SynDesCo

Division of C. S. Howat & Associates Lawrence, Kansas 66049-1840

Memo To: Memo From: Memo Date:

C&PE 624 Students CSH March 14, 2005

Memo Number: 2 Re: Propylene Oxide Polymerization Project 2 This memo provides the basis for Project 2. I will issue a memo assigning groups shortly. You are to design the Polyol Reactor and supporting equipment to the specifications given. You have the opportunity to put in multiple reactors in series if you find it economical and/or safe. The primary emphasis for this project is risk reduction. You are to synthesize the reactor to the capacity limitations given. You have the flexibility to choose batch times and batch sizes to meet your goal. You are to use a rigorous simulation of this system. While MathCAD, Polymath and the like could be acceptable (particularly for preliminary design), those models will only be accurate if you do not take any shortcuts. The preferable alternative is Chemcad either through sequential unsteady state simulation or invoking the batch reactor module which we are authorized to use. The results are the typical material and energy balances, equipment sizes, batch campaign analysis, equipment costs and utility charges. The final simulation included in your report must be one based on the actual equipment sizes. I want the final simulation in rating mode. We will supply a preliminary flowsheet in Chemcad and Polymath. This will allow you to focus on the risk assessment, inherent safety and layers of protection of this system since David has done all of the preliminary programming. Process simulation using Chemcad is absolutely required. But, you need to invoke the full Conceptual Process Design Structure which includes inherent safety and process control. Further, when inherent safety isn't adequate, you must invoke appropriate layers of protection, independent and otherwise. I expect you do the following: hazard identification, event tree analyses, excursion analysis (simulations), LOPA, layer of protection installation including but not limited to reliefs, flares, dikes etc., consequence estimation and probability reduction. You must

also include a plant layout and elevation including control building and P&I. I expect plan and elevation drawings. The final product from this work will be a full process design report. The groups will also make a final presentation of their design and safety analysis. This will be on the last Monday of classes. Found on the last page of this memo is a sketch of the reactor. We should all recognize that this is just a conceptual, back of the envelope process design. We should expect that there will be considerable modifications to this reactor system as we begin to analyze the process design synthesis hierarchy discussed in design and found on the lecture notes CD. Despite this, this is the beginning point. The current industrial process for manufacturing polyethers is a semi-batch process. You are asked to design a semi-batch reactor system to manufacture a 3000 molecular weight, straight propylene oxide polyether. The manufacturing process for producing this polyether is to add propylene oxide to the multiple functional alcohol, glycerin. The catalyst potassium hydroxide must be present for the reaction to occur. The first step in the preparation of this polyether is to activate glycerin with potassium hydroxide. The activated glycerin is actually a unique chemical species, specifically potassium glycerate. The generation of an activated initiator and the reaction with propylene oxide is illustrated in Figure 1.

CH OH
2

CH OK
2 KOH

CH 2OH CH OH
2 Glycerin

CH 2OH CH OH
2 Activated Initiator

H O 2

(1)

O m ROK Abbreviation for Activated initator n CH 2

CH CH3

CH3 m R( OCH - CH ) OK 2 n Polyether

(2)

Propylene Oxide

Figure 1

Polyether Reactions

You will work with both reactions. Reaction (1) is fast. There are no heat effects. The potassium migrates within the reaction mass from one hydroxyl to another within a single molecule and

from one molecule to another. Potassium does not saturate the available hydroxyls. The final product has approximately equal length chains on each molecule. The molecular weight of this polyether should be approximately 3000. Your design should facilitate a six step process: 1) Add glycerin to the reactor and then add the aqueous potassium hydroxide catalyst (3 wt % KOH or 0.03 X [lb. of glycerin + lb. of KOH]) to the reactor; 2) Heat the mass to the reaction temperature; 3) Remove the water down to 0.5% water by vacuum stripping; 4) Add the propylene oxide, remove the heat of the exothermic reaction to control the temperature, and continue the addition to form the 3000 mol. wt. product; 5) React, at the end of the addition period, the free oxide down to 1%; and, 6) Transfer the hot product to the next process step. A batch reactor cannot be used for this polyether reaction because it is prohibitively hazardous; that is, the large amounts of free oxide at the beginning of the reaction could easily become an uncontrolled runaway reaction. Industry uses a semi-batch reactor; i.e. PO is added to the reactor at a uniform rate over the addition period to limit the amount of free propylene oxide (in the liquid phase) in the reactor. Flexibility in processing eliminates any advantages that a continuous reactor might have. Design Basis 1. Capacity: 100 million pounds per year of a 3000 mol. wt. polyether 2. Chemistry: Start with glycerin, catalyst, and propylene oxide. All of the KOH reacts with the glycerol. As a design basis, the potassium hydroxide is limited to 3 % because potassium hydroxide may precipitate as a solid when the concentration exceeds approximately this 3% limit. 3. Reactor Configuration. Semi-batch 4. Utilities: Steam ( 50psig, 312F) $3.50/1000lb (150psig, 390F) $4.25/1000lb (400psig, 450F) $6.00/1000lb Cooling Water $0.05/1000 gal 90F supply, 120F return (max) Summer conditions Electricity $0.045/kW hr Condensate/Boiler Feed Water $0.70/1000 gal Waste Disposal $0.003/lb treated Fuel $3.50/106 Btu Heat Transfer Fluid $10/gal make-up 20% charge over fuel value Refrigeration Propane at -40F; $7.00/106 Btus Nitrogen Price unknown 5. Process conditions and constraints: Maximum temperature of the 260 OF (it is known that the product degrades at or above this temperature). Minimum temperature of 212oF. Materials of construction: stainless steel. Use stainless steel.

6. Basis for investments: Economics follow the same guidelines used in Design I, i.e. Guthrie or Chemcad. Physical Properties - Kinetics The kinetics of a propylene oxide to polyether reaction that is catalyzed with potassium is shown below: dCO r= = kCK C O (1) dt 15099 k = 9.84 1011 exp T poundstotal k= ( pounds potasium ) ( hour ) where T is degrees Rankin, CK and CO are weight fraction of potassium (not potassium hydroxide) and propylene oxide, respectively, and r is: poundsO r= ( poundstotal )( hour ) The standard reaction sequence for this reaction in a semi-batch reactor is divided into two steps or periods: the addition period (propylene oxide is added and reaction occurs) 0 t A the reaction period (propylene oxide feed is shut off and reaction continues) In this semi-batch reactor, the catalyst concentration changes as the oxide is added as shown in Equations 2 and 2.
CK = CK 1WB Wtotal WO t A

(2) (3)

Wtotal = WB +

where: CK1 is the pounds of potassium per pound of glycerin plus potassium WB is the total pounds of glycerin plus the pounds of potassium WO is the total pounds of propylene oxide added over the entire addition period A is the addition period in hours. The addition rate is constant. The WO is the total amount of oxide that is required to manufacture a 3000 molecular weight polyether. During the addition period the maximum free PO (C0) is limited to 20 % (this is a design constraint). The reaction sequence is to add all of the required oxide during the addition period using Equation 4, followed by reacting the oxide down to the 1 % level during the reaction period using Equation 5.
4

Equation 7 and 8 are used to compute the oxide concentration in the liquid phase. The oxide in the vapor phase is a function of its partial pressure. Assume that the oxide in the vapor phase is a part of the 1 % free oxide that leaves the reactor at the end of the reaction period.
dCO (WO / A ) kCO CK 1WB CO (WO / A) = dt Wtotal Wtotal Wtotal Addition Reaction Dilution

(4)

Note that Equation 4 ignores the vapor phase mass. During the reaction period, all the oxide has been added, therefore: CK1WB C W CK = = K1 B WB + (WO / A ) A WB + WO and
dCO kC C W = O K1 B dt WB + WO

(5)

We use weight fraction instead of mole fraction because in this polymerization reaction the moles of the product (polymer) is constant throughout the entire reaction plus weight fraction is normal industrial practice. Physical Properties For hand calculations or simple input into math solvers, use these physical properties. Use reasonably close values for Chemcad simulations. Component Property Units 80 O C 100 O C 140 O C 180 O C PO Vapor psia 60 100 220 440 Pressure Polymer Vapor psia 0 0 0 0 Pressure PO Heat cal/g/OC 0.33 0.34 0.37 0.42 Capacity Polymer Heat cal/g/OC 1.0 1.1 1.2 1.3 Capacity PO Heat of cal/g 120 98 82 55 Vaporization Polymer Heat of cal/g 0 0 0 0 Vaporization PO Density g/cc 0.76 0.74 0.66 0.55 Polymer Density g/cc 0.90 0.85 0.80 0.75 PO Viscosity Centipoises 0.25 0.25 0.25 0.25 Polymer Viscosity Centipoises 300 250 200 150 O PO Thermal cal/cm/s/ C 35 33 32 32 Conductivity (x 10-5)
5

Polymer PO Polymer

Thermal cal/cm/s/OC Conductivity (x 10-5) Heat Transfer Coefficient BTU/hr/ft2/O F Heat Transfer Coefficient BTU/hr/ft2/O F

50

45

40

35

50 20

60 25

70 30

80 35

The heat of reaction is 660 BTU/pound of PO. Flammability Regions; see Figure 3

100

20
per cen t

80
ene pyl Pro ent erc ep lum , vo ide Ox

ir ric A met chio Stoi

Ox yge n, v olu me

40

60

60

40

UFL = 36 %

ble ma am t Fl No

Flammable 80 LFL = 2.3 % 100 0 20

20

Not Flammable

0 100

40 60 Nitrogen, volume percent

80

Figure 3 Flammability Limits of Propylene Oxide

Assume that the polymer has no vapor pressure. The partial pressure of propylene oxide over the reacting mixture (P0) can be approximated using: P0 = 2.175 C0 P0Sat (6)
6

where P0Sat is the propylene oxide vapor pressure; P0 and P0Sat have the same units. When handling PO in a reactor, the vapor phase over the reaction mass needs to be controlled to below the flammability region by adding nitrogen. See Figure 3. When removing water by evaporation, you are to assume that the partial pressure is equal to the weight fraction times the vapor pressure. Assume that the density of the reaction mixture is constant throughout the entire reaction cycle (addition and reaction periods). Assume a mixture density of 57-lb./cu. ft.

KOH(aq) To Additional Equipment Glycerin To Additional Equipment Propylene Oxide H PA TA H CWS COND TC STM CWR

KURATA THERMODYNAMICS LABORATORY UNIVERSITY OF KANSAS

Preliminary Proplyene Oxide Polymerization Reactor For Discussion Purposes Only

JOB:

C&PE 624

BY:

C. S. Howat

DATE:

3/14/05

DWG:

REV: