两种催化裂化干气加工利用方案的对比

催化裂化干气直接加工利用是炼厂副产气体综合利用的重要内容。本文选择工艺技术比较成熟的两种加工方案进行技术经济对比,结论是烃化制乙苯方案的经济性能比羰基化制丙醛、丙酸方案差,但从工艺开发成熟程度和市场需求来看,前一方案的发展规模将比后一方案大。     

干气制乙苯塔底高沸物组成的气相色谱和气相色谱-傅里叶变换红外光谱分析

炼厂干气含有许多组分,其中乙烯占12%～20%[1]。利用干气中的稀乙烯制取乙苯会产生副产物[2]。国内外对塔底高沸物组分研究的不多,仅利用气相色谱 质谱联用进行定性分析[3]。我们利用气相色谱(GC)、气相色谱 傅里叶变换红外光谱(GC FTIR)技术,对干气制乙苯工艺中多乙苯装置     

催化干气制乙苯技术工艺进展

催化干气制乙苯是利用石化副产干气中的乙烯与苯反应生产乙苯的过程,经过20多年的发展与创新,我们相继开发了具有自主知识产权的干气制乙苯第一代至第五代技术,并在石化行业得到了广泛应用.本文从工艺角度综述了催化干气制乙苯的技术发展历程.     

催化裂化干气与苯烷基化催化蒸馏制乙苯反应网络热力学研究

 高温气相反应条件下的催化裂化干气制乙苯过程中，容易生成甲苯和二甲苯等副产物；在该过程中采用催化蒸馏技术，使苯与乙烯在低温条件下进行反应，可大幅度降低产品中二甲苯的含量．通过对催化裂化干气与苯烷基化催化精馏过程中的各反应步骤进行分析与热力学计算，结合反应的实际产物组成，提出了苯与乙烯烷基化的反应网络，探讨了苯与乙烯烷基化反应过程中甲苯和二甲苯的形成机理及影响因素．结果表明，增大苯／乙烯比对提高乙烯平衡转化率及乙苯收率有利；在较低温度下进行烷基化反应，可大大减缓C－C键裂解速度，抑制甲苯和二甲苯生成，提高乙苯产品质量．     

炼厂裂化干气及醛化反应产物的气相色谱分析

干气是石油裂解后将常温可液化组分提取后剩下的气体,主要是C_1/C_4烃类,通常都作为燃料使用。但其中含有20％乙烯和6％左右的丙烯,这两种组分是石油化工的宝贵原料。将干气直接进行醛化反应制得丙醛,进而制得酸和醇,可制取食品和饲料添加剂、增塑剂等。此项工作要求对干气中乙烯和丙烯以及干气醛化产物丙醛进行定性定量分析。干气组分是有机物中沸点最低的,物性又最相近,前人曾用其他类型柱子和采用多柱进行分离,不但费事     

干气制乙苯结炭沸石催化剂烧炭再生研究

以苯和炼厂干气中的乙烯合成乙苯结炭催化剂为研究对象，对结炭催化剂上积炭的性质及不同温度下的烧炭情况进行了研究，考察了再生前后催化剂的酸性、活性、晶相、比表面及孔结构等性能的变化。结果表明，催化剂孔的内表面积炭占据了酸性中心，致使催化剂活性降低；在烧炭时温度大于300 ℃才开始烧炭，最佳烧炭温度应控制在500℃～550℃，600 ℃可将炭完全烧净。程序升温脱附（TPD）实验表明，550 ℃实验室烧炭后催化剂酸种类及其比例可完全恢复，酸量可恢复到95%。晶相、孔结构基本未变，催化剂的活性得到良好恢复。     

晶化时间对ZSM-5分子筛物化性质及催化性能的影响

 考察了ZSM－5分子筛在晶化过程中的变化规律及其在苯与乙烯气相烷基化制乙苯反应中的催化性能．结果表明,当晶化时间为70h时,分子筛晶体开始出现;晶化90h时无定形物相基本消失．晶化时间从90h再延长至150h,ZSM－5分子筛晶粒的大小、形貌和体相硅铝比都基本不变,但分子筛表面的硅铝比逐渐降低．以晶化时间为90h的ZSM－5分子筛原粉为活性组元制备的催化剂,对苯与乙烯气相烷基化制乙苯反应表现出最佳的催化性能．     

毛细管气相色谱法测定炼厂气中单体烃组分的含量

采用PLOT／Al2O3石英毛细管气相色谱柱和氢火焰离子化检测器，建立了炼厂气中单体烃组分含量测定的毛细管气相色谱法，当炼厂气中单体烃组分的含量大于或等于2．1％时，RSD≤0．95％，当炼厂气中单体烃组分的含量为0．5％－2．1％时，RSD为0．95％－10．0％，当炼厂气中单体烃组分的含量为0．2％－0．5％时，RSD为10．0％－25．0％，该方法对单体烃组分的测定结果与行业标准SH／T0230－92《液化石油气组成测定法》的测定结果基本一致。     

乙烯齐聚制α-烯烃反应体系的热力学研究

利用Benson基团贡献法计算了乙烯齐聚制α-烯烃反应各物质的标准摩尔生成焓、标准摩尔熵和摩尔定压热容,在298～700 K温度范围内对乙烯齐聚制α-烯烃反应体系的反应热、吉布斯自由能以及反应平衡常数进行了详尽的计算,分析了不同反应步骤的热力学平衡与限度,对不同反应发生的热力学可能性与顺序进行了判断,考察了反应温度和压力对乙烯齐聚制α-烯烃反应化学平衡的影响,确定了乙烯齐聚制α-烯烃反应体系适宜的工艺条件.结果表明:乙烯齐聚制α-烯烃反应为放热反应;从热力学上看,温度低于546 K时,乙烯齐聚生成直链α-烯烃反应为自发过程,且比α-烯烃异构化和烯烃歧化反应更容易进行;低温、高压有利于乙烯齐聚制α-烯烃反应的进行;乙烯齐聚制α-烯烃反应体系适宜的工艺条件为温度323～473 K,压力5～20 MPa,且在SHOP法的工艺条件下(温度363 K,压力10.3 MPa),乙烯齐聚生成直链α-烯烃反应的热力学平衡转化率接近于100%.     

蓓萨罗丁的合成及优化

以2,5-二甲基-2,5-己二醇为原料,经氯代、F-C烃化、F-C酰化、Wittig反应、水解反应等七步反应制得抗肿瘤药物蓓萨罗丁,并对其合成工艺进行优化,降低成本和操作难度,提高了产率。     

Removal of nitric acid from a simulated high level liquid waste by a safe chemical denitration

The heat and off-gas generation behavior was experimentally examined during a safe chemical denitration, pre- and mild-denitration, of simulated HLLW with a nitric acid concentration of 2 to 7.5 M. The maximum heat and off-gas generation were no more than 100 cal/s·1 and about 0.8 l/min, respectively. The solution temperature does not reach boiling temperature and no solution was squirted out from the denitration vessel. The pre-and mild-denitration technique could be considered as one of safe methods for removing nitric acid from the HLLW with various nitric acid concentrations. The pre- and mild-denitration also has an advantage to improve the filtration characteristics of precipitates produced by the denitration of simulated HLLW. The denitration of HLLW with 7.5M nitric acid concentration induced formation of “very easy-to-filter” solid. Moreover, a good filter cake washing is possible.     

Detection of volatile metabolites of <Emphasis Type="Italic">Escherichia coli</Emphasis> by multi capillary column coupled ion mobility spectrometry

Detection and immediate quantification of microbial metabolic activities is of high interest in fields as diverse as biotechnology and infection biology. Interestingly, the most direct signals of microbial metabolism, the evolution of volatile metabolites, is largely ignored in the literature, and rather, metabolite concentrations in the microbial surrounding or even disruptive methods for intracellular metabolite measurements (i.e., metabolome analysis) are favored. Here, the development of a multi capillary column coupled ion mobility spectrometer (MCC-IMS) was described for the detection of volatile organic compounds from microbes and the MCC-IMS was used for characterization of metabolic activity of growing Escherichia coli. The MCC-IMS chromatogram of the microbial culture off-gas of the acetone-producing E. coli strain BL21 pLB4 revealed four analytes that positively correlated with growth, which were identified as ethanol, propanone (acetone), heptan-2-one, and nonan-2-one. The occurrence of these analytes was cross-validated by solid-phase micro-extraction coupled with gas chromatography mass spectrometry analysis. With this information in hand, the dynamic relationship between the E. coli biomass concentration and the metabolite concentrations in the headspace was measured. The results suggest that the metabolic pathways of heptan-2-one and nonan-2-one synthesis are regulated independent of each other. It is shown that the MCC-IMS in-line off-gas analysis is a simple method for real-time detection of microbial metabolic activity and discussed its potential for application in metabolic engineering, bioprocess control, and health care.     

Treatment of off-gas evolved from thermal decomposition of sludge waste

Korea Atomic Energy Research Institute (KAERI) started a decommissioning program of a uranium conversion plant. The treatment of the sludge waste, which was generated during the operation of the plant, is one of the most important tasks in the decommissioning program of the plant. The major compounds of sludge waste are nitrate salts and uranium. The sludge waste is denitrated by thermal decomposition. The treatment of off-gas evolved from the thermal decomposition of nitrate salts in the sludge waste is investigated. The nitrate salts in the sludge were decomposed in two steps: the first decomposition is due to the ammonium nitrate, and the second is due to the sodium and calcium nitrate and calcium carbonate. The components of off-gas from the decomposition of ammonium nitrate at low temperature are NH₃, N₂O, NO₂, and NO. In addition, the components from the decomposition of sodium and calcium nitrate at high temperature are NO₂ and NO. Off-gas from the thermal decomposition is treated by the catalytic oxidation of ammonia and selective catalytic reduction (SCR). Ammonia is converted into nitrogen oxides through the oxidation catalyst and all nitrogen oxides are removed by SCR treatment besides nitrous oxide, which is greenhouse gas. An additional process is needed to remove nitrous oxide, and the feeding rate of ammonia in SCR should be controlled properly for evolved nitrogen oxides.     

Electron beam induced purification of dilute off gases from industrial processes and automobile tunnels

The electron beam process has proved to be an efficient method for the removal of inorganic pollutants from flue gas. Since it simulates natural processes which occur in the atmospheric photochemistry, it appeared attractive to investigate the potential of the e-beam process to clean off-gases which contain hydrocarbon and inorganic trace components. Such emissions arise from industrial processes and from automobile tunnels. Commercial solvents were vaporized in air and irradiated with energetic electrons (300 keV). CO, CO₂ and aerosol particles were found as products and were determined quantitatively. The aerosol particles can be collected by a gravel bed filter and can be removed by combustion or biological degradation. From experiments and model calculations it was found that the e-beam process is a very economic tool to remove hydrocarbons from large off-gas volumes at initial concentrations of 50–100 mg C/m³, and that NO_x can be removed very efficiently from tunnel off-gas.     

Development of a safety denitration method to remove nitric acid from mixtures

In order to reduce heat and off-gas generation rates at early stage of the chemical denitration of high and medium level liquid wastes from the reprocessing of nuclear fuel, a safety denitration method, Pre- and Mild-denitration technique, was originated. In the Pre-denitration step, the formic acid of 0.06 to 0.3 times nitric acid concentration ([HCOOH]/[HNO₃]=0.06 to 0.3) was poured into a nitric acid solution at 80°C and denitration was initiated (Pre-denitration). Then additional formic acid was injected into the Pre-denitrated solution at a constant injection rate in 80°C and the solution mixture was heated up to the boiling condition (Mild-denitration). In the Mild-denitration step, the denitration reaction was smoothly initiated and a leak out of solution from a abrupt boiling has never occurred. The maximum heat and off-gas generation rates were about 50 cal/s-l and about 1.01/min respectively even in the 10M nitric acid solution. These measured values were low enough to ensure the safety operation of denitration.     

Online monitoring of coffee roasting by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS): towards a real-time process control for a consistent roast profile

A real-time automated process control tool for coffee roasting is presented to consistently and accurately achieve a targeted roast degree. It is based on the online monitoring of volatile organic compounds (VOC) in the off-gas of a drum roaster by proton transfer reaction time-of-flight mass spectrometry at a high time (1 Hz) and mass resolution (5,500 m/Δm at full width at half-maximum) and high sensitivity (better than parts per billion by volume). Forty-two roasting experiments were performed with the drum roaster being operated either on a low, medium or high hot-air inlet temperature (= energy input) and the coffee (Arabica from Antigua, Guatemala) being roasted to low, medium or dark roast degrees. A principal component analysis (PCA) discriminated, for each one of the three hot-air inlet temperatures, the roast degree with a resolution of better than ±1 Colorette. The 3D space of the three first principal components was defined based on 23 mass spectral profiles of VOCs and their roast degree at the end point of roasting. This provided a very detailed picture of the evolution of the roasting process and allowed establishment of a predictive model that projects the online-monitored VOC profile of the roaster off-gas in real time onto the PCA space defined by the calibration process and, ultimately, to control the coffee roasting process so as to achieve a target roast degree and a consistent roasting.     

Buffer gas effect on the detection of iodine by laser induced fluorescence

Laser-induced fluorescence (LIF) coupled with photon-counting technique to detect molecular iodine at ultratrace level is reported. Electronic quenching rate constants for N₂, NO₂ and H₂O, as well as for the mixture of NO₂ and H₂O has been measured. The application of the LIF method to monitoring¹²⁹I₂ in spent fuel reprocessing off-gas streams is evaluated.     

Characteristics of major dioxin/furan congeners in melted slag of ash from municipal solid waste incinerators

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in slag of fly ash from three municipal solid waste (MSW) incinerators were analyzed to observe any changes in characteristics and distribution of their congeners by melting process. Actual concentration and Toxic Equivalent (TEQ) concentration profiles of 17 major congeners of PCDDs/PCDFs for gas, fly ash and melted slag were compared. The distributions of PCDDs/PCDFs in different streams macroscopically showed similarities with the generally known profiles for emission gas from a municipal waste incinerator. The total concentrations of PCDDs/PCDFs in off-gas and fly ash have been known to be a function of incineration conditions and of air pollution control device utilization; however, their normalized distributions were independent of such conditions. The concentrations of PCDDs/PCDFs in the melted slag of fly ash were not related to the concentrations of PCDDs/PCDFs congeners in fly ash but were rather a function of the melting furnace type and operation. The total amount of PCDDs/PCDFs in the melted slag of fly ash contained almost 150–27,000 times less dioxin than that in fly ash, however, the TEQ of dioxin in the slag was reduced by 435–43,500 times, which could enable them to be utilized as recycled construction materials. In normalized TEQ concentration profiles of 17 congeners of PCDDs/PCDFs, the ratio of PCDFs to PCDDs changed from 1.32 to 2.19 by melting, which showed relatively higher portion of furans left in melted slag than those in fly ash. By comparing reduction ratios of different congeners, PCDDs (dioxins) were relatively easier to destruct than PCDFs (furans) during melting process. The most difficult congener to destruct could be octa-chlorinated dibenzofuran (OCDF) among major congeners. For slag cooling methods, dioxin concentration in TEQ of slow cooled slag by air was four times higher than that of fast cooled slag by water. Thus cooling by water is more appropriate with the added beneficial effect of producing granules/particles, which can be utilized as roadbed materials.     

Coal-tar-chemical β-picoline fraction as the complex raw material in the manufacture of heterocyclic medicinal preparations (review)

The characteristics of the coal-tar-chemical -picoline fraction and its composition are presented, and methods for the separation of its components by the application of chemical and physical methods are reviewed. The value of the -picoline fraction as a raw material in the manufacture of pyridine, piperidine, and quinuclidine medicinal preparations with cardiovascular, neurotropic, and chemotherapeutic action is examined. Particular attention is devoted to the results of research conducted by Soviet specialists in the complex utilization of all of the components of the -picoline fraction. The question of the need for the more nearly complete recovery of coal-tar-chemical gases and for the more efficient utilization of coal not only as a fuel and in the manufacture of coke but also as the most valuable complex raw material in the chemical and pharmaceutical-chemical industries is raised.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 435–447, April, 1981.