Acetone Production Report

SUMMARY The process purpose is to produce acetone from isopropyl alcohol (IPA) at the given conditions. This report is formed, some properties, manufacturing process of acetone. In manufacturing process, feed drum, vaporizer, heater, reactor, furnace, cooler, condenser, flash unit, scrubber, acetone and IPA columns are used. This profile envisages the establishment of a plant for the production of acetone with a capacity of 100 tons per annum. The present demand for the proposed product is estimated at 70 tons per annum. The demand is expected to reach at 137.7 tones by the year 2017. The plant will create employment opportunities for 20 persons. The total investment requirement is estimated at Birr 6.17 million, out of which Birr 2.84 million is required for plant and machinery. The project is financially viable with an internal rate of return (IRR) of 14 % and a net present value (NPV) of Birr 1.71 million, discounted at 8.5%.

NOMENCLATURE MW=Molecular Weight [kg/kmol] N = mole [mol/h] Y = mol or mass fraction of gas stream X = mol or mass fraction of liquid stream P Tn = Total Pressure [bar] Pi*n= Vapour Pressure of Component [bar] Pv* = Vapour Pressure [bar] F = Feed Flow Rate [k mol/h] V = Flow Rate of Vapour [kmol/h] L = Flow Rate of Liquid [kmol/h] T = Temperature [° C] ∆ Hvap = Latent Heat of Vaporization [kJ/kg] TC = Critical Temperature [° C] PC = Critical Pressure [bar] Tb = Normal Boiling Point [° C] Q = Heat [kJ] M = Mass Flow Rate [kg/h] K = Activity Coefficient

Introduction:Acetone is the organic compound with the formula (CH3)2CO, a colorless, mobile, flammable liquid, the simplest example of the ketones. Acetone is miscible with water and serves as an important solvent in its own right, typically as the solvent of choice for cleaning purposes in the laboratory. About 6.7 million tons were produced worldwide in 2010, mainly for use as a solvent and production of methyl methacrylate and bisphenol A. Familiar household uses of acetone are as the active ingredient in nail polish remover and as paint thinner. It is a common building block in organic chemistry. Acetone is naturally produced and disposed of in the human body as a result of normal metabolic processes. It is normally present in blood and urine. Diabetic people produce it in larger amounts. Reproductive toxicity tests show that it has low potential to cause reproductive problems. In fact, the body naturally increases the level of acetone in pregnant women, nursing mothers and children because their higher energy requirements lead to higher levels of acetone production. Ketogenic diets that increase acetone in the body are used to reduce epileptic attacks in infants and children who suffer from recalcitrant refractory epilepsy. Acetone (dimethyl ketone, 2-propane, CH3COCH3) formulation weight 58,079 is the simplest and the most important of the ketones. It is a colorless, mobile, flammable liquid with a mildly pungent and somewhat aromatic odour. It is miscible in all proportions with water and with organic solvents such as ether, methanol, ethyl alcohol, and esters. Acetone is used as a solvent for cellulose acetate and nitrocellulose, as a carrier for acetylene And as a raw material for the chemical synthesis of a wide range of products such as ketene, Methyl methacrylate, bisphenol A, diacetone alcohol mesityl oxide, methyl isobutyl ketone, Hexylene glycol (2-methyl-2, 4-pentanediol), and isophorone. Acetone is produced in various ways; 1. The Cumene Hydro peroxide Process for Phenol and Acetone 2. Isopropyl Alcohol Dehydrogenation 3. Direct Oxidation of Hydrocarbons to a Number of Oxygenated Products Including Acetone 4. Catalytic Oxidation of Isopropyl Alcohol 5. Acetone as a By-Product of the Propylene Oxide Process Used by Oxirane 6. The p-Cymene Hydro peroxide Process for p Cresol and Acetone 7. The Diisopropylbenzene Process for Hydroquinone (or Resorcinol) and Acetone In this report isopropyl alcohol dehydrogenation was investigated.

PHYSICAL AND CHEMICAL PROPERTIES: Appearance: -

Liquid. Clear.

Molecular wt.:-

58.079

Colour: -

Colourless.

Density/specific gravity (g/ml):-

0.79 Temperature (°C): 20

Melting Point

-94.60C

Boiling Point

56.130C (at 760 mm Hg)

Vapour Pressure: -

24 .7 KP at Temperature (°C):

20Evaporation Rate: -

.6

Volatile by vol. (%):-

10

Solubility description: -

Miscible with water.

Solubility Value (g/100g H 2O20°C ):Auto Ignition Temp. (°C):-

100 540

Flammability limit (lower) (%):-

2.1

Flammability limit (upper) (%):-

13.0

Stability and Reactivity: Stability: -

Stable under normal conditions of use.

Conditions to avoid: -

Avoid contact with: Strong oxidising agents. Avoid Contact with acids. Avoid heat, flames and other

. Materials to avoid: -

Sources of ignition Potassium sulphate, sodium hydroxide, sulphuric acid, Nitric acid, hydrogen peroxide, chloroform, activated Carbon, Bromine.

Hazardous Decomp.Product -

Thermal decomposition or burning may release oxides Of carbon and other hazardous gases or vapours

.

Uses-: About a third of the world's acetone is used as a solvent, and a quarter is consumed as a precursor to methyl methacrylate. Solvent use: Acetone is a good solvent for most plastics and synthetic fibers including those used in laboratory bottles made of polystyrene, polycarbonate and some types of polypropylene. It is ideal for thinning fibreglass resin, cleaning fiberglass tools and dissolving two-part epoxies and superglue before hardening. It is used as a volatile component of some paints and varnishes. As a heavy-duty degreaser, it is useful in the preparation of metal prior to painting; it also thins polyester resins, vinyl and adhesives. It is also useful for high reliability soldering applications to remove solder rosin after soldering is complete. This helps to prevent the Rusty bolt effect from occurring due to dirty solder contacts. Storage of acetylene Although flammable itself, acetone is also used extensively as a solvent for the safe transporting and storing of acetylene, which cannot be safely pressurized as a pure compound. Vessels containing a porous material are first filled with acetone followed by acetylene, which dissolves into the acetone. One litter of acetone can dissolve around 250 litters of acetylene. Methyl methacrylate This application begins with the initial conversion of acetone to acetone cyanohydrins: (CH3)2CO + HCN → (CH3)2C (OH) CN In a subsequent step, the nitrile is hydrolyzed to the unsaturated amide, which is esterified: (CH3)2C (OH) CN + CH3OH → CH2= (CH3) CCO2CH3 + NH3 The third major use of acetone (about 20%) entails its condensation with phenol to give bisphenol A (CH3)2CO + 2 C6H5OH → (CH3)2C (C6H4OH) 2 + H2O

Bisphenol A is a component of many polymers such as polycarbonates, polyurethanes, and epoxy resins. Medical and cosmetic uses Acetone is used in a variety of general medical and cosmetic applications and is also listed as a component in food additives and food packaging. Acetone is commonly used in chemical peeling. Common agents used today for chemical peels are salicylic acid, glycolic acid, 30% salicylic acid in ethanol, and trichloroacetic acid (TCA). Prior to chemexfoliation, the skin should be cleaned properly and excess fat removed. This process is known as defatting. Acetone, Septisol, or a combination of these agents is commonly used in this process. Laboratory uses In the laboratory, acetone is used as a polar aprotic solvent in a variety of organic reactions, such as SN2 reactions. The use of acetone solvent is also critical for the Jones oxidation. It is a common solvent for rinsing laboratory glassware because of its low cost and volatility. H\however, it does not form an azeotrope with water (see azeotrope (data)). Despite its common use as a supposed drying agent, it is not effective except by bulk displacement and dilution. Acetone can be cooled with dry ice to −78 °C without freezing; acetone/dry ice baths are commonly used to conduct reactions at low temperatures. Acetone is fluorescent under ultraviolet light, and its vapour may be used as a fluorescent tracer in fluid flow experiments. Domestic and other niche uses Acetone is often the primary component in cleaning agents such as nail polish remover. Ethyl acetate, another organic solvent, is sometimes used as well. Acetone is a component of superglue remover and it easily removes residues from glass and porcelain. It can be used as an artistic agent; when rubbed on the back of a laser print or photocopy placed face-down on another surface and burnished firmly, the toner of the image transfers to the destination surface. Make-up artists use acetone to remove skin adhesive from the netting of wigs and moustaches by immersing the item in an acetone bath, then removing the oftened glue residue with a stiff brush.

MARKET TREND -: Past Supply and Present Demand The country's requirement for acetone is totally met through import. Data obtained from the Ethiopian Customs Authority with regard to import of acetone for the period covering 1997 2011 is given in Table-

IMPORTANCE OF ACETONE YEAR

QUANTITY(Mt.Tons)

1997

41.6

1998

90.6

1999

52.7

2000

24.7

2001

154.3

2002

34.0

2003

34.3

2004

57.7

2005

47.5

2006

84.2

2007

70.5

2008

74.9

2009

80.2

2010

85.8

2011

91.8

Projected Demand -: Acetone is used as a solvent in the production of paint, varnish, lacquer, cellulose acetate, potassium iodide and permanganate. It is also used to clean dry parts of precision equipments, delusterant for cellulose acetate fibre and specification testing of vulcanized rubber products. This clearly indicates that demand for acetone is directly related with the development of the industrial sector. Taking this in consideration, annual average growth of 7% is applied to forecast the future demand. The forecasted demand up to the year 2017 is given in Table 3.2. 55-6 import figures were much higher than the imports in the following years. In 1998, the import figure was about 90.6 tonnes while in the following years, i.e., 1999 and 2000 the import figure dropped to 52.7 tonnes and 24.7 tonnes respectively. Similarly, import figure in the year 2001 was about 154 tones while in the following four consecutive years, i.e., from 2002 - 2005 import ranges from only 34 tonnes to about 58 tonnes. This probably indicates that the high imports in some years were used as buffer stocks for the following years. Hence, some portions of the imports were distributed among the subsequent years in which recorded import figures were found to be comparatively low. By looking to the above argument, the present effective demand is estimated using the following methodology. The average import figures in the recent past six years, i.e., 2001- 2006 is taken as an effective demand for the year 2007 since the product is directly related with the growth of the manufacturing sector, an annual average growth rate of 7% (which is recorded by the industrial sector in the past) is applied to arrive at the current (year 2007) demand.

PROJECT DEMAND OF ACETONE YEAR

QUANTITY(Mt.Tons)

2012

98.2

2013

105.1

2014

112.4

2015

120.3

2016

128.7

2017

137.7

METHODS OF PRODUCTION:(a) Catalytic Dehydrogenation of Isopropanol (b) Oxidation of Isopropyl benzene (c) Co product of Glycerine- H2O2 process (d) Oxidation of Butanol (e) Oxidation of Propylene (a) Acetone by oxidation of Propylene: A process for acetone production by direct oxidation of propylene using air. In this process the catalysis consists of a solution of copper chloride containing small quantities of palladium chloride. The overall reaction is as follows C3H6+1/2O2

CH3COCH3

(b) Oxidation of Butanol: Catalytic oxidation of n butane using either cobalt or manganese acetate produces acetic acid at 75-80% yield. By products of commercial value are obtained in variable amounts. In the Celanese process the oxidation reaction is performed at a temperature range 150-2250C and pressure of approx 505 atm. CH3CH2CH2CH3 + O2

CH3COOH + CH3COCH3

(c) Co product of Glycerine- H2O2 process: When Glycerine is produced from propylene via acrolein then acetone is produced as a by product. CH3CH═CH2 + H2O

CH3CHOHCH3 + O2

CH3COCH3 + H2O2

(d) Oxidation of Isopropyl Benzene (Cumene):Cumene is synthesised from propylene and benzene, followed by oxidation for the formation of hydro peroxide and splitting the same into acetone and phenol. The crude products are then fractionated to get pure acetone and phenol.

(e) Dehydrogenation

of

Isopropanol:

Acetone

is

produced

from

catalytic

dehydrogenation of isopropanol. The catalyst used in this process is ZNO.The crude product obtained from this process is fractioned and pure product is obtained. (CH3)2CHOH

(CH3)3CO + H2

The acetone produced in the reactor passes into a phase separator and then into a separation system that includes one stripping and two distillation columns. A recycle stream takes a mixture of unreacted isopropyl alcohol and water, with a trace amount of acetone, back into a mixer that feeds the reaction system. Using the catalyst which will be employed throughout this analysis, the reaction is first order with respect to the concentration of isopropanol and has an Arrhenius dependence on temperature with E=72.38 MJ/kmol and k=351,000 cubic m gas/cubic m reactor sec.

Reason

for selecting

the

process: (Catalytic

dehydrogenation of

Isopropanol): Acetone production from Cumene process is a serious competitor for the isopropanol dehydrogenation process. Catalytic dehydrogenation of isopropanol can be chosen as a synthetic route when high-purity acetone is required, such as in biomedical applications. In this process 88% of isopropanol is recycled so this process is cost effective. Catalytic dehydrogenation of isopropanol gives approx 99% pure product. Catalytic dehydrogenation of isopropanol: In the simplified process, an aqueous solution of isopropyl alcohol is fed into the reactor, where the stream is vaporized and reacted over a solid catalyst at 2 atm. The reactions occurring within the reactor are as follows: CH3-CHOH-CH3



Isopropyl alcohol (IP) CH3-CHOH-CH3 + ½ O2 IP

CH3-CO-CH3 Acetone (AC) 

+

H2 Hydrogen (HY) CH3-CO-CH3 Acetone

+

H2O Water

Flow Sheet of Acetone Production

Process Description: Feed drum is a kind of tank used for the mixing of the recycle stream and feed stream. Recycle stream concentration was assumed to be same with the feed stream. The temperature of the feed stream is assumed to be 250C at 2 bar pressure, which is assumed to be constant. The temperature of recycle stream was calculated as 111.50C. The temperature of the leaving stream was calculated as 32.890C, by the energy balance around feed drum. In the vaporizer molten salt was used for heating. The temperature at the entrance of the unit is the temperature of the mixture leaving the feed drum, which is 32.890C. And the leaving temperature is the bubble point temperature of the mixture, which is 109.50C. The pressure is 2 bars, and assumed to be constant. Since the temperature leaving the vaporizer is not enough for the reaction a pre-heat was used. The unit is working at 2 bars, and assumed to be constant. The entrance and leaving temperatures are 109.50 C and 3250 C. The reactor was the starting point for the calculations. The temperature values for the entering and leaving streams were found from literature, which are 3250C and 3500C, respectively. The reaction taken place inside is endothermic, for this reason the reactor has to be heated. For heating, molten salt was used. The pressure is 1.8 bar, and assumed to be constant. The entrance temperature of the cooler is 350 0C and leaving is 94.70C. For cooling, water was used. Instead of water a refrigerant may be used. Better results may get. But since it costs too much, it wasn‟t chosen as the cooling material. From the temperature values it‟s easily seen that the load is on the cooler not on the condenser, for this process. But in reality the unit cannot cool that much, and the load is mostly on the condenser. In this process, the mixture cooled down to its dew point. The pressure is 1,5 bar, and assumed to be constant.- 5 - The temperature of the entering stream is the dew point and the leaving temperature is the bubble point of the mixture. In the condenser water was used as cooling material. In the calculation of the dew and bubble points Antoine Equation was used. Trial and error was used with the help of Excel. The mixture includes acetone, i- propyl -alcohol, water and hydrogen. But hydrogen was not taken into consideration in the calculations. Since the condensation temperature of hydrogen is very low, it is not condense in the condenser. It stays in the for this reasons it has no affect on bubble and dew point calculations. Also since it does not affect the temperature calculations it‟s not taken into consideration on mole and mass fraction calculations. The leaving and entering temperatures are 94.70 0C and 81 0C, respectively. The pressure is 1.5 bar, and assumed to be constant. Flash unit was assumed to be isothermal, for this reason temperature was not changed. It is 81 0C in the entrance and exit. The pressure is 1.5 bar, and assumed to be constant. By trial and error method, (V / F) value was found to be

0.2. The entrance temperature of the unit is the bubble point of the mixture, but if it was its dew point the (V/F) value would be much higher. Scrubber was assumed to be adiabatic. The temperature of water entering the unit was assumed to be 25 0C. The temperature of the off gas, including hydrogen and a very little amount of acetone, was assumed to 70 0C. But this assumption is too high, a lower temperature should have been assumed, since a lot of water is used in the unit. It should have been around 40 0C – 50 0C. The temperature of the leaving stream was found to be 28.1 0C.The pressure of the unit is 1.5 bar, and assumed to be constant

Raw Material Propylene or ISO-propyl alcohol is the only raw material used for manufacturing of acetone in the presence of a catalyst. Packaging materials are required for delivering this product. The annual materials requirement and cost of the plant is given in Table 4.1. ANNUAL CONSUMPTION OF RAW MATERIALS AND COST ANNUAL CONSUMPTION OF RAW MATERIALS AND COST Description Propylene Catalyst (silver or copper) Water Packaging Total

Unit of meas.

Qty.

Cost in '000 Birr F.C

tonnes " 3

m Barrel

120 0.5 80

918 17 -

625

935

L.C 162 3 0.26

T.C 1080 20 0.26

188 188 353.26 1288.26

7.2 MATERIAL BALANCE: 7.2.1 Material Balance on Reactor: CONVERSION = 90%

Nacetron5= 100*0.9 =90kmole/hr Nh25 =100*0.9 =90 kmole/hr NH2o 5 =49.25kmole/hr Nipa =100*0.1= 10 kmole/hr Ntotal= naceton +nh2o + nh2 5 +nipa =239.25kmole/hr

Yacetone =90/239.25= 0.376 Yh2 5=90/239.25 =.376 YH2o= 49.25/239.25= o.206 yipa=10/239.25 =0.042

7.2.2 Material Balance on Flash Unit:

It is assume that there is no change at temp. and pressure. Ki == pi*/pp= yi/xi

(at bubble point = 810c)

For Acetone Logp*aceton =7.0947 – 1161/ (224+81) P*aceton= 1651.6mmHg Kaceton =1651.6/ ((1.5/1.013)*760) = 1.467 For IPA Log p*= 8.37895- 1788.02/ (227.438+81) P*ipa =381`.89 mmHg Kipa = 381.89/1125.092 =0.339 For H2O Log p*H2O = 7.96681 – 1668.21/ (228+81) P*H2O = 369.89

KH2O = 369.89/1125.092 = 0.328 For Trail error F/V = 0.2 Ft= nacetone +nH2O + nipa =149.25 F=V+L V/F =0.2 Solving V = 29.85kmole/hr

, L= 119.4 Kmole/ hr

YV = K * xl F*ZF = Vx *yv + z* xl For Acetone Yv = 1.467 * xL 90=29.85 yv + 119.4* xL After solving Xl=0.551 Yv = 0.809 For IPA Yv = 0.339 * xL 10= 29.85 * yv + 119.4 * xl After solving Xl ==0.077

Yv = 0.026

For water Yv = 0.328 *xl 49.25 = 29.85 * yv + 119.4 * xl X l = o.381 Yv = o.125

At Stream 8: V= 29.85 kmol/hr. Yacetone= 0.809 Nacetone8= (0.809)*(29.85) = 24.148 kmol/hr Yipa= 0.026 Nipa8= 0.026*29.85= 0.766 kmol/hr YH2O =0.125 NH2O= (0.125)*(29.85) =3.731kmol/hr At Stream 9 L= 119.4kmol/hr Xacetone=0.551

nacetone= (0.551)*(119.4) = 65.789 kmol/hr

Xipa=0.077

nipa9= (0.077)*(119.4) = 9.149 kmol/hr

Xwater=0.381

nacetone= (0.381)*(119.4) = 45.491 kmol/hr

7.2.3 Material balance for Scrubber: T=(81oC) = 354.15 K, P=1.5bar Assume: 1/1000 of inlet acetone is off gas. Nacetone12= 0.024148 kmol/hr Nacetone10=24.148-0.024148=24.124kmol/hr

Ntotal= nacetone+nH2,8+nH2O+nipa

24.148+90+3.731+0.776 = 118.655 kmol/hr

nacetone12= nacetone12+nH2,12

0.024148+90 = 90.024kmol/hr

Yacetone=0.024148/90.024= 2.68*10-4 Yacetone8= 24.148/118.655 =0.203 Yacetone12/ Yacetone8=1-A/1-A6 M= e (10.92-3598/T)/P

Where A =L11/m* V8

take P=1.48

T=354.15

M= 1.445 Yacetone12/ Yacetone8=2.68*10-4/0.203 = 1.320*10-3= 1-A/1-A6 From trial error A is found is 3.523 L11= m*A*V8= 1.445*3.523*118.655 = 604.041 kmol/hr NH2O10= nH2O8+ nH2O11

3.731+604.041 =607.772 kmol/hr

Ntotal10= nacetone10+nH2,10+nipa10

24.124+607.772+0.776= 632.6724 kmol/hr

7.2.4 Material balance for Acetone Column Nacetone13= Nacetone9+nacetone10= 65.789+24.124= 89.913kmol/hr Nipa13= Nipa9+ Nipa10= 9.194+0.776 = 9.97 kmol/hr NH2o13= NH2o9+ NH2o10= 45.491+607.772=653.263 kmol/hr

Assume: 1/1000 of acetone is in bottom product. Nacetone15=89.913/1000= 0.089kmol/hr Nacetone14= 89.913-0.089= 89.824kmol/hr Since acetone purity is 99%. Nipa14=89.824*(0.01/.99)= 0.907kmol/hr Nipa15=nipa13-nipa14=9.97-0.907=9.063kmol/hr

NH2O15=nH2o13=653.263kmol/hr 7.2.5 Material Balance for IPA column:

All the ipa is at the top product Nipa17 = nipa 15 = 9.063 kmole/hr Nacetone17 = nacetone15 = 0.089kmole/hr Assume the composition of the recycle stream is as feed stream so that Yacetone = 0.33

yipa =o.67

N H2O 17 = 9.063 * 0.33/o.67 = 4.469kmole/hr nwater

=

nwater - nwater = 653.263 - 4.464 = 648.729kmole/hr

7.2.6 Material Balance for Feed Drum: INPUT = OUTPUT Nipa 12 = nipa - nipa 17 = 100 - 9.063 = 90.933kmole/hr NH2O = nH2O + nh2o 17 NH2O = 49.25 - 4.464 = 44.786kmole/hr Sience 115000tonns/day acetone is wanted to produce all of these calculation should be correlated as this amount, these new value are shown in lable Amount = 89.824 kmole/hr * 58.08 kg/1 * 1 ton/1000 * 8760/1 yr

= 45700.726 tpy Scale factor Sf = (115000ton/yr)/ 45700.726 = 2.516

7.3 ENERGY BALANCE 7.3.1 For Feed Drum

MH2O=2029.966kg/hr

1

T=250C Mipa=13749.785kg/hr

Feed Drum

2

T=32.890C

Mipa=15120.159kg/hr

Mwater=2232.293kg/hr 3 Mipa=1370.369kg/hr

Tref =250C

Cp.pia=2497kj/kg

Cp.water=4178kj/kg

For stream 1,2 and 17 calculate Cpmix Cpmix = (2497*0.87)+(4178*0.13) =2715 kj/kg Mtotal1=13749.785+2029.966= 15779.75 kg/hr

Mwater=202.326kg/hr

Mtotal2=15120.154+2232.293=17352.447kg/hr Mtotal3=1370.369+202.326= 1572.695 kg/hr Qin=Qout 15779.75*2.715*(25-25) +1572.695*2.715*(111.5-25) = 17352.447*2.715*(T-25) T=32.830C

7.3.2 For Vaporiser:

T=32.830C MIPA =15120.15kg/hr MH2O =2232.293kg/hr T =109.50C Mipa=15120.154 Kg/hr Mwater = 2232.293kg/hr At 32.83 0c Cpipa = 145kj/kmole K =

2.413 kj/kg K

CpH2o = 4.179 kj/kg K For Water Tc = 508.3 K Tb = 394.399K ΔHf = 39838 kj/kmole ΔHvap ,H2O = H [(Tc-T)/(Tc-Tb)]o.38 = 41370.970 kj/kmole

= 2296.4731 kj/kg For IPA Tc = 647.3 K Tb = 375K ΔHf = 40683kj/kmole ΔH vap , ipa = 40683[(647.3k-382.5k)/(647.3k-375k)]0.38 =40253.505 kj/kmol = 66982kj/kg Q = (mipa * Cpipa * Δ T) + ( mwater * Cpw * ΔT) + (mw *Δ H vep, wat) + (mpipa * ΔHvap ,ipa) = 9.652 * 106 kj Molten Salt: We assume Δ T = 20 Q = m * Cpmolt.salt * Δ T 9.652*10^6 kj = 156 kj/kg * m * (20) M = 309.358 tons 7.3.3 Pre Heater:

Heater T=109.50C

T=3250C

Mwater=2232.253kg/hr

Mwater=15120.154kg/hr

Mipa=15120.154kg/hr

Mipa=2232.293kg/hr

Tref=109.50C

Cp,pia=24.6kj/kgk

CpH2O=2019kj/kgk

Q=(mwater*Cpwater*∆T)+(mipa*Cpipa*∆T)

=[(2232.293*2.468*(325-

109.5)+(15120.154*2.019*215.5)] = 1.845*106 kj Molten Salt: We assume ∆T= 1500C Q=m*Cp molten salt*∆T= 1.845*106=156*m*150 M=7.855 ton 7.3.4 For Reactor: (CH3)2CHOH

(CH3)2CO+ H2

COMPOUND Nin kmol/hr

Hf kj/kmol

Nout kmol/hr

(CH3)2CHOH

251.6

-272.290

25.16

CH3)2CO

0

-216.685

226.44

H2

0

0

226.44

T=3250C

T=3500C

Reactor

MH2=435.144kg/hr Mipa

=1512.015kg/hr Mipa=15120.154kg/hr Mwater=2232.293kg/hr Mwater= Macetone=13151.635kg/hr

2232.293kg/hr

∆Hin ipa= -272.29+25∫325(32.427+1.886*10-1T+6.405*10-5T2-9.261*10-8T5)dT ∆Hin ipa= -272.29+20.104 = -252186 kj/mol -27229+25∫350(32.427+1886*10-1T+6405*10-5T2-9261*10-8T3)dT

∆Hout

ipa=

∆Hout

ipa= -249.691

kj/kmol

∆Hout acetone= -216.685+25∫350(71.96+20.1*10-2T+12.78*10-5T2+3.476*10-8T3)dT ∆Hout acetone= -182.745 kj/mol ∆Hout

350 (28.84*10-3+0.3288*10-8T2+0.00765*10-5T-0.8698*10-12T3)dT H2= 25∫

∆Hout

H2=9.466

kj/kmol

∆Hr0=(-216.685kj/kmol)-(-272.29)kj/kmol ∆Hr0= 55.605kj/kmol ∆Hr=226.44*55.685/1 =12591kj Q= ∑outniHi - ∑inniHi+∆Hr Q= [ 25.16( -249.691)+226.44(-182.745)+226.44(9.466)] – [252.6(-252.106)] +2591.196 Q=30521.67 kj Molten Salt Cp(molten salt b/w 3600C- 4100C) = 156kj/kg Q=m*Cp*∆T 30521.67=156*m*50 M=391.300kg/hr

7.3.5 For Cooler T = 3500C MIPA = 1512.015kg/hr MH2O = 2232.293kg/hr

T= 94.70c ,

Macetone = 13151.635kg/hr

mipa =1512.015kg/hr

MH2 = 455.144kg/hr

m H2O =2232.293

kg/hr Macetone =13151.635 kg/hr MH2 455.144kg/hr

Tref = 94.70c CpH2 = 12.608 kj/kg K CpH2O= 2.035 kj/kg K Cpipa =2.536kj/kg K Cpacetone = 1.096 kj/kg K We know Q =[(mH2 *CpH2) + (mH2O * CpH2O) + (mipa * Cpipa) + (macetone * Cpacetone)] * del T Q = - 10.123 * 106 kj Water Δ T water = 35- 20 =20 CpH2O =4.179 kj/hr

=

Q = m * CpH2o * Δ T 10.123 *106kg = 4.179kj/kg * m * 20

m = 121.117 ton/hr

7.3.6 For Condencer:

T

94.70C

=

T = 81 0c MIPA =1512.O15Kg/hr MH2O =2232.293 kg/h

mh2o= 2232.293kg/hr

Macetone = 1315.635kg/hr

m acetone

=13151.635kg/hr Mh2= 455.144 kg/hr

mH2 = =455.444k/hr

Log P* = a – b/(c+Tdp) Assumption = PT = 1.5 bar = 1125 mmHg [(yacetone * pt )/(p*acetone * Tdp)] + [(yh2o * pt )/(p*water *Tdp)] + [(yipa * pt)/( pipa* * Tdp)] + [(yH2 *pt)/(pH2* * Tdp)]

=1

From Literature : For acetone A = 7.02447

B = 1161

C = 224

For H2O A = 7.96681 For IPA

B = 1668.21

C = 228

A = 8.3789 Using

B = 1788.02 yaceton = 0.6

C = 227.938

yH2o = 0.33

yipa = 0.07

Tdp = 94.7 0C

By trial error For aceton At 14.70C

&

1.5 bar

Cpacetone = 1.297 kg /K Qacetone== m * Cp * del T = 13151.6322 * 1.297 [(81+273.15) - (943.7 +273.15)] = - 233.690 * 10-6 kj Δ Hvep = Δ Hf [(Tc - T)/(Tc-Tb)]0.38 = 29140 kj/kmole Tc 508.1 K Δ Hvap

=

Tb= 341.5 K

=28289.029kj/kmole

=

For IPA At 94.70c & 1.5 bar Cpipa

=

1.761 kj / g KS

Cpipa = 1.761 kj.kg K Qipa = =1512.015 * 1.761 *(354.15-367.85) = -36.487 * 10^-3 Kj ∆ H vep =delHf [(Tc -T)/(Tc –Tb)]0.38 ∆HF = 39850 kj/kmole Tc =508.3K ∆Hvap = 4116935kg/kmole

Tb = 366.6K

487.07 kj/ kg

∆Hvap = 685128 kj/kg For H2O At 94.7 oC & 1.50bar CpH2o = 1.898 kj/kgK QH2o = 2232.293 *1898 *(354.15 -367.85) = -58.045 *10^3 kj ∆Hvap = 40683 kj/kmole Tc = 647.3 K

Tb = 385.106K

∆HVAP = 40683 * [(6473-354)/(6473-385.126)].38 = 42442.0561 kj/kmole =2356845 kj/lg For H2 At 94.70c & 1.5 bar CpH2 = 13.255 kj/kg K QH2

= 435.144 kg * 13225 * (354.15 – 367.85) = -82.464 * 103 kj

∑ m.Cp .∆ T = -410.677 *103 kg ∑mi ∆Hvap =12.702 * 106 kg QTOTAL = ∑mi CP,t ∆T + ∑mi . ∆Hvap = 12.3 *10^6

For H2O ∆T for water = (35-15)= 20 Cpwater =40182 kj/lg

Q = m*Cpwater *∆ T 682691.799kj = 40182 kj/kg * m *20 m=147.038 ton/day ∆H vap == 40683 *[(647.3 -354)/(647.3 -385.186)]0.38 =2356.845 kj/kgmole

7.3.7 For Scrubber: Qin = Qout Tref = 250C 455.144 * 14.419 *(81-25)+ 3528.708 *1.259*(81- 25) + 169.107 * 4.193 *(81-25) + 117.307 * 1.716 *(81-25) = 455.144 *14.401 *(70-25) + 3.485 *1229*(70-25) + 35.25.224 * 1249 *(T-25) + 27547.709 *4.183 *(T -25) + 117.307 * 1710 * (T-25) 4222.8319 = 18777.661 + (T-25)*755114.9 T = 28.10C

7.3.8 For Acetone column: ∆ Hvap = ∆Hf[(Tc -T)/(Tc- Tb)]0.38 Befor the application the boiling temp (Tb) for each of the component must be find at 1.1 bar pressur. For the boiling point calculation, ln psat = A - (B/T ) will be used Condenser: For Acetone - Pc= 47 bar

Tc= 508.1K P= 1.0133 bar T= 329.2K

ln1.0133= A-B/329.2

ln47= A-B/508.1

then A=10.91 B= 3587.3 At 1.1 bar pressure boiling point is- ln1.1= 10.91-(3587.3/Tb) Tb= 331.706K For ipa Pc=47.6 bar

Tc=508.3K

P= 1.0133 bar

T= 355.35K

ln1.0133= A-(B/355.35) ln47.6= A-(B/508.3)

A=12.807

B= 4546.375

At 1.1 bar pressure boiling point is ln1.1 = 12.807-(4546.375/ Tb)

Tb= 357.653K

Substituting the result to the first equation: ∆Hacetone= 29140*[(508.1-375.3) / (508.1-331.706) ]0.38 = 26160195 kj/ kmol ∆Hipa= 39858*[(508.3-375.3) / (508.3-357.653) ]0.38 ∆Hipa= 38014 kj/kmol For the mixture: ∆Hmix= 450.417*0.99+632.618*0.01 = 452.24 kj/kg MT=13263.045kg For the energy balance of the mixture: Q= mT*∆Hmix= 6*106 kj For Water: Pc= 220.5 bar

Tc= 647.3K P= 1.0133 bar T= 373.15K

ln1.0133= A-(B/373.15)

ln220.5= A-(B/647.3)

then A=12.72 B= 4743.39

At 1.1 bar pressure boiling point ln1.1= 12.72-(4743.39/Tb)

Tb=375.723K

Reboiler: ∆Hvap, aceton =29140 *[(508.1-378)/(508.1-331.706)]0.38 =25956.795 kj/kmole =446.951 kj/kg

FOR H2O ∆Hvap,H2O = 40683*[ (647.3-378)/(647.1-375.723)] 0.38 ∆Hvap, H2O = 40533.043kj/kgmole = 474.872 ∆Hvap, ipa = 39838 *[(508.3-378)/(508.3-337.653)]0.38 = 627.722 kj/kmole Yacetone = 4.364 * 10-4

yH2O = 0.955

∆H vap,mix= 446915 *6364 *10-4 + 674872 * 0.955 + 627.722*0.045 =672.945 kj/kg Balance; Q = mt . ∆ x vap mix = 30993.013*672.945 =20.86*106kj

7.3.9 IPA Column Tb ipa = 84.6530C

TbH2o = 102.7230C

yipa =0.045

∆Hf,H2o =40683kj/kmole

del Hf,ipa =39858kg/kmole

∆Hf,aceton = 29140 kj/kmole ∆Hvap,h2o =40294.194 kj/kmole= 2236.081kj/kg ∆Hvap,ipa = 38014 kj/kmole = 632.618kj/kg ∆Hvap,acetone = 26160.195 kj/kmole sience aceton is neglected YH2O = 0.13

Yipa = 0.87

∆Hvap,mix =2236.081*632.618 = 841.068 kj/kg For the energy balance for mixing Q = mT. ∆Hmix = 1941.326*841.068 =1.633 *106kj

Reboiler: ΔHvap, water = 40683 * [(647.3-384.5)/(647.1-375.723)]0.38 =40179.523 kj/kmole =2230.892kj/kg Q = mT.ΔH.vap,water = 2230.892*29407.290 = 65.604 *106kj

Preliminary equipment summary table for acetone process Equipment MOC POWER(Shaft) (KW) Efficiency

P-401 A/B P-402 A/B Carbon Steel Carbon steel 0.43 1.58 40%

_

_

_

32

20

1.90

_

_

3.30

_

_

_

0.80

0.75

_

_

2.40

2.25

_

_

Horizontal

Centrifugal/ Electric Op.Temreperatu 32 0 ( C) Pressure In 1.25 (bar) Pressure Out 3.10 (bar) Diameter(m) _

50%

V-402 Carbon steel _

_

Type/Drive

Height/Length (m) Orietionnt

V-401 Carbon steel _

Centifugal/ Electric 360

Intenals

_

_

_

Op. Pressure (bar) Maximum Allowable Op.Prs.(bar)

_

_

1.0

_

_

3.0

Horizontal SS Demister 1.63 3.2

Preliminary equipment summary table for acetone process (cont’d) Equipment MOC

T-401

H-401

Corban steel

Carbon steel

R-401 Carbon steel

Diameter

0.32

_

Width=4.57m

Height/Length(m)

3.20

_

Orientation

vertical

_

Depth=6.10m Height=5m Vertical

Internals

2.5m of packing (1”Ceremic Rashing Rings)

Op. Pressure (bar)

1.6

Maximum Allowable Op.prs.(bar)

3.2

Type Design Duty(Mj/h) Maximum Duty (Mj/h) Area Radiant (m2) Area Convectiv (m2)

_

3.0 Tube side 4.0

Fluidized bed Containing 7.5m3 of catalyst+7.8m3 of inert particle HTA=188m2 2.16 in bed 2.70 in tube 3.2 in bed 4.0 in bed

_

Fired heat

_

_

3436

3436

_

3800

_

_

13.0

_

_

37.0

_

Design Calculations Vertical Tube Vaporizer

Conditions Vapor leaves at 2.16 bar and 101C (saturated vapor). The shell side is assumed to be well mixed and at 101C. Heat Transfer Calculations 1. Regulate steam pressure to give a 10C temperature driving force T sat = 111C which corresponds to a P sat = 1.48 bar. 2. Heat Duty = 2850 MJ/h , Cpl = 2880 J/kgºC 3. Limiting heat transfer resistance is on boiling organic side, shell = 1000 W/m2 shell C.  Uh shell = 1000 W/m2C Tln = T = 10C

A=Q/U•Tlm (F=1) = 285010 6 /3600/1000/10 = 79.2 m2

1110c 1010c T

Shell side well mixed

320c Lenth along tubes

Note: over the range of ∆T = 7 to 250c it is known that hT 1/3 for boiling isopropanol.

Reactor Heat Transfer Calculations Assume that the fluidized bed is well mixed, thus the feed gas immediately heats to the reactor temperature of 350C. The molten salt approach temperature is 10C and therefore the molten salt temperature leaving the reactor is 360C. The temperature vs. Q diagram is shown below:

Tin 3600c 3500c

3500c

1010c Length of reactor Q=3436 MJ/h Cp,gas = 1780 J/kgºC (inlet) and 2500 J/kgºC (outlet) Use Hi TecTM molten salt with the following average physical properties: C p = 1.72 kJ/kg K,  = 1980 kg/m3,  = 2.1 cP, Maximum operating temperature = 1000C Use a T = 50C for the circulating salt  Tin = 410C Tlm= (410-360)/ln[(410-350)/(360-350)] = 27.9C

Energy balance on molten salt Q=MCpT 3436106 = (M)(1720)(50) M = 39,950 kg/h = 11.10 kg/s Vol flow of salt = M/ = 11.10/1980=5.60510-3 m3 /s Evaluation of U Fluidized Bed to tube wall, ho = 200 W/m2C [this will not change much with fluidization velocity in the range of 2 – 5 umf ] Inside heat transfer coefficient [molten salt to wall], h i = ? Assume that the velocity in the tubes is 2 ft/s = 0.61 m/s Use ½” diameter tube 18 BWG with inside diameter = 0.01021 m Re = (0.61)(0.01021)(1980)/(0.0021) =5872 Nu = 0.023Re 0.8 Pr 0.33 = (.023)(5872) 0.8 (17200.0021/0.606) 0.33 = 42.9 (actually Seider-Tate is only good for Re>10,000 - check this later) hi = Nu[k/d] = (42.9)(0.606)/(.01021) = 2546 W/m2C Below 500C molten salt should not foul so h f = very large Overall heat transfer coefficient, U = [d0/(dihi) + 1/ho]-1 = [1.244/2546+1/200]-1 = 182 W/m2C Heat transfer area, Ao = Q/Uo T lm = (343610)/[(3600)(182)(27.9)] = 188 m2

Check tube arrangement and molten salt velocity External surface area of 20 ft tubes =•doL = (3.142)(0.0127)(20)(0.3048) = 0.243 m2 Number of tubes = (188)/(0.243) = 773 Use 110 parallel sets of 7 tubes piped in series Cross sectional area (csa) for flow of molten salt = (110)(3.142)(0.01021)2/4 = 0.0090 m2 Velocity of molten salt in tubes = 5.60510-3/0.0090 = 0.622 m/s This gives Re = 5988 and Nu = 43.6 and hi = 2588 and U = 182 W/m 2C no change For Re