Acid Alkylation Research Articles

Polyethylene Film Surface Modification via Benzoic Acid Grafting.

A polyethylene (PE) film surface modification method is proposed via benzoic acid (BA) alkylation grafting to improve the surface affinity to polar substances. The procedure involves sequentially spraying AlCl3 and BA onto the heat-softened PE surface. The occurrence of the alkylation reaction was evaluated through comparative chemical, morphological, and thermal analyses. It was demonstrated that the grafting reaction of BA onto the PE film surface took place, limited to the surface layer, while preserving the bulk properties of PE. The reaction resulted in the formation of aluminum benzoate complexes, which improved the surface affinity to polar compounds. The impact of grafting on the surface properties of PE was further assessed by comparing the behavior of PE films treated with BA and untreated PE films when painted with watercolors. The PE film grafted with BA exhibited increased affinity towards watercolors, providing strong evidence of a change in surface polarity from hydrophobic to hydrophilic. These findings indicate that the proposed methodology effectively renders the PE surface paintable, even with non-toxic water-based inks, making it suitable for applications such as packaging.

Machine Learning-Supported Designing of Human–Machine Interfaces

The design and functionality of the human–machine interface (HMI) significantly affects operational efficiency and safety related to process control. Alarm management techniques consider the cognitive model of operators, but mainly only from a signal perception point of view. To develop a human-centric alarm management system, the construction of an easy-to-use and supportive HMI is essential. This work suggests a development method that uses machine learning (ML) tools. The key idea is that more supportive higher-level HMI displays can be developed by analysing operator-related events in the process log file. The obtained process model contains relevant data on the relationship of the process events, enabling a network-like visualisation. Attributes of the network allow us to solve the minimisation problem of the ideal workflow–display relation. The suggested approach allows a targeted process pattern exploration to design higher-level HMI displays with respect to content and hierarchy. The method was applied in a real-life hydrofluoric acid alkylation plant, where a proposal was made about the content of an overview display.

Multicationic Quaternary Ammonium Compounds: A Framework for Combating Bacterial Resistance.

During previous stages of research, high biocidal activity toward microorganism archival strains has been used as the main indicator in the development of new antiseptic formulations. Although this factor remains one of the most important characteristics of biocide efficiency, the scale of antimicrobial resistance spread causes serious concern. Therefore, focus shifts toward the development of formulations with a stable effect even in the case of prolonged contact with pathogens. Here, we introduce an original isocyanuric acid alkylation method with the use of available alkyl dichlorides, which opened access to a wide panel of multi-QACs with alkyl chains of various lengths between the nitrogen atoms of triazine and pyridine cycles. We used a complex approach for the resulting series of 17 compounds, including their antibiofilm properties, bacterial tolerance development, and antimicrobial activity toward multiresistant pathogenic strains. As a result of these efforts, available compounds have shown higher levels of antibacterial activity against ESKAPE pathogens than widely used commercial QACs. Hit compounds possessed high activity toward clinical bacterial strains and have also demonstrated a long-term biocidal effect without significant development of microorganism tolerance. The overall results indicated a high level of antibacterial activity and the broad application prospects of multi-QACs based on isocyanuric acid against multiresistant bacterial strains.

Results of Development of a Jet Reactor Design for Second-Stage Sulfuric Acid Alkylation

Results of Development of a Jet Reactor Design for Second-Stage Sulfuric Acid Alkylation

Optimization of the content of isobutane in the feed stream of the plant for sulfuric acid alkylation of isobutane with olefins

The raw materials for the industrial production of moto- and air-alkylates are isobutane and butane-butylene fractions containing in their composition a component, n-butane, which is inert for the reaction of sulfuric acid alkylation of isobutane with olefins. In accordance with the Specifications TU 0272-024-00151638-99, the content of n-butane in the isobutane fraction, depending on the grade of the fraction, is 0.7÷20% wt. Its presence reduces the useful reaction volume of the alkylation reactor, and when separating the components of the alkylation reaction mass, it is necessary to use a distillation column (debutanizer). The possibility of including an additional column in the technological scheme for removing n-butane from the composition of the fraction (respectively, isobutane concentration) before it is fed into the alkylation reactor is being considered. This is of particular importance for factions with a brand below "High Brand". The study is conducted using the Honeywell UniSim Design software system. The Peng-Robinson method was used to calculate the properties of process stream components. The theoretically optimal design of the apparatus was calculated: when using a distillation column with a pressure in the apparatus of about 400 kPa to reduce the content of n-propane in the distillate (obtained isobutane fraction) to 0.001 mol. the share will require 48 theoretical plates, the accepted reflux ratio R = 8.9, the temperatures in the condenser and reboiler are 26.88 and 47.27 °C, respectively. A computational experiment has shown that in order to achieve the practical absence of n-butane in the obtained isobutane fraction (concentration of about 0.1% wt.), it is possible to use a distillation column with the following technological modes: the number of plates is 60, the feed plate is 15, the efficiency of contact devices is 0.8; the pressure in the column is about 400 kPa, the temperature in the condenser and reboiler is Тk=28.91÷29.05 ℃ and Тр=46.72÷47.25 ℃, respectively, reflux ratio R=20.41. This fraction also does not contain pentanes.

Correction to: Enhancing Efficiency of a Jet Sulfuric Acid Alkylation Reactor

Correction to: Enhancing Efficiency of a Jet Sulfuric Acid Alkylation Reactor

New type jet turbulent contactor for sulfuric acid alkylation of isobutane with olefins

The modernization of the reactor equipment for the industrial process of sulfuric acid alkylation of isobutane with olefins is considered.

Simultaneous Process Mining of Process Events and Operator Actions for Alarm Management

Alarm management is an important task to ensure the safety of industrial process technologies. A well‐designed alarm system can reduce the workload of operators parallel with the support of the production, which is in line with the approach of Industry 5.0. Using Process Mining tools to explore the operator‐related event scenarios requires a goal‐oriented log file format that contains the start and the end of the alarms along with the triggered operator actions. The key contribution of the work is that a method is presented that transforms the historical event data of control systems into goal‐oriented log files used as inputs of process mining algorithms. The applicability of the proposed process mining‐based method is presented concerning the analysis of a hydrofluoric acid alkylation plant. The detailed application examples illustrate how the extracted process models can be interpreted and utilized. The results confirm that applying the tools of process mining in alarm management requires a goal‐oriented log‐file design.

Risk Assessment and Material Suitability Evaluation on Static Equipment of Hydrofluoric Acid Alkylation Unit

In 2005, a 60 kt/a alkylation (ALK) unit began to resume production in the Second Oil Refinery Plant of Beijing Yanshan Petrochemical Company. There have been many leak cases from pipeline welds, valve body, flange, etc. After a half-year period of operation, production process is stable. However, the operation of the hydrofluoric (HF) acid ALK unit has been suffered from corrosion problems. There are no clear answers and references to the following problems. What types of corrosion are currently in the main equipment for HF acid ALK unit? What does cause equipment corrosion? What are the main influencing factors for corrosion? What measures can be taken to reduce the corrosion of HF acid? In this paper, considering the acid-related conditions of the ALK unit, the damage mechanism and damage rate analysis were carried out to calculate the safety risk of the static equipment of the ALK unit. Based on the damage mechanism and failure history, the material suitability of the ALK unit was investigated. The anti-corrosion measures and recommended materials for important corrosion parts of the ALK unit were proposed. It is meaningful for reducing the number of shutdowns of ALK units and maintaining safe and stable operation of the unit.

Quality vs. quantity of alarm messages - How to measure the performance of an alarm system

Despite significant efforts to measure and assess the performance of alarm systems, to this day, no silver bullet has been found. The majority of the existing standards and guidelines focus on the alarm load of the operators, either during normal or upset plant conditions, and only a small fraction takes into consideration the actions performed by the operators. In this study, an overview of the evolution of alarm system performance metrics is presented and the current data-based approaches are grouped into seven categories based on the goals of and the methodologies associated with each metric. Deriving from our categorical overview, the terminological differences between the academic and industrial approaches of alarm system performance measurement are reflected. Moreover, we highlight how extremely unbalanced the performance measurement of alarm systems is towards quantitative metrics instead of focusing on qualitative assessment, invoking the threat of excessive alarm reductions resulting from such a unilateral approach. The critical aspects of qualitative performance measurement of alarm systems is demonstrated in terms of the comparison of the alarm system of an industrial hydrofluoric acid alkylation unit before and after the alarm rationalization process. The quality of the alarm messages is measured via their informativeness and actionability, in other words, how appropriate the parameter settings are for the everyday work and how actionable they are by the operators of the process.

Coalescence-adsorption coupling treatment instead of alkaline washing-water washing process for efficient removal of sulfuric acid and sulfates

C4 alkylate oil is an ideal blending component of automotive gasoline, and the green removal of sulfuric acid and sulfates from the high-temperature sulfuric acid alkylation reaction products (SAARP) has always been a hot issue in the field of clean alkylation production. In this paper, a novel coalescence separation-depth adsorption (CS-DA) coupling dry separation technique is introduced to efficiently separate acid-hydrocarbon emulsions, with the aim to supersede the alkaline washing-water washing (AW-WW) process in alkylation unit. Lateral line tests were conducted on the coupling treatment of the alkylation reaction products (ARP) produced in the STRATCO alkylation unit of Sinopec Tianjin Branch. The sulfur morphology analysis shows that the sulfides in the ARP mainly come from C4 feedstocks and alkylation reaction, including mercaptans, thioethers, thiophenes, trace hydrogen sulfide and sulfur dioxide. The mechanism of coalescence separation reveals that the efficient removal process of sulfuric acid by fiber coalescence separation also has a function similar to "pickling extraction" to remove sulfates. In addition, we investigated the influence of CS-DA coupling treatment on the total sulfur and sulfuric acid content in the ARP and performed the copper corrosion and water-soluble acid assays. The research findings indicated that the back sideline of the acid coalescer had the most outstanding separation effect relative to the front and rear lateral lines of the heat exchanger. The total sulfur content in the ARP after separation can be reduced to less than 5 mg/L, without water-soluble acid and copper corrosion (1a). The industrial application shows that the CS-DA coupling dry separation technique can completely replace the AW-WW process, which makes the various indicators of alkylate oil strictly controlled and the sulfur content up to the industrial standard. The novel dry separation technique provides a promising alternative for solving the difficulties in the emulsion treatment of high-temperature sulfuric acid alkylation and promoting the clean production of alkylation.

<i>Para-tert</i>-butylcumene synthesis

Objectives. This study describes a new approach to obtain para-tert-butylcumene by alkylation of cumene with isobutylene in the presence of catalysts, such as Amberlyst 36 Dry, KU-2-8, aluminum chloride, and tert-butyl alcohol and concentrated sulfuric acid.Methods. To determine the qualitative and quantitative composition of the compounds and reaction masses, the following analysis methods were used: gas–liquid chromatography (on the Kristall 2000M hardware-software complex), chromatomass spectrometry on an Agilent 6850 instrument equipped with an Agilent 19091S-433E capillary column (30 m × 250 μm × 0.25 μm), and nuclear magnetic resonance spectroscopy (on a Bruker DRX 400 instrument with an operating frequency of 400 MHz).Results. A significant quantity of meta-tert-butylcumene was obtained by the alkylation of cumene with isobutylene using several catalysts, along with para-tert-butylcumene. This study also showed that the use of the catalysts Amberlyst 36 Dry and KU-2-8 during alkylation in a closed system (autoclave) led to the formation of isobutylene oligomers, often in quantity greater than the target reaction product. Simultaneously, the alkylation of cumene with tert-butyl alcohol in the presence of concentrated sulfuric acid enabled the obtainment of only one isomer, para-tertbutylcumene, which is essential for the further production of high-purity para-tert-butyl phenol.Conclusions. Sulfuric acid alkylation of cumene with tert-butyl alcohol enabled the obtainment of an individual para-isomer of tert-butylcumene with a yield of 87–89% for the loaded tert-butyl-alcohol with a cumene conversion of ~30%.

РЕКОНСТРУКЦИЯ СОЕДИНЕНИЯ ТРУБ С ТРУБНОЙ РЕШЕТКОЙ В АППАРАТАХ ВОЗДУШНОГО ОХЛАЖДЕНИЯ

The article analyzes the types of pipe connections with a pipe grid in air-cooling devices. Based on this analysis, it is proposed to change the design of pipe fastening instead of rolling to
 tightening nuts in ABO-103/1-2 of the sulfuric acid alkylation unit

Efficient removal of acid from sulfuric acid alkylation reaction products by fiber coalescence technique: Lab-scale and industrial experiments

Removing acid from sulfuric acid alkylation reaction products through fiber media is a new and challenging process in the industry. In this paper, a filler braided from stainless-steel fiber and polytetrafluoroethylene fiber is used to separate the acid-hydrocarbon emulsion. The selected filler characteristics (fiber diameter is 50 μm, bed porosity is 58.3%) and operation condition (superficial velocity is 37.5 m/h) based on lab-scale experiments were applied in the industrial tests, and a good acid-hydrocarbon separation performance was obtained. The separation efficiency was 99.82% and the pressure drop was 43.4 kPa at the superficial velocity of 37.5 m/h. In addition, through the study of fiber wettability, the coalescence mechanism was revealed, which is that the special braided structure induces acid droplets and hydrocarbon droplets to move in different directions, and the droplets on the fiber continue to migrate, coalesce and grow up, thereby achieving the rapid separation of acid and hydrocarbon phases. These findings can facilitate further applications of the sulfuric acid alkylation technology and significantly improve environmental benefits.

ПОВЫШЕНИЕ ЭФФЕКТИВНОСТИ АППАРАТА ВОЗДУШНОГО ОХЛАЖДЕНИЯ УСТАНОВКИ СЕРНОКИСЛОТНОГО АЛКИЛИРОВАНИЯ

The study of the efficiency of the heat transfer process in the air cooling apparatus, which is part of the installation of a sulfuric acid alkylation, at different finning coefficients of heat exchange pipes

ПОВЫШЕНИЕ ЭНЕРГОЭФФЕКТИВНОСТИ ТЕХНОЛОГИИ РЕГЕНЕРАЦИИ СЕРНОЙ КИСЛОТЫ В ПРОЦЕССЕ СЕРНОКИСЛОТНОГО АЛКИЛИРОВАНИЯ

The main approaches to energy efficiency analysis of sulfuric acid regeneration technology in the process of sulfuric acid alkylation are considered

Problem of Updating Design of Horizontal Cascade Reactor for Sulfuric Acid Alkylation of Isoparaffins by Olefins

Technical solutions ore offered for updating several horizontal cascade sulfuric acid alkylation reactor units to increase reliability and efficiency of the reactor.

The Mysteries of Science in Solving Applied Problems

The solution of various applied problems usually leads to the need to find answers to purely scientific fundamental questions and discover new phenomena. The article gives examples of such discoveries. It was discovered that flammability of polymeric materials can be decreased by dispersion of a material containing microencapsulated low-boiling flame retardants on exposure to an external fire source. The composition of the Earth’s atmosphere is analyzed in terms of dynamic equilibrium of the processes of oxygen production from forests and the consumption for their combustion during fires. The study of the amazing kinetics of the preparation of polyformaldehyde from formaldehyde and its cyclic trimer, trioxane, was explained, firstly, in the creation of the theory of reversible heterogeneous polymerization of trioxane and led to a fundamentally new, thermodynamic, method of regulating the molecular and supramolecular structure of the polymer. Secondly, on the example of polymerization of formaldehyde, a possible advantage of “diffusion” over “kinetic” modes was discovered. A similar effect was confirmed for the process of sulfuric acid alkylation of high-octane gasoline production.

History, Current State, and Prospects for Development of Isobutane Alkylation with Olefins

The history of the formation, development, current state, trends, and prospects for the development of isobutane alkylation with olefins are discussed. It is shown that this process is carried out using various catalysts and technologies, among which sulfuric acid alkylation has a predominant use in refining around the world. Characteristics of domestic and foreign alkylation processes are compared. Data on the construction and beginning of operation of the first domestic industrial sulfuric acid alkylation plants in Grozny are discussed. In addition, data on alkylation plants obtained by lend-lease and built at refineries in Gur’ev, Orsk, Krasnovodsk, and Kuibyshev in 1945–1955 are presented. The prospect of developing the alkylation of isoparaffins with olefins is aimed at the development of technologies using solid catalysts, mainly based on various zeolites. The main foreign companies that have developed promising technologies for the alkylation process on solid catalysts are Mobil Oil Corporation, Sun Oil Company, Universal Oil Products Company, CLG (United States), Akzo Nobel (Holland), Haldor Topsoe (Denmark), INL (United States), UOP (United States), EXELUS (United States), Lurgi (Germany), etc. Among leading domestic research institutes, the following should be named: Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences; Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences; and Grozny State Oil Technical University.

Conjugation of N‐(3‐(9‐Ethynyl‐6H‐indolo[2,3‐b]quinoxalin‐6‐yl)propyl)‐2,2,2‐trifluoroacetamide Intercalator to a Triplex Forming Oligonucleotide, a Three‐Way Junction, and a G‐Quadruplex

A new intercalating nucleic acid monomer Z comprising an 3‐(9‐((4‐oxyphenyl)ethynyl)‐6H‐indolo[2,3‐b]quinoxalin‐6‐yl)propan‐1‐amine moiety was synthesized. When Z was inserted into triplex forming oligonucleotides, high thermal stability was observed for its corresponding Hoogsteen‐type triplexes. Three‐way junction (TWJ) was studied by targeting a DNA strand to the foot of a DNA or an RNA hairpin. When Z was inserted into the DNA strand, this resulted in the highest increase of thermal melting ever reported for a TWJ modified by insertion of an intercalator into the junction site. Experiments with mismatches confirmed formation of the TWJ. Improvements in stability of a G‐quadruplex were achieved by insertion of the monomer Z by replacement of one of the nucleotides in the TGT loop. The first steps in the synthesis of the monomer Z were condensation of 5‐iodoisatin with o‐phenylene diamine under reflux in acetic acid and subsequent alkylation reaction with 2‐(3‐bromopropyl)isoindoline‐1,3‐dione followed by suitable reduction led to 3‐(9‐Iodo‐6H‐indolo[2,3‐b]quinoxalin‐6‐yl)propan‐1‐amine which in turn was treated with ethyl trifluoroacetate with formation of 2,2,2‐trifluoro‐N‐(3‐(9‐iodo‐6H‐indolo[2,3‐b]quinoxalin‐6‐yl)propyl)acetamide. This compound was reacted by Sonogashira coupling conditions to give the diol which was converted into the DMT‐protected phosphoramidite, which in turn was used to incorporate the monomer Z into oligonucleotides.