Thiết kế qui trình công nghệ sản xuất vinyl axetat

ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 1: Thiết kế qui trình Công nghệ sản xuất Nitrobenzen. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:…………………………………… ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 2: Thiết kế qui trình Công nghệ sản xuấn Ankyl benzensunfonic. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:…………………………………… ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 3: Thiết kế qui trình Công nghệ sản xuất Axetanilit. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:…………………………………… ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 4: Thiết kế qui trình Công nghệ sản xuất Etyl axetat. HỌ TÊN SINH VIÊN: 1:TRẦN MINH THIỆN 2:VŨ THỊ VƯƠNG ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 5: Thiết kế qui trình Công nghệ sản xuất Vinyl axetat. HỌ TÊN SINH VIÊN: 1:NGÔ THANH TRÍ……………………………………. 2:NGUYỄN MINH TRUNG…………………………………… ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 6: Thiết kế qui trình Công nghệ sản xuất Formandehit từ metanol. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 7: Thiết kế qui trình Công nghệ sản xuất Axit axetic. HỌ TÊN SINH VIÊN: 1:VÕ PHƯỚC TUYỂN……………………………………. 2:NGUYỄN HỮU VƯƠNG……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 8: Thiết kế qui trình Công nghệ sản xuất Anilin. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 9: Thiết kế qui trình Công nghệ sản xuất Phenol. HỌ TÊN SINH VIÊN: 1. NGUYỄN VĂN VIỆT 2. LÊ TRÍ ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 10: Thiết kế qui trình Công nghệ sản xuất Etyl benzen. HỌ TÊN SINH VIÊN: 1:ĐOÀN DUY TÙNG 2:TRỊNH ĐÌNH TUYỀN ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 11: Thiết kế qui trình Công nghệ sản xuất Etyl Acrylat. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 12: Thiết kế qui trình Công nghệ sản xuất MTBE. HỌ TÊN SINH VIÊN: 1:PAHN VĂN TRUNG 2:NGUYỄN VĂN TRƯỜNG ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 13: Thiết kế qui trình Công nghệ sản xuất ETBE. HỌ TÊN SINH VIÊN: 1:HUỲNH KIM Ý 2:PHẠM THANH TÙNG ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 14: Thiết kế qui trình Công nghệ tách Hydrocacbon thơm. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 15: Thiết kế qui trình Công nghệ tách n-parafin. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 16: Thiết kế qui trình Công nghệ sản xuất Dicloetan. HỌ TÊN SINH VIÊN: 1:LÂN QUỐC VIỆT 2:ĐẶNG MINH VƯƠNG ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 17: Tìm hiểu Công nghệ tái sinh dầu nhờn. HỌ TÊN SINH VIÊN: 1:NGÔ BÁ THÙY TRANG 2:LÊ THỊ MỸ VÂN ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 18: Công nghệ thu hồi và xử lý dầu loang. HỌ TÊN SINH VIÊN: 1:HÀ ANH TUẤN 2:NGUYỄN ĐÌNH VŨ ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 19: Tổng quan về phụ gia cho xăng Etanol. HỌ TÊN SINH VIÊN: 1:NGUYỄN HỮU VƯƠNG 2:VÕ PHƯỚC TUYỂN ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 20: Tìm hiểu qui trình tổng hợp nhiên liệu sạch từ nguồn nguyên liệu biomass Việt Nam bằng công nghệ tổng hợp F -T ở áp suất thường. HỌ TÊN SINH VIÊN: 1:NGUYỄN MINH TRUNG 2NGÔ THANH TRÍ ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 21: Tìm hiểu công nghệ sản xuất ethanol từ xenlulo. HỌ TÊN SINH VIÊN: 1:NGUYỄN CHÍ TRUNG 2:NGUYỄN NHẬT TRƯỜNG ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 22: Thiết kế qui trình công nghệ tổng hợp etanol bằng phần mền mô phỏng Hysys. HỌ TÊN SINH VIÊN: 1:PHAN THANH TÚ 2:LÊ MINH TUẤN ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 23: Tìm hiểu qui trình công nghệ tổng hợp mỡ nhờn canxi. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 23: Chưng cất dầu thô bằng phần mền hysys. HỌ TÊN SINH VIÊN: 1:NGUYỄN THỊ KIM YẾN 2:ĐINH VĂN YÊN 2. Vinyl Acetate 2.1. Properties Physical Properties. Vinyl acetate [108-05-4], CH 3 CO 2 CH=CH 2 , M r 86.09, is a colorless, flammable liquid with a characteristic, slightly pungent odor, bp 72.8 °C, density at 20 °C 0.932 g/mL, mp – 93.2 °C, viscosity 0.43 mPA · s, vapor pressure 12 kPa at 20 °C, 42.6 kPa at 50 °C, coefficient of cubic expansion 0.0014 K –1 , flashpoint – 8 °C, ignition temperature 385 °C. Lower/upper flammability limits in air 2.3/13.4 vol %, ignition group (VDE 0165) G 2, specific heat 1.926 kJ/kg; heat of evaporation 379.3 kJ/kg at 72.7 °C, heat of combustion 2082.0 kJ/mol, refractive index 1.3956, heat of polymerization 1035.8 kJ/kg, solubility of water in vinyl acetate 0.9 wt % at 20 °C, solubility of vinyl acetate in water 2.3 wt % at 20 °C, azeotrope with water bp 66 °C/100 kPa, water content 7.3 wt %. Chemical Properties. The chemical property which is exploited almost exclusively is the capacity to polymerize (see Section Use, Economic Importance). Other reactions of vinyl acetate: halogens give 1,2-dihaloethyl acetates [6], hydrogen halides give 1-haloethyl acetates [7], acetic acid gives ethylidene diacetate (see Section Production), hydrogen cyanide gives 2-acetoxypropionitrile [8], hydrogen peroxide gives hydroxyacetaldehyde [9], and dienes, such as butadiene or cyclopentadiene, give Diels – Alder products [10]. Transesterification with carboxylic acids produces the corresponding vinyl carboxylate and acetic acid [11] (see also Section Quality Specifications, Analysis,Storage, Transport, and Toxicology) and with alcohols gives the corresponding acetate and acetaldehyde. Thermal cleavage gives ketene and acetaldehyde [12]. Acid-catalyzed [13] or thermal [14] hydrolysis produces acetaldehyde and acetic acid. Vinyl acetate can be epoxidized with peracetic acid (84 % yield) [15]. It undergoes addition of H-active compounds, e.g., dimethyl phosphite gives dimethyl acetoxyethylphosphonate [16]. 2.2. Production There are various possible routes for vinyl acetate production: 1.Addition of acetic acid to acetylene: a.in the liquid phase in the presence of homogeneous mercury salt catalysts b.in the gas phase in the presence of heterogeneous catalysts containing zinc salts 2.Addition of acetic anhydride to acetaldehyde giving ethylidene diacetate, and subsequent cleavage of the latter to form vinyl acetate and acetic acid 3.Reaction of ethylene with acetic acid and oxygen a.in the liquid phase in the presence of palladium/copper salts as homogeneous catalysts b.in the gas phase on heterogeneous catalysts containing palladium 4.Reaction of methyl acetate or dimethyl ether with carbon monoxide and hydrogen in the liquid phase in the presence of homogeneous catalysts, e.g., rhodium salts or noble metals of the platinum group, giving ethylidene diacetate; cleavage of the latter giving acetic acid and vinyl acetate Acetylene, which is expensive, has mostly been replaced by the cheaper alternative, ethylene; ca. 80 % of the available capacity is used for process 3 b and ca. 20 % for process 1 b. Processes 1 a, 2, and 3 a are no longer used, while process 4, although allegedly developed to an industrial level, has not yet been used industrially. It may become more important because the starting materials can readily be produced from coal or naphtha. 2.2.1. Addition of Acetic Acid to Acetylene Liquid-Phase Process The addition of carboxylic acids to acetylene using mercury salts as the catalyst [17] is now of historical interest only. For more details see [18], [19]. Gas Phase Process The first process was developed in Munich by Consortium f. Elektrochemische Industrie [20]. It was further developed and used industrially by Wacker Chemie in Burghausen. Until 1965, almost all vinyl acetate was produced by the acetylene gas-phase process. Only two smaller plants used the ethylidene diacetate process [21]. Zinc salts on activated charcoal have proved to be effective catalysts. The development of suitable types of activated charcoal has improved the process [22]. Most of the industrial development work was concerned with carrying out the reaction. In the shaft furnaces used initially as reactors, controlling the heat of reaction was difficult. An occasional runaway of the reaction led to baking of the catalyst. Exothermic autodecomposition of the acetylene could not always be avoided. For better heat removal, other types of reactor employing a cooling medium were used. At Hoechst, Fischer furnaces were initially used, and at Wacker-Chemie tube furnaces. As far as is known, all producers using the solid bed catalysts have started to use tube reactors because of the defined gas flow, the easier charging and discharging of the catalyst, and the good temperature control. Only at Kurashiki in Japan, Du Pont in the United States, and in some plants in the former Soviet Union have fluidized-bed reactors been used. Solid bed and fluidized bed processes are considered of equal value. Process Description. The modes of operation of individual producers no longer differ significantly [23]. The process used by Hoechst until 1975 is described as an example (Fig. 1). Process data are given later in this section. Figure 1. Acetylene gas phase process for vinyl acetate production a) Acetic acid evaporator; b) Reactor; c) Heat transfer oil, cooling loop; d) Quenching tower; e) Recycle gas blower; f) Liquid ring pump; g) Washing column; h) Regenerating column; i) Lightends column; j) Pure vinyl acetate column; k) Crotonaldehyde column; l) Acetic acid column; m) Residue column; n) Degassing column; o) Acetaldehyde column; p) Acetone column; q) Water removal [Full View] The circulated acetylene is preheated at the exit of the reactor in a countercurrent, and is then mixed with acetic acid vapor. The circulating gas can also be fed directly through the acetic acid evaporator (a). The gas, heated to the reaction temperature, enters the tube reactor (b). The heat of reaction is removed by heat transfer oil in the cooling loop (c). The mixture leaving the reactor is cooled in stages. The last cooling stage takes place in the quenching tower (d). In this packed column, the gas mixture is cooled to 0 °C. The condensate itself is used for cooling. It is circulated from the bottom to the top of the quenching tower via a brine – cooled condenser. The liquid product stream is removed; excess acetylene is recycled via a circulating gas blower (e). The crude vinyl acetate produced at the bottom of the quenching tower is distilled giving acetic acid, which is recycled, and pure vinyl acetate. Some 90 % of the circulating gas is acetylene; the remainder is CO 2 , CO, and methane formed from thermal decomposition, acetaldehyde, N 2 , and other inert substances. To prevent enrichment of the impurities in the circulating gas, a small portion is removed behind the quenching tower (d) and then purified. The acetylene from the gas stream, which has been brought to ca. 100 kPa overpressure by means of a liquid ring pump (f), is extensively absorbed in a washing column (g) containing brine-cooled vinyl acetate. The inert substances are led as waste-gas to flare. The sump product from (g) is freed from dissolved acetylene in a regeneration column (h) by boiling. The acetylene is recycled. The crude vinyl acetate formed in the bottom of the quenching tower (d) contains ca. 62 – 63 wt % vinyl acetate and 30 –35 % acetic acid. It also contains dissolved acetylene, acetaldehyde, crotonaldehyde, acetone, methyl acetate, ethylidene diacetate, and acetic anhydride. In the lightends column (i) acetaldehyde, acetone, methyl acetate, dissolved acetylene, some vinyl acetate, and water (originating from the starting materials) are first distilled overhead. The sump product is fractionated in distillation columns ( j – m). Pure vinyl acetate is removed as the top product of the column ( j). In (k) crotonaldehyde distills at the head as an azeotrope after addition of water. The bottom of the acetic acid column (l) also contains, besides acetic acid, the high-boiling ethylidene diacetate and acetic anhydride (unless they have already been hydrolyzed in the crotonaldehyde column), and very small quantities of polymers. Column (m) is operated under vacuum, and to some extent batchwise; the residual acetic acid distills so extensively that the liquid sump product which remains can subsequently be incinerated. The distillate from the lightends column (i) contains mainly acetaldehyde, acetone, methyl acetate, vinyl acetate, and water. It is purified in distillation columns (o – q). Stabilizers. To avoid polymerization during the distillative work-up of the crude vinyl acetate, polymerization inhibitors are added. The preferred stabilizer is hydroquinone. Copper resinate, phenothiazine, or methylene blue are also used. Materials and Environmental Aspects. The plant is made from mild steel in the hot area of the reaction section and in places where no liquid acetic acid is present. These areas include the reactor, the gas – gas heat exchanger, and the circulating gas blower. For the distillation section and the equipment in the reaction section which comes into contact with liquid product, stainless steel 316 L is used. The process has almost no polluting waste streams. All gaseous or liquid byproducts (high-boiling, crotonaldehyde, and acetone – methyl acetate fractions) can be incinerated. Waste circulating gas is passed to the excess gas burner. Process Data. The catalyst consists of zinc acetate on activated charcoal (particle size 3 – 4 mm) as the carrier material. The zinc content is 10 – 15 wt %. The catalyst is produced by dipping. As the activated charcoal can contain traces of copper, small quantities of other components are added to the catalyst to prevent the formation of cuprene, which can block the tubes. The operating time is ca. 5000 – 7000 h, depending on the type of activated charcoal used. It also depends on the purity of the acetylene and the circulating acetic acid. When using acetylene produced from carbide, the type of carbide is important. Because of the varying contents of phosphorus hydrides, hydrogen sulfide, arsine, and ammonia in the acetylene, it sometimes has to be further purified before being used in vinyl acetate production. This involves several steps. Acetylene produced from petrochemicals does not contain these components. The decrease in catalyst activity is caused to a small extent by migration of zinc acetate out of the catalyst, but to a greater extent by formation of byproducts or by foreign components, which either act as catalyst poisons or adhere to the catalyst surface and pores [24], [25]. Vinyl acetate itself does not appear to contribute to the deactivation of the catalyst under the reaction conditions. The space – time yield for the vinyl acetate is normally 60 – 70 g per liter catalyst per hour. The reaction temperature is 160 – 170 °C, depending on the type of activated charcoal used as catalyst, but increases to 205 – 210 °C as the catalyst activity decreases. At the elevated temperature in the reactor, more byproducts are formed. The pressure can increase a little during the operating time of a catalyst charge. This is caused by a slight increase in the flow resistance of the catalyst. The maximum pressure is ca. 40 kPa overpressure. Plants are protected against overpressures greater than 40 – 50 kPa because acetylene can undergo exothermic autodecomposition at high pressures and temperatures: The acetylene pipes leading to the plant therefore contain barriers which inhibit the acetylene autodecomposition. The plants are also provided with equipment for automatic flushing with inert gas. The molar ratio acetic acid : acetylene is normally between ca. 1 : 4 and 1 : 4.5. The load per m 3 catalyst is ca. 135 m 3 (STP) recycle gas per hour and 76 kg acetic acid per hour. The recycle gas consists of ca. 90 % acetylene. Acetylene conversion is ca. 15 % and acetic acid conversion ca. 55 %. The yields based on acetic acid can reach 99 %, or 98 % based on acetylene, if the acetaldehyde formed (2 – 3 kg per 100 kg vinyl acetate) is included in the yield. 2.2.2. Ethylidene Diacetate Process The process was developed by Celanese Corporation of America [26] and was operated industrially in the United States from 1953 to 1970, and then replaced by the ethylene gas- phase process. A small plant (Celmex) operated in Mexico until 1991. Acetic anhydride is converted to ethylidene diacetate with acetaldehyde in the liquid phase using catalysts such as iron(III) chloride. The ethylidene diacetate is then cleaved thermally to vinyl acetate and acetic acid, using catalysts such as toluenesulfonic acid. Some of the ethylidene diacetate is converted back to acetic anhydride and acetaldehyde. 2.2.3. Reaction of Acetic Acid with Ethylene and Oxygen Liquid-Phase Process. The formation of vinyl acetate from ethylene and acetic acid in the presence of palladium chloride and alkali acetate in glacial acetic acid was first described by MOISEEW [27]: Addition of benzoquinone to the reaction mixture was said to reoxidize the palladium to palladium chloride. The reaction corresponds to the Wacker – Hoechst process, in which acetaldehyde is obtained from ethylene and water in the presence of palladium chloride: The palladium formed is reoxidized to Pd 2+ with copper(II) chloride. The copper(I) chloride formed is reoxidized with oxygen (→ Acetaldehyde). Production of vinyl acetate by a similar route has been widely investigated [28-30]. Corresponding production plants were commissioned by ICI in England, Celanese in the United States, and Tokuyama Petrochemical in Japan [31], but later shut down. Now only the ethylene gas-phase process uses ethylene as the starting material (see below). In the liquid-phase process, a recycle ethylene gas stream is passed through a reaction solution containing acetic acid, water, high-boiling byproducts analogous to those of the acetaldehyde process, PdCl 2 , and CuCl 2 . Oxygen is passed into the reaction solution at the same time to reoxidize the palladium and the CuCl. The reaction and regeneration of the catalyst take place in one step: Water is formed in the reoxidation of CuCl; part of the vinyl acetate formed is hydrolyzed to acetaldehyde and acetic acid. Part of the acetaldehyde is also formed directly from ethylene, as in the acetaldehyde process. [...]... Poly (Vinyl Esters), and for the production of poly (vinyl alcohol) (→ Paints and Coatings – Poly (Vinyl Alcohol)) and polyvinylbutyral (→ Paints and Coatings – Poly (Vinyl Acetals)) Vinyl acetate – ethylene copolymers (→ Poly (Vinyl Esters) – Properties) are processed to give resins, paints (→ Paints and Coatings – Poly (Vinyl Esters)), and sheeting Floor coverings and gramophone records are made from vinyl. .. Azeotrope column; b) Wastewater column; c) Drying/lightends column; d) Pure vinyl acetate column [Full View] Figure 4 Ethylene gasphase process for vinyl acetate production; variant for workup of crude vinyl acetate a) Dehydration column; b) Pure vinyl acetate column; c) Wastewater column [Full View] The liquid products contain 20 – 40 wt % vinyl acetate and ca 6 – 10 vol % water The rest consists of acetic... from vinyl acetate – vinyl chloride copolymers Vinyl acetate is also used in small quantities as a comonomer in polyacrylic fiber production Uses differ according to the region In Japan, ca 70 % of vinyl acetate is used in the production of poly (vinyl alcohol), while in the United States and Europe more than half is processed to give poly (vinyl acetate) The total capacity for vinyl acetate production... defined temperature Storage As a flammable liquid, vinyl acetate is assigned to VbF, group A, class 1, and ignition group T 2 according to VDE 0165 It can be stored in steel, aluminum, or stainless steel containers under nitrogen It is not necessary to add stabilizers at lower temperatures If the vinyl acetate is to be warmed, stabilizers, such as hydroquinone, hydroquinone monomethyl ether, or diphenylamine... Ethylene gas-phase process for vinyl acetate production; work-up of crude vinyl acetate a) Azeotrope column; b) Wastewater column; c) Drying/lightends column; d) Pure vinyl acetate column Figure 4 Ethylene gas-phase process for vinyl acetate production; variant for work-up of crude vinyl acetate a) Dehydration column; b) Pure vinyl acetate column; c) Wastewater column AXIT AXETIC 1 Introduction Acetic... the liquid products to give acetic acid (which is recycled) and pure vinyl acetate is carried out in various ways, depending on the location of the plant and on the relative importance of energy consumption and investment costs Besides the systems shown in Figures 3 and 4, combinations of both versions are used Figure 3 Ethylene gasphase process for vinyl acetate production; workup of crude vinyl acetate... the acetic acid, vinyl acetate, or water The dew point is generally not reached The gas mixture is then led into the predehydration column (l) and then cooled to about room temperature in (e) The liquid product consists of an acetic-acid-free mixture of vinyl acetate and water The mixture is separated in a phase separator (m) into an aqueous phase, which is removed, and an organic vinyl acetate phase,... e.g., ethylidene diacetate and ethyl acetate To work up the liquid products (Fig 3) a vinyl acetate – water mixture can be distilled at the head in a first distillation (a) This mixture separates into two phases The dissolved vinyl acetate is distilled from the water phase in wastewater column (b) The remaining water is wastewater The organic vinyl acetate phase is freed as the top product in a second... a mixture with acetic acid, water, and vinyl acetate [44] If an additional column is used for the work-up, only the dissolved water is distilled over in the second distillation, in the third the light ends, and in the fourth the pure vinyl acetate [45] In another version (Fig 4) the water contained in the crude vinyl acetate is removed as an azeotrope with the vinyl acetate together with volatile products,... energy consumption is ca 3 t of heating steam per tonne of vinyl acetate produced As a result of process improvements, modern plants have a heating steam consumption of 1.2 t per tonne of vinyl acetate The yields are up to 99 % based on acetic acid, and up to 94 % based on ethylene, if the acetaldehyde, formed in small quantities by hydrolysis of vinyl acetate during the distillative work-up, is included . NGÀNH ĐỀ TÀI 3: Thiết kế qui trình Công nghệ sản xuất Axetanilit. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:…………………………………… ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 4: Thiết kế qui trình Công nghệ sản xuất Etyl axetat. HỌ. 5: Thiết kế qui trình Công nghệ sản xuất Vinyl axetat. HỌ TÊN SINH VIÊN: 1:NGÔ THANH TRÍ……………………………………. 2:NGUYỄN MINH TRUNG…………………………………… ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 6: Thiết kế qui trình Công nghệ. NGÀNH ĐỀ TÀI 8: Thiết kế qui trình Công nghệ sản xuất Anilin. HỌ TÊN SINH VIÊN: 1:……………………………………. 2:……………………………………. ĐỒ ÁN CHUYÊN NGÀNH ĐỀ TÀI 9: Thiết kế qui trình Công nghệ sản xuất Phenol. HỌ