液相法三相淤浆床甲醇合成技术

液相法三相淤浆床甲醇合成技术是一种使用三相淤浆床反应器将合成气转化为甲醇的生产新技术。与传统生产工艺相比，三相淤浆床甲醇合成工艺具有单程转化率高，出口甲醇浓度高；床层等温，反应条件优良；温度易于控制，换热简单；生产的技术经济指标优良等优点，因此成为一种应用前景非常广阔的新兴甲醇生产新技术。     

三相淤浆床甲醇合成反应器大型冷模研究

以空气－水－催化剂和空气－液体石蜡油－催化剂两种系统为对象,研究了内置垂直管束式换热器三相淤浆床甲醇合成反应器的流体力学性质－－平均气含率、床层压降、固体完全悬浮的临界表观气速。考察了各种因素对流体力学性质的影响。并得到关于气含率的经验关联式：εＧ／（１－εα）＾４＝０．００５７４４〔ｕＧμＬ／σ〕＾０．１０〔１＋ｃｓ／〔１－ｃｓ／ｐｓ〕σＬ＋ｃｓ〕＾－１．７３。     

三相鼓泡淤浆床甲醇合成工艺及装置开发进展

甲醇是碳－化学的支柱和核心,甲醇是清洁的燃料,又是一系列碳一化学产品的基础产品。目前国内外以煤、石油及天然气为原料生产甲醇都采用气－固催化法,由于气、固相反应器中床层温升及可逆反应化学平衡的限制,由原料气制得的合成气一次通过气－固相甲醇合成反应器仅能得到3％－6％的甲醇。甲醇合成率不高,大量的未反应的合成气必须循环使用,耗费了大量的循环压缩功。     

三相淤浆床甲醇含成反应器大型冷模研究

以空气-水-催化剂和空气-液体石蜡油-催化剂两种系统为对象,研究了内置垂直管束式换热器三相淤浆床甲醇合成反应器的流体力学性质──平均气含率、床层压降、固体完全悬浮的临界表观气速。考察了各种因素对流体力学性质的影响,并得到关于气含率的经验关联式：     

三相淤浆床冷态特性研究──空气─水─石英砂系统

本文研究了空气─水─石英砂三相淤浆床的流体力学特性．同时回归山含气率与其影响因素的关联式：εｇ＝０．０４９７ｕｇ１．０３７Ｃｓ－０．２５７．本文为研究三相淤浆床甲醇合成提供了流体力学数据。     

三相床甲醇合成研究进展

文章简要归纳了国内外从７０年代起,对三相床甲醇合成在催化剂,溶剂,反应动力学,流体力学,中试,工业化开发等方面的研究工作以及近年来国内的研究情况,阐明了三相床甲醇合成技术的先进性与发展前景。     

三相淤浆床冷态特性研究—气体—石腊油—催化剂系统

本文研究了气体－石腊油－催化剂三相体系在淤浆床反应器中的流体力学特性，考察了各种因素对气含率和压降的影响，并回归得到如下关联式：εｇ＝０．１１５２ｕｇ＾０．４１ｃｓ＾０．０９３ρ＾０．０１８。     

超临界介质中三相浆态床甲醇合成

在总压6.0～7.0 MPa、合成气分压3.0～3.7 MPa、温度235～260 ℃、气体质量空速450～1600 L(STP)•（kg cat）^-1•h^-1的实验条件下,采用液体石蜡为惰性液相热载体,正己烷作为超临界介质,于机械搅拌反应釜中对催化剂C302-2进行了介质处于超临界状态的三相浆态床甲醇合成过程研究,考察了操作条件对CO转化率和甲醇出口摩尔分数的影响,结果表明在正己烷处于超临界状态的反应温度范围内CO转化率和甲醇出口含量皆随温度的增大而减小,随质量空速的增加而降低.此外,对使用超临界介质和不使用超临界介质的三相浆态床甲醇合成过程进行了对比实验,超临界状态下三相浆态床甲醇合成的CO转化率和甲醇出口含量皆高于三相浆态床甲醇合成,验证了超临界状态下三相浆态床甲醇合成的优越性.     

液相法甲醇合成过程中机械搅拌反应器的模拟

本文对C301及C302两种不同催化剂条件下机械搅拌反应器内液相法甲醇过程进行了模拟,模拟中节气液之间的传质过程及催化剂气固相本征反应动力学,主要模拟条件：温度483K－528K,压力2．0MPa-6．0MPa,原料气中CO浓度0．06－0．45。模拟结果表明,在C301与C302催化剂条件,隆成总体速率的模拟计算与实测值相吻合,平均偏差分别为7．98％和11．92％,可以认为,气固相本征动力学模型应用于液相甲醇合成过程的工程设计与过程分析是适用和可靠的。     

高速碰撞共沉淀法铜基甲醇合成催化剂的研制

开发出高速碰撞共沉淀制备铜基甲醇催化剂的新方法。用此法一步共沉淀制得的ｂ 催化剂,其分散度和催化剂表面单位Ｃｕ 原子的ＣＯ 转化数比ｅ 催化剂分别增加２０％ 和１４ ％ 。在催化剂Ｃｕ 质量分数减少３７％ 的情况下,其催化剂活性仍相当高,因此这是一种值得推广应用的催化剂制备新方法。     

液相加氢法合成H-酸工艺研究

介绍了以CaCO3代替氨水进行脱硝物中和，经Na2CO3置换，用催化加氢代替铁粉还原，再进行碱熔，H－酸离析制得H－酸的工艺，重点对液相加氢工艺进行了研究，该工艺砍掉了T－酸离析工序，减少了三废，降低了原料成本，提高了H－酸收率及产品质量，具有一定的经济效益和社会效益。     

CATALYSTS DESIGNED FOR USE IN THE WENTWORTH PROCESS FOR METHANOL AND HIGHER ALCOHOL SYNTHESIS

I would like to begin this paper with a personal accolade for Donald Othmer. It has been my pleasure to work with him for the last twelve to fifteen years and with T.O. Wentworth who, together with the author, are co-inventors of the process as described in U.S. Patent 4,235,799. Don has been a very devoted advocate to the research resulting in the generation of the patent. In meetings with him and Ted Wentworth, Ted and I were always amazed at the speed with which Don comprehended any new concept and immediately was able to respond with his own extension of the ideas. In addition to his mental skills, which are legendary, he also has ways with people. Always having a ready smile and quick wit and ready humor, his generosity is exceptional and is well known. As stated above our association was primarily in the derivation, researching and patenting of the unique methanol synthesis process covered by the above numbered patent which was assigned to Wentworth Bros. Inc. Wentworth Bros. Inc., in addition to other areas of expertise, are designers of methanol synthesis processes and have been in this business for at least fifty years.     

用于多联产的浆态床液相法甲醇合成模拟研究

能直接使用煤基合成气作为原料的浆态床液相法甲醇合成技术是多联产系统的关键技术之一，是耦合动力、化工过程的桥梁．从多联产的角度对浆态床液相法甲醇合成技术进行了模拟研究和经济分析，明确了浆态床反应器适合直接使用富CO的煤基合成气作为原料，采用一次通过工艺与发电构成多联产系统．     

EFFECTS OF PORE DIFFUSION ON THE SYNTHESIS OF METHANOL

The hierarchical model concept is applied for solving of the test-problem. Three levels of hierarchy are defined. On the first one the reaction rate at an inner point of a pore in the catalyst pellet is examined. On the 2-nd level, taking pore diffusion into account and introducing the so-called distortion factor, the mean reaction rate concerning a pellet is calculated. On the 3-rd level, the rate of reaction at an inner point of the reactor is given, and the parametric study of industrial reactor is carried out.     

AN EXPERIMENTAL STUDY OF CONCENTRATION FORCING APPLIED TO THE METHANOL SYNTHESIS REACTION

The effect of square-wave concentration-forcing operation on the rate of methanol production over two industrial catalysts was studied at 513 K and 2.86 MPa total pressure. Improvements as high as 25 percent relative to the optimal steady-state methanol production rate, in moles per gram catalyst per unit time, were obtained over BASF's S 3-85 catalyst. This occurred in a laboratory-scale fixed-bed reactor with gas mixing for a cycling time of τ = 12 seconds and for a cycle split relative to carbon monoxide of γ_CO = 0.20, the rest of the cycle being hydrogen. Improvements as high as 15 percent were also obtained over Imperial Chemical Industries ICI 51-2 catalyst, in a differential plug-flow reactor for τ = 24 seconds and γ_CO = 0.15. These improvements were obtained for pure-component steady cycling between carbon monoxide and hydrogen with a constant carbon dioxide molar concentration of 2 per cent (BASF catalyst) or 3 percent (ICI catalyst) present in both parts of the cycle. On the other hand, no improvement over the optimal steady state was found for cycling between carbon monoxide and carbon dioxide with a constant molar concentration of 61 % hydrogen nor between hydrogen and mixtures of carbon monoxide and hydrogen such as 19.6/78.4 mole percent mixture of CO/H₂.     

浆态床甲醇合成技术的新进展和经济评价

浆态床甲醇合成技术是美国能源部为推进煤炭间接液化技术而安排的研究开发工作中的关键部分。本文就浆态床甲醇合成技术的优越性,拉波特中试研究进展、示范装置计划和经济评价作一扼要的介绍。     

EFFECT OF THE WATER-GAS REACTION ON THE METHANOL SYNTHESIS

The effect of the water-gas reaction as a parallel running process is investigated by adding two elementary steps to the reaction mechanism and the rale equations defined by Berly el at. The methanol synthesis and shift reactions interact, mostly through the common step of hydrogen chemisorption. The detailed rate expression is derived and the Vekron-I Test Problem is developed, Analysing a simplified rate equation version it can be stated that the driving force expression for both processes is incorporated in both rates.     

SIMULATION OF A THREE PHASE REACTOR FOR THE SOLVENT METHANOL PROCESS

Single pass conversions in conventional vapor phase methanol synthesis are low, necessitating recycle of large quantities of unconverted reactants. In the Solvent Methanol Process (SMP), the use of an inert and highly selective solvent in the synthesis loop enables the removal of methanol as soon as it is formed and helps overcome equilibrium limitations that exist in the vapor phase process. An industrial scale, packed bed, adiabatic reactor with cocurrent upflow of synthesis gas and solvent has been simulated for the SMP. The simulation shows that very high single pass conversions of CO and H₂ are attainable such that recycle can be eliminated. Reaction rates are however lower than vapor phase rates due to pore diffusion limitations.