Manufacturing of MAN PDF

MANUFACTURING OF MALEIC ANHYDRIDE
Chapter 1 INTRODUCTION
MALEIC ANHYRIDE
Maleic anhydride (MA) is a versatile monomer and important chemical intermediate.It is an organic compound with the formula C2H2(CO)2O.Other names for maleic anhydride are 2,5furandione, dihydro-2,5dioxofuran,toxilicanhydride, and cis-butenedioic anhydride. Maleic acid is also called (Z)-2-butenedioic acid, toxilic acid, malenic acid, or cis-1,2-ethylenedicarboxylic acid. Maleic anhydride was traditionally manufactured by the oxidation of benzene or
other aromaticcompounds. As of 2006, only a few smaller plants continue to use benzene; due to rising benzene prices, most maleic anhydride plants now use n-butane as a feedstock: 2 CH3CH2CH2CH3 + 7 O2 2 C2H2(CO)2O + 8 H2O The primary use of MA is in the manufacture of alkyd resins. These resins are added to fiberglass reinforced plastics to make a strong, lightweight, and corrosion resistantmaterial that is found in boats, cars, trucks, pipelines and electrical devices. In asecondary capacity, MA is employed in the manufacture of lacquers, lube-oil additives, and agriculturalproducts. The addition of MA to drying oils decreases the required drying time and improves the coating quality of lacquers:dispersants derived from MA prolong oil change intervals and improve the efficiency of automotive engines. Agriculture productsmade from MA include herbicides, pesticides, and plant growth regulators. Furthermore, fumaric and maleic acid are important MA derivatives used in paper sizing resins and as food and beverage acidulants. Moreover, MA can be used as a starting material for synthesis of1,4-butanedial.Maleic anhydride (1), maleic acid (2), and fumaric acid(3) are multifunctional chemical intermediates that find applications in nearly every field of industrial
chemistry. Each molecule contains two acidcarbonyl groups and a double bond in the ,position.
Maleic anhydride and maleic acid are important raw materials used in the manufacture Of phthalic-type alkyd and polyester resins, surface coatings, lubricantadditives, plasticizers, copolymers, and agricultural chemicals.Both chemicalsderive their common names from naturally occurring malic acid.Other names for maleic anhydride are 2,5-furandione, dihydro2,5dioxofuran,toxilicanhydride, and cis-butene dioic anhydride. Maleic acid is also called (Z)-2butenedioic acid, toxilic acid, malenic acid, or cis-1,2-ethylenedicarboxylic acid.
TECHNOLOGY STATUS: IN INDIA: The present consumption of MA is, about, 4,200 tonnes per annum and its growing rate is 11.5%per annum. Benzene and normal butane are,the main feed stocks, for maleic anhydride industry. In India, both the present plants are based on benzene. Presently benzene is in short supply. In order to bridge this gap, benzene is imported. On the other hand, natural gas is available in India, in large quantities and normal butane is a constituent of natural gas. Using butane for production, foreign exchange, spent on benzene can be saved, while, at the same time, reducing the cost production, of MA.
INTERNATIONAL: The present, global production of MA, is, about 500,000 TPA and the demand growth rate is, around 5% per annum. New catalyst with higher, selectivity, life and stability, have been developed. There is also, a shift in feed stock, from benzene to butane, because of economics and pollution control laws. Till recently, fixed bed tubular reactors used to be general choices for plants. However, recently fluidized bed reactor and transport bed reactors have been developed and are more suited, for MA production.
INDUSTRIES: 1. Navjyot Chemicals & Commodities Private Limited,Santacruz West, Mumbai, Maharashtra - 400 054, India 2. Sarvottam Vegetable Oil Refinery Private Limited,Indore, Madhya Pradesh
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3. Qinhuangdao Ouke Chemical Co., Ltd.Hebei, China 4. Adarsh Chemicals & Fertilizers Ltd., at Odhna, Gujarat. 5. Allied Aromatics Ltd., at Kalyani, West Bengal.
Chapter 2 LITERATURE SURVEY
PHYSICAL PROPERTIES:

Physical state : Solid flakes
Appearance : White when in solid form &Colourless in liquid
Odour :acidodour. Molecular formula :2 2 ()2 Molecular weight : 98.06 Melting point : 52.8C
Boiling point : 202C
Vapour Density : 3.4 (air = 1) Density : 1.43gm/cm3 SOLUBILITY o Water : Insoluble in water o Acetone at 25C : 227 g/100 g o Ethyl acetate : 112 g/100 g o Chloroform : 52.5 g/100 g
at room temperature
Sp.gravity :1.48 (at 20 C/20 C solid) 1.3 (at 70 C/70 C molten) Auto ignition temperature : 447C Flash point : o Open Cup 110 C (230 F) o Closed Cup 102 C (216 F)
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CHEMICAL PROPERTIES:
Formation of acid by hydration: Molten maleic anhydride reacts exothermally & rapidly with liquid water to formthe maleic acid.
+ H20 Maleic Esters from Alcohols: Maleic anhydride has been converted into a range of acrylate esters on treatment with a suitable alcohol using triphenylphosphine as a catalyst. Maleic anhydride reacts with unhindered alcohols to provide acrylate esters in a process catalyzed by triphenylphosphine.
Sulfonation: Maleic anhydride is sulfonated to a-sulfomaleic anhydride with sulfur trioxide.
+ SO3
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Alkylation of Maleic Anhydride: Normal alpha olefins and maleic anhydride react to form alkenyl succinic anhydrides
Electrophilic Addition: Electrophilic reagents attack the electron-deficient bond of maleic anhydride. Typical addition reagents include halogens, hydrohalic acids, and water.
Esterification: Both mono - and dialkyl maleates and fumarates are obtained on treatment of maleic anhydride or its isomeric acids with alcohols or alkoxides . An extensive review is available. Alkyl fumarates often are made from isomerization of the corresponding maleate.
APPLICATIONS:
1. Alkyd resins: The largest single end use of maleic anhydride is the preparation of alkyd resins. About 95% of alkyd resins are used in surface coatings. They have some desirable properties such as Quick Dry characteristics, outstanding weather & exposure resistance, flexibility& excellent adhesion to the surface to be protected. 2. Plasticizers: The second largest use of maleic anhydride is the production of plasticizers of various synthetic resins or plastics. Most of the maleic esters end up in the Di-butyl maleate co-onomer. These are used Lube oil additives, textile finishing agents, Ingredient in bonding agents used to manufacture plywood. Used in the manufacture of coating resins and polyester resins for plastics. 3. Dyes &intermediates: The third largest end use of maleic anhydride is in the preparation of various classes of dyes & intermediates. The most important are the2(pN,N-dimethyl-amino-phenyl)-3-nitromaleic anhydride. It is done by condensation reaction between maleic anhydride with 4-flouoroanisole. 4. Retarders: It is also used as a retarder in rubbers, retarders are the ingredients used to protect against scratch hazard. 5. Metallic & acid salts: Maleic anhydride is also used in the manufacture of metallic salts & acids such as sodium salt etc. 6. Pharmaceuticals: Maleic anhydride is also used in the preparation of some pharmaceuticals such as Pyran. 7. Agriculture: Maleic anhydride is also used in the preparation of maleic hydrazine &Endothall salt for improving the fertility of soil.
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STRUCTURE OF MALEIC ANHYDRIDE:

From the single crystal x-ray data, Maleic anhydride is a planar molecule with the ring oxygen atom lying 0.003 nm out of the molecular plane. A twofold rotation axis bisects the double bond & passes through the ring oxygen atom.
Bond distances in nm for the structure of maleic anhydride is determined by single crystal x-ray diffraction methods at 110K.The maleic anhydride molecule is nearly planar. The plane containing the 1 ,4 and 5 atoms has no other atomic nuclei in the molecule deviating from the plane by more than 0.0036 nm.
HANDLING AND STORAGE:

Maleic Anhydride must be stored in a cool, dry, well ventilated area. Areas where there is high potential risk of fires must be avoided. Outdoor or detached storage is preferable. The material should be separated from other storage, especially from alkali metals or amines. It must be very well protected from moisture and oxidizing materials.
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PRECAUTIONS:
Maleic Anhydride is a powerful irritant, in contact it causes conjunctivitis ,cornea damage, nausea, headaches, pulmonary edema and dermatitis. Personnel must not be exposed to the concentrated vapours. Protective clothing, chemical goggles, gloves and if necessary gas mask should be worn when handling the material.
SHELF LIFE:
3 Months from date of production . NB : Due to the effect of atmospheric moisture on Maleic Anhydride the solidification point may be decreased and the Maleic Acid content may exceed the limit quoted if the material is stored for a lengthy period under humid conditions.
SHIPMENT:
Molten maleic anhydride is shipped in tank rail cars, tank trucks, and isotanks (for overseas shipments). Tank rail cars are typically constructed of lined carbon steel and are insulated and equipped with steam coils. Tank rail cars of up to 20k gallons are used. Tank trucks are typically constructed of stainless steel, insulated, and equipped with steam coils. Tank trucks of up to 4.5k gallons are used. Isotanks are typically constructed of stainless steel and are insulated and equipped with steam coils. Isotanks of up to 4.5k gallons are used.
PACKAGING:
Bags 25 Kg ( 40 bags per pallet )
Typical bag construction is either polyethylene or multi-ply paper with at least one polyethylene layer. Solid form maleic anhydride can be stored in bags for several months in a cool, dry location.
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Chapter 3 VARIOUS TYPES OF PROCESSES
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PROCESS TECHNOLOGY EVOLUTION:

Maleic anhydride was first commercially produced in the early 1930s by the vapor-phase oxidation of benzene . The use of benzene as a feedstock for the production of maleic anhydride was dominant in the world market well into the 1980s. Several processes have been usedfor the production of maleic anhydride from benzene with the most common one from Scientific Design. Small amounts of maleic acid are produced as a by-product in production of phthalic anhydride.
There are two types of processes available for the manufacturing of maleic anhydride.
1. BENZENE BASED PROCESSES. 2. BUTANE BASED PROCESSES.
1. BENZENE BASED TECHNOLOGIES: The catalyst used for the conversion of benzene to maleic anhydride consists of supported vanadium oxide. The support is an inert oxide such askieselguhr, alumina ,or silica and is of low surface area. Supports with higher surface area adversely affect conversion of benzene to maleic anhydride. The conversion of benzene to maleic anhydride is a less complex oxidation than the conversion of butane, so higher catalyst selectivitys are obtained. The vanadium oxide on the surface of the support is often modified with molybdenum oxides. There is 70% vanadium oxide and 30% molybdenum oxide in the active phase for these fixed-bed catalysts. The molybdenum oxide is thought to form either a solid solution or compound oxide with the vanadium oxide and result in a more active catalyst .
a) BENZENE BASED FIXED BED PROCESS TECHNOLOGY: The benzene fixed-bed process is very similar to the butane fixed-bed process and, in fact, the Scientific Design butane process has evolved directly from its benzene process. Benzene-based processes are easily converted to butane-based processes. Typically, only a catalyst change, installation of butane handling equipment, and minor modifications to the recovery process are required. The benzene reaction is a vapour-phase partial oxidation reaction
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using a fixed-bed catalyst of mixed vanadium and molybdenum oxides. The reactors used are the 3 saltsdescribed in the section on the butane process. The benzene concentrations same multi tubular reactors cooled by circulating a molten mixture of 3 2 used are 1.5 mol% or just below the lower flammable limit of benzene in air. Unlike the butane reaction, the reactor normally operates at conversions>95% and molar yields >70%. The benzene oxidation reaction runs a little cooler than the butane oxidation reaction, with typical reactor temperatures in the350400C range. The reactor off-gas is cooled by one or more heat exchangers and sent to the collection and refining section of the plant. Unreacted benzene and by-products are incinerated.
BUTANE BASED TECHNOLOGIES:
The increased importance of the butane-to-maleic anhydride conversion route has resulted in efforts being made to understand and improve this process. Since 1980,over 225 U.S. patents have been issued relating to maleic anhydride technology. The predominant area of research concerns the catalyst because it is at the heart of this process. The reasons for this statement are twofold. First, there is the complexity of this reaction: for maleic anhydride to be produced from butane, eight hydrogen atoms must be abstracted, three oxygen atoms inserted, and a ring closure performed. This 14-electron oxidation occurs exclusively on the surface of the catalyst. The second reason for the emphasis placed on the catalyst is that all the commercial processes use the same catalyst. This catalyst is the only commercially viable system that selectively produces maleic anhydride from butane. The catalyst used in the production of maleic anhydride from butane is vanadiumphosphorus oxide (VPO). Several routes may be used to prepare the catalyst. In different industrial processes, the oxidation of n- butane differs in the type of reactor, type of recovery and type of purification.
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There are three types of reactors which are used for the production of maleic anhydride: Multi Tubular Fixed bed Reactors Fluidised-bed Reactors and Transport bed reactors.
The main difference between the individual recovery sections is the choice of an aqueous or an organic solvent. The purification (if necessary) is carried out by means of batch distillation or continuous distillation. Unreacted n-butane is mostly burnt to carbon oxides.
a) BUTANE BASED FIXED BED PROCESS TCHNOLOGY:
Maleic anhydride is produced by reaction of butane with oxygen, using the vanadium phosphorus oxide heterogeneous catalyst. The butane oxidationreaction to produce maleic anhydride is very exothermic. The main reaction byproducts are carbon monoxide and carbon dioxide.
Stoichiometry and heat of reaction for the three principal reactions are as follows:
C4H10 + 3.5 O2 C 4H2O3 + 4 H2O H 1236 kJ/mol ( 295.4 kcal/mol) C4H10 + 6.5 O2 4 CO 2 + 5 H2OH 2656 kJ/mol ( 634.8 kcal/mol) C4H10 + 4.5 O2 4 CO + 5 H 2OH 1521 kJ/mol ( 363.5 kcal/mol)
Air is compressed to modest pressures, typically 100200 kPa (15-30 psig) and 350-450C with either a centrifugal or radial compressor, and mixed with superheatedvaporized butane. Static mixers are normally employed to ensure good mixing. Butane concentrations are often limited to <1.7 mol% to stay below the lowerflammable limit of butane.The highly exothermic nature of the butane-to-maleic anhydride reactionand the principal by-product reactions require substantial heat removal fromthe reactor. Thus the reaction is carried out in what is effectively a large multitubular heat exchanger that circulates a mixture of 53% potassium nitrate 3 , 40% sodium nitrite ,2 ; and 7% sodiumnitrate, 3 .
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Despite the rapid circulation of salt onthe shell side of the reactor, catalyst temperatures can be 40608C higher thanthe salt temperature. The butane-to maleic anhydride reaction typically reachesitsmaximum efficiency (maximum yield) at 85% butane conversion.Reactor operation at 8085% butane conversion to produce maximum yields provides an opportunity for recycle processes to recover the unreactedbutane in the stream that is sent to the oxidation reactor. b) BUTANE-BASED FLUIDIZED-BED PROCESS TECHNOLOGY:
Fluidized bed processes offer the advantage of excellent control of hot spots by rapid catalyst mixing, simplification of safety issues when operating above the flammable limit, and a simplified reactor heat-transfer system. Some disadvantages include the effect of back mixing on the kinetics in the reactor, product destruction and by-product reactions in the space above the fluidized bed, and vulnerability to large-scale catalyst releases from explosion venting. Compressed air and butane are typically introduced separately into the bottom of the fluidizedbed reactor. Heat from the exothermic reactionis removed from the fluidized bed through steam coils in direct contact withthe bed of fluidized solids. Fluidized-bed reactors exploit the extremely highheat-transfer coefficient between the bed of fluidized solids and the steamcoils. This high heat-transfer coefficient allows a relatively small heat-transfer area in the fluid-bed process for the removal of the heat of reaction in comparisonto the fixed-bed process. The product stream contains gases and solids. The solids are removed by using either cyclones, filters, or both in combination. Fluidized-bed reaction systems are not normally shut down for changing catalyst. The process includes facilities for adding back both catalyst fines and fresh catalyst to the reactor.
c) BUTANE-BASED TRANSPORT-BED PROCESS TECHNOLOGY:
Du Pont announced the commercialization of a moving-bed, recycle-based technology for the oxidation of butane to maleic anhydride. Athoughmaleic anhydride is produced in the reaction section of the process and could be recovered, it is not a direct product of the process. Maleic anhydride is recovered as aqueous maleic acid for hydrogenation to Tetrahydrofuran. The
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reaction technology known as transport bed is a circulating solids technologyin which the oxygen required in the oxidation of butane to maleic anhydride is provided by the VPO catalyst and the catalyst is reoxidized in a separate step. Fresh butane mixed with recycled gas encounters freshly oxidized catalyst at the bottom of the transport-bed reactor and is oxidized to maleic anhydride and Coxduring its passage up the reactor. Catalyst densities (80-160 kg/3 ) in the negative effect of back mixing on reaction selectivity. Reduced catalyst is separated from the
transport-bed reactor are substantially lower than the catalyst density in a typical fluidized-bed
reactor (480-640 kg/3 ). The gas flow pattern in the riser is nearly plug flow which a voids the reaction products by cyclones and is further stripped of products and reactants in a separate stripping vessel. The reduced catalyst is re oxidized in a separate fluidized-bed oxidizer where the exothermic heat of reaction is removed by steam coils. The rate of re oxidation of the VPO catalyst is slower than the rate of oxidation of butane, and consequently residence times are longer in the oxidizer than in the transport-bed reactor.Maleic anhydride in the product stream is removed and converted to a maleic acid solution in a waterscrubbing system. The maleic acid is sent to the hydrogenation to produce THF while the reactor off-gasafter scrubbing is sent to the recycle compressor. A small purge stream is sent to incineration.
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MERITS AND DEMERITS OF BUTANE AND BENZENE AS RAW MATERIAL:
BUTANE MERITS:
BENZENE MERITS: Benzene gets Easily oxidized.
It is cheaply available as compared to benzene.
High selectivity for feedstock
The butane can be easily recovered from natural gas.
Energy required is less as compared to that for benzene process.
Not a hazardous product.
Proven, safe design that provides for long-term, performance. high, stable reactor
Lower air requirements as compared with fixed-bed technology, which allows

for lower capital investment cost and ongoing energy requirements for new build plants.
Lower maintenance costs and higher reliability (greater than 99% on-stream time) as compared to fixed-bed
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processes. Ability to scale to higher production capacities system. with a single reactor
DEMERITS:
DEMERITS:
There is a complexity of reaction. Causes abrasion of the catalyst. Inefficient feedstock because of
removal of two excess carbon atom present in benzene ring.
Conversion rate is low. By product formation Considered as hazardous material. Rapid increase the cost of benzene.
Large energy inputs are required
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SELECTION CRITERIA ANHYDRIDE:
FOR MANUFACTURING OF MALEIC
The abundance and low cost of light alkanes have generated in recent yearsconsiderable interest in their oxidative catalytic conversion to olefins, and nitriles inpetroleum and petrochemical industries. One of the most fascinating and unique catalytic processes is the 14- electrons selective oxidation of n-butane to maleic anhydride (2,5-furandione) by vanadyl phosphates. It is the only industrial process of selective vapor- phase oxidation of an alkane that uses the dioxygen. Since 1974, n-butane has been increasingly usedinstead of benzene as the raw
material for maleic anhydride production.At present more than seventy percent of maleic anhydride is produced from n-butane.Many studies on n-butane oxidation by vanadyl phosphate catalysts indicate that crystalline vanadyl(IV) pyrophosphates are present in the most selective oxidation of n-butane to maleic anhydride. From a raw material viewpoint, the relatively low purchase price of C4 is much more attractive than the expense of benzene. Other influential factors that favor C4s are safety, health, and the environment.Benzene is a known carcinogen and one of the chemicals most stringently regulated by the government. The flammability limits for 4 HC are also lower than those for benzene, which is an additional safety advantage of the used commercially since 1985 in the United States. The advantages of a fluidized-bed reactor over a packed bed are claimed to be the following: Avoids hot spots.(Fluidized beds are nearly isothermal because the heat capacity of the solid catalyst particles far exceeds that of the gas, and because the solids circulate.) Enables use of separate feed streams for n-butane and air, so that one can operate overall within the combustible range.This reduces the air requirement, the compressor size and power, the reactor size,and the size of the downstream separation equipment, and permits use of an incinerator for the waste gas with production of valuable steam. Cost is much lower than for tubular reactors cooled by a molten salt.
Easy to load and unload. Can generate valuable steam while cooling the reactor. 21
process. For all of these reasons, the fixed-bed process with n-butane has been the only MA route
Chapter 4 PROCESS DESCRIPTION
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Raw material: Butane, Oxygen. Catalyst: Vanadium phosphorus oxide (VPO)
By product: fumaric acid, carbon di oxide, carbon monoxide, Type of reactor: Fluidized bed reactor. Properties of butane:
Molecular weight : 58.123 g/mol
Solid phase
Latent heat of fusion (1,013 bar, at triple point) : 80.165 kJ/kg Liquid density (1.013 bar at boiling point) : 601.4 kg/m3 Liquid/gas equivalent (1.013 bar and 15 C (59 F)) : 239 vol/vol Boiling point (1.013 bar) : -0.5 C Latent heat of vaporization (1.013 bar at boiling point) : 385.6 kJ/kg
Liquid phase

Critical point

Critical temperature : 152 C Critical pressure : 37.96 bar Gas density (1.013 bar at boiling point) : 2.7 kg/m3 Gas density (1.013 bar and 15 C (59 F)) : 2.52 kg/m3 Compressibility Factor (Z) (1.013 bar and 15 C (59 F)) : 0.9625 Specific gravity (air = 1) (1.013 bar and 21 C (70 F)) : 2.076 Specific volume (1.013 bar and 21 C (70 F)) : 0.4 m3/kg Heat capacity at constant pressure (Cp) (1.013 bar and 25 C (77 F)) : 0.096 kJ/(mol.K) Heat capacity at constant volume (Cv) (1.013 bar and 15.6 C (60 F)) : 0.088 kJ/(mol.K) Viscosity (1.013 bar and 0 C (32 F)) : 0.0000682 Poise Thermal conductivity (1.013 bar and 0 C (32 F)) : 13.6 mW/(m.K)
Gaseous phase

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PROCESS:
Pure butane and compressed air (100 to 200 KPa) at 350-400C,are mixed and fed to fluidized bed reactor, where butane reacts with oxygen to form maleic anhydride. Air is compressed to modest pressures, with either a centrifugal or radial compressor. Heat from the exothermic reaction is removed from the fluidized bed through steam coils in direct contact with the bed of fluidized solids. Fluidized-bed reactors exploit the extremely high heat-transfer coefficient between the bed of fluidized solids and the steam coils. This high heat-transfer coefficient allows a relatively small heat transfer area in the fluid-bed process for the removal of the heat of reaction compared to the fixed-bedprocess.Fluidized-bed reaction systems are not normally shut down for changing catalyst. Fresh catalyst is periodically added to manage catalyst activity and particle size distribution. The process includes facilities for adding back both catalyst fines and fresh catalyst to the reactor. The product stream contains gases and solids. The solids are removed by using either cyclones, filters, or both in combination. Cyclones are devices used to separate solids from fluids using vortex flow. The product gas stream must be cooled before being sent to the collection and refining system. The process uses cyclones as a primary separation technique with filters employed as a final separation step after the off-gas has been cooled and before it is sent to the collection and refining system . The reactor off-gas which is separated from solids is cooled from reaction temperatures in a gas cooler upwith generation of steam. The off-gas is then sent to a tempered water-fed after cooler, where it is cooled below the dew point of maleic anhydride. The liquid droplets of maleicanhydride are separated from the off-gas by a separator. The condensed crude is pumped to a crude tank for storage. The maleic anhydride remaining in the gas stream after partial condensation is removed in awater scrubber by conversion to maleic acid which accumulates in the acid storage section at the bottom of the scrubber. The acid solution is converted to crude maleic anhydride in a dual purpose dehydrator/stripper.Xylene is used as an azeotropic agent for the conversion of maleic acid to maleic anhydride.Water from the dehydration step is recycled to the scrubber.
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When the conversion of the acid solution to crude maleic anhydride is complete, condensed crude maleic anhydride is added to the still pot and a batchdistillation refining step is conducted. In the distillation column, maleic anhydride and water are separated. The distillate, is sent to waste treatment and the bottoms, consists of 99-wt% maleic anhydride.
CATALYST: Unsupported vanadium phosphorus oxide (VPO) catalysts are preferred for the fixed bed as well as fluidized bed reactors. Promoters such as lithium, zinc, and molybdenum are commonly used. Recent research has shown that Mg, Ca, and Ba ions are also effective promoters, generating higher conversion, yield, and selectivity than the unmodified VPO catalyst.The ratio of phosphorus to vanadium determines the activity of the catalyst, and, in turn, the life. Catalyst activity is greater at high phosphorus-vanadium ratios, but the catalyst life is sacrificed as the activity increases. A phosphorus-vanadium ratio of 1.2 in the catalyst appears to provide the optimal balance between activity and catalyst life. Only the surface layers of the catalyst solid are generally thought to participate in the reaction. This implies that while the bulk of the catalyst may have an oxidation state of 4+ under reactor conditions, the oxidation state of the surface vanadium may be very different. It has been postulated that both V4+ and V5+ oxidation states exist on the surface of the catalyst, the latter arising from oxygen chemisorption. Phosphorus enrichment is also observed at the surface of the catalyst. The exact role of this excess surface phosphorus is not well understood, but it may play a role in active site isolation and consequently, the oxidation state of the surface vanadium. Preparation of the catalyst begins by mixing the V-P with nearly anhydrous phosphoric acid and an organic solvent. Next, the mixture is heated and the organic solvent is removed by volatilization. The product is dried and calcined to yield the catalyst precursor, which is then pelletized or formed into spheres. Finally, the catalyst is loaded into the reactor where it is activated under carefully controlled conditions.
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SAFETY FACTORS:
Inhalation: Remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Call a physician. Ingestion: Induce vomiting immediately as directed by medical personnel. Never give anything by mouth to an unconscious person. Skin Contact: In case of contact, immediately flush skin with plenty of soap and water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Call a physician immediately. Eye Contact: Immediately flush eyes with plenty of water for at least 15 minutes, lifting lower and upper eyelids occasionally. Get medical attention immediately.
Accidental Release Measures Remove all sources of ignition. Ventilate area of leak or spill. Wear appropriate person a protective equipment as specified in Section 8. Spills: Clean up spills in a manner that does not disperse dust into the air. Use non-sparking tools and equipment. Reduce airborne dust and prevent scattering by moistening with water. Pick up spill for recovery or disposal and place in a closed container. Evacuate area of all unnecessary personnel. US Regulations (CERCLA) require reporting spills and releases to soil, water and air in excess of reportable quantities.
Personal Respirators (NIOSH Approved): If the exposure limit is exceeded, and engineering controls are not feasible, a full-face piece respirator with an organic vapor cartridge and particulate filter (NIOSH type N100 filter) may be worn up to 50 times the exposure limit, or the maximum use concentration specified by the appropriate regulatory agency or respirator supplier, whichever is lowest. If oil particles (e.g. lubricants, cutting fluids, glycerine, etc.) are present, use a NIOSH type R or P particulate filter.
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FIRE FIGHTING MEASURES : Flash point: 102C (216F) Auto ignition temperature: 477C (891F) Fire Extinguishing Media: Alcohol foam, carbon-dioxide. DO NOT USE dry chemical, multipurpose dry chemical, or loaded stream media because of explosion potential due to reactivity of basic compounds in these extinguishing media.
ENVIRONMENTAL HAZARDS:
Environmental Fate:
When released to air, soil and water; maleic anhydride will probably hydrolyze to maleic acid and be processed as follows. When released into the soil, this material is expected to leach into groundwater. When released into thesoil, this material is expected to readily biodegrade. When released into water, this material is expected to readily biodegrade. When released into water, this material is not expected to evaporate significantly. When released into the air, this material is expected to exist in the aerosol phase with a short half-life. When released into the air, this material is not expected to be subject to wet deposition. When released into the air, this material is expected to bedegraded by reaction with ozone and photochemically produced hydroxyl radicals. This material is not expected `to significantly bioaccumulate. This material has an estimated bioconcentration factor (BCF) of less than 100.
Environmental Toxicity:
When released to soil and water; maleic anhydride will probably hydrolyze to maleic acid and be represented bythe following data for maleic acid. TLm /Fathead minnow/5ppm/96 hr./fresh water.
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TLm/Mosquito fish/240 ppm/24-48 hr./fresh water.
Chronic Toxicity:
Inhalation reference exposure level: 0.7 g/m 3 (2.5 ppb) Critical effect: Neutrophilic infiltration of the nasal epithelium; irritation of the respiratory system in rats,hamsters and monkeys Hazard index target: Respiratory system
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Chapter 5 THERMODYNAMICS & KINETICS OF PROCESS
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The knowledge of thermodynamics help us to identify whether the given chemical reaction may occur spontaneously & to assist how far the reaction will proceed. As most of the chemical reactions are accompanied by evolution or absorption of heat, heat formation, entropy & free energy are some vital items of thermodynamics. Thermodynamics help us to calculate the free energy of reaction which shows whether the reaction is feasible at given temperature or not. The free energy change for a process is denoted as G0. For manufacture of maleic anhydride from feed stock of n-butane, the reaction consists of vapour phase oxidation of n-butane to give maleic anhydride & water. C4H10 + 3.5O2 C4H2O3 + 4H2O For this process, we have to find out the free energy of reaction at reaction conditions. By combining Gibbs helmoltz equation & integrated Vanthoffs equation as.
G0 = -RTlnk CALCULATION OF GIBBS ENERGIES OF MALEIC ANHYDRIDE: Groups No.of Groups G298(KJ/mole)
CO2 CO C2H2
1 1 1
-394.38 -137.27 209.9
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G298=G273+ Gn1 G298 = 60.98+ (-394.38-137.27+209.9) G298 = -260.77 KJ/Kmole for Butane, G298 = -115.26KJ/Kmole For Water, G298 = -228.5 KJ/mole G298 = Gproduct Greactant = -260.77 + (4x-228.59) 115.26 +(3.5x0) G298= -1059.51 KJ/Kmole
CALCULATING R0 For maleic anhydride, R0 = - 469.8 KJ/Kmole For Butane, R0 = - 125.6 KJ/Kmole For Water R0 = - 241.820 KJ/Kmole
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For enthalpy change taking place at 2980k is given as R0 = (298) product (298) reactant R0 = [(-469.8) + 4x (-241.82)]- [(-125.6) + (3.5x -279.9)] R0 = -331.83 KJ /Kmole Also, R0 is given by the reaction, R0 = 00 + aT + bT2/2 + cT3/3 + dT4/4 For the reaction, C4H10 + 3.5O2 C4H2O3 + 4H2O a = aMAN + 4aH2O (aC8H10 + 3.5aO2) Similarly, we can calculate b,c,andd. a = [(-13.07) + 4(32.49)] [(-2.4511)+( 3.5x26.025)] a = 28.244 b = bman + 4bH20 - bC4H10 + bo2 [3.483 x 10-3 + (4x0.0796 x 10-3) ] [(391.82x 10-3) + (3.5 x 11.75x 10-3)] b = -0.43296 c = cMAN + cH2o - cC4H10 + c02 c = 0.2187 x 10-6 + (4x 13.2107 x 10-6) [(-202.98 x 10-6) + (3.5 x -2.34 x 10-6) c = 2.6423 x 10-4
33
Since d is very small so we neglect it , Substituting in the above equation, -1059.51 = 00 + [28.24x(298)]- [0.4329x(298)2/2 ]+ [2.6423x10-4x(298)3/3] 00 = 7417.79 KJ/Kmole From the integrated Vant Hoffs Equation & Gibbs Helmoltzs Equation, we get, G = = H00 + aT + bT2/2 + cT3/3 + dT4/4 + I(T) Where I = Integration constant 1059.51 = 7417.79 + [28.24x(ln 298)x(298)] [0.4329x(298)2/2 ]+ [2.6423x 10-4x(298)3/6 ]+ I(298) I = -128.41 At reaction temperature, i.e. 673K G673 = 7417.79+ [28.24x(ln 673)x (673)] [0.4329x(673)2/2] + [2.6423 x 10-4x(673)3/6 ] [128.41x(673)] G673 = - 39852.14 KJ/Kmole This shows that the reaction is thermodynamically feasible at reaction temperature, From Gibbs Equation, G0 = -RTlnk - 39852.14 = -8.314 x 673 x lnk k = 1.2394x103
34
Chapter 6 MATERIAL BALANCE
35
Basis : 3 Tons/day of pure Maleic Anhydride is produced According to us patent #4317778 air is provided in the ratio Bu : O2 1 : 8.65
From Encyclopedia, Butane unreacted = 17% Butane converted to maleic anhydride = 73% Butane converted to acrylic acid = 1.1% Butane converted to formic acid = 1.07% Maleic anhydride produced = 123 kg/hr = 1.255 kmole/hr Assuming 3% loss ( 2% in scrubber & 1% in distillation column) Maleic anhydride to be produced = 127 kg/hr = 1.306 kmol/hr Consider the reaction C4H10 + 3.5 O2C4H2O3 + 4H2O 1 kmole of butane = 1 kmole of Maleic anhydride = 1.306 kmole of Maleic anhydride Butane reacted = 1.306 kmole/hr = 75.74 kg/hr
36
= 75.74 kg/hr Butane supplied = 75.74\0.73 = 103.75 kg/hr = 1.78 kmole/hr O2 required = 3.5 * 1.78 = 6.23 kmole/hr = 199.36 kg/hr O2 supplied = 6.23 * 8.65 = 53.88 kmole/hr = 1724.464 kg/hr N2 supplied = 1724.464 * (0.79/0.21) = 5748.25 kg/hr = 205.3 kmole/hr Total dry air = 7472.714 kg/hr = 257.67 kmole/hr H2O with air = 7427.714 * 0.03 = 222.83 kg/hr = 7.683 kmole/hr
37
Input to reactor components N2 O2 C4H10 H2O Total Kg/hr 5748.25 1724.464 103.75 0 7575.25 Kmole/hr 205.3 53.88 1.788 0 260.96
So butane unreacted = 0.17 * 1.78 = 0.3206 kmole/hr = 17.56 kg/hr Butane converted to Maleic anhydride = 0.73 * 1.78 = 1.3 kmole/hr = 127.34 kg/hr
Butane converted to Acrilic acid = 0.011 *1.78 = 0.019 kmole/hr = 1.409 kg/hr Butane converted to formic acid = 0.0107 * 1.78 = 0.019046 kmole/hr = 0.5713 kg/hr
38
Total butane in butane consumed = butane coming out of reactor 1.78(1.3 + 0.019 + 0.019046 + X) = 0.3206 Where X is the amout of butane available for COx X = 0.1213 kmole/hr = 7.038 kg/hr Reactions C4H10 + 3.5 O2 C4H2O3 + 4H2O ------------- (1) C4H10 + 5.5 O2 2CO2 + 2CO + 5H2O --------------(2) C4H10 + 3.5 O2 C3H4O2 + CO2 + 3H2O -------------(3) C4H10 + 6 O2 CH2O + 3CO2 + 4H2O -------------------- (4) O2 Balance:O2 consumed in reaction (1) = 3.5 * 127.34 = 445.69 kg/hr = 13.92 kmole/hr O2 consumed in reaction (2) = 5.5 * 7.038 = 38.709 kg/hr = 1.209 kmole/hr O2cosumed in reaction (3) = 3.5 * 1.409 = 4.9315 kg/hr = 0.154 kmole/hr
39
O2 consumed in reaction (4) = 6* 0.5713 = 3.4278 kg/hr = 0.1711 kmole/hr O2 unreacted = O2 feed O2 consumed = 1724.464-(445.69 + 38.709 + 4.9315 + 3.4278) = 1231.705 kg/hr = 38.49 kmole/hr CO2 balance: CO2 produced in reaction (2) = 2 * 7.038 = 14.076 kg/hr = 0.3199 kmole/hr CO2 produced in reaction (3) = 1.409 kg/hr = 0.0320 kmole/hr CO2 produced in reaction (4) = 3* 3.4278 = 10.283 kg/hr = 0.233 kmole/hr Total CO2 produced = 26.398 kg/hr = 0.599 kmole/hr
40
CO Balance: CO produced in reaction (2) = 2 * 7.038 = 14.076 kg/hr = 0.3199 kmole/hr
H2O Balance:H2O produced in reaction (1) = 4 * 127.34 = 509.36 kg/hr = 28.29 kmole/hr H2O produced in reaction (2) = 5 * 7.038 = 35.19 kg/hr = 1.955 kmole/hr H2O produced in reaction (3) = 3 * 1.409 = 4.227 kg/hr = 0.2348 kmole/hr H2O produced in reaction (4) = 4 * 0.5713 = 2.285 kg/hr = 0.1296 kmole/hr Total H2O produced = 30.61 kg/hr Total H2O at outlet = 30.61 kg/hr = 1.7kmole/hr
41
Output from the Reactor:
Component N2 O2 H2O CO2 C4H2O3 CO C4H10 CH2O C3H4O2 Total
Kg/hr 5748.25 724.46 30.61 26.398 127.34 14.076 17.56 0.5713 11.53 6717.07
Kmole/hr 205.3 22.64 1.7 0.59 1.3 0.525 0.3027 0.01904 0.1601 232.16
42
AROUND COOLER In gas cooler the gas is cooled up to dew point f maleic anhydride up to 120C and it is send to separator for separating gas & liquid Input = output 6717.07 kg/hr = 6717.07 kg/hr
SEPERATOR:In a separator 40% of maleic anhydride , 2 % of water , 1% of formic acid which is condensed get separated at bottom which is Stored in crude tank while the gas goes for further process. Maleic anhydride condensed = 0.4 * 127.34 = 50.936 kg/hr = 0.519 kmole/hr Water condensed = 0.02 * 30.61 = 0.6122 kg/hr = 0.0340kmole/hr Formic acid condensed = 0.01 * 0.5713 = 0.005713 kg/hr = 0.0001904kmole/hr
43
Composition of bottom stream: Components Maleic anhydride Water Formic acid Total Kg/hr 50.936 0.6122 0.005713 56.009 Kmole/hr 0.519 0.0340 0.0001904 0.8008
Composition of top stream: Component N2 O2 H2O CO2 C4H2O3 CO C4H10 CH2O C3H4O2 Total Kg/hr 5748.25 724.46 29.998 26.398 76.404 14.076 17.56 0.5655 11.53 6647.79 Kmole/hr 205.3 22.64 1.667 0.59 0.7796 0.525 0.3027 0.0188 0.1601 232
44
AROUND SCRUBBER Absorption is done by using water as a solvent. Let 1% of maleic anhydride produced is lost in vent stream & all butane while formic acid leaves the scrubbed liquid. Maleic anhydride lost = 0.01 * 76.404 = 0.76404 kg /hr Maleic anhydride converted to maleic acid = (76.404 0.76404) = 75.64 kg/hr Assuming liquid to vapour ratio as 1.2 G = 6647.79 kg/hr L= 6647.8 * 1.2 = 7977.336 kg/hr H2O lost= 7977.336-75.64 = 7901.696 kg/hr = 438.983 kmole/hr Maleic acid produced = 75.64 kg/hr Maleic acid leaving stream= 75.64 kg/hr
45
Total moles in vent stream excluding water components N2 O2 CO2 CO C4H10 C4H2O3 Total Kg/hr 5748.25 724.46 19.93 7.832 7.22 75.64 6583.32 Kmole/hr 205.29 22.64 0.453 0.28 0.124 0.7718 229.56
Assuming gases leaving in vent stream saturated with water vapour partial pressure of water at 50C & 152 kpa = 12.55 kpa Y = 12.55/152 = 0.08 Total moles of gases in vent = (229.56/0.92) = 249.52kmole/hr Moles of water in vent stream = 29.99 * 0.08 = 2.392kmole/hr =43.056 kg/hr Water in scrubbed liquid =438.983 -2.392 = 436.51 kmole/hr = 7859.18 kg/hr
46
Composition of vent stream: components N2 O2 CO2 CO C4H10 C4H2O3 H2O Total Kg/hr 5748.25 724.46 19.93 7.832 7.22 0.76404 43.02 6867.73 Kmole/hr 205.29 22.64 0.453 0.28 0.124 0.007796 2.392 248.75
Composition of bottom:-
component Maleic acid Formic acid water Total
Kg/hr 75.64 0.5655 7859.18 7935.26
Kmole/hr 0.772 0.01885 436.61 437.40
47
AROUND DEHYDRATOR In dehydrator maleic acid is back to maleic anhydride C4H4O4 C4H2O3 + H2O In addition to above reaction some maleic acid may irreversibly convert to fumeric acid according to following reaction. C4H2O3 + H2O C4H4O4+ C4H4O4 Assuming 0.5% of maleic acid converts irreversibly to fumeric acid & rest 99.5% convert back to maleic anhydride & 95 % of water is removed by azeotropic distillation dehydrator. Azeotropic composition Water = 77.5 % mole O-xylene = 22.5 % mole Maleic acid coming from absorber = 75.64 kg/hr Fumeric acid produced = 75.64 * (0.5/100) = 0.3782 kg/hr Maleic acid converted to maleic anhydride = 75.64 0.3782 = 75.262 kg/hr Maleic anhydride produced = 75.262 kg/hr H2O produced = 75.262 kg/hr Total water in dehydrator =7859.18 + 75.262 = 7934.4 kg/hr
48
O-xylene:= 0.225 * 43.056 = 9.68 kg/hr As 95% water is removed from the dehydrator so bottom stream contains Water = 0.95 * 7934.4 = 7537.68 kg/hr O-xylene = 0.05 * 9.68 = .484 kg/hr Composition of top stream component water Maleic anhydride O-xylene Fumeric acid Formic acid Total Kg/hr 396.72 75.262 .484 0.3782 0.5655 476.96 Kmole/hr 22.04 0.768 0.0387 0.0126 0.0188 22.87
Bottom component O-xylene water
Kg/hr 9.196 7537.68
Kmol/hr 0.088 418.76
49
AROUND MIXER In mixer one input stream from crude tank while second input stream from denhydrator they are mixed together then feed to distillation. Stream from crude tank + stream from dehydrator = feed to distillation column For maleic anhydride = 50.936 + 75.262 = 126.2 kg/hr For water = 396.76 +0.6122 = 397.37 kg/hr =22.07 kmol/hr For formic acid = 0.5655 + 0.005713 = 0.5712 kg/hr Output from mixer: component Maleic anhydride Water Formic acid Fumeric acid Total Kg/hr 126.2 397.37 0.57122 0.3782 524.51 Kmole/hr 1.29 22.07 0.01904 0.00326 23.50
50
AROUND DISTILLATION COLUMN Assuming 99% of Maleic anhydride is recovered from bottom And 98% water recovered from top. 98% fumaric acid at top and 2% at bottom of the total amount. Overall material balance F= D+W 524.51= D+W Maleic anhydride balance 126.2= .02 D+.99W Solving both the equations D=405.22 kg/hr W=124.16 kg/hr So in distillate: MAN = 0.99*124.16 =123 kg/hr 2.95 ton /day = 3 tonns. Water = .01*124.16 =1.24 kg/hr Fumeric acid = 0.3782 *.02 = 0.007564 kg/hr
51
Formic acid In the top :
= .5*0.57 =0.28kg/hr
Water = .98*409.15 = 400.96 kg/hr MAN= .02 * 409.15 =8.183 kg/hr Fumeric acid= .98 * 0.3782 =.3706 kg/hr Formic acid = .5*0.57 =0.28kg/hr Composition of bottom stream: components Maleic anhydride Fumeric acid Formic acid water Total Kg/hr 123 0.00657 0.280 1.24 122.06 Kmole/hr 1.255 0.0000581(negligible) 0.009348(negligible) .0689 1.3364
52
Composition of top stream components water Kg/hr 400.96 Kmole/hr 22.27 0.0835 .003279(negligible) 22.36
Maleic anhydride 8.183 Fumeric acid total 0.3706 409.8
Material balance summary
components
1 Air inlet Maleic anhy 0 Nitrogen Oxygen butane Co2 CO water
2 Butane inlet 0
3 Reator outlet 1.3 205.3 22.64 .3027 .59 .525 14.08
4 Gas cooler 1.3 205.3 22.64 .3027 .59 .525 14.08
5 Seperator top .7796 205.3 22.64 0.3027 .59 .525 13.79
6 Separator bottom .519 0 0 0 0 0 .2816 .8008 0 0 0
7 (top) abs .0077
8 (bottom abs) 0.772
205.3 0 53.88 0 0 0 0 7.7 1.788 0 0 0 0 0 0 0
205.25 0 22.64 0.124 0.453 0.28 19.96 0 0 0 0 0 0 0 0 433.67 0.01885 0 00 0
Formic acid 0 Acrylic acid 0 Fumeric acid O- Xylene 0 0
0.01904 0.01904 .0188 0.1601 0.1601 .1601 0 0 0 0 0 0
53
components
9 dehy
10 Dehy op
11 mixer
12 Dc top
13 Dc bot
Maleic anhy
0.768
1.29
.0835
1.255
Nitrogen
Oxygen
butane
Co2
CO water
0 0
0 21.89
0 22.17
0 22.27
0 .0689
Formic acid
0.0188
0.019
0.0092
.0093
Acrylic acid
Fumeric acid
0.0126
.0032
.0032
.00005
O- Xylene
.774
0.0387
54
Chapter 7 ENERGY BALANCE
55
AROUND AIR COMPRESSOR:Inlet condition Outlet condition Inlet flow rate Temperature = 303K Pressure = 101 Kpa pressure = 200 Kpa = 7695.54 kg/hr = 0.0737 kmole/s Inlet volumetric flow rate V = V=
0.07378.314303 101
V= 1.83 m3/s
From fig 3.6 of colusonvol 6 for this flow rate centrifugal compressor would be used with efficiency p = 70% Outlet temp:T2 = T1(2 )m 1
Where m=(
1
for air = 1.4
substituting the value of &Pwe get m = 0.408
T2 = 303(200 )0.408 101

T2 = 400K T2 = 127C 56
To calculate work per kmole W = ZTR ( Where n=(

1
) [( 2 ) 1
- 1]
substituting all the value & (z =1) in above equation w = 1982.57 Kj/kmole Power required = =
) = 1.68
1982.5710^3 0.7
= 2.83 MW
AROUND AIR PREHEATER:Inlet condition : Outlet condition : Moisture in air Heat taken by air Q = (mCpdry air) * (Tout Tin) = [(265.36*0.2414)]*(260-127) = 8519.70 Kcal/hr Amount of dowtherm required to raise the temperature
57
Temperature = 127 C Temperature = 260C = 7.683 kmole
pressure = 200 Kpa pressure = 200kpa
Q = m 8519.70 = m*71.04 m = 119.92 kgmole/hr
AROUND BUTANE PREHEATER:Inlet condition: Outlet condition : Temperature = 30C Temperature = 100C Pressure = 101 Kpa Pressure = 101 Kpa
Heat taken by butane preheater Q = mcpT = 103.75* 0.544*(100-30) = 3950.8Kcal/hr Amount of steam required to raise the temperature Q = m 3950.8 = m* 541.68 m = 7.29kgmole/hr Data for feed mixture at 180C components Kg/hr Kmole/hr Mole fraction Hf (kcal/Kmol) Butane Air 103.75 7472.71 7576.46 1.78 257.66 259.44
58
Cp (kcal/kgmoleC) 0.43 0.2447
0.00686 0.9931
525.76
Cpavg of mixture = xicpi = (0.0065*0.43 + 0.9479*0.2447 +0.0455*1.004) Cpavg of mixture = 0.245 kcal/kmoleC
COMPONENT IN REACTOR:compnents MAN CO CO2 N2 O2 H2O CH2O Kg/hr 127.34 14.076 26.98 5748.25 724.46 253.44 0.5713 11.53 17.56 6924.23 Kmole/hr 1.3 0.5027 0.613 205.29 22.63 14.08 0.01904 0.1601 0.3027 244.59 Mole fraction 0.00531 0.00205 0.002506 0.839 0.0925 0.0575 0.0000778 0.000654 1.23 * 10-3 -57800 -41769 -17881 Hf(kcal/kmol) Cp (kcal/kgmoleC) 0.301 -96000 -26420 -94050 0.25 0.238 0.249 0.223 0.438 0.331 0.421 0.43
C3H4O2
C4H10 Total
To calculate the enthalpy of product & reactant H = Hf + 1 = 4266.76 kcal/kmole

59
2
Hbutane= 525.76 + 0.43(180-30) * 58
Hair= 0.2447 * (180-30) * 29 = 1064.44 kcal/kmole HMAN = -96000 + 0.331*(350-30) * 98 = -85619.84 kcal/kmole
HCo= -26420 + 0.25 *(350-30)* 28 = -24180 kcal/kmole
HN2 = 0.249 * (350-30) * 28 = 2231.04 kcal/kmole HO2 = 0.223*(350-30) * 32 = 2283.52 kcal/kmole HH20 = -57800+ 0.438*(350-30)* 18 = -55277.12 kcal/kmole Hformicacid = -41769 + 0.331 *(350-30)*30 = -38591.4 kcal/kmole Hacyrilicacid= - 17881 + 0.421 *(350-30) * 72 = - 8181.16 kcal/kmole Heat of reaction = (Hproduct-Hreactant) = (-207334.96) (5331.2)
60
HR
= -212666.16 kcal/kmol
Heat given by reactor = heat taken by LP tseam Hi + HR Ho = HSo HSi
Hi= heat content of feed inlet stream Hi = mcpT + mbutane = 271.81 * 0.282*(180-30)+1.78 *(628.84) Hi = 12616.89 kcal/hr Ho = heat capacity of product gas Ho = mcpT + m = 244.59 * 0.259*(350-30) + (1.3*7112) + (14.08* 4512)+(0.0190*2977)+ (0.1601*2653.9) = 93527.63 kal/hr HR = -212666.16 *(1.78) = -378545.76kal/hr Heat content of steam= mcpT HSo + HSi = m*(0.0566)*(140-120) (12616.89 +378545.76 93527.63) = m*(0.0566)*(140-120) m = 262.92 * 103kgmole/hr
61
AROUND GAS COOLER:Stream from reactor is cooled from 350C to 120c before it goes to separator. compnents Kg/hr Kmole/hr Mole fraction Cp (kcal/kgmoleC) MAN CO CO2 N2 O2 H2O CH2O C3H4O2 C4H10 Total 127.34 14.076 26.98 5748.25 724.46 253.44 0.5713 11.53
17.56
1.3 0.5027 0.613 205.29 22.63 14.08 0.01904 0.1601

0.3027
0.00531 0.00205 0.002506 0.839 0.0925 0.0575 0.0000778 0.000654

1.23 * 10-3
0.2184 0.249 0.231 0.241 0.2215 0.426 0.261 0.32

0.41
6924.23
244.59
Cpavg at 120C = xiCPi = 0.25 Heat given by product gases = heat taken by dowtherm mcpT = mcpT = m(0.00453*(120-30))
62
(244.59*0.25*(350-120))
m = 34.49 * 103kgmole/hr AROUND SCRUBBER:Operating temperature of scrubber is 50C (heat in feed entering) + (heat absorbed by cooling water) + (heat of reaction) = (heat at bottom) + (heat carried by vent stream) C4H2O3 + H2O C4H4O4 Heat in feed stream Component Kg/hr Kmole/hr Mol fraction Cp kcal/kgmoleC 0.241 0.2215 0.456 0.231 0.2184 0.249 0.41 0.261 0.32 . H = -290.56 kcal
N2 O2 H2O CO2 C4H2O3 CO C4H10 CH2O C3H4O2 Total
5748.25 724.46 248.37 26.398 76.404 14.076 17.56 0.5655 11.53 6867.61
205.3 22.64 13.79 0.59 0.7796 0.525 0.3027 0.0188 0.1601 244.106
0.8410 0.09274 0.0565 0.002416 0.003193 0.00215 0.001313 7.7 * 10-5 6.5 *10-4
63
Cpavg = XiCpi = 0.25 Q = mcpT = 244.106 *0.25*(80 50) = 1830.75 kcal/hr Heat at bottom stream component Kg/hr Kmole/hr Mol fraction Maleic acid Formic acid water Total 75.64 0.5655 7806.06 7882.26 0.772 0.01885 433.67 434.46 1.776*10-3 4.34*10-5 0.998 Cp kcal/kgmole C 0.321 0.21 1
Cpavg = XiCpi = 0.99 Q = mcpT = 434.46*0.99*(80-50) Q = 11730.42 kcal/hr
64
Heat of vent stream components Kg/hr Kmole/hr Mol fraction Cp kcal/kgmoleC N2 O2 CO2 CO C4H10 C4H2O3 C3H4O2 Total Cpavg = XICpi = 0.212 Q = mcpT Q = 228.95 *0.212*(80-50) Q = 1456.122 kcal/hr (1830.75+ (m * 0.97 * (80-30) + (-290.56)) =(11730.42+ 1456.122) Amount of water required m = 240.13kgmole/hr 5748.25 724.46 19.93 7.832 7.22 0.76404 11.52 6519.9 205.29 22.64 0.453 0.28 0.124 0.007796 0.1601 228.95 0.825 0.0910 1.82*10-3 1.12*10-3 4.98*10-4 3.13*10-5 0.08024 0.23 0.225 0.21 0.22 0.39 0.3
65
AROUND DEHYDRATOR:top plate temperature = 55C Bottom temperature = 120C C4H4O4C4H2O + H2O Feed to dehydrator component Kg/hr Kmole/hr Mol fraction Maleic acid Formic acid water Total 75.64 0.5655 7806.06 7882.26 0.772 0.01885 433.67 434.46 1.77*10-3 4.34*10-5 0.998 Cp kcal/kgmole C 0.31 0.20 1.006 H = -320 kcal/hr
Cpavg =1 Q= mcpT = 434.46*(1*(55-50)) = 2172.3 kcal/hr Feed to condenser Overhead product is condensed from 55C to 45C at 15.2 Kpa Boiling point of water at 15.2 Kpa = 53.6 C Boiling point of O-xylene at 15.2 Kpa = 85.05C
66
components water O-xylene Total
Kg/hr 7881.29 80.83 7962.12
Kmole/hr 437.84 0.76 438.6
Molfrac 0.99 1.72*10-3
Cp kcal/kgC 0.97 0.44
Cpavg = 0.98 Q = mcpT 438.6*0.98*(55-30) = 10745.7 kcal/hr Feed leaving condenser components Kg/hr Kmole/hr Molfrac Cp kcal/kgmoleC water O-xylene Total 7881.29 80.83 7962.12 437.84 0.76 438.6 0.99 1.72*10-3 0.97 0.44
Cpavg = 0.98
Q = mcpT 438.6*0.98*(45-30) = 6477.42 kcal/hr

67
(heat duty of over head condenser) = (heat duty in) (heat duty out) = (10745.7) - (6477.42) = 4268.28 kcal/hr Bottom of the dehydrator composition component water Maleic anhydride O-xylene Fumeric acid Formic acid Total Kg/hr 394.07 75.262 4.0415 0.3782 0.5655 474.31 Kmole/hr 21.89 0.768 0.0387 0.0126 0.0188 22.72 Molfrac 0.96 33.80* 10-3 1.70* 10-3 5.54* 10-4 8.27* 10-4 Cpkal/kgmoleC 0.97 0.366 0.45 0.52 1.3
Cpavg = 0.94 Q = mcpT + 22.72*0.94*(120-50) + 10763.96 = 12258.9 kcal/hr Total heat load in reboiler = (heat carried by bottom stream) +( heat fed to condenser) +(heat of reaction)(heat carried feed stream) = (12258.9) + (10745.7) + (-320) (2172.3)
68
= 20512.3kcal/hr
AROUND DISTILLATION COLUMN:Top plate temperature = 110C Reboiler temperature = 185C Feed stream temperature = 160C component Kg/hr Kmole/hr Mol fraction Maleic anhydride Water Formic acid O-xylene Fumeric acid Total 126.2 399.13 0.57122 4.0415 0.3782 530.32 1.29 22.17 0.01904 0.03806 0.00326 23.50 0.0548 0.943 8.14*10-4 1.62 * 10-3 1.38 *10-4
Cpavg = 0.945 component Feed (kmole/h r) Maleic anhydride Water Formic acid O-xylene 1.29 22.17 0.01904 0.03806 Feed (mol fraction) 0.0548 0.943 8.14*10-4 1.62 * 10-3 0.0387 1.74 *10-3 0.0128 22.17 Distillate (kmole/hr) Distillate (mol fraction) 5.76 *10-4 0.997 0.00326 2.48 *10-4 1.29 Residue Residue
Kmole/hr Mol fraction 0.99
69
Fumeric acid Total
0.00326 23.50
1.38 *10-4 22.22
0.0190 1.31
0.014
Reflux ratio = = 1.9 L = 1.9D
L= 1.9 * 22.22 = 42.21kmole/hr V = L+ D = 42.21+ 22.22 V= 64.43kmole/hr
L components (kmole/hr)
V (kmole/hr)
Mole fraction
Kcal/kmole
MAN water Formic acid 0-xylene Fumeric acid Total
0.03056 22.17 0.01904 0.03806 0.00326
0.0466 33.84 0.029 0.0058 0.004975 33.92
0.001373 0.99 0.000854 0.000171 0.000146
14417.59 9750.24 3614.4 8841.37 2476.35
70
avg = Xii = 9677.49 kcal/kmole Condenser load Qc = mavg = 33.92 * 9677.49
= 328260.46 kcal/hr Condenser load = heat taken by water Qc = 328260.46 mCpT = m*1*(100-30)
m = 4689.43 kg/hr To calculate reboiler load QB + Hf = QC + HD +HW Heat content of feed at 160C =mCpT Hf=23.50*0.935*(160-30) = 2993.9 kcal/hr Heat content of distillate at 110C = mCPT HD = 22.22*0.96*(110-30) = 1706.49 kcal/hr Heat content of Residue at 180C = mCPT HW = 1.29 * 0.37*(180-30)
71
= 71.59 kcal/hr QB = 4689.43 + 71.59 + 1706.49 2993.9 = 3473.61 kcal/hr Reboiler load = heat given by HP steam 3473.61 = m *CpT = m * 0.99 *(200-180) m = 175.43kgmole/hr
72
Chapter 8 DESIGN OF DISTILLATION COLUMN
73
In industry it is common practice to separate a liquid mixture by distillating the component, which have lower boiling points when they are in pure condition from those having higher boiling points. This process is accomplished by partial vaporization and subsequent condasation. Here in our project production of maleic anhydride from n-butane maleic anhydride is separated from water.
The choice between plate and packed column Vapour liquid mass transfer operation may be carried either in plate column or packed column. These two types of operations are quite different. A selection scheme considering the factors under four headings.
i.
Factors that depend on the system i.e, Scale , foaming, fouling factors, corrosive systems, heat evolution, pressure drop, liquid holdup.
ii. iii.
Factors that depend on the fluid flow moment. Factor that depends upon the physical characteristics of the column and its internals i.e, maintenance, weight, side stream, size and cost.
iv.
Factors that depend upon mode of operation i.e, batch distillation, continous distillation, turndown, intermittent distillation.
The relative merits of plate over packed column are as follows: I. Plate column are designed to handle wide range pf liquid flow rates without flooding. II. If a system contains solid contents , it will be handled in plate column, because solid will accumulate in the voids and coating the packing materials and making it ineffective. III. Dispesion difficulties are handled in plate column when flow rate of liquid are low as compared to gases.
74
IV.
For large column heights, weight of packed column is more than plate column.
V.
If periodic cleaning is required, main holes will be provided for cleaning. In packed columns packing must be removed before cleaning.
VI. VII. VIII. IX.
For non- foaming systems the plate column are preffered. Design information for plate column are more readily available. Inter stage cooling can be provided to remove heat of reaction. When temperature change is involved, packed may be damaged.
DISTILLATION COLUMN DESIGN
a) Feed composition & flow rate: component Maleic anhydride Water Formic acid Fumeric acid Total Kg/hr 126.2 399.13 0.57122 0.3782 530.32 Kmole/hr 1.29 22.17 0.01904 0.00326 23.50 Mole fraction 0.237 0.7526 .001077 .0007131 1
75
b) Top product composition and flow rate: components water Maleic anhydride Formic acid Fumeric acid Total Kg/hr 400.96 8.183 .28 0.3706 409.8 Kmole/hr 22.2 0.0835 Mole fraction 0.978 .0199
.009334(negligible) .0000683 .003279(negligible) .0000904 22.36 1
c) bottom product compositions and flow rates: components Maleic anhydride Fumeric acid Formic acid Water Total ASSUMPTION: Binary distillation (water and maleic anhydride) Ideal gas behaviour of vapours. Kg/hr 123 0.00657 0.280 1.24 124.7 Kmole/hr 1.255 0.0000581(negligible) 0.009348(negligible) .06889 1.33 Mole fraction .986 .0000526 .002245 .0099 1
1. BOTTOM TEMPERATURE ( ): Bubble point calculations: = 1.2 atm

76
Components
=185C
Xb=Xi .986 .0099 1.00
V.P(psia) 11.76 1.8
Ki=v.p/Pt 0.8 12.24
Yi=Ki.Xi .788 0.1211 .98
Maleic anhydride Water total
2. TOP TEMPERATURE ( ): Dew point calculations: =1.2tm Td=110C (assume)
Components Maleic anhydride Water Total
Yi=Xf .0199 .978 1.00
V.P(psia) 0.7 23
Ki=v.p/Pt 0.048 1.56
Xi=Yi/Ki 0.4145 0.627 1.04
3. TEMPERATURE OF FEED: = 160C
4. FEED CONDITIONS Dew point calculations:
77
T=160.5C Components water Maleic anhydride total = .7526 0.237 0.99 V.P(psia) 100 5.17 =V.P/ 6.8 .325 =Yi/Ki .1106 .7292 1
Since the dew point of feed is same as feed temperature so feed is at its dew point.
5. CALCULATION OF RELATIVE VOLATILITY (): =feed temperature (C)= 160C
Light key component (LK)=water Heavy key component (HK) = maleic anhydride
component Top = 1 32.5 bottom =Ki/Khk 1 15.3 Average Ki Maleic anhydride Water 0.048 1.56
0.8
1 23.9
12.24
6. MINIMUM NUMBER OF PLATES(NM):

Fenske equation:
1xb x ln d1x xb d
Nm =
ln(AB )av
78
xd =mole fraction of more volatile component in the overhead distillate xb =mole fraction of more volatile component in the bottoms. ( ) = = 23.9 = 2.64 = 3
7. CALCULATION OF (MINIMUM REFLUX RATIO): UNDER WOOD METHOD;

.
As feed is at its new dew point so q = 0. And we get = 12.3. Using eqn of min. Reflux ratio,
.
= 1-q
A= water, LK
= + 1
B= maleic anhydride, HK = mole fraction of component corresponding to light key in feed. = 1.52
= mole fraction of component corresponding to heavy key in feed. 8. REFLUX RATIO (R) R= 1.25 ( )
79
= 1.9 9. ACTUAL NUMBER OF THEORITICAL STAGES: From kirk bride relation

+1 = 0.75 [ 1- +1
0.566
N = 7.19= 7
10. COLUMN EFFICIENCY:

1 E = 0.17- 0.616* log10 .
Where
= viscosity of water at 293K
1 =viscosity of liquid at mean tower temperature = mol fraction of components in feed.
Mean tower temperature = 147.5C = 420.5K 1 = 0.174cp = .83cp =0..7526
For maleic anhydride 1 =0.485cp =0.83cp
80
=0.237 so, E= 0.496
11. ACTUAL NUMBER OF PLATES: Taking reboiler as a stage,
= 1
Where, =actual no of plates. N= theoretical plates. E= efficiency. = 12.47= 13 12. FEED PLATE LOCATION: log[ ]= 0.206 * [

= no of stages above the feed plate B= molar flow rates of bottom =no of stages below the feed plate
( ) 2 )
D= molar flow rate of distillate =mole fraction of light key comp

81
= mole fraction of heavy key comp. Put B=1.33kmol/hr D=22.36 kmol/hr / = .8106
- = 0.8106 =7.7 , =6.2 So feed enters the column at 7th stage
13. COLUMN PRESSURE DROP: Assume 170 mm water pressure drop per plate. Total pressure drop = 9.81*103 . Where, =total plate pressure drop( mm liquid) = actual no of plates
=
= density of liquid at 25C 20734.66 pa
By putting values in above eqn
Top pressure = 121.6*103 pa Estimated bottom pressure = 142334.66 pa = 1.404 atm

82
14. LIQUID VAPOUR FLOW FACTORS:

.5
Where, = vapour flowrate(kg/sec) = / R = 1.9 ( calculated) D = 22.36 kmol/hr L = 1.9* 22.36 L =42.48 kmol/hr L = 0.21242 kg/sec = liquid flowrate (kg/sec)
FOR TOP: Balance around condenser = + D = 42.48 + 22.36 = 64.84kmol/hr =0.3242 kg/sec = 110C
Avg mol wt = 19.6 kg/kmol =0.75 kg/3 So =0.0176

83
=963.95 kg/3
FOR BOTTOM: Balance around reboiler = +B 42.48= + 1.33
= 0.205 kg/sec
=41.15 kmol/hr
=185C =3.7kg/3
Avg mol wt= 96.3 =1302.2 kg/3 . ( from table) Putting values =0.05522 15. FLOODING VELOCITY:
Uf =K1
Uf = flooding vapour velocity Corrected 1 = 1 0. 02 =surface tension

4
=. *1012
.2
By sudgenparachor method
where
= surface tension M = mol wt. AT TOP:1 =0.095
=sudgens sparachors constant
84
=54.2 K = 0.114
=50 mJ/2
Uf = 4.08 m/s
=0.85*Uf =2.2m/s Bottom AT BOTTOM: From fig 3.1, 1 = 0.090 =216.6 =21.7*103 N/m 1 = 0.0912 Uf =2.58m/s
Designing at 85% flooding at maximum flow rate = 0.85*Uf = 3.47 m/s Top
16. MAXIMUM VOLUMETRIC FLOW RATE: top: = 64.84 kmol/hr
85
=.018 kmol/sec Max volumetric flow rate =

bottom:-
= 0.47 3 /s
V = 41.15kmol/hr = .0114kmol/sec Max volumetric flow rate =

= 0.2953 /sec 17. NET AREA REQUIRED:

. A =
=0.1352
=0.1342 18. COLUMN CROSS SECTIONAL AREA:Taking down comer area as 12% of total = 0 .88
= 0.88
= 0.1542 =0.1522
86
19. COLUMN DIAMETER:D=

4
= 0.442m
=0.433 m
20. LIQUID FLOW PATTERNS: MAXIMUM VOL. FLOW RATE = =density of liquid( kg/3 ) = liq flow rate (kmol/hr) Put =64.84 kmol/hr =963.95 kg/3 M = 19.6
3600 x M
So max vol flow rate= 1.79x103 3 /sec
87
21. PROVISIONAL PLATE DESIGNING:Sieve plate selected Column dia = = 0.442m Column area= =0.1542 Downcomer area= = 0.12 = 0.018482 Net area = = - = 0.135522 Active area = = -2 =0.117042 From fig 3.3

(12% of )
=hole area(total)= x 0.1= 0.0117042 =0.76
(10% of )
=weir length =0..335m Take weir height = 50 mm Hold diameter = = 5mm Plate thickness = 5 mm
88
22. CHECK WEEPING: Max liquid flow rate = Where

3600
=liquid flow rate below feed plate (kmol/hr) Put =64.84 kmol/hr
M wt = 96.3
Max liq flow rate= 1.734 kg/sec Max liq flow rate at 70% turndown = 0.7*1.734=1.214 kg/sec
Weir liquid crest: =750 x Where

Lw
lw xl
=weir crest (mm liquid) lw =weir length Lw = Liquid flow rate,kg/sec
l = liquid density at bottom, kg/3
89
For minimum Put lw =0.335m
Lw =1.214, kg/sec So,
l = 1302.2 kg/3 = 14.83(mm liquid)
For maximum Put lw =0.335m
Lw =1.734 kg/sec So,
l =1302.2 kg/3 = 18.82(mm liquid)
At minimum rate,
+ = 65.5 mm liquid =50.67 mm liquid =14.83 mm liquid
90
23. WEEP POINT:-
a. Minimum vapour velocity through holes:

[ 2 0.90 (25.4 )] U 1 h= 2
= vap density at base =hole dia, mm 2 =constant Put
=3.7 kg/3 =5mm 2 =30.3 So,
U h = 6.2m/s
91
b. Actual minimum vapour flow velocity:

= ( 0.7x0.295) / 0.01170 = 17.7 m/sec Since the total minimum vapour rate is above weep point, no weeping occurs.
U =
24. PLATE PRESSURE DROP:-
I.
Maximum vapour velocity through holes: =

max . ()
= 0.47/0.011704 = 40.15m/sec
II.
Pressure drop through dry plate:2
Where,
= 51
0
At plate thickness / hole dia = 5mm/ 5mm=1

0 = constant =0.1
Put
&0 = 0.87
=0.75 kg/3
=963.95 kg/3
92
=89 mm liq III.
Residual head: =
12.5 103
= 12.96 mm liquid IV. Total pressure drop: =( + ) + + Where = pressure drop through dry plate = weir liquid crest(max) = residual head Putting values = 171.6 mm liq = weir height
. .
25. DOWN COMER BACK UP: a) Down comer pressure loss:Take = - 10 =40mm = weir height b) Area under apron: =
93
= height of bottom edge of apron above plate =weir length= .335 =.01342
c) Head loss in downcomer: = 166

2
= head loss in down comer (mm) = liquid flowrate in downcomer = area for clearance
Put
=1.734 kg/sec Am = 0.018482 So =.947 mm =963.95 kg/m3
d) Back up in downcomer: = + ( + ) +
Put
=.947 mm
=50 mm
94
= 190.6 mm liq. So
=18.82 mm
. . . . . . . . . . . . . . . . . (already assumed )
= 260.36mm = .2603 m 0.260< 0.275
.260< (plate spacing + weir height)
So our plate spacing 0.5 m is acceptable.
26. DOWNCOMER RESIDENCE TIME: =

Where
=liquid flow rate in downcomer =dead liquid backup =0.2603 m =downcomer residence time =0.018482 So
=1.734 kg/s = 3.61 sec > 3 (satisfactory)

95
27. CHECK ENTRAINMENT:% flooding = Where

= flooding velocity =
= actual velocity based upon net area max . . ( )
Putting the values max . = 0.47 =3.468 m/s = 0.135522
Since
=4.08 m/s
% flooding = 77% 28. NUMBER OF HOLES:
Dia of holes (D) = 50mm =.05m Area of single hole (1 ) =4 2 = 1.96*105 m2 Total no. of holes = /1 = 597.14
96
29. HEIGHT OF DISTILLATION COLUMN: No of plates =15 Tray spacing = 0.5 m Distance between 15 plates = 15 * .5 = 7.5m Take Top clearance = 0.5m Bottom clearance = .5 m Plate thickness = 5mm / plate = 5*103 m/plate = 75 mm
Total thickness of plates = 5 * 103 *15 = .075 m Total column height = (7.5 +.5+.5+.075) m = 8.6 m
30. MECHANICAL DESIGN:Shell material = carbon steel Sieve plate material = stainless steel 316 Operating pressure = 1.2 atm Taking design pressure 40% more than operating pressure Design pressure = 1.68 atm = 0.168 MPa Shell diameter = 0.86m Shell height = 8.6 m Shell thickness = =
2
P = design pressure = 0.168 MPa j = joint efficiency = 0.85
+C
97
C = corrosion allowance for carbon steel = 2mm f = allowable stress = 96.26 MPa D = internal diameter = 0.046 m = 46 m
98
Chapter 9 MATERIAL OF CONSTRUCTION
99
Any engineering design,particularly for the chemical processes plant,is only useful when it is translated into reality by using available material of construction combined with appropriate techniques of fabrication which play a vital role in success or failure of a new chemical plant. The task of an engineer is to sort out the available choices and to arrive at the most cost effective solution to the problem of corrosion. Traditionally the one employed set of conditions for plant equipments. Plant equipmentsis protected by coating the equipment with paint. Wet ,damped and high humidity conditions all contribute to corrosion & premature equipment failure if not treated properly. These problems are an uphill task to be considered by an engineer. A engineer must be familiar with the material of construction for all equipments and must be aware of diverse corrosion control technique involving coating metal, cathodic technique, use of plastics and even the use of inhibitors.
CORROSION CONTROL METHODS: The product & its production as well as cleaning purposes and storage involves large amount of use of water. They require a large amount of extensive water facilities. Furthermore the product is an acidic liquid is aggressive to low carbon steel This is futher complicated that the presence of iron ions in the product drastically affects its shelf life. Wet ,damped and high humidity conditions all contribute to corrosion & premature equipment failure if not treated properly. These problems are an uphill task to be considered by an engineer.
100
A engineer must be familiar with the material of construction for all equipments and must be aware of diverse corrosion control technique involving coating metal, cathodic technique, use of plastics and even the use of inhibitors
IMPORTANT MATERIAL OF CONSTRUCTION Material of construction is mainly divided into two parts metals and non metals. Pure metals and metallic alloys are included under the first classification.
The list of important material of construction include the following: Iron & steel Stainless Steel Nickel and its alloys Copper Aluminium Lead Hastelloy Coating Floor materials Plastics
RECOMMENDED MATERIAL OF CONSTRUCTION: Maleic anhydride when pure shows corrosive action till its boiling point. Therefore special material of construction is used in the production & handling of maleic anhydride. Pure maleic anhydride is probably less corrosive towards stainless steel. Although many materials have greater corrosion resistance than carbon but cost aspects favors the use of carbon
101
steel. As a result they often use material of construction when it is known as some corrosion will occur. Although major equipment in the production of Industrial Maleic Anhydride is recommended to be manufactured by carbon steel some equipment where concentrated H2SO4 and dilute acid make the use of stainless steel 304 & 316 are mainly used. Otherwise lining of corrosion resistant material can be used. So recommended material of construction is stainless steel. MATERIAL OF CONSTRUCTION FOR THE SELECTED PROCESS
The material of construction used in the manufacturing of maleic anhydride from n-butane has to be selected very carefully taking in consideration the reactive and corrosive nature of maleic anhydride. The material of construction selected for the main process equipment in the process holds a great significance in the yield and conversion of the product ie, productivity and also a main factor in deciding the life of the equipment &plant. Thus the material of construction sums up for both the technical as well as economic aspect of the production unit. The material of construction used in construction of the super heater is carbon steel with a design temperature of 460 f & design pressure of 220 psi. The air compressor is also made from the same material of carbon steel. The air heater is made up of stainless steel with design temperature of 850 f & design pressure of 30 psi. It is also provided with a 6" refractory lining. The reactor is made up of stainless steel with internal rubber lining of 5.75 ".The reactor provided with the design temperature of 800 f & 50 psi. the steam pot is of stainless steel with design temperature of 650 f & design pressure 377 psi. The gas cooler used in the equipment is made up of carbon steel with design temperature of 470-900 f &design pressure of 315-375 psi. The separator or cyclone in this case is made of stainless steel with design temperature if 30 psi. The distillation column has to be made from stainless steel with design temperature of400f & 25 psi. It is provided with 20 trays,14 gauge & .250 openings (392 per tray).The last but not the least material used in piping is made of PVC (poly vinyl chloride) as the liquid flowing through the streams is very corrosive.
102
Chapter 10 COST ESTIMATION
103
SR NO 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
EQUIPMENTS Reactor Absorber Distillation column Dehydrator Compressor 1 Filter Gas cooler Separator Preheater1 Preheater 2 Mixer
COST ( IN RUPEES) 29654999.5 9982000 28181116.5 583702 87213.5 21000 695501 120000 106729.5 98800 97000 69628062
TOTAL
DIRECT COST :-
Equipment installation cost = .47 *69628062 = Rs 32725189 Instrumentation & process control cost = 0.12 * 69628062 = Rs8355367 Piping (installed) = 0.66* 69628062 = 45954520 Building (including services) = .18 *69628062 =Rs 12533051 Yard improvement = 0.1 *69628062 =6962806 Service facility (installed) = 0.7 *69628062=48739643 Land = 0.06 * 69628062 =Rs 4177683
104
Total = Rs.159448259 Total direct cost= Rs 229076321
INDIRECT COST:
Engineering cost=0.33* 69628062= Rs. 5015098.5 Construction cost = 0.6* 69628062 = Rs.41786403.5 TOTAL=10419168 TOTAL COST: Direct cost + indirect cost =229076321+12419168 = Rs 239495489 Contractor fees = 0.1 * total cost =0.1*239495489 =Rs 24102775 Contingency = 0.2*239495489 =Rs 48203882 Total =Rs 35924323 FIXED CAPITAL INVESTMENT :105
= total direct cost+ indirect cost + contractor fees + contingency =B+C+D = Rs 311802146
WORKING CAPITAL:5% of Fixed capital investment= 0.05 *311802146 = Rs 15590107.3 Total capital investment = FCI + Working capital =311802146+15590107.3 =Rs 327392253.3 FIXED COST:Cost (in Rs) Maintaintance cost 5% of FCI Operating labour Laboratory cost 20% of OL Supervision 20% of OL Plant overhead 25% of OL Capital charge 1% of FCI Insurance 3% of FCI Local taxes 1% of FCI Royalties total 15590107 1000,000 200,000 200,000 250,000 311802 9354064 3118021 2256220 32280214
106
VARIABLE COST : Raw material (rs 29000/MT) = 29,000,000 Electricity (rs 10/MT) = 10,000 Direct production cost = 10% FCI = Rs 31180214.6 Total = Rs 60190214.6 ANNUAL PRODUCTION COST: Fixed cost + variable cost =Rs 92470429.2 Cost / MT =
= 92470.429
1000
92470429.2 1000
Cost / Kg =92.47 Gross profit = 75000/MT Profit = selling price cost price 75000* 1000 = selling price 92470429.2 = 167470429.2 Taxes = 40%of sales price = .4 * 167470429.2
107
= Rs 66988171.68 (Taxes on rawmaterial,electricity&etc)=40% of cost of rawmaterial,electricity&etc =0.4*91370429 =Rs 36548171 TOTAL TAXES=103536342.7 Depreciation = 10% of FCI = .1*311802146 =31180214.6 Net profit = selling price (SP) taxes = 166370429 -103096342.6 = Rs 63934086.52
PAY BACK PERIOD:=
+ 63934086.52+31180214.6 311802146
=3.27 years
RATE OF RETURN:=

*100 =
63934086.52 311802146
*100 =20.50%
108
Chapter 11 PLANT LOCATION & LAYOUT
109
Plant location
Plant location is often the result of compromise among conflictory ,social , economic, geographical & government considerations.One can get all favourablefactors but ultimately the aim is lowest cost of production. The choice of the site for the plant location is very important to be considered as it affects the economy of the whole process.The proper choice of the site can drastically increase the cost of production & simultaneously limit the area in which the product can sold profitably. The proper choice of the site is based on judgement due to experience & thorough knowledge of co-ordination of the various factors governing it.Some of the important factors are: Availability of raw material Transport facilities Market for finished product Power,labour&water supply at cheap rates. Land & taxation liberty,which can encourage the production. Banking & other facilities Site consideration Waste disposal problem
Though n-butane is the main raw material in this factory it is not imported outside but manufactured at the side plant. n-butane is manufactured economically fromnatural gas. In India, Ankeleshwar in Gujrat & Chennai are the states which can fulfill the demand of natural gas. So Gujrat becomes ultimate choice.
110
The site conditions involve not only the selection of site but we have to consider some ther factors as follows:
Atmospheric pressure & temp Max & min humidity Wind,velocity& snowfall Water characteristics. Soil conditions
111
Plant layout
It can be called as the internal orgiation of the fixed asset of their company, The right man in the right place,with the right machine,in the right motive is the key to successful production.
The layout has been made taking following point in to consideration:
There is a steady flow of work & no cross flow of traffic i.e. absence of back traffic
Adequate space has been provided for future expansion.
Disposal aspects
112
113
Chapter 12 MATERIAL SAFETY DATA SHEET
114
1. PRODUCT IDENTIFICATION AND MANUFACTURER/SUPPLIER IDENTIFICATION Product Name: Maleic Anhydride Synonyms: cis-Butenedioic Anhydride Product Use: Chemical Synthesis, intermediate, CAS NUMBER: 108-31-6 EINECS-NR. 203-571-6 Chemical Formulation: C4H2O3 Product Identification Number: 78800/MANBRI 2. COMPOSITION OF INGREDIENTS Chemical Name: Cas. no. Maleic Anhydride 108-31-6 3. HAZARDS IDENTIFICATION % by wt 99 % min
DANGER! CORROSIVE - CAUSES EYE AND SKIN BURNS HARMFUL OR FATAL IF SWALLOWED HARMFUL IF ABSORBED THROUGH SKIN GRINDING MAY PRODUCE FLAMMABLE DUST/AIR MIXTURES MOLTEN PRODUCT CAN CAUSE THERMAL BURNS CAUSES RESPIRATORY TRACT IRRITATION AND CAN CAUSE DAMAGE MAY CAUSE ALLERGIC SKIN AND RESPIRATORY (ASTHMA LIKE) REACTION HMIS Hazard Ratings Health - 3, Flammability - 1, Chemical Reactivity - 1 4. FIRST AID MEASURES Ingestion: Inhalation: Skin Contact:
Do not induce vomiting. Have a conscious person drink several glasses of water or
Allow the victim to rest in a well ventilated area. Seek immediate After contact with skin, wash immediately with plenty of water. If irritation persists Eyes: Immediately flush with water for at least 15 minutes, keeping eyelids open. Seek 5. FIRE FIGHTING MEASURES Extinguishing Media: Small fire: Carbon dioxide, water, foam. Large fire: Water spray, fog or foam, do not use water jet. DO NOT USE DRY CHEMICAL: Large volumes of gases could be produced by Special Fire-Fighting Wear self-contained breathing apparatus with full face piece operated Procedures: in the Hazardous Combustion Carbon Dioxide, Carbon Monoxide. Unusual Fire and Explosion Unstable, or air-reactive or water-reactive chemical involved (see Hazards: Section 10). Vapors from melted material can be ignited. Keep melted material away from ignition sources. May form flammable dust-air mixtures when finely 6. ACCIDENTAL RELEASE MEASURES
115
Personal precautions:
Avoid breathing dust. Pressure demand air supplied respirators should always be worn when the airborne concentration of the contaminant or oxygen is unknown. Personal precautions contd: Recycle, if possible. Use appropriate tools to put the spilled solid in a Otherwise, wear respiratory protection and other personal protective waste disposal container. If necessary, neutralize the residue with a dilute solution of sodium hydroxide. Do not dry sweep or use methods that increase dusting. Prevent entry into sewers 7. HANDLING AND STORAGE d Handling: Eye wash and safety shower should be available nearby when this product is handled or used. Minimum feasible handling temperatures should be maintained. Avoid generating mist or dust. Exercise care when opening bleeders and sampling ports. Do not breathe gas, fumes, vapor or spray. Do not ingest. Avoid contact with skin and eyes. After handling, always wash hands thoroughly with soap Store away from incompatible materials. Store at temperatures not exceeding 70C (158F). Contains moisture sensitive material -- store in a dry place.
Storage:
8. EXPOSURE CONTROLS/PERSONAL PROTECTION Eye/Face Protection Skin Protection Avoid eye contact. Chemical type goggles with face shield must be worn. Do not Protective clothing such as coveralls or lab coats must be worn. Gloves resistant to chemicals and petroleum distillates required. When handling large quantities, impervious suits, gloves, and rubber boots must be worn. Remove and dry-clean or launder clothing soaked or spoiled with this material before reuse. D l concentrations i Airborne should be kept to the lowest levels possible. If vapor, mist or dust is generated and the occupational exposure limit of the product is exceeded, use appropriate NIOSH or MSHA approved air purifying or air supplied i t to ft t i i th i b limits (see below) t ti f th Adequate meet d occupational exposure
Respiratory Protection
Ventilation
116
Exposure Limits
TLV-TWA: 0.1 ppm 8 hours (ACGIH TLV, United States, 2002) TWA: 0.25 ppm 8 hours (OSHA PEL, United States, 1971) 3 8 hours (OSHA PEL, United States, 1971) TWA: 1 mg/m Color Odor Threshold Vapor Pressure Melting Point Solubility in Water Solubility in Other Solvents Water white 0.5 ppm 0.2 mm Hg at 25C 52.5C (126.5F) Very soluble Chloroform, acetone, ethyl acetate, benzene, h d 1.4% b UFL: di 7.1% LFL: >150C
9. PHYSICAL PROPERTIES Physical Form: Molten liquid Odor Strong irritating acrid Specific Gravity Molten: 1.3 at 70C (water = 1.0); Solid: 1.48 at 20C ( Vapor Density 3.38 (Air1 =0) 1.0) Boiling Point 202C (395F) pH 2.42 (0.01 M solution) Flash Point Autoignition Temperature
102C (215F) (PMCC) Flammable Limits 477C (890F) Thermal Decomposition
117
10. STABILITY & REACTIVITY Chemical Stability The product is stable except when in contact with water Conditions to Avoid Incompatible materials, moisture Incompatible materials May react violently with amines, alkali metal ions such as Sodium or Potassium, and bases. At temperatures above 150C, these materials, at concentrations as Hazardous Decomposition Toxic levels of Carbon monoxide, carbon dioxide, irritating aldehydes Products and ketones may be formed on burning. Heating in air may produce irritating Hazardous Polymerization Will not self-polymerize but can undergo uncontrolled copolymerization in the presence of other monomers and catalysts (see Incompatible Materials, 11. TOXICOLOGICAL INFORMATION Oral LD-50 (rat) Skin irritation (rabbit) Dermal LD-50 2620 mg/kg Eye irritation extremely irritating (rabbit) Sensitization The limited number of animal studies investigating the dermal or respiratory sensitization potential of maleic anhydride have not shown conclusive evidence of sensitization potential. Although there have been reports of human dermal or i i i i in case f l i contact h d id h of eye b Effects of Acute Exposure Extremely dangerous of skin (corrosive, irritant), contact (irritant) and inhalation. Very dangerous in case of ingestion. Slightly dangerous in case of skin contact (sensitizer). Eye contact can result in corneal d Effects of Chronic Exposure: Carcinogenic effects Not available. Mutagenic effects: Not available. Teratogenic Effects: Not available. Toxicity of the product to the Reproductive system: Not available. Repeated exposure of the eyes to low level dust can produce irritation. Repeated skin exposure can cause local skin destruction or dermatitis. R t d 12. ECOLOGICAL INFORMATION Aquatic Toxicity LC50 - 96hr 230 mg/liter (mosquito fish) practically nontoxic LC50 - 24hr 150 mg/liter (blue gill sunfish) practically nontoxic Mobility This product is not likely to volatilize rapidly into the air because of its low vapor Bioaccumulative potential This product is not expected to bioaccumulate through food chains in the Remarks This product will hydrolyze rapidly to the acid. Expected to be slightly toxic to 13. DISPOSAL CONSIDERATIONS 1030 mg/kg corrosive
118
Waste Disposal Methods
Remarks
Recycle if possible. Consult your local authorities. This product has the RCRA characteristics of corrosivity, and is identified under RCRA as Maleic Anhydride. If discarded in its present form, it would have the hazardous waste numbers D002 Do not allow to enter drains or sewers. Do not allow to drain into surface waters.
14. TRANSPORT INFORMATION TDG Classification DOT Classification Maleic Anhydride Class 8, UN 2215, PG III, Label: Corrosive Maleic Anhydride Class 8, UN 2215, PG III, Label: Corrosive, Reportable Quantity: 5000 Lbs (2268 Kg)
15. REGULATORY INFORMATION WHMIS Classification Class D, Div 1, Subdiv B: Material causing immediate and serious toxic effects (TOXIC) Class D, Div 2, Subdiv A and B: Material causing other toxic effects (VERY TOXIC) Class E: Corrosive Solid Section 302: This product is not regulated under Section 302 of SARA and 40CFR Part 355 Section 311: Maleic Anhydride, Immediate (Acute) Health Hazard, Delayed (Chronic) Health Hazard Section 313: Maleic Anhydride 100% Maleic Anhydride 100%, RQ 5000 lbs. Pennsylvania RTK: Maleic Anhydride (environmental hazard, generic environmental hazard) Massachusetts RTK: Maleic Anhydride New Jersey RTK: Maleic Anhydride Connecticut RTK: Maleic Anhydride Florida RTK: Maleic Anhydride Illinois RTK: Maleic Anhydride Rhode Island RTK: Maleic Anhydride California prop. 65: no products were found
SARA Title III
CERCLA 102a State Regulations
119
Inventories
Canada Inventory (DSL): listed on inventory US Inventory (TSCA): listed on inventory
16. OTHER INFORMATION
Bartek Ingredients Inc. cannot anticipate all conditions under which this information and its product, or the products of other manufacturers in combination with its product, may be used. It is the users' responsibility to ensure safe conditions for handling, storage and disposal of the product, and to assume liability for loss, injury, damage or expense due to improper use. This information is given in good faith, but no warranty, express or implied is made.
120
PIPING & INSTRUMENTATION FLOWSHEET
121
122
CONCLUSION
123
Conclusion:-
The Report generated gives a higher value of the Total Potential Environmental Impact suggesting that the process has to be modified for environmental purposes. The high value of the PEI is because of the excess amounts of carbon dioxide released into the atmosphere. By analyzing all the individual output streams, it can be clearly observed that output stream has quiet high values of the total PEI. It is because of the release of the purge gas from the gas cooler directly into the atmosphere. As a process improvement step, we can use incinerator to convert the Carbon monoxide to carbon dioxide before it is released into the atmosphere. As an alternative a scrubber can be used to scrub all the harmful gases and prevent them from entering into the atmosphere. The other outlet streams mostly contain water other than the product, so they have less environmental impact. Changing the solvent in the absorption column from Sucinic anhydride to water can increase the environmental attractiveness of the process but the required product yield cannot be attained.
124
BIBLIOGRAPHY: R. Winckler, Annalen der Pharmacie 4, 230 (1832); J. Pelouze, Annalen der Pharmacie 11, 263 (1834).
J. R. Skeen, Chem. Eng. News 26, 3684 (1948).
S. V. R. Mastrangelo, Anal. Chem. 29, 841 (1957); H. G. M. De Wit and co-workers, Thermochim.Acta 65, 43 (1983).
J. A. Dean, ed., Langes Handbook of Chemistry, 14th ed., McGraw-Hill Book Co.,Inc., New York, 1992.
Y. Suzuki, K. Muraishi, and K. Matsuki, Thermochim. Acta 211, 171 (1992).
Maleic Anhydride, Monsanto Technical Bulletin Pub. No. 9094, Monsanto Chemical Co., St. Louis, Mo., 1988.
C. W. Davies and V. E. Malpass, Trans. Faraday Soc. 60, 2075 (1964).
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MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

Chapter 2 LITERATURE SURVEY

MANUFACTURING OF MALEIC ANHYDRIDE

Physical state : Solid flakes

Appearance : White when in solid form &Colourless in liquid

Boiling point : 202C

MANUFACTURING OF MALEIC ANHYDRIDE

Sulfonation: Maleic anhydride is sulfonated to a-sulfomaleic anhydride with sulfur trioxide.

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

STRUCTURE OF MALEIC ANHYDRIDE:

HANDLING AND STORAGE:

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

Chapter 3 VARIOUS TYPES OF PROCESSES

MANUFACTURING OF MALEIC ANHYDRIDE

PROCESS TECHNOLOGY EVOLUTION:

1. BENZENE BASED PROCESSES. 2. BUTANE BASED PROCESSES.

MANUFACTURING OF MALEIC ANHYDRIDE

BUTANE BASED TECHNOLOGIES:

MANUFACTURING OF MALEIC ANHYDRIDE

a) BUTANE BASED FIXED BED PROCESS TCHNOLOGY:

MANUFACTURING OF MALEIC ANHYDRIDE

c) BUTANE-BASED TRANSPORT-BED PROCESS TECHNOLOGY:

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MERITS AND DEMERITS OF BUTANE AND BENZENE AS RAW MATERIAL:

BENZENE MERITS: Benzene gets Easily oxidized.

It is cheaply available as compared to benzene.

High selectivity for feedstock

The butane can be easily recovered from natural gas.

Energy required is less as compared to that for benzene process.

Not a hazardous product.

Lower air requirements as compared with fixed-bed technology, which allows

MANUFACTURING OF MALEIC ANHYDRIDE

removal of two excess carbon atom present in benzene ring.

Large energy inputs are required

MANUFACTURING OF MALEIC ANHYDRIDE

SELECTION CRITERIA ANHYDRIDE:

FOR MANUFACTURING OF MALEIC

MANUFACTURING OF MALEIC ANHYDRIDE

Chapter 4 PROCESS DESCRIPTION

MANUFACTURING OF MALEIC ANHYDRIDE

Raw material: Butane, Oxygen. Catalyst: Vanadium phosphorus oxide (VPO)

Molecular weight : 58.123 g/mol

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

MANUFACTURING OF MALEIC ANHYDRIDE

TLm/Mosquito fish/240 ppm/24-48 hr./fresh water.

MANUFACTURING OF MALEIC ANHYDRIDE

HCo= -26420 + 0.25 (350-30) 28 = -24180 kcal/kmole