eparate Organics by Melt Crystallization

Here is a guide to when and why to use this technique for large-scale separations.

Nicholas P. Wynn, Sulzer Canada Inc.

• A falling-film melt crystallizer for para-dichlorobenzene purification at a Delaware plant.

The use of melt crystallization for the large-scale separation of organics has boomed over the past few years. In the U. S. alone, total onstream capacity will soon approach one billion pounds per year. The technique now is routinely used to purify naphthalene, para-xylene, dichlorobenzenes, acrylic acid, monochloracetic acid, bisphenol A, and many other chemicals.

Two factors are responsible for this growth - escalating requirements for purity and increasing environmental concerns. Melt crystallization can easily reach the ppm purity levels associated with crystalline materials. It does so, however, without the need for organic solvents.

Despite its newfound popularity, many

52 • MARCH 1992 • CHEMICAL ENGINEERING PROGRESS

chemical engineers are unfamiliar with melt crystallization. Therefore, we will outline the fundamentals of melt crystallization, and also will characterize the separations in which it can be used to advantage. In addition, we will survey the various proprietary processes available from specialist vendors.

The basics

Melt crystallization is in essence very simple. If an impure molten material is cooled to its freezing point and further heat is removed, then some of the material will solidify: In most systems, this solid will be a pure component. Impurities will concentrate in the remaining melt, which is known as the residue. Purified product is recov-

t.

ith melt outline ization, tions in ln addiprietary endors.

;e very erial is ier heat 'ial will will be .oncenknown recov-

ered by separating the solid from the residue and remelting it.

This contrasts with better-known solvent crystallization in which a pure solute is crystallized from an impure solution. The most obvious example is crystallization of common salt from brine. Use of melt crystallization to purify common salt is an impractical proposition given its melting point of 801° C. Water is a cheap and harmless solvent that allows the process to run at benign temperatures.

When crystallizing nonpolar organics the situation is normally quite the reverse, however. Solvent crystallization requires organic solvents, which are in general neither cheap nor harmless. On laboratory scale their use is manageable, but largescale processing becomes expensive because of the effort required to prevent solvent emissions.

In addition, most organics have melting points that are relatively low. Figure 1 shows how the melting points of common organics are distributed. Over 70% of these substances have a melting point in the range of 0-200°C. These chemicals are prime candidates for melt crystallization.

Crystallizing without using a solvent has other advantages:

• The volume of material being processed is considerably less; equipment costs and energy consumption are thus much lower;

• No solvent recovery is necessary. The impurities are recovered in molten form and can be recycled, incinerated, or treated in some other fashion without an intermediate solvent-removal step; and

• The product is not contaminated with solvent.

Crystallizing from a solvent instead of from the melt is like evaporating under vacuum or with an inert gas - the only reason to consider it is for reducing operating temperature. Table 1 summarizes the differences between melt and solvent crystallization.

Applicability of melt crystallization

To understand the fundamentals of melt crystallization, we must first look at the phase equilibria that drive the separation. Two types of system predominate:

Eutectic systems - Most crystalline

<I)
.,
<..> 200
c::
co
..
.c
::>
en
'0
~ 100
.c
E
::>
z ·100

o

100

200

300

Melting Point, C"

• Figure 1. Melting points of common organic chemicals.

solids are immiscible with other solids because the geometry of the rigid crystal lattice is peculiar to the particular substance. Impurities cannot fit in. When a crystal is formed, impurities will be rejected from the lattice. If the temperature is low enough that two components are solidified, then two distinct solid phases will be formed even though they may be intermixed on a macroscopic scale. This situation can be explored further using the Phase Rule, which is simply stated as follows:

P+F=C+2

(1) where P is the number of phases, F is the number of degrees of freedom, and C is the number of components. If pressure is held constant, the number of degrees of freedom is reduced by one and the Phase Rule becomes:

P + F = C + I (2) Consider, for example, a binary system.

C is two; so, the number of degrees of freedom can then be expressed as:

F=3-P

(3)

Table 1. How fractional crystallization techniques differ.

Melt crystallization

Solution crystallization

Higher operating temperature Good selectivity

Higher viscosity fluid Moderate growth rate Compact equipment

No solvent recovery

Reduced environmental hazard

lower operating temperature Better selectivity

lower viscosity fluid

Higher growth rate

larger equipment

Solvent recovery required Possible environmental hazard

CHEMICAL ENGINE6RING PROGRESS • MARCH 1992 •

SEPARATION TECHNOLOGY

Liquid
Liquid T8
.~ ~
a ::>
~ ~
CD '"
0. C.
E Solid A Solid B E
~ ~
+ Liquid + Liquid TA
Te Te
e
Solid A + Solid B pI
di
w
fr
di
til
I al
~
t c
p'
ir
11
SI
P
d
f
I ~

Solid Solution

A

We Liquid Composition

B

A

Liquid Composition

B

• Figure 2. Phase diagram oj binary eutectic system.

This means that three phases can coexist only at a single point on a composition/temperature plot. At all other compositions, a liquid phase can coexist with only a single solid phase. Because a single solid phase can consist of only one component, we must have a pure solid phase in equilibrium with a liquid mixture.

The characteristic phase diagram for such a simple binary system is shown in Figure 2. The point at which the three phases coexi st is called the eutectic point and systems exhibiting such behavior are called eutectic systems.

Solid solution systems - Much less common are situations in which the components can substitute for each other in the crystal lattice. In such a case, there can be at most only two phases, a solid and a liquid. A phase diagram for this type of system is shown in Figure 3. It takes the same form as the more familiar vaporJliquid equilibrium diagram, which is another case where only two phases can mise.

A study by Matsuoka (1) found that over 85% of systems of binary mixtures were eutectic ones.

This means that most organics can in theory be purified completely in a single stage of melt crystalliza-

54 • MARCH 1992 • CHEMICAL ENGINEERING PROGRESS

• Figure 3. Phase diagram oj binary solid-solution system .

tion. The only restriction is that enough of the crystallizing component must remain liquid to prevent the liquid phase from approaching the eutectic composition.

In most melt-crystallization cases, phase equilibrium allows high product purity but recovery is limited.

Melt crystallization VS. distillation

Superficially, melt crystallization is analogous to distillation, with solid/liquid equilibria used to effect a separation instead of vaporJliquid equilibria. There are, however, some fundamental differences. Comparing the two separation processes highlights the peculiarities of melt crystallization.

Both separation techniques depend on three elements:

• phase equilibria that provide the driving force for separation;

• mass-transfer rates that allow phases to equilibrate; and

• phase separability.

Table 2 summarizes how solid/liquid systems differ from vaporJliquid ones in these critical areas.

The critical steps in melt crystallization are quite different from those

found in distillation. Equilibria are generally much more favorable in melt crystallization. Mass-transfer rates are much slower; therefore, long residence times are needed for the bulk of the phases to approach equilibrium. This mandates large equipment and makes the processing step costly. Also, phase separation after contacting, which is a trivial step for vapor/liquid systems, is always problematical for solid/liquid ones. Even with long residence times, complete separation is rarely achieved.

Note that a first assessment of a distillation process can be made from predicted vaporlliquid equilibria. This sets the required reflux ratio and allows the column, condenser, and reboiler to be sized. Unfortunately, in melt crystallization, the critical steps are rate dependant. They cannot be predicted accurately from theory. Laboratory or pilot-plant data must be generated before even process feasibility can be established.

Directly or indirectly, the lower temperatures inherent in melt crystallization slow down the rate processes and make them critical. On the one hand, this is a drawback. On the other, though, it provides a real niche for the technology. If a material is

SEPARATION TECHNOLOGY

TA Liquid
Liquid Te
.~ ~
a :>
~ "§
... CIl
0. a.
E Solid A Solid B E
~ ~
+ Liquid + Liquid TA
T. e Te
.
Solid A + Solid B Solid Solution A

We Liquid Composition

B

A

Liquid Composition

pI
di
w
fr
di
til
al
~
C
P
it
n
SI
p
B d • Figure 2. Phase diagram oj biliary eutectic system.

This means that three phases can coexist only at a single point on a composition/temperature plot. At all other compositions, a liquid phase can coexist with only a single solid phase. Because a single solid phase can consist of only one component, we must have a pure solid phase in equilibrium with a liquid mixture.

The characteristic phase diagram for such a simple binary system is shown in Figure 2. The point at which the three phases coexist is called the eutectic point and systems exhibiting such behavior are called eutectic systems.

Solid solution systems - Much less common are situations in which the components can substitute for each other in the crystal lattice. In such a case, there can be at most only two phases, a solid and a liquid. A phase diagram for this type of system is shown in Figure 3. It takes the same form as the more familiar vapor/liquid equilibrium diagram, which is another case where only two phases can arise.

A study by Matsuoka (1) found that over 85% of systems of binary mixtures were eutectic ones.

This means that most organics can in theory be purified completely in a single stage of melt crystalliza-

54 • MARCH 1992 • CHEMICAL ENGINEERING PROGRESS

• Figure 3. Phase diagram oj binary solid-solution system .

tion. The only restriction is that enough of the crystallizing component must remain liquid to prevent the liquid phase from approaching the eutectic composition.

In most melt-crystallization cases, phase equilibrium allows high product purity but recovery is limited.

Melt crystallization vs. distillation

Superficially, melt crystallization is analogous to distillation, with solid/liquid equilibria used to effect a separation instead of vaporlliquid equilibria. There are, however, some fundamental differences. Comparing the two separation processes highlights the peculiarities of melt crystallization.

Both separation techniques depend on three elements:

• phase equilibria that provide the driving force for separation;

• mass-transfer rates that allow phases to equilibrate; and

• phase separability.

Table 2 summarizes how solid/Jiquid systems differ from vapor/liquid ones in these critical areas.

The critical steps in melt crystallization are quite different from those

found in distillation. Equilibria are generally much more favorable in melt crystallization. Mass-transfer rates are much slower; therefore, long residence times are needed for the bulk of the phases to approach equilibrium. This mandates large equipment and makes the processing step costly. Also, phase separation after contacting, which is a trivial step for vapor/liquid systems, is always problematical for solid/liquid ones. Even with long residence times, complete separation is rarely achieved.

Note that a first assessment of a distillation process can be made from predicted vaporlliquid equilibria. This sets the required reflux ratio and allows the column, condenser, and reboiler to be sized. Unfortunately, in melt crystallization, the critical . steps are rate dependant. They can-

not be predicted accurately from theory. Laboratory or pilot-plant data must be generated before even process feasibility can be established.

Directly or indirectly, the lower temperatures inherent in melt crystallization slow down the rate processes and make them critical. On the one hand, this is a drawback. On the other, though, it provides a real niche for the technology. If a material is

em.

.ia are ble in ansfer efore, ed for iroach

large essing ration trivial TIS, is /liquid jence rarely

It of a ~ from .ibria. io and r, and lately, ritical y canm thet data 11 proed. lower rystalcesses Ie one Ie othniche rial is

prone to decomposition at distillation temperatures, it will likely be stable at its freezing point. Compared to distillation, melt crystallization may be slower but it is also gentler and kinder.

When to use melt crystallization

Table 2. How distillation and melt crystallization compare.

Distillation

Both liquid and vapor phases are totally miscible.

Liquid phases are totally miscible; solid phases are not miscible.

Conventional vapor !Iiquid equilibrium.

Neither phase is pure.

Separation factors are moderate and

decrease as purity increases.

Ultra-high purity is difficult to achieve.

No theoretical limit on recovery.

Eutectic system.

Solid phase is pure, except at eutectic point.

Partition coefficients are very high (theoretically, they can be infinite).

Ultra-high purity is easy to achieve.

Recovery is limited by eutectic composition.

High mass-transfer rates in both vapor and liquid phases.

Mass-transfer kinetics

Close approach to equilibrium.

Adiabatic contact assures phase equilibrium.

Only moderate mass-transfer rate in liquid phase, zero in solid.

Phase densities differ by a factor of 100-10,000:1.

Phase separability

Viscosity in both phases is low.

Phase separation is rapid and complete.

Countercurrent contacting is quick and efficient.

are tried are the results of thermal decomposition quantified.

Dirnerization or polymerization can cause real operating problems in distillation columns. Stabilizers are only effective if they remain in the liquid. If local temperature gradients separate the stabilizer, then polymerization may start and lead to column blockage. Acrylic acid, for one, is difficult to purify for this reason. Melt crystallization is now the preferred method for production of high-quality glacial acrylic acid.

2. Will the material crystallize? Because rate processes are critical in melt crystallization, it is difficult to predict how a mixture will sepa-

Slow approach to equilibrium; achieved in brief contact time. Included impurities cannot diffuse out of solid.

There are a number of points to look at when making a desktop evaluation of melt crystallization for a specific separation.

Consider the following points in turn:

1. Can the mixture be distilled?

Distillation is a much faster process than crystallization. If distillation can produce specification product, it is unlikely that melt crystallization will be cheaper to install or operate. Particular difficulties with distillation arise, however,

i 1 two areas: low relative olatility and thermal instaiility. Consider, for c x a mp le , a mixture of dichlorobenzene isomers. The boiling points of the para- and artha-isomers of dichlorobenzene are only 2° C apart. Separation by distillation requires a large number of stages and a high reflux ratio. Even then, top

purities cannot be reached. In contrast, the para-isomer crystallizes particularly well from the melt. Therefore, melt crystallization is used exclusively to purify paradichlorobenzene, and end purities of 99.99% are easily reached.

Thermally unstable compounds actually are quite often distilled. Either decomposition rates are low or vacuum distillation is employed to lower temperature and minimize the rate of decomposition. The color or odor of a product can, however, be spoi led by decomposition products that are very difficult to remove. Only when top purity becomes an issue and other separation methods

Solid phase must be remelted and refrozen to allow phase equilibrium.

Phase densities differ by only about10%.

Liquid phase viscosity moderate, solid phase rigid.

Phase separation is slow;

surface-tension effects prevent completion.

Countercurrent contacting is slow and imperfect.

rate without pilot-plant results. If a chemical has not been pilot tested, then a simple freeze test in the laboratory will give some indication of its behavior. Performing such a lab freeze test is straightforward (see the sidebar).

If the freeze-test analyses show a promising degree of purification, say, a halving or better in total impurity. then an industrial separation process may well be feasible. Remember that solid/liquid separation is nearly always the problematic step, so proper pilot testing will still be necessary to give any information to estimate plant size. Nevertheless, the lab freeze test is a useful first

CHEMICAL ENGINEERING PROGRESS • MARCH 1992 • 5!

SEPARATION TECHNOLOGY

r

.......................... .---------------------------------------------------~~

step. If carried out by specialists,

for example. at one of the companies promoting a particular process. the test can be particularly useful. Such specialists can easily compare the separation with others that they have tried under similar conditions.

In the absence of any test data, molecular structure is the only clue to how suitable a material may be for purification by melt crystallization. Most ring compounds with their compact structures will crystallize well. If there are problems distilling them or if ultrahigh purities are sought, they can be considered good candidates.

Disubstituted benzenes, such as • Figure 4. Impurity removal from para-

dichlorobenzenes or nitrochloro- dichlorobenzene per falling-film stage.

benzenes. form close-boiling isomers; all crystallize well from the melt. Some ring compounds, such as diamines, behave spectacularly. Fused-ring compounds like naphthalene can be purified, in spite of a tendency to form solid solutions. Coal-tar-derived naphthalene is commonly purified by melt crystallization to remove both sulfur and color.

Carboxylic acids can be separated using progressive freezing processes that we will describe later. Top-quality acrylic acid and monochloracetic acid are both produced in this way. Fatty acids can also be separated, despite mediocre phase separation.

Again, discussion with specialists is always useful. Even specialty chemicals are apt to have structural

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PDCB in Stage Feed, %

similarities to substances whose

behavior is known to those working in the melt-crystallization field.

3. Is melting point important? Extremes of melting point present difficulties for melt crystallization.

These difficulties are usually manageable, depending on the process used. Refrigeration is required to crystallize low-melting-point compounds. The lower the temperature, the more expensive the refrigeration becomes. Insulation costs also increase and, at temperatures below _350 C, the ductility of materials of construction becomes an issue.

On the other hand, high-meltingpoint materials are subject to unwanted freeze-ups. Tracing is required if ambient temperature can fall below

56 • MARCH 1992 • CHEMICAL ENGINEERING PROGRESS

the freezing point. If the melting point is high, say, more than 100-1500 C above ambient, then full jacketing is needed. The costs for this are significant when one considers that vent systems and equipment such as valves and pumps as well as pipes and vessels require jacketing or tracing.

Progressive freezing techniques are much less susceptible to freeze-ups than continuous suspension processes. Periodic heating of the heat-transfer surface to sweat and melt down suspended crystals avoids the problems from insidious heat leak that often destabilize the operation of suspension processes.

4. How important is product purity?

In the majority of situations, as we have discussed, the crystalline component is inherently pure. Imperfections in solid/liquid separation account for whatever impurities appear in the final product. Multi staging is used to minimize these. If the solid/liquid separation functions the saine in each stage, then clearly the impurity concentration will go down by the same factor in each stage - that is, the impurity level will decrease exponentially with the number of purification stages.

Actually, solid/liquid separation nearly always improves with increasing product purity because the crystal structure has fewer imperfections, less surface area, and better drainage. This accounts for the dramatic increase in impurity removal seen with some compounds at high purities. Figure 4 shows measured values for para-dichlorobenzene, crystallized from a falling film.

Such is not the case with distillation. Stage efficiency is not normally a function of purity; so, ultra-purities can be difficult to reach. If ppm or lower impurity levels are necessary, then melt crystallization may be the better process.

5. How important is product recovery?

Recovery in most systems is limited by the existence of a eutectic.

Fl si th se bf til e( le at th ty 111 til

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~ melting ore than mbient, needed. gnificant hat vent

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product

ions, as rstalline y pure.

separaipurities roduct. inimize paration .1 stage, ncentrame facis, the

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iaration increashe crys'ections, rainage. 'amatic 'al seen gh purij values crystal-

distillaonnally -purities ppm or cessary, , be the

.roduct

. is limutectic.

Further crystallization at this point simply freezes both components in the same proportion as they are present in the melt. This mayor may not be important for a particular separarion. If the residue is passed to an t~quilibrium reactor, then recovery is less critical. If the residue is incinerated, then recovery directly impacts the bottom line. Of course, feed puritv is the most critical factor in determining recovery. If the feed is pure, then the residue stream will be small and its composition unimportant.

In some cases, melt crystallization will reach higher purities than distillation, but at the expense of recovery. In such a case, both techniques :an be combined. The feed is first (,redistilled to remove the bulk of the Impurities and then melt crystallized to polish the final product. Figure 5 shows just such a combination.

I

Industrial melt crystamzation pr'ocesses

Melt crystallization processes fall basically into two distinct categories:

Suspension processes- In these, he crystals are freely suspended in a melt. Such processes depend on density difference to promote countercurrent transport of crystals and melt.

Progressive freezing processes - Here, a crystal layer is grown on a heat-transfer surface. Phase separation to facilitate countercurrent contacting is by gravity draining and functions irrespective of density difference.

Both types of process are used industrially. Table 3 compares the fundamental characteristics of each.

Suspension crystallization processes

Solvent crystallization processes operate in suspension. Solvent is cooled or evaporated from a suspension of crystals in mother liquor and the resulting supersaturation causes nucleation and crystal growth. A balance is maintained by continuously removing crystals from the suspension by sedimentation. The thickened crystal slurry is centrifuged and the product cake is washed with pure

t

i

J

I

J

Table 3. How suspension crystallization and progressive freezing differ.

Suspension crystallization

Progressive freezing

trysta( growtll

Crystals freely suspended in melt.

Crystals grown as a layer on heattransfer surface.

Crystals and melt at the same temperature.

Crystals are colder than melt.

Driving force is supersaturation.

Driving force is temperature gradient.

Large interfacial area.

Moderate interfacial area.

Poor interfacial turbulence.

High interfacial turbulence.

Low mass-transfer rates.

Moderate mass-transfer rates.

Phase separation

Large interfacial area.

Moderate interfacial area.

Sepllration by filters, centrifuges, or decanters.

Separation by gravity draining.

Driving force is the solid/liquid density difference.

Driving force is the liquid/gas density difference.

Solid/liquid separation is difficult.

Solid/liquid separation is easy.

Product can be washed to improve purity.

Product can be washed or sweated to improve purity.

Product is in solid form.

I!roduct is in liquid form.

Ultra pure Product

Melt Crystallization

Recycle

• Figure 5. Combining distillation with melt crystallization call offer advantages.

CHEMICAL ENGINEERING PROGRESS • MARCH 1992 • 57

SEPARATION TECHNOLOGY

........................ .-------------------------------------------------~

solvent to remove adherent mother liquor.

Melt crystallization in SLlSpension is a much more difficult proposition. There is no solvent to evaporate or with which to wash crystals. Melt viscosities are much higher and systems are prone to freeze-ups and instabilities.

Direct injection of refriger-

ant is one way to generate the crystal suspension, but this introduces a second fluid into the system. The most common method is to use scraped-wall crystallizers. The thickened suspension from the crystalliz-

er normally is centrifuged to remove as much melt as possible. Typically, the crystalline material will be pure. Given high melt viscosity and small density differences, however, solid/liquid separation is not

easy. Often a centrifuge cake

will contain 15-20% liquor. Unless a solvent is used to wash the cake, multistaging will be required to reach final product purity.

Purification columns are often used to reduce the need for multistaging: The crystal slurry is introduced to the top of a column that contains melt. Crystals sink to form a bed in the lower part of the column where they are melted. Part of this molten stream is retluxed upward to displace impure melt from the surface of the crystals in the bed. The remainder is taken from the bottom of the column as pure product. Impure melt is taken from the top of the column.

Column performance depends on a uniform countercurrent flow of crystals and mel t. Various features have been included in different column designs to promote this. In the Phillips column, for example, developed for purifying para-xylene, pulsing is used.

Because of the inherent solid/liquid separation difficulties, columns cannot provide more than a few countercurrent stages. They are often used in conjunction with multistaging to give a final polish to the prod-

58 • MARCH 1992 • CHEMICAL ENGINEERING PROGRESS

this layer by gravity and pure product is recovered by remelting the layer. No slurries are handled whatsoever and no mechanical devices are required. (See the sidebar.) Sophisticated variants of this process account for 80% of the new melt crystallization plants built in the last five years (3).

Static crystallization - This is the simplest progressive freezing technique. The crystal layer is slowly grown on a cooled surface immersed in quiescent melt. Horizontal shell-and-tube heat exchangers are often used, with the melt on the shell side and coolant in the tubes. First the shell side is filled with feed, then coolant temperature is ramped slowly down to grow the crystal layer. After the crystal layer is grown, the shell side of the exchanger is drained, leaving crystals on the outside of the tubes. The coolant temperature is then carefully ramped up to sweat the crystals. Finally, the sweated crystals are melted off the tubes as product.

Specially designed static systems are available from vendors such as BEFS and Sulzer Chemtech. The crystal layer is grown on vertical, cooled plates. Sweating and draining are faster and piloting the operation of a single plate allows accurate scaleup. The optimized performance of such designs is significantly better than "homegrown" systems using horizontal-tubular exchangers.

Static crystallization is, unfortunately, very slow. Crystal-layer growth rates have to be limited to around I in.!IO h. Faster growth rates lead to impurity buildup at the solid/liquid interface, which in turn lowers the freezing point locally. Layer growth becomes unstable, resulting in a porous crystal structure from which residue does not drain.

Falling film crystallization - This technique is now used in large and medium capacity plants on a wide range of products and is shown in Figure 6. It has largely replaced

Phase 1:

A crystalline layer is grown from a falling film of melt on the inside of a tube which is cooled externally by a cocurrent falling film of a heat transfer fluid.

Phase 1 a:

The melt is drained off.

Phase 2:

The tube wall is heated to induce

partial melting (sweating); the melted material is drained off.

Phase 3:

The remaining crystal layer is melted off and collected as

(intermediate) product.

• Figure 6. How progressive freezing from a falling film works.

uct. The biggest problem is scaleup, because column diameter has a major influence on axial dispersion.

A Japanese company, Tsukishima Kikai, has introduced a multistage suspension process with scrapedwall crystallizers and a final purification column. Its novel feature is the use of hydrocyclones, instead of centrifuges, to thicken the slurry from each stage. Plants have been built to purify para-xylene and paradichlorobenzene (2).

Progressive freezing processes

Progressive freezing is a technique that is peculiar to melt crystallization. Instead of scraping crystals from the heat-transfer surface, a uniform crystalline layer is allowed to grow. Impure melt is drained from

rd pure remelt-ies are and no s are . Iebar.) of this a of the I plants s (3).

1011 - ~ressive

crystal n on a rsed in zontal hangers melt on It in the side is coolant slowly tI layer.

yer is of the

leaving

of the ierature d up to lly, the Ited off

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nfortut -layer .ited to th rates at the in turn ocally. stable, ructure ram. ion - n large ts on a

shown .placed

Feed

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Residue Melt Storage Tanks

Heat Ca rrier Conditioning Pump

Collecting iH----t Tank

Residue _~~ .. _... ... ....:-ct Product

How Progressive Freezing Works

Progressi ve freezing is also referred to as layer growth or directional solidification. It involves the following sequence

of steps: "'.:,;.

1. A surface ill contaCtlwith a batch of melt is 'Cooled andsmaterial freezes onto it.)n·'mosr;;cases, the melt is agitatedito~~s~~!jfimpu:·;.

.rity, transport ,a way t\9,~'"tfit:.~,~QI-;/ i d/l i q uid=in terfacetd uririg;jtl;t,y{

freezing process.,:."~~~r~~~~g:.

2. Thefreezina proces~iisTtialt::i:

. '-.~-""~' o. ·c:'"_-·.-_.i't-,"_::-,,:,,~,_ f,f~

ed when a ·certaiu·proP9}:tiQ,R;.9t.

the original batch ls'(froie'll.' Impurities areconcentrated " in the

remaining melt. ., "" . ,,',,<? IF(!.

3. Thelen~ainil1g'~flI1eltr(the' resid ue ). isdrained awaYrPQ1n-;th,e;" frozen I ayeLSometi mes~to~ aS~si$t;& .the, draining" proces,s,Jhet.JC[yS.FhJ~,

-layer-is-gendy w.ah1il.§!(~l~!'~,tba'§~ impurities incLnded:inkthe~CIy:sta~;i structure aresweated .ou.L,;,~ .~IJ\;:i < . \'

4. Producn.is ;ec.O\t~recNibn; heating the heat-transfer _sli(face to' . meltof;f the-frozen

side cross-flow is also prevented. Because each tube sees exactly the same hydraulic and thermal conditions on both sides, scaleup is trivial, Pilot-plant tests on a single full-size tube are used to design plants with several thousand tubes.

Multistaging - Even with sweating, the product from a single stage may not be at the specified product purity, so mu l ti s tag i n g may be required. Impurities can be included inside the crystal structure or the crystal surface may simply be wetted with residue. In this case, the product is reprocessed by repeating the crystallization, sweating and melting steps.

In the Sulzer Chemtech system, all the stages are normal! y run in one and the same crystallizer. Adding a purification stage does not mean adding a second crystallizer, but reprocessing material in the one unit. At the end of the first stage, molten product ends up in the collecting

CHEMICAL ENGINEERING PROGRESS • MARCH 1992 • 5

Melt

• Figure 7. Flow diagram for a falling-film melt crystallization plant.

static crystallization for processing naphthalene, disubstituted benzenes, .nd monochloracetic acid. The pro,~ess has also been used to pioneer ultra-purification of a whole range of monomers by melt crystallization - in world-scale plants with capacities up to 300 million lb/yr. Initially developed by the MWB company in Switzerland (4), the process has been further developed and is now marketed by Sulzer Chemtech (5).

Instead of flooding the crystallizer, a film of melt is made to fall continuously over the cooled surface on which the crystal layer grows. The resulting shear at the solid/liquid interface transports impuri ties rapidly into the bulk of the melt, even with viscous melt. This allows much faster crystal growth rates without interphase instabilities. It is possible to grow solid slabs of crystals at rates in excess of I in.lh, or ten times faster than typical rates for static systems.

Figure 7 shows the process schematically. The crystallizer contains vertical tubes in which the crystal layers grow as cylinders. The collecting tank beneath the

tubes is built integrally with the crystallizer. At the start of a stage, it is filled with a batch of material. The circulating pump then is started to irrigate the tubes, while coolant temperature ramping is begun on the shell side of the crystallizer. The melt circulation rate is high compared to the rate of crystal deposition so that conditions of temperature and composition are uniform down the length of the tubes.

Shell-side temperature is ramped down at a constant rate until the collecting-tank level drops to a preset value, indicating the desired amount of product is suspended in the tubes. At this point, melt circulation ceases and the crystals drain free of residue. Shell-side temperature is then ramped up to a value just below the product's melting point to sweat out included impurities and assist the draining process.

In the Sulzer Chemtech design, shell-side coolant also flows as a falling film. A large pumparound rate and uniform distribution to the top of each tube allows precise control of temperature ramping, particularly important for sweating. Shell-

SEPARATION TECHNOLOGY

Feed

• Figure 8. Reflux technique for progressive freezing can reduce yield loss when reprocessing product.

tank. This material then is recrystallized using the same equipment.

Normally, a reflux technique is used to reduce yield loss when reprocessing the product. Figure 8 shows the procedure for a three-stage process. Residue from each of the last two stages is refluxed to the next lower stage in the subsequent cycle, that is, the subsequent batch. Note that these residue quantities must be stored until this stage is run, so buffer tanks are required.

This method allows each stage to be run with the same mass balance, rather like the stages in a distillation column. Stages can simply be added until the desired product purity is reached, without sacrificing recovery.

Residue Stripping - Reprocessing of the product is nearly always employed to improve product purity. Reprocessing residue enhances recovery.

Consider the previous process example with a reflux ratio of 1.3:1, a typical value. Clearly without residue stripping, 30% of the feed is lost as residue. If the feed is pure, this represents a substantial loss of product.

Residue stripping entails reprocessing residue to recover more product. The reject stream from the process is correspondingly enriched in impurities. In practice, residue batches from the feed stage are collected until enough material has accumulated to fully load the crystal-

60 • MARCH 1992 • CHEMICAL ENGINEERING PROGRESS

lizer. In the example, a residue stage is run every third cycle. Product from the residue stage offsets the feed quantity required in the next feed stage.

More stripping stages can be added to further minimize the quantity of residue. In many systems, the eutectic composition can be approached so that recovery is maximized. In some systems, however, this is not possible due to poor crystal structure at low-melt purities.

The future

What challenges will chemical engineers face in the coming decade? Certainly there will be new products to manufacture, some as a result of new market needs and some as a result of new technologies.

We can also be sure that change will impact upon existing manufacturing processes. Engineers will continue to develop better processes to produce higher quality products. In the chemical process industries, high quality products will increasingly become synonymous with purer products. And better processes will be those with less environmental problems.

The U. S. CPI are already pioneering the use of melt crystallization to meet this challenge. Top quality chemicals are now being made, without solvent emissions, on a scale undreamt of a decade ago. [3IDJ

LITERATURE CITED

1. Matsuoka, M., and H. Fukushima, "Determination of Solid Liquid Equilibrium," Bunri Gijutsu Sep. Proc. Eng., 16, p. 4 (1986).

2. Meyer, D. W., "Using Crystallization for Organic Separations," Chem. Proc., 53, p. 50 (Jan. 1990).

3. "Fractional Crystallization," Publication 28.56.06.40, Sulzer, Winterthur, Switz. (April 1991).

4. Saxer, K., "A Large-Scale Industrial Process for Fractional Crystallization, Chemische Produktion, p. 28 (Nov. 1980) .

5. Jancie, S. J., "The Sulzer MWB Fractional Crystallization System," Tech. Rev., Sulzer,. Winterthur, Switz. (1986).

FURTHER READING

Sloan, G. J., and A. R. McGhie, "Techniques of Melt Crystallization" in "Techniques of Chemistry" 19, Wiley, New York (1988).

Fischer, 0., S. J. Jancic, and K. Saxer, "Purification of Compounds Forming Eutectics and Solid Solutions by Fractional Crystallization," in "Industrial Crystallizations, p. 153, Elsevier, New York (1989).

Gilbert, S. W., "Melt Crystallization Process Analysis and Optimization," A1ChE Journal, 37, p. 1,205 (Aug. 1991).

N. P. WYNN is manager of crystallization systems for the Chemtech Div. of Sulzer Canada Inc., Rexdale, Onto (416/674-2034; Fax: 416/673-7058). After joining Sulzer Brothers in Switzerland, he spent 12 years working on process development and plant engineering in hydrometallurgical processing, heavy water production, and gas processing. areas in which he holds several patents. He is now responsible for the firm's melt crystallization activities in the U. S., Canada, and Mexico. He received a BS in mechanical engineering from the Univ. of Surrey (U. K.), and an MS in chemical engineering from Massachusetts Inst. of Technology, He is a member of AIChE and is a registered Professional Engineer.

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