5

Glycerine
Keith Schroeder
CC Engineering, Ltd.

1. INTRODUCTION 1.1. Chemistry Glycerine (sometimes called glycerin) is the name of the commercial product consisting of glycerol and a small amount of water. Glycerol is actually trihydric alcohol C2H5(OH)3, which is more accurately named 1,2,3-propanetriol. Its chemical structure is shown in the formulas given below. Much of the naturally produced (as opposed to synthetic) glycerine is a coproduct of saponication of fats using caustic soda. The reaction is (1)
H2 C O

R1

C O

O H2 C CH OH H2 C

R1

C O

Na

R2

C O

CH C H2 C H2

C R3

+ 3NaOH

HO

H2 OH + R2 C C O Na O R3 H2 C C O O Na

Triacylglycerol

Cautic

Glycerol

Soap

1
Baileys Industrial Oil and Fat Products, Sixth Edition, Six Volume Set. Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.

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The resulting coproduct stream, called spent lye, typically contains 1025% glycerol (depending on the production process) as well as contaminants such as salt (NaCl), water, and various organics usually known as matter organic nonglycerol (MONG). Probably the more abundant source of glycerol is the hydrolysis (splitting) of fats and oils, which produces fatty acid and glycerol. This reaction is (1)
H2 C OH

R1

C O

O H O H H2 C CH OH H2 C

R1

C O

R2

C O

CH C H2 C H2

C R3

+ 3

HO

OH + R 2

H2 C

C O

OH

R3 Triacylglycerol Glycerol

H2 C

C O

OH

Water

Fatty Acid

2 The concentration of glycerol in the resulting sweetwater is 1018% and gets its name from the characteristic sweet taste imparted by the glycerine (2). Glycerin is also recovered as the coproduct of methyl esters (from fats and oils) and fatty alkanolamides; the amount produced from these sources has historically been relatively small but has increased signicantly due to worldwide construction of fatty alcohol plants and, more recently, methyl ester biodiesel plants. There are some other interesting sources of glycerol, which will be discussed below. This Chapter concentrates on the recovery of glycerol from soap lyes (water and glycerol from soap making) and sweetwaters, as they represent the majority of the recovery applications. Synthetic glycerine will not be covered, as it is not derived from fats and oils. 1.2. History of Glycerine Processing Glycerine was rst identied in 1770 by Scheele, who produced it by heating olive oil and litharge. In 1784, he observed that the same substance could be produced from other vegetable oils and animal fats, such as lard and butter. He called this new substance the sweet principle of fats due to glycerines characteristic sweet taste (3). In 1811, Chevreul, while studying Sheeles Sweet, as it had come to be called, coined the modern name glycerine from the Greek word glyceros, meaning sweet. After closely studying glycerol, he was awarded the rst patent relating to its manufacture in 1823. Chevreul also distinguished himself by doing some important early research work on fats and soaps. By 1836, Pelouze had determined the formula for glycerol, and nally Berthlot and Luce published the structural formula in 1883 (4). Nitroglycerine was discovered in 1847 by Sobrero. This compound is dangerously unstable, which limited its potential for commercial applications. In 1863,

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Alfred Nobel demonstrated nitroglycerines explosive capabilities, and in 1866 he invented dynamite. He followed that discovery by the invention of blasting gelatin, a mixture of nitroglycerine and nitrocellulose, in 1875. Nobels commercial success and humanitarian efforts are well known, but equally important was the vital role his inventions played in advancing the Industrial Revolution. The demand for his explosive products helped to form a large and growing demand for glycerine. The history of glycerine is closely related to the history of soap making because one of the earliest commercial sources of glycerine was recovery from soap lyes, and soap lyes continue to be a common feed stock for glycerine recovery today. In the early 1870s, the rst U.S. patent for the recovery of glycerine from soap lyes by distillation was issued. The process was further developed by Runcorn in 1883. In the decades following, the soap industry began recovering glycerine from the waste streams of their soap-making operations on a relatively large scale, thus making glycerine a readily available commodity. A prominent source of glycerine is from the sweetwaters of fat splitting, which initially came from the manufacture of stearine for candle making (3). The famous Twitchell process for fat splitting was developed at the turn of the century. Twitchell developed a process for splitting fat using a catalyst and dilute sulfuric acid that produced an acceptable product (5). This was followed by high-pressure autoclave splitting, which relied on high-pressure steam for hydrolysis of fat and produced a superior product. Todays modern fat-splitting plants, using stainless steel columns with counter current ow of fatty acid and sweetwater, are the latest development in the splitting process. The high-quality sweetwaters obtained allow efcient rening into the high-purity grades of glycerine used today. 1.3. Economics The consumption of glycerine has remained strong over the years, and trends indicate that this is not likely to end soon. Although glycerine is a mature product with a multitude of uses that continue to increase, the Soap and Detergent Association is trying to develop new uses for the product. In 2003, the market price of natural USP glycerine in the United States was at $0.550.75/lb., but has been as low as $0.25/lb. and as high as $1.00/lb. throughout the 1990s. The U.S. production of glycerine is approximately 600 million pounds (270 million kg) per year and grows 25% annually. Imports add about 10% more supply, while only a small amount is exported. The world glycerine production is well over one billion pounds (450 million kg) per year (6). Many new fatty acid splitting facilities have come online, especially in Asia, where palm and coconut plantations are plentiful. China continues to add capacity as more products come into demand. Synthetic glycerine is produced in the United States by a single supplier. There are only three producers worldwide. The strong supply of natural glycerine and the rising cost of feedstock (propylene) are likely to pressure producers to revise their production. Also, some epichlorohydrin, an intermediate product, can be diverted into other products of potentially high protability. Synthetic glycerine may contain

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small quantities of chlorinated hydrocarbons, which has caused some concern in the health care applications. 2. PROCESSING PRINCIPALS AND DETAILS 2.1. Sources of Glycerine Natural glycerine is essentially a coproduct of certain processes performed on animal or vegetable fats and oils: 1. Fat splitting under high pressure and temperature, in the presence of water, to obtain fatty acids and sweetwater glycerine. The fat-splitting process provides the majority of glycerine in the United States. Processing of splitter sweetwater requires less intensive processing and lower equipment costs because salt content is not high and common stainless steels can be used as the material of construction. 2. Saponication of fats with sodium hydroxide (caustic soda, NaOH), yielding spent lyes containing glycerol, water, sodium chloride (NaCl), and other impurities; depending on the process for saponication and soap washing, the concentration of the glycerol varies greatly. The presence of high salt levels requires higher cost metallurgies as is discussed later in this chapter. The chemical reactions for these processes were given earlier in formulas 1 and 2. 3. Transesterication of fats, typically with methanol, using sodium methoxide as a catalyst, to produce methyl esters and glycerol (7). The chemical reaction for this process is as follows:
R1 C O R2 C O O C H2 CH C H2 O C R3 Methanol Catalyst Glycerol Methyl Ester O + 3 H3C O H O
NaOCH3

HO

H2 C CH OH

H2 C

OH + 3RCOOCH 3

Triacylglycerol

3 Although the initial chemical reactions for the above processes yield high theoretical concentrations of glycerol, subsequent washing steps dilute the glycerol to typical values:
Fat Splitting Saponication, kettle Saponication, continuous Transesterication 1018% 1015% 2025% 2530%

Synthetic glycerine is produced (Dow process) by chlorinating propylene to allyl chloride, converting this to dichlorohydrin, which is then converted to glycerine

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195

through the addition of small amounts of dilute sodium hydroxide and sodium carbonate (8). 2.2. Pretreatment Techniques The purpose for treatment of spent soap lyes or sweetwater is to prepare the feedstock for glycerine recovery by removing impurities that cause operating problems in subsequent processing steps, resulting in a poor-quality product. In the handling of dilute glycerol feedstocks, care must be taken to prevent fermentation, which can cause serious loss of glycerine due to the formation of trimethylene glycol (TMG), (1,3-propyleneglycol), gases, and acids during decomposition. Fermentation can occur in glycerol solutions of 25% by wt. held at temperatures of 125 F or less. Glycerol solutions above 25% prevent bacterial growth as does the presence of salt or caustic. Furthermore, these gases produced by the bacteria may cause problems in evaporation of the lyes, and any TMG can be difcult to separate from the glycerine by distillation due to their similar vapor-pressure characteristics. Excess impurities in soap lye crudes can act as nucleation sites for crystal growth in the evaporator, and aid the growth of larger, more easily separated salt crystals. Spent soap lyes, as they are drawn from the continuous saponication area or soap kettles, consist primarily of glycerine, sodium chloride, and water as well as small quantities of sodium hydroxide, sodium sulfate, sodium carbonate, soap, and fatty acids, and also some albuminous and oleaginous matter. To remove these impurities, the soap lye is generally treated in batches. First, a cooling and settling step is used to separate the soaps and fatty acids. The fatty acids are less soluble at lower temperatures and rise to the surface, where they can be removed by skimming. Other heavy materials will settle to the bottom and remain in the tank until it is cleaned periodically. This skimming of the fatty acid is best done in the soap plant before the lyes are transferred to the treatment plant (Figure 1).
First filter press Second filter press

Cake

Caustic soda Carbon from bleaching columns

Cake

Acid Alum Air

Soap lye from skimming tanks

First treatment Air tank agitator

Second Air treatment tank agitator

Filtrate tank

Figure 1. Batch soap lye treatment owsheet. Courtesy of Crown Iron Works Co. (9).

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Second, the skimmed and settled lye is transferred to the rst treatment tank. It is good practice to heat the lye to 5060 C during the transfer pumping or in the treatment tank; the treatment process is most efcient at this temperature. In the rst tank, the lye is acidulated to pH 4.65.0 with sulfuric or hydrochloric acid. Hydrochloric acid is recommended to avoid the formation of sulfates. These sulfates can build up in the recovered salt, which is returned to the soap-making area where sulfates are not desirable. This acidulation step liberates fatty acids, which may be skimmed, as most are insoluble in water. Third, a coagulant may be added to cause the residual fatty acids to form insoluble soaps, which coagulate. The pH is adjusted to 4.5. At the same time, compressed air is bubbled into the tank and is used for mixing and to ensure oxidation. The coagulant is usually either aluminum sulfate or ferric chloride. If ferric chloride is used, the air agitation is particularly needed to oxidize the iron to its ferric state (10). Although ferric chloride is more difcult to handle than aluminum sulfate, it is strongly corrosive to iron, and is more expensive, but is usually preferred because the salts formed using aluminum sulfate introduce additional sulfates. The precipitates of either aluminum hydroxide or ferric hydroxide will adsorb other impurities such as fatty acids or proteinaceous matter. The chemical reactions for these two precipitants neutralizing the excess sodium hydroxide are described below. It takes 1 kg of ferric chloride to neutralize approximately 0.44 kg of sodium hydroxide, according to the following formula: FeCl3  6H2 O 3NaOH ! FeOH3 3NaCl 6H2 O 4

Exactly 0.36 kg of sodium hydroxide is required to neutralize 1 kg of aluminum sulfate according to the following reaction: Al2 SO4 3  18H2 O 6NaOH ! 2AlOH3 3Na2 SO4 3NaSO4 18H2 O

The composition of the rst treatment can be checked by ltering a sample in the laboratory and then adding a small amount of dilute ferric chloride or aluminum sulfate to the ltrate. Any precipitate indicates that the reaction has not been taken to completion (1113). The contents of the rst treatment tank are then ltered, typically in an open plate and frame lter. The lter cake is discharged periodically for disposal. Filter aid can be added, if required. Finally, the ltrate from the rst press ows to the second treatment tank, where sodium hydroxide is used to adjust the pH to approximately 9.0. Compressed air is again used to agitate and oxidize the batch, before ltration through a second press. A smaller amount of precipitate is produced in this step, and therefore the lter can be sized for less area. In addition, spent bleaching carbon from the glycerine distillation plant can be added at this point, with the goal of recovering some residual glycerine into the treated lye.

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197

Treatment can also be carried out using a continuous or semicontinuous operation. In each case, accurate, in-line pH measurement is needed to control the addition of the treatment chemicals. Filtration can be accomplished on a semicontinuous basis using plate and frame lters by sizing the treatment tanks to allow surge capacity for lter cleanout intervals, or a continuous vacuum drum lter can be used. These processes lend themselves to the large capacity plants. Treatment of sweetwaters is less involved than the treatment of soap lyes as described above. The purpose of treating sweetwaters is to remove any unreacted fats and to prevent bacteriological growth in the glycerine. Typically, the sweetwater is settled for several hours to allow any free fats and fatty acids to rise to the surface, where they are skimmed off the top. Then, using air agitation, an excess of lime is added to neutralize the fatty acids still present. Excess lime is calculated as 0.23% of calcium oxide, and the batch must be adjusted appropriately to obtain this excess (1). The sweetwater is then ltered. Sodium carbonate is sometimes used to remove the calcium excess as carbonate. Some processes treat using barium chloride and sulfuric acid, which is a more effective and expensive process. Also, it has been shown that addition of a small amount of polyelectrolyte, such as used in water treatment, will signicantly improve the quality of the crude glycerine (10). An alternative method for treating sweetwater, implemented in many facilities, is to settle the sweetwater for approximately 24 h at 8090 C and a pH of 45. Phosphoric acid is sometimes used to help break any emulsion, but this is not always required. The fats and fatty acids are decanted from the top of the sweetwater and returned to the splitter feed for recycle. The settled sweetwater is then sent to the evaporators for concentration. This alternative method requires two tanks, one for settling and one for collecting the sweetwater. The tanks are alternated every 24 h to run continuously. 2.3. Evaporation
2.3.1. Overview Following treatment, the soap lyes or sweetwaters are concen-

trated to 8088% glycerol through an evaporation process. This is an energyintensive process and, depending on the plants capacity and energy costs, can have either a single-, double-, or even triple-effect evaporator. The primary design consideration is the amount of water to be evaporated. With soap lyes, the secondary consideration is the method for handling the salt that precipitates as the water is evaporated. The amount of water to be evaporated is calculated from the amount of liquor (soap lye or sweetwater) and its glycerol concentration. Table 1 shows the

TABLE 1. Example of Concentrations in Soap Lye and Crude Glycerine. Substance Glycerol Salt Water Percent 10 11 79 Weight (kg) 100 110 790 Percent 80 9 11 Weight (kg) 100 14 16 Change None 96 kg Salt 774 kg Water

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GLYCERINE

concentrations that occur, starting with a dilute soap lye and concentrating to 80% crude glycerine. The table does not include losses that occur. Two general types of evaporators are used, and their names refer to the type of circulation used to transfer heat to the liquor for evaporating the water. Natural circulation evaporators rely on a thermosiphon to circulate liquors while forced circulation units use a pump to achieve the required circulation. The heating tubes may be inside or outside the evaporator body, but most designs, especially the older calandria style evaporators, use internal tubes for heating (Figure 2). Forced circulation heating is used for most new evaporation plants for several reasons. Primarily, pumping the liquor allows the selection of a higher owrate and velocity than can be achieved by natural convection, which improves heat transfer, thus reducing the surface area required for heating and evaporation of water. Higher velocities in the tubes also reduce fouling and scaling of the tube surfaces. One drawback to forced circulation is the increase in energy consumption from pump motors. In addition, if the velocity is too high, there can be problems with crystallization and crystal growth when processing soap lye.
Two stage air ejector vacuum pump

Barometric condenser

Flick centrifugal catchall and entrainment separator

Sight glass

Effective baffles Upward flow of vapors through tubes Outside steam connection

Downward flow of liquor in larger downcomer Feed line Improved catchall return Outside condensation drain

Salt extractor Hot well

Figure 2. Calandria-style single-effect evaportor with ick separator. Courtesy of Crown Iron Works Co. (9).

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199

Evaporation can be either single effect or multiple effect, depending on the number of evaporation stages used. Single-effect evaporation offers the simplest process and minimum equipment investment. In a single-effect evaporator, a batch of dilute glycerine can be evaporated to a half crude state with a concentration of 4050% glycerol and stored. When sufcient quantities of half crude are available, it is processed to full crude (80% concentration). The steam economy for a single-effect evaporator is 0.81.0 kg of water evaporated for each kilogram of steam used. Single-effect evaporators, operating as a semicontinuous unit, as described above, have been used with some frequency in the past, but are now primarily used for small plants because of the economy and convenience of operation inherent in continuous multieffect plants. Multiple-effect evaporation is accomplished by joining two or more evaporators in series using the heat in the waste vapor from one effect to heat the subsequent effect. Live steam is added in the rst effect only. The difference in the working pressure in each effect (each effect working at a lower pressure than the previous one) allows the use of lower pressure heating steam in the following effects. This pressure difference also allows transfer of liquor from one effect to the other. As a rough guideline, it can be assumed that approximately 0.8 kg of water can be evaporated per kilogram of steam for each evaporator effect. Thus, one effect will evaporate 0.8 kg of water per kilogram of steam, two effects will evaporate 1.6 kg, and three effects will evaporate 2.4 kg (14). Multiple-effect evaporators are most often used in glycerine recovery plants of medium to large size, with the typical plant having a two-effect evaporator. The user must calculate and compare the savings in steam use for operating additional effects against the additional equipment and maintenance costs as well as space and operational complexity for additional effects. Additional economy in steam consumption can be obtained through implementation of thermal vapor recompression (TVR). Water vapor from the evaporator is captured and recompressed in a thermocompressor, using high-pressure motive steam, so the vapor can be condensed in the rst effects heat exchanger. The pressure after the thermocompressor is between that of the water vapor and motive steam. Only a portion of the vapor is recompressed in the thermocompressor, with the remaining vapor used to heat the subsequent effect. The thermocompressor can be used on a single-effect evaporator or on the rst effect of multieffect units. This equipment favors low T in the heat exchanger to minimize the compression ratio. The thermocompression effect will add additional economy equivalent to at least half of an additional evaporation effect at a modest extra cost, typically just a fraction of the cost of an additional effect. Recovered condensate can be economized by using it to preheat incoming liquor (15). The operation of a two-effect, continuous evaporator is shown in Figure 3. Treated lye or sweetwater is fed continuously and regeneratively heated with condensates coming from the heaters. Water is evaporated in the rst evaporation chamber, which is kept at a pressure slightly above atmospheric pressure (46 psig), using heat provided by the thermocompressor. The thermocompressor takes part of the vapor from the rst-effect heater and recompresses it to increase its temperature

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H.P. steam Thermocompressor H.P. steam Vacuum system C.W. C.W.

First effect evaporator

Steam

Second effect evaporator

Air Hot water Air Steam

Hot water

Salt receiver

Salt receiver

Salt extractor Liquor feed Economizer Salt

Salt extractor

Condensate system Condensate

Crude glycerine

Hotwell

Figure 3. Double-effect evaporator with thermocompressor owsheet. Courtesy of Crown Iron Works Co. (9).

and pressure. The remaining vapors go to heat the second effect. In the rst evaporator, about 60% of the water is evaporated (In a three-effect evaporator, the rst effect evaporates about 4550% of the water, with the remaining two effects roughly splitting the amount of water evaporated). The liquor from the rst effect is then fed by gravity and by pressure difference to the second effect, which is under a slight vacuum (115 mm Hg absolute). There, it is concentrated to 80% for soap lyes or up to 88% for sweetwater crude (containing no salt) and then pumped to crude glycerine storage. As soap lyes are concentrated, the concentration increases until the dissolved salts begin to come out of solution and form crystals. These crystals grow and settle in the bottom of the evaporator, where they are removed as described below. Some salt crystals will drop out in the rst effect, but most of the salt will drop in the second effect. The proportions are determined by several factors, including the operation of the evaporators, the characteristics of the soap lye, and the concentrations reached in each effect. The solubility of sodium chloride in glycerol is relatively unaffected by temperature, however.
2.3.2. Entrainment Separation

Some kind of entrainment separation is necessary to reduce losses of glycerine entrained in the vapor stream from each evaporator. Control of the vapor velocity by proper evaporator and duct sizing will minimize the amount of entrainment. An entrainment separator should be installed at the outlet of each evaporator body, and the glycerol recovered should be returned

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201

to its evaporator. The separator is usually of the cyclonic type, which can be equipped with internal impingement bafes (Flick type). Mesh- or bafe-type separators are possible, but care must be taken to prevent any buildup on the internal components, which would cause excessive pressure drop. Figure 2 shows a Flick separator installed. As the glycerol concentration increases during evaporation of soap lyes, salt crystals begin to form as the liquor saturates. These salt crystals, as they grow, will tend to sink to the cone in the bottom of the evaporator. Proper treatment and ltration of the soap lye is important to ensure proper crystal growth in this stage because impurities in the soap lye can hamper the growth of crystals. There are several methods to recover the salt from the evaporators, and all of the methods address the need to wash as much glycerol from the salt as practical. Washing is done with water and sometimes lyes, with the purpose of recovering glycerol that is removed with the salt. The wash liquor is subsequently returned to the treatment plant. Obviously, any water that is added must be evaporated, so an economic balance must be achieved between glycerol loss and water to be evaporated.
2.3.3. Salt Removal All salt removal systems start with the salt crystals (and

some glycerol) being removed from the evaporator, through an open valve, and collected in a salt receiver or directly into a salt extractor, depending on the conguration of the plant. If a salt receiver is used, the salt level is allowed to build up to a certain level, determined by observation through a sight glass or by time interval. Then the valve above the receiver is closed, the one below it is opened, and the salt slurry is blown to a salt extractor using compressed air or steam. Salt extractors are usually provided in pairs and used alternatively. The valves are then returned to their original positions for recovering salt. If salt receivers are not used, the salt is dropped directly into the salt extractor, in a similar manner as described above. Salt receivers are placed below each evaporator and under a salt settling tank (Figure 4). The salt extractor is tted with a screen to catch the salt and allow the liquor to pass out of the extractor by being returned to the salt receiver from which it originated. Several batches of salt from the receivers are accumulated in a salt extractor before the salt is removed. The salt is then washed to remove glycerol that is contained with the salt. The wash uid can be soap lye for the rst wash and water for subsequent washes. The wash water is returned to the treatment plant. Some plants remove the salt manually by shoveling it out through a door in the salt extractor. Before this salt is removed, it is dried in the extractor by steaming. Removal of dried salt can be a labor-intensive practice. The salt is usually returned to the soap plant, where it is dissolved into brine to be used again in the soapmaking operation. Other plants will dissolve the salt in the salt extractor. There, after the nal wash, water is introduced into the extractor, the salt is dissolved, and the brine is pumped back to the soap plant. Centrifugal separation can be used to extract and wash the salt obtained in the evaporation process. The centrifuge used for this process can be either a continuous

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Barometric condenser

Second effect evaporator First effect

Flick separator

Flick evaporator separator

Salt receivers

Figure 4. Double-effect evaporation with forced circulation and external heating. Courtesy of Crown Iron Works Co. (9).

or a batch operation model. The continuous model typically offers higher capacity and efciency, but at a higher cost. The salt slurry is fed to the centrifuge in a similar fashion as described above for feeding a salt extractor, but there is typically a slurry tank ahead of the centrifuge. A batch centrifuge has a basket with a ne screen (or cloth bag), which catches the salt while the liquor is drained back to the evaporation plant. The centrifuge is fed with salt slurry from the evaporators and is spun until the basket is full of salt. Then the salt is washed with treated lye or water to remove glycerol contained with the salt, and then the salt is removed. The salt can be removed by mechanical means or dissolved for reuse in the saponication plant. In the case of the cloth-bag type centrifuge, the entire bag of salt is lifted out of the basket, and a new bag is installed. The salt is then dissolved from the bag in a separate tank, freeing up the centrifuge for salt extraction. Batch centrifuges require a relatively high amount of operator attention. The continuous centrifuge is fed with salt slurry from the evaporators. Figure 5 shows the main components and operating principles for this type of unit. The salt slurry from the evaporators is continuously fed from the top inlet where it falls between the helicoidal blades of the extractor and the conical basket. The basket

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Figure 5. Continuous centrifuge operation diagram. 1, Frame; 2, discharge channel; 3, conical basket; 4, screen; 5, helicoidal blades; 6, reduction gear unit; 7, electric motor. Courtesy of Guinard Centrifugation. (16).

has a specially designed, slotted screen installed over it to contain the salt crystals. The slurry experiences a centrifugal load of 300500 g, due to the spinning of the basket. The liquid passes through the screen and is collected in the discharge channel. The extractor rotates at a positive differential speed relative to the screen, which pushes the salt that has settled toward the bottom of the screen where it is discharged out the bottom of the machines frame. The salt can be continuously washed while it is on the screen. Some machines have more than one washing zone, allowing the use of different wash liquor concentrations for more efcient washing. The efciency of salt removal depends on crystal size. For best results, the crystals should be at least 100 mg in size (17).
2.3.4. Fat Settling and Saponication For sweetwaters that have been pre-

treated by settling alone, the concentrated crude glycerine will require an additional step before the rening step. In this step, any excess fat that has been forced out of the solution during evaporation requires decanting and saponication. In the crude glycerine settling step, the crude is fed to one of two (or more) tanks. The crude glycerine is maintained at 8090 C and the fat and fatty acids are allowed to rise to the top of the crude glycerine for a 24-h period. As with the sweetwater settling step, alternate tanks are used in parallel. One tank is for collecting the concentrated crude glycerine and one tank is used for settling the crude glycerine. After settling, the crude glycerine is drawn off to another set of tanks for saponication.

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The saponication step involves reacting any fats and fatty acids remaining in the crude concentrated sweetwater with sodium hydroxide. The resulting sodium soap will be removed with the foots, or pitch, that make up the still bottoms. A sample of crude glycerine is analyzed for saponication (SAP) value using the AOCS Ofcial Method Cd 3-25 analytical test (18). The SAP value is then converted to a sodium hydroxide basis. This number represents the pounds (or kg) of pure sodium hydroxide that must be added to 1000 pounds (or kg) of the crude glycerine. Typically, an excess of sodium hydroxide is added based on the batch size. This excess is usually in the range of 0.10.25%. This excess must be minimized because excess sodium hydroxide will generate polyglycerols in the distillation step. Empirical evaluations have shown approximately seven pounds (or kg) of glycerine are lost as polyglycerols for every pound (or kg) of excess sodium hydroxide present in the crude glycerine. The saponication reaction is carried out at a temperature of 90 C with agitation. This process is typically accomplished on a batch basis using alternate tanks to simultaneously carry out the reaction in one tank and feed the distillation system with reacted crude glycerine from a second tank. The system can be run on a continuous basis with this two (or more) tank system.
2.3.5. Vacuum System

The vacuum system for the evaporation plant plays a dual role by condensing the water evaporated and providing the required vacuum of approximately 50 mm Hg absolute pressure. The vapor-condensing function and initial vacuum device is either a barometric condenser, using water spray and a barometric leg discharging into a hotwell, or a water-cooled surface condenser. Despite a somewhat higher equipment cost, the surface condenser system offers several signicant advantages over a barometric condenser: (1) Any glycerine in the vapor that is condensed is recovered and is not lost into the hotwell water, and, (2) The surface condenser is cooled with clean water, typically circulated from a cooling tower. In a barometric system, the spray water becomes contaminated, requiring a separate cooling tower system from the clean cooling water used elsewhere in the plant. The dirty cooling tower water must be periodically cleaned or replaced to prevent excess buildup and fouling in the cooling system. Following the condensing section, and depending on the utility situation at the plant site, either a liquid ring vacuum pump or a two-stage steam jet with an intercondenser is used. A booster ejector is not required to maintain the vacuum level required for evaporation.

2.4. Rening of Glycerin

2.4.1. Distillation

Distillation of glycerine is accomplished through distillation with steam, under high vacuum, and at elevated temperatures. The vapor pressure of glycerine at atmospheric pressure is 760 mm Hg at 290 C, and because glycerol will begin to polymerize at approximately 200 C, distillation must occur at low pressure. When distilling with steam, the partial pressure of the glycerol is reduced,

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while maintaining the same total pressure, as related by the following well-known equation: Weight of glycerine vapor Partial pressure of glycerine vapor Weight of water vapor Partial Pressure of water vapor MW of glycerine MW of water Glycerine distillation plants typically operate at 56 mm Hg absolute pressure and at about 165 C. Certain undesirable chemical reactions can occur in crude glycerol at distillation temperatures: 1. Formation of nitrogen compounds from proteinaceous matter present in the crude glycerine (not removed in the treatment process) by thermal breakdown; these, along with volatile decomposition products, form impurities in the rened glycerin; therefore, it is important to limit the time the glycerol is at high temperature as well as the maximum temperature it is exposed to. 2. Formation of volatile glycerol esters by reaction with soaps (low molecular weights) by the following equilibrium reaction: C2 H5 OH3 R COONa ! C3 H5 OH2 O CO R NaOH 6

The formation of ester is reduced in the presence of alkali. 3. Formation of polyglycerols, which occur in the presence of NaOH; thus, it can be seen that it is important to control the alkalinity of the crude glycerol to an optimum level. 4. Formation of acrolein (CH2 CHCHO), which is an odor constituent that is difcult to eliminate. The amount of total stripping steam for distillation is about 20% of the amount of glycerol processed. This amount is greater with poorer quality feedstocks. However, not all of this steam is injected, as the water in the incoming crude glycerine (80%) ashes to steam and provides a signicant portion of the stripping steam requirement. It may be undesirable to produce crude glycerine at a higher concentration in the evaporation stage, as additional steam would be needed.
2.4.2. Residue Recovery and Disposal After the glycerine has been distilled

from the crude glycerine, a residue remains that is continuously removed from the still. The residue contains some glycerol, polymerized glycerol, aldehyde resins, organic products of decomposition, and salt, which must not be allowed to become too concentrated as buildup of residue will cause quality and capacity problems in the plant (19). If the residue is allowed to concentrate in the still, it displaces volume for incoming crude glycerol, thus reducing the stills capacity. At least two methods of removing the residue are used:

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H.P. steam Vacuum system

Vapor scrubber

Phosphoric acid

Scavenging condenser Condenser To hotwell

substandard To receiver substandard glycerine storage

Crude still
Steam

Deodorizer

Steam

Foots still

Bleaching columns

Crude glycerine

C.W.

C.W.

C.W.

Economizer/ Residue cooler

C.P. glycerine Cooler Polishing Cooler filters

Figure 6. Flowsheet of Wurster & Sanger glycerine rening plant. Courtesy of Crown Iron Works Co. (9).

1. A residue receiver vessel placed below the still accumulates residue, which is periodically discharged to the treated lye tank for reprocessing. 2. Residue is removed continuously from the still and is redistilled to recover the remaining glycerine; the concentrated residue from the bottom of the foots still is discharged to a drum for disposal, typically to land ll as solid waste. The details of glycerine rening via the Crown Iron Works Co. process, which is representative of the continuous distillation process used by a large portion of suppliers for soap lye crude glycerine, are detailed here (Figure 6). The crude glycerine is preheated regeneratively by hot distilled glycerine. The liquor then enters the still heater where it is further heated to about 165 C and circulated by means of a circulation pump. The circulated liquor is partially vaporized through the aid of vacuum (6 mm Hg) and sparging steam in the ashing chamber. The vapor rises through an entrainment separating section and then enters the condensing section. Here, the glycerine vapors are condensed in a layer of packing, wetted by recirculated, cooled, distilled glycerine. The remaining vapors enter the scavenging condenser where remaining traces of glycerine are condensed and recovered as 8090% substandard glycerine, which is sent to intermediate storage. The substandard glycerine is re-rened after sufcient quantities have been collected for a 2- to 3-day run every month. Typically, the substandard glycerine is processed into a lower grade of glycerine, such as high gravity or dynamite grade. The residue in the bottom of the still is continuously discharged from the crude still to the foots still. The residue should be kept rich in glycerol (>25%) to improve handling and distillation characteristics. A small amount (0.51%) of

PROCESSING PRINCIPALS AND DETAILS

207

phosphoric acid is added to keep the residue soft by lowering the pH to retard the formation of polyglycerols. Here, it is reheated by recirculation through an external heater to about 175 C and partially vaporized, under vacuum and with about 25% stripping steam. Most of the vapors are condensed in the foot stills condenser, and the condensate is returned to the crude still. Any remaining glycerine is recovered where the vapors pass through the scavenging condenser. The residue at the bottom of the foots still is discharged to a drum for disposal. The distilled glycerine from the crude still is re-evaporated in the deodorizer at about 130140 C, again in the presence of high vacuum and stripping steam and with external heating, to ensure optimal removal of odoriferous materials and residual moisture. The vapor passes through a packed section where the incoming feed condenses the vaporized glycerine. Proper reux rates are needed to ensure removal of close boiling impurities. Residual volatiles are condensed in the scavenging condenser. An alternate method for distilling glycerine, especially sodium-hydroxidetreated sweetwater crude glycerine, has been implemented in many facilities and differs from the above system in many features (Figure 7). Most notably is the use of a fractional (or partial) condenser for the glycerine product followed by a nal condenser to capture a yellow glycerine stream. A wiped lm evaporator is used for recovering glycerine from the foots, or pitch, stream.

Figure 7. Hydrolyzer crude rening system process ow diagram. Courtesy of CC Engineering, Ltd. (20).

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GLYCERINE

The still for this system is a simple ash still with a forced circulation reboiler. The saponied, crude glycerine stream is fed into the recirculation pump on the suction side. The recirculation rate is in the range of 4050 times of the crude glycerine feed rate. The top of the still vessel is equipped with a pad style entrainment separator to eliminate carryover. The still bottoms are drawn off and sent to a second distillation step to remove as much of the remaining glycerine as possible. This system can be a small still, similar to a foots still, or a wiped lm evaporator. The foots still bottoms, or pitch, from this step is comprised mostly of sodium soaps, polyglycerols, salts, and minor quantities of organic compounds formed in the treatment and distillation steps. The glycerine and water vapors leave the still and enter the partial condenser. This condenser is a vertical, shell and tube heat exchanger that condenses the glycerine on the shell side. The tube side of the heat exchanger is congured to allow water to boil in the tubes. The tube side outlet is equipped with a valve to control the pressure of the steam leaving, thereby controlling the temperature at which the water boils and glycerine vapors are condensed. Typical condensing temperatures are 115135 C. A balance must be reached with the temperature of condensation so that odor and color impurities are at a minimum, yet the glycerine yield is economically sufcient. The remaining glycerine and water vapor leaves the partial condenser and enters the full condenser. This condenser is a shell and tube type condenser that condenses the remaining glycerine and a small amount of the water. This glycerine stream is a low-gravity glycerine and is very yellow. This stream is collected and can be run as a separate recycle batch as mentioned above. The full condenser uses cooling tower water on the tube side. Water vapor leaves the full condenser shell side and goes through the vacuum system where it is condensed. An alternate method of distilling glycerine is by using a wiped lm evaporator system (Figure 8). Pfaudler Corp. describes the process as follows. Feed material enters the inlet [2] and ows onto a distributor plate [5], which is part of the rotor assembly. The initiation of feed to the WFE occurs at the same time that the drive and motor [1] are started. As the rotor unit turns, centrifugal force spreads the feed from the distributor plate onto the heated wall of the WFE. Volatile components, such as glycerine, are rapidly evaporated. Slotted wiper blades [8] connected to the rotor evenly distribute the feed material into a uniform, agitated, thin lm and continuously move material down the heated wall, including highly viscous materials. The vaporized glycerine stream passes through the entrainment separator [10] and condenses on the internal U-tube condenser [9]. Droplets of material entrained with the vapor stream impinge on the entrainment separator and ow back to the heated wall through centrifugal force of the rotating assembly. Distillate ows out the distillate outlet [11] and noncondensables ow out through the vacuum outlet [13].
2.4.3. Wiped Film Evaporator (WFE)

PROCESSING PRINCIPALS AND DETAILS

209

Figure 8. Wiped lm evaporator with internal condenser components. Courtesy of Pfaudler Corporation. (21).

The bottoms, or residue, continues to move down the heated wall into the bottoms collector and out through the residue/bottoms outlet [12]. Optional extruder blades [16] mounted on the bottom of the rotor assembly act to push highly viscous material out through the residue/bottoms outlet. The heating temperature is chosen based on the vapor pressure of glycerine. The WFE is typically under a high vacuum (35 mm Hg). Noncondensables and water vapor are removed by the vacuum system. One option used in many facilities is to use a WFE that is not equipped with an internal condenser. The vapor stream is then taken from the WFE to the partial condenser inlet for fractional condensation previously discussed. The advantages of this type of continuous process over batch or continuous distillation in a still pot include low residence time (12 minutes) and a small difference between the vapor temperature and the liquid lm temperature. The temperature of the glycerine can be tightly controlled, thereby reducing the formation of odor, color, and other impurities. This system does not require stripping

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GLYCERINE

steam, which reduces the capital and operating costs of the vacuum system and overall energy consumption. Wiped lm evaporators are very effective for processing sweetwater crudes. Yields of glycerine are very good and the quality of nished product is equal to glycerine from other distillation systems discussed previously. Salt crudes can be distilled in these systems, but special modications are required to handle the salt that precipitates out during distillation.
2.4.4. Vacuum System

The vacuum system for the distillation plant is typically a single system for the still, deodorizer, and foots still (if supplied). To achieve a vacuum of 210 mm Hg required in the distillation equipment, the vacuum system is usually designed for 18 mm Hg absolute, to allow for equipment pressure differentials, ducting losses, leaks, etc. Most systems have a surface condenser or a barometric condenser, followed by a booster jet or multiple-stage vacuum pump. The cooling and condensing water going to the hotwell is typically of good quality, as virtually all condensables are removed by the condensing sections.

2.4.5. Carbon Adsorption Distilled glycerine requires one nal processing step

prior to nal storage and shipment. The nal step is processing through activated carbon columns. The carbon adsorption process step removes any nal traces of odor and color from the distilled glycerine and enhances stability to provide a glycerine product that will not degrade in the nal storage tanks (22). Typical activated carbon usage is in the range of 0.51.0%. This can vary depending on the amount of odor and color impurities in the distilled glycerine. The typical carbon column conguration (Figure 9) consists of three carbon columns in series with a standby carbon column lled with fresh carbon. The column

Figure 9. Carbon adsorption process ow diagram. Courtesy of CC Engineering, Ltd. (20).

PROCESSING PRINCIPALS AND DETAILS

211

is lled with dry, activated carbon using any of several methods, including bag dumping, supersacks, or pneumatic conveying. The column is then lled with water or with heated (7585 C) nal glycerine product to saturate the carbon and displace air from the carbon granules. The lled column needs to settle while vented to the atmosphere. This ensures the carbon bed is thoroughly saturated, all air has been expelled, and channeling of glycerine through the carbon bed is prevented. Channeling in the carbon bed leads to increased carbon usage and poor-quality glycerine that does not meet required specications. Heated (7585 C) glycerine is pumped to the carbon column system from the distilled glycerine storage tank. It is critical to the adsorption process to avoid bumping the carbon beds with a sudden surge of glycerine because this disrupts the beds and can cause odor and color quality degradation in the nished glycerine. The bumping of the carbon bed can sometimes occur with a centrifugal pump. A positive displacement pump, preferably equipped with a variable frequency drive, is recommended to feed the glycerine at a constant ow rate. A lter is used after the carbon columns to remove any carbon nes from the glycerine. The lter is typically a bag type using polypropylene or PTFE cloth bags with a pore size of 510 micron. The bleached and deodorized glycerine product is then sent to nal storage for shipment. 2.5. Storage and Stability Dilute and crude glycerine contain certain amounts of suspended material (precipitates, salt, etc.) that tend to settle out during storage. Therefore, to avoid introducing these materials into the process when liquor is drawn, it is recommended to have discharge nozzles be approximately six inches above the bottom of the tank. It is necessary to empty and clean the storage tank(s) periodically. Dilute solutions of glycerol (<50%) are subject to fermentation, which reduce yields and introduce breakdown products that degrade the glycerol. Holding the glycerol above 70 C or higher concentrations will alleviate this problem. Concentrated glycerine is difcult to pump at lower temperatures because of its high viscosity. It is recommended that glycerine be pumped at 4050 C; lower temperatures make pumping difcult and higher temperatures can affect the color. If heating coils or steam tracing are used, it is important to use low-pressure steam so as not to overheat the glycerol and cause breakdown of products. Stainless steel vessels or stainless-steel-lined vessels are recommended to prevent the formation of color complexes, especially if moisture or residual fatty acids are present in a carbon steel tank. Since glycerine is hygroscopic, care should be taken to exclude moisture from the rened glycerine storage tank. Glycerine subjected to heat should not be stored in vessels containing copper or tin, as copper or iron salts will catalyze oxidation of glycerine under those conditions (23). 2.6. Odor and Color As noted, color and odor problems can be mostly avoided by using a high-quality raw material, treating and storing crude glycerol properly, and avoiding high

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GLYCERINE

temperatures for an extended time period. Impurities in crude glycerine, especially matter organic nonglycerol (MONG), affect the quality and quantity of distilled glycerine. If the MONG content is high (35%), odor, taste, and color reversion problems may exist in the nal product. Tremethylene glycol, which is present in MONG, can affect the color of glycerine and lead to problems in storage. A properly designed deodorizer or stripper vessel, located after the distillation column and operating at high vacuum and with open or sparging steam, will remove close boiling impurities and most odor bodies. Remaining color bodies are removed by adsorption with activated carbon. Acrolein may be formed in the presence of iron, iron salts, acid, or neutral salts: C3 H5 OH3 C3 H4 O 2H2 O: 7

Acrolein odor is distinctive and is detectable to the human nose in small quantities (ppm). It has been found that glycerine left inside processing vessels, especially carbon columns, can degrade and develop hard-to-remove odors. Therefore, process equipment should be cleaned completely after shutdown, and carbon columns blown down with air and washed with water. Also, fresh carbon can sometimes contain odor-causing impurities. The carbon can be washed with distilled glycerine that can be subsequently redistilled or sold as a lower grade.

3. PROCESSING PLANTS 3.1. Layout Considerations Plant layout considerations for a glycerine recovery plant are similar to those for other processing plants: adequate space must be allowed for equipment installation, operation, and maintenance, as well as operator safety. As some of the operation requires material handling, consideration must be given to these specic requirements. These operations include batch feeding of treatment chemicals (most of which are hazardous), disposal of lter cake, and charging of the bleaching columns with carbon. It generally makes sense to arrange the equipment in order of process ow, as piping and other connections can be made much more conveniently. In addition, if process tanks are located to allow gravity feeds, some pumps can be eliminated. Locating equipment on several levels also helps in reducing the overall footprint, or oor space requirements. All areas should be equipped with wash-down equipment, and all levels must have adequate oor drains with the oor surfaces properly pitched. Care must also be exercised when selecting ooring materials, as glycerine is slippery; this is a real concern, because spills and leaks inevitably occur. Provisions must be made in the plant for efcient cleaning procedures for the equipment, piping, and building.

PROCESSING PLANTS

213

3.2. Material and Construction

3.2.1. Overview Careful selection of the materials of construction is important

to ensure adequate life of equipment in the glycerine processing plant and to ensure a high-quality nished product. This is especially true when recovering glycerine from soap lyes, where the presence of sodium chloride, in crystal and solution forms, greatly increases the corrosion potential. The reader is encouraged to consult textbooks and manufacturers data sheets regarding corrosion for the compounds and materials in the glycerine plant.
3.2.2. Pretreatment Plant When treating sweetwater glycerine, ductile iron

(DI) can generally be used for pumps, although lined DI and stainless steel pumps can be used with an expectation of longer life. More care must be used when selecting material for treating spent lye. Treatment vessels can be either lined carbon steel or stainless steel. Fiberglass-reinforced polyester (FRP) is a good choice for both tanks and piping in the treatment plant, but care must be taken to ensure that the temperature range of the FRP material is observed and that the pipelines are correctly supported. Also, steam blowing of pipes should not be allowed as the high temperature can damage the FRP piping. The open plate and frame lter presses used typically have cast iron frames with polypropylene plates that give excellent life. Filter clothes are usually constructed of synthetic materials such as polypropylene felt, rather than natural bers such as cotton. Plastic tools must be used to clean cake from the clothes to avoid damage. A plate and frame heat exchanger is sometimes used to preheat incoming soap lye, as treatment is more effective with warm lye. The plates can be of 316L stainless steel, or even titanium for effective corrosion resistance.
3.2.3. Evaporation Plant Material selection for the evaporation plant is the

greatest challenge in the glycerine recovery plant, again, especially if there is salt present. For evaporating splitter sweetwater, 304L stainless steel may be used. The corrosive nature of the brine-glycerol solution makes carbon steel and most grades of stainless steel a poor choice for evaporators handling soap lye. The heavy-walled, cast-iron callandria that have been used extensively for soap lye evaporation in the past have long lives, however, economic considerations discourage new evaporators of that style from being built. The material of choice for the past 25 years for welded plate evaporators (and related components handling salt or brine) is copper-nickel alloy. The two principal alloys to consider are 9010 (90% copper, 10% nickel), which has the best corrosion resistance to the glycerol-brine solution, and 7030, which has a higher cost (24). An interesting class of materials that should be considered for evaporator service are the duplex stainless steel alloys. These high-performance stainless steel alloys have a duplex structure. The alloy contains both the austenitic and ferritic phases

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GLYCERINE

in the grain structure at the same time. These materials have shown high resistance to stress corrosion cracking in chloride-bearing environments and have the characteristics of high corrosion and erosion resistance. (A description of the corrosion protection mechanism is outside the scope of this chapter; the reader is referred to corrosion handbooks and manufacturers data sheets for more information.) Two alloys that show promise for this application are Sandviks SAF 2205 and SAF 2507 (20, 25). Other, more expensive alloys, such as Ferralium 225, Hastelloy, and Monel, have been used in various applications. Pumps for the evaporation plant must stand up under the hot glycerol-brine solution and are also generally of the centrifugal design. Cast stainless steels (CF8M alloy) are often used for this application, but a superior material for pumps is a chromium-nickel-copper-molybdenum stainless steel known as CD-4M, which should be considered when choosing the pump material. The extra cost is usually not signicant. Seals for pumps are generally mechanical. If the uid contains salt crystals, which are abrasive, it is recommended that water be used to ush the seal. Both seal faces on the pump side should be of a hard material; using carbon for one of the seal faces has not proven to be successful. The reader is again urged to contact seal manufacturers for their recommendation.
3.2.4. Rening Plant Materials for the rening plant can be selected based on

the impurity content of the glycerol being handled. The initial distillation vessel or residue still, if it is handling crude glycerine with salt in it, should be a high grade of stainless steel. The L grades generally exhibit slightly better corrosion resistance than their base versions. The 316 and 316L stainless steels are recommended for stills handling soap lye crude glycerine, while 304 and 304L stainless steel is adequate for sweetwater stills, vapor scrubbers, condensers, deodorizers, and bleaching equipment where salt is not present. The 316L is especially recommended for foot stills where salt is present but water is not. In some cases, more corrosion-resistant materials have been used; the Ittner rening stills in use at some Colgate-Palmolive plants were fabricated from pure nickel. The life of such equipment is exceptionally long (26). Pumps for handling glycerine can be centrifugal as long as the temperature and viscosity of the product is satisfactory for the pump being used. For lower temperatures and pumping residue, a positive displacement pump with a pressure relief loop (internal) should be used.

3.3. Instruments and Controls Control techniques for glycerine plants have not changed much over the years, as it is necessary to control pH, levels, temperatures, and vacuums in the various portions of the plant. Most operations can be accomplished manually, and traditionally, manual operation of these plants have been the norm. However, the development

PROPERTIES OF GLYCEINE

215

and renement of digital single-loop controllers and associated sensing equipment have increased the ease and accuracy of control. Reliable inline pH monitoring has made treatment plants easier to operate. A caution must be given, however, to select instrumentation that can handle the sometimes severe conditions in the glycerine recovery plant. The crude glycerine in the evaporation and crude rening sections contains both dissolved and suspended salt, while the residue in the rening plant contains salt as well as other impurities that make the viscosity of the residue high. Vane-type ow meters have been used successfully for measurement of difcult ows such as residue from the crude still. Rotameters often will be plugged by suspended solids and are recommended only for ows that are clean and will maintain a constant viscosity over time. Mass ow meters (Corealis effect), such as those manufactured by Micromotion, have proven successful in many areas of the treatment and rening plants. These ow meters have no moving parts and can handle a wide range of viscosities and densities. Materials of construction for wetted portions of the instrumentation must be selected using similar considerations to those used for the equipment itself. In addition, plastic diaphragm seals are available to cover and protect the pressure-sensing faces of immersed level transmitters. This allows the use of stainless steel in applications where, if unprotected, the corrosion rate would be unacceptably high on the thin face of the instrument. A diaphragm seal is recommended for pressure instruments in the presence of suspended or entrained solids.

3.4. Piping Considerations In addition to the few suggestions on material selection given earlier, other issues need to be considered when designing or evaluating the piping for a glycerine recovery plant. As in any piping system, the piping must be properly supported, be given correct slopes for proper ow and self drainage, accommodate thermal expansion, and be designed with adequate bypasses for equipment maintenance and proper operational control. In addition, consideration should be given for sampling points, drains, and for blowout-wash-down connections. Fluid velocities should be maintained within standard design limits. The above information can be obtained in reference books dealing with industrial piping design. Another area of concern may be the possible problem of electrolysis as a result of dissimilar materials used together in the piping system.

4. PROPERTIES OF GLYCEINE Glycerine has a unique set of physical properties that allow glycerine to be used in a variety of industries. Some of these properties are summarized in the following tables:

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GLYCERINE

TABLE 2. Physical Properties of Glycerine. Molecular Weight Boiling Point Melting Point Freeze Point (eutectic) Specic Heat Refractive Index Flash Point Fire Point Autoignition Point Heat of Combustion Surface Tension 92.09 290 C (760 mm Hg) 18.17 C (66.7% glycerol solution) 46.5 C 0.5795 cal/gm C (26 C) (Nd20) 1.47399 (99% glycerol) 177 C (99% glycerol) 204 C (on platinum) 523 C (on glass) 429 C 397.0 Kcal per gram 63.4 dynes cm (20 C) 58.6 dynes cm (90 C) 51.9 dynes cm (150 C) 0.0006115 (1525 C Temp. Interval) 0.000610 (2025 C Temp. Interval) 0.000691 cal cm deg/sec (0 C) 159.8 Kcal/mol (25 C) 47.5 cal/gram 21,060 cal/mol (55 C) 19,300 cal/mol (105 C) 18,610 cal/mol (175 C)

Coefcient of Thermal Expansion Thermal Conductivity Heat of Formation Heat of Fusion Heat of Vaporization

TABLE 3. Vapor Pressure of Pure Glycerine. mmHg



1 125.5

5 153.8

10 167.2

20 182.2

40 198.0

60 208.0

100 220.1

200 240.0

400 263.0

760 290.0

TABLE 4. Viscosity of Glycerine-Centipoise.



80 32.18

90 21.2

100 14.60

110 10.48

120 7.797

130 5.986

140 4.726

150 3.823

158 3.282

167 2.806

cp

5. QUALITY AND TESTING 5.1. Glycerine Grades Several grades of glycerine have been established or are in common use in North America. U.S. Pharmacopoeia (USP) or chemically pure (CP) glycerine standards have been established for the highest grades of glycerine, water (white in color), and with glycerol contents of not less than 95%. It conforms to standards given in U.S. Pharmacopeia. It is used by the food and pharmaceutical industries because of the high purity. Both natural and synthetic glycerine meet these specications (Table 5).

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TABLE 5. Rened Glycerine Specications. Characteristic Specic Gravity, 25/25 C Color Ash Chlorides Sulfate Arsenic Heavy metals Readily carbonizable Chlorinated Compounds Acrolein, glucose and ammonia compounds Fatty acids and esters (FA & E) PH 99.7% USP 1.26092 25 hazen maximum, APHA 10 maximum 0.01% maximum 10 ppm maximum 20 ppm maximum 1.5 ppm maximum 5 ppm maximum 30 ppm maximum Not yellow, no ammonia odor 1.0 milliequivalent/ 100 gm MAX. Neutral 99.5% USP 1.26073 25 hazen maximum, APHA 10 maximum 0.01% maximum 10 ppm maximum 20 ppm maximum 1.5 ppm maximum 5 ppm maximum Not darker than matching uid H 30 ppm maximum Not yellow, no ammonia odor 1.0 milliequivalent/ 100 gm MAX. Neutral 99.0% USP 1.25945 25 hazen maximum, APHA 10 maximum 0.01% maximum 10 ppm maximum 20 ppm maximum 1.5 ppm maximum 5 ppm maximum Not darker than matching uid H 30 ppm maximum Not yellow, no ammonia odor 1.0 milliequivalent/ 100 gm MAX. Neutral

High-gravity glycerine is a commercial grade of glycerine, near white in color, and with a high glycerol content (>98.7% with specic gravity minimum of 1.2583 at 25/25 C). It conforms to Federal specication O-G-491C and to ASTM D1257. Dynamite glycerine meets all high-gravity specications, except that a darker color is allowed. Hydrolyzer (88%) and soap lye (80%) crudes are crude, unrened grades of glycerine offered for sale to glycerine reners. Hydrolyzer crude is concentrated sweetwater from fat splitting, while soap lye crude comes from soap making and contains some salt. For salt crude glycerine, the typical concentration for sale is 80%. Adjustments in price can be made for concentrations above or below 80%, however, these adjustments are negotiated by buyers and sellers. The standard for ash content in salt crude is 10% maximum. The standard for water is 10% maximum. Limits on minor constituents include a 0.5% limit for trimethylene glycol (TMG), 2.5% limit for MONG, and a limit of 2 ppm for arsenic. Hydrolyzer (sweetwater) crude glycerine is traded at a standard 88% glycerol. Limits on minor constituents include ash at 1% maximum, MONG at 1.5% maximum, and TMG at 0.5% maximum. The limit on arsenic is 2 ppm maximum. 5.2. Test Methods The American Oil Chemists Society (AOCS) has published several methods for sampling and testing of glycerine (18). Included are procedures for sampling crude glycerine and test methods for glycerol, apparent specic gravity at 25/25 C,

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moisture, and color (Table 6). Tests are usually conducted to analyze the amount of ash, alkalinity, salt, and organic residue. In addition, the refractive index of glycerine can be used to estimate its concentration (13, 25). Color is determined using the APHA scale. APHA color is determined using AOCS Method Ea 9-65, which measures color by comparison with articial empirical standards (23).

6. PROCESSING LOSSES Losses are a natural part of any processing plant. The control and reduction of the losses will, in part, determine the economic effectiveness of the plants operation. All areas of the glycerine recovery plant can produce losses. In storage, fermentation can cause serious losses of glycerine due to the formation of trimethylene glycol, gases, and acids during decomposition. In the evaporation plant especially, glycerine can be carried out with the vapor during evaporation and lost in the vacuum systems condensing of water. The amount of carryover can be minimized in several ways: 1. Entrainment separators, or catchalls, and mist eliminator pads can be installed where the vapor is removed from the vessel by the vacuum system; the recovered product can be returned to the process at an appropriate point. 2. Control the vapor velocity and maintain an adequate vapor space at the top of the vessel; it becomes important to control the liquid level to maintain the required vapor space. 3. Use a surface condenser to recover any additional condensable material that escapes into the vacuum system. The treatment process should be done carefully to control any tendency to foam. Other sources of glycerine losses include the following: 1. Glycerine is carried out with salt coming from soap lyes; proper washing of the salt is required to minimize this loss. 2. The lter cake and skimming from the treatment plant contain glycerine. 3. Spent bleaching carbon contains glycerine of the highest concentration produced in the plant. It should be allowed to drain and then the columns should be blown down with air or nitrogen to extract as much free glycerine as possible. Then, the spent carbon can be added to the rst treatment tank, where additional glycerine will be washed from the carbon. The carbon is separated in the lter press and disposed of with the rest of the lter cake. 4. Residue removed from the distillation process contains a certain percentage of glycerine; much of the glycerine can be recovered from this residue by a separate distillation step in a wiped lm evaporator, or foots still. 5. Glycerine leaks into heat exchangers.

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219

6. There is spillage from all sources; careful plant design and operation are needed to minimize spills from overlling tanks, equipment malfunctions, and other operational errors. 7. Opening of equipment for maintenance can result in loss of product. Where possible, the liquid should be blown into the previous or next process vessel or drained back into a bucket for recovery. Any product that is recovered that is not badly contaminated can be returned to a separate storage tank upstream in the process. If a substandard or off-spec glycerine tank is provided in the rening section, it can be equipped with an easily removable cover.

7. WASTE MANAGEMENT The three primary waste streams from a glycerine recovery plant are skimming and lter cake from the treatment plant, contaminants in the vacuum system condensing water, and residue (foots) from the glycerine rening plant. Filter cake discharge is typically sent to a solid landll. The concentrated residue from a foots still, when allowed to cool, will typically solidify and must be disposed of as required by the local environmental authority. Contaminants that get into the vacuum systems condensing water supply are a dual problem. There is glycerol and other condensables that are carried over from the vapor stream from the evaporation plant. First, the glycerol represents a loss of product. Second, these contaminants will foul the condensing water supply, which is typically recirculated through a cooling tower. A certain amount of the condensing water is generally bled away and replaced with makeup water to maintain an acceptable water-quality level. An important alternative here is the inclusion of a closed-loop system that incorporates a surface condenser cooled with clean water recirculated from a cooling tower. The surface condenser, usually a horizontal shell and tube heat exchanger, replaces the barometric condenser in the vacuum system and, while using clean cooling water, allows any condensables to be recovered.

8. USES, APPLICATIONS, AND ECONOMICS The number of uses of glycerine is truly phenomenal (Figure 10). Depending on the publication surveyed, up to 1700 uses have been identied. Its wide range of applications is, in part, related to a few of its key properties: 1. Glycerine is a natural product, nontoxic, and generally recognized as safe (GRAS) for human consumption. 2. It is an excellent humectant, emulsier, and plasticizer. 3. It is compatible with a wide variety of materials and mixes well. 4. It possesses antioxidant properties.

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GLYCERINE

Alkyd resins (36%)

Cosmetics/pharmaceuticals (30%)

Explosives (2%) Urethane uses (6%) Tobacco products (16%) Food/beverages (10%)

Figure 10. Glycerine uses.

Below is a list of some of the more prominent or interesting uses for glycerine (4, 23).     Adhesives, used for plasticizing and penetrating properties. Agriculture, used in sprays, dips, and washes. Antifreeze: properties include low freezing point and excellent compatibility. Cleaners and polishes, used in a wide range for the home and automotive markets.  Corrosion prevention, used in gums and resins for surface-coating metals. Cosmetics, acting as a bodying agent, emollient, humectant, lubricant, and solvent; present in skin creams and lotions, shampoos and hair conditioners, soaps, and detergents. Dental creams, up to 50% of typical dental creams, used as a humectant, to ensure good dispersion and to serve as a vehicle for dyes and avorings. Explosives, a large amount is consumed in the manufacture of nitroglycerinebased explosives. Food and beverages, used in a wide variety of applications; serves as a solvent, carrier, emulsier, conditioner, freeze preventer, and coating; used in wine, liqueurs, chewing gum base, confectioneries, and chewy bars; kosher glycerine is used in kosher foods. Leather, used in tanning and nishing processes. Metal processing, widely used for pickling, quenching, stripping, electroplating, galvanizing, and soldering. Paper, acts as a humectant, plasticizer, softening agent, and barrier against grease and solvents; used for greaseproof and glassine papers. Pharmaceuticals, used in salves and dressings, antibiotic preparations, capsules, and suppositories; used as a vasodialator for angina pectoris (nitroglycerine). Photography, properties include wetting and plasticizing. Resins, includes ester gums, phthalic acid and malic acid resins, polyurethanes, and epoxies. Textiles, facilitates printing and dying, lubricating and snagproong; used for treatments for antistatic, antishrink, anticrease, waterproong, and ameproong. Tobacco, used as a humectant, softening agent, and avor enhancer.

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9. FUTURE CONSIDERATIONS 9.1. Technology Future technologies that appear most likely to impact the production of natural glycerine center around recovery of glycerine from nontraditional sources. As demand for biodiesel fuel from vegetable oils grows, large amounts of high-quality glycerine will become available. Other technologies that show promise for use in glycerine recovery include ultraltration and reverse osmosis. As processes become more effective and efcient and as economic conditions change, some of these processes may come into more common use. An interesting source of glycerol is through recovery from ethanol fermentation still bottoms by chromatographic separation and ion exchange process. In a process proposed by IWT/US Filter, raw stillage is rst claried by ltration through a membrane, concentrated (by evaporation), and then fed to the ADSEP chromatography process where the glycerol is separated. The glycerol is then further puried by ion exchange, followed by traditional concentration and distillation (27). 9.2. Future Economics The future economics of glycerine worldwide will be sure to change as fundamental changes on the supply side occur. Animal fat is a signicant raw material for glycerine production, both for fat splitting and saponication. Recent health trends emphasizing lower fat content in meats has caused animal producers to develop leaner meats, reducing the supply of animal fats. Other uses of fat add additional price pressures. However, the soap and detergent industry is expected to increase its use of glycerine as nonionic surfactants. Additional glycerine production is being added from several growing and significant sources. The Asian fatty alcohol and fatty acid industry is expected to add an additional 30,00060,000 tons to the world market in the next few years. There is a similar amount expected to arrive in the market, primarily from the European biodiesel (methyl ester production from vegetable oil) industry. Other developing sources of glycerine, such as glycerine recovery from ethanol stillage, may add further stocks to the world supply. The purication of glycerine from these sources is obtained using the traditional methods outlined in this chapter. However, the economics of production of the crude glycerol will determine how these new sources affect the world market.

REFERENCES
1. K. P. Radhakrishnan, in L. Spitz, ed., Soap Technology for the 1990sGlycerine Processing from Spent Lye and Sweet Water, AOCS, Champaign, Illinois, 1990, p. 128. 2. W. I. Rowell, FatSplitting and Glycerine Recovery, AOCS, Champaign, Illinois, 1987.

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3. L. L. Lamborn, Modern Soaps, Candles, and Glycerin, Van Nostrand Co., New York, 1906, p. 542. 4. A. A. Neuman, Glycerol, CRC Press, Cleveland, Ohio, 1968. 5. A. S. Langmuir, J. Soc. Chem. Ind., 36, 180 (1917). 6. J. Hoffman, Chem. Market. Reporter, 243, 5 (1993). 7. B. Freedman, Methyl EstersManufacture and Utilization, USDA. 8. A. A. Neuman, The History of Glycerol, CRC Press, Cleveland, Ohio, 1968, ch. 1. 9. Crown Iron Works Co. 10. E. Woollatt, The Manufacture of Soaps, Othe Detergents and Glycerine, Elliss Horwood Ltd., Chichester, United Kingdom, 1985. 11. O. H. Wurster, Oil Soap, 13, 246253 (1936). 12. O. H. Wurster, Oil Soap, 13, 283286 (1936). 13. C. S. Miner and N. N. Dalton, eds., Glycerol, Reinhold Publishing Co., New York, 1953, ch. 6. 14. Bulletin. SW-200R, Swenson Evaporators. 15. P. E. Minton, Handbook of Evaporation Technology, Noyes Publications, Park Ridge, New Jersey, 1986. 16. Guinard Centrifugation. 17. Centrifuge Type C, brochure, Guinard Centrifugation. 18. American Oil and Chemists Society. 19. J. W. Lawrie, Glycerol and the Glyecrols, Chemical Catalog Co., New York, 1928. 20. CC Engineering, Ltd. 21. Pfaudler Corp. 22. Glycerine Purication, brochure, CC Engineering. 23. Glycerine: An Overview, Soap and Detergent Assoc., New York, 1990. 24. APV Evaporator Handbook, 3rd ed., APV Crepaco, Inc. 25. L. F. Hoyt, Oil Soap, 10, 4347 (1933). 26. M. H. Ittner (to Colgate Palmolive), U. S. Patent 2,164,274, June 27, 1939. 27. B. D. Burris, Recovery of Glycerol from Still Bottoms, Illinois Water Treatment, 1987.