpha-cellulose using oscillatory baffled reactor (OBR) technology

Enzymatic saccharification of pure α-cellulose was conducted in oscillatory baffled (OBR) and stirred tank (STR) reactors over a range of mixing intensities requiring power densities (P/V) from 0 to 250 Watts per cubic metre (W/m³). Both reactor designs produced similar saccharification conversion rates at zero mixing. Conversion increased with increasing mixing intensity. The maximum conversion rate occurred at an oscillatory Reynolds number (Re_o) of 600 in the OBR and at an impeller speed of between 185 and 350 rpm in the STR. The OBR was able to achieve a maximum conversion rate at a much lower power density (2.36 W/m³) than the STR (37.2–250 W/m³). The OBR demonstrated a 94–99% decrease in the required power density to achieve maximum conversion rates and showed a 12% increase in glucose production after 24 h at 2.36 W/m³.     

Influence of centrifugal field on free‐radical polymerization kinetics

It has been observed that when a prepolymer mix of styrene, poly(styrene), toluene, and benzoyl peroxide is transferred from a conventional stirred tank reactor (STR) to a spinning disc reactor (SDR), the rate of polymerization is substantially increased. Furthermore, the molecular weight and the molecular weight distribution of the polymer formed at conversions up to about 80% in the SDR is virtually unchanged from that of the polymer formed at 60% conversion in the STR. These results seem to indicate that the increase in polymerization rate is not the result of the well‐known Trommsdorff–Norrish effect, which would be expected to lead to an increase in polydispersity. We believe that shear and centrifugal forces experienced by the film provide intense mixing and extension flow effects, which are responsible for the above‐described observations. In this report an explanation has been put forward to describe the observed effects. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2283–2286, 2002     

反应级数对理想反应器组合方式效率的研究

对于不同级数的不可逆反应,研究了其在全混流反应器(CSTR)与平推流反应器(PFR)不同组合方式中的最终转化率。对两种理想流动反应器的不同组合方式,如CSTR+PFR串联、PFR+CSTR串联及CSTR与PFR并联,反应的最终转化率随反应级数的不同而变化。当反应级数为负值时,CSTR与PFR并联组合方式的最终转化率最高;当反应级数为0~1之间的数值时,CSTR+PFR串联组合方式的最终转化率最高;而当反应级数大于1时,PFR+CSTR串联组合方式的最终转化率最高;当反应级数为0时,三种组合方式具有相同的最终转化率;但当反应为一级不可逆反应时,两种反应器串联时的最终转化率相同,并高于两种反应器并联时的最终转化率。     

Rh负载的泡沫独石上甲烷部分氧化的基元反应动力学模拟

Rh负载的泡沫独石催化剂上进行的甲烷催化部分氧化反应,能够在自热、毫秒级接触的条件下达到接近平衡的转化率和选择性.采用CH4在Rh催化剂上发生部分氧化反应的基元反应动力学网络结合平推流模型,进行了一维的反应流模拟,揭示了毫秒级催化反应的反应历程.CH4/O2摩尔比在1.7～2.3,外界温度550～800℃的范围内,模拟结果和实验结果能够很好地吻合.模拟不仅给出了催化剂床层内气相和表面物种的变化情况,还揭示了催化剂有效内表面积和甲烷吸附能力对反应的影响,发现一定程度下有效内表面积的增加和甲烷吸附能力的增强,能够大幅度地提高反应的转化率和选择性.     

甘蔗渣在水与四氢萘混合溶剂中的液化工艺优化实验

通过正交试验考察了蔗渣在水与四氢萘混合溶剂中液化过程的5个因素对蔗渣转化率的影响.蔗渣在混合溶剂中的优化工艺为:反应温度270 ℃、反应时间30 min、固液比(蔗渣与溶剂质量比)1:6、碱浸预处理NaOH用量4%、四氢萘用量(占总溶剂质量分数)50%.各因素的影响次序:NaOH用量>反应温度>四氢萘用量>固液比>反应时间.在此工艺条件下,蔗渣转化率可达到97.9%.实验结果表明,四氢萘部分取代液化溶剂中的水,可以有效提高蔗渣液化效率,同时降低反应温度及压力,促进实验操作条件的改善.     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

共轭双烯聚合物选择性加氢反应器技术进展

对以橡胶、弹性体为代表的含共轭双烯聚合物进行烯属双键的选择性加氢,可显著提高聚合物的稳定性;加氢反应器和反应工艺是制约加氢度和产率的关键技术之一。该文综述了目前共轭双烯聚合物选择性加氢反应器的技术进展,包括以机械搅拌反应器、鼓泡反应器、外循环反应器为代表的全混流型反应器;以填料塔和静态混合管式反应器为代表的平推流型反应器;以及各种反应器的组合技术、特殊操作方式。结合加氢体系的流体力学特征和反应动力学特征,分析了制约加氢度和产率的关键问题,总结了进一步提高加氢度和产率、降低能耗物耗的潜在途径。     

纸浆蔗渣酶法水解反应过程的考察

以蒸煮时间5．5小时,温度为155－160℃,P=0.6MPa,pH为4．5的40目的纸浆渣为底物,日本Yakult生物化学试剂公司的Onozuka-R-10纤维素酶为催化剂,在50℃,PH为4．8（乙酸－乙酸钠缓冲液）的条件下,考察了釜式和固定床反应器对酶解反应过程的影响,测定了在不同底物浓度时的酶解反应还原糖得率,探讨了酶的吸附以及酶活性在酶解反应过程的变化情况。实验结果表明,在本实验条件下,底物浓度高,转化率则低,固定床反应器对酶的吸附比釜式反应器略多;酶的活性变化在两种反应器中几乎没多大差别。     

Vapor phase dehydrogenation of methanol to methyl formate in the catalytic membrane reactor with Cu/SiO2/ ceramic composite membrane

The Cu/SiO₂/ceramic composite membrane was prepared on the SiO₂/ceramic mesoporous membrane by an ion exchange method, and vapor phase dehydrogenation of methanol to methyl formate in the catalytic membrane reactor was investigated. It showed much better performance in the catalytic membrane reactor than that in the fixed-bed reactor under the same reaction conditions. At 240 °C, 57.3% conversion of methanol and 50.0% yield of methyl formate were achieved in the catalytic membrane reactor and only 43.1% conversion of methanol and 36.9% yield of methyl formate were achieved in the fixed-bed reactor.     

Hierarchical control of a train of continuous polymerization reactors

A multilayer control scheme is synthesized for a series of polymerization stirred tank reactors to control the monomer conversion over the reactor line. In this work two layers of control are implemented. In the' first level digital PI or self-tuning regulators (STR) are used to control the reaction temperature of each reactor in the series by manipulating the flowrates of the coolant streams. In the second layer, a locally linear state space model, that can predict the monomer concentration in each reactor, is derived based on steady-state energy balances. A quadratic performance index is then minimized to obtain the optimal reaction profile that will bring the monomer distribution over the reactor line to its desired target value.