200 Years in Innovation of Continuous Distillation

Norbert Kockmann[1]*

Abstract
Distillation is one of the oldest and most frequently
used purification methods today. In 1813, Jean-Baptiste Cellier-Blumenthal patented the first continuously working distillation column, starting an impressive development of process equipment. New
product areas were discovered as well as improved

equipment installations. 100 years ago, Fritz Raschig

patented his rings as packing material. Current developments are guided by deeper knowledge of heat
and mass transfer as well as the integration of various process functions.

Keywords: Alcohol distillation, Coal tar refining, Cryogenic air separation, Continuous distillation, Process intensification,
Structured packing
Received: October 31, 2013; accepted: November 19, 2013
DOI: 10.1002/cben.201300003

Introduction

The discussion of innovation in technical development must

include the social, cultural, and political situation, too. The
pathway often doesnt follow a stringent, engineering-like argumentation with precision and reliability; it includes jumps,
gaps, or inconsistencies. Innovation in distillation is indeed
influenced by many technical and nontechnical factors and its
history gives many illustrative examples guiding also the developments of today. Distillation is a well-defined separation unit
consisting of the partial evaporation of a liquid mixture and
successive condensation with a different composition than the
original material. The word distillation comes from the Latin
verb destillare to drop down or to trickle down. The meaning
of rectification origins from Latin, too: rectificare to purify or
enhance, but has a broader meaning. In ancient and medieval
times, nearly all purification and separation operations were
subsumed under the term of distillation, such as filtration, crystallization, extraction, sublimation, or mechanical pressing of
oil. Today, distillation is often combined with other process
steps such as extraction or chemical reaction [1], hence it is
now closer to the original meaning.
The first civilizations started in Mesopotamia, Egypt, Syria,
and China and spread from there. Conclusions can only be
drawn from excavations in Iraq about the processing of foods
or pharmaceutical products [2] such as perfumes, balsam, tinctures, or creams more than 5500 years ago. Chinese activities in
distillation are reported from ancient times [3]. Early types of
pots similar to Fig. 1 were found in China around 2000 BC.
The equipment from Alexandria during the Hellenic and Roman era [4] did not change so much until the 16th century
AD. With the increased knowledge transfer by printed books
and larger demand of distilled products such as concentrated

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alcohol or mineral acids, the development of various stills

thrived and in part already to the extent of mass production.
French scientists, English industry and business men as well as
German engineers brought the equipment to lab and industrial
application maturity. Important milestones are the patent on
the first continuous distillation column and process 200 years
ago by Jean-Baptiste Cellier-Blumenthal in France [4] and 100
years ago the patent of Fritz Raschig on his rings for mass
transfer equipment [5].
There are many publications on the history of distillation
dealing with the development until the beginning of the last
century [4, 611]. This contribution gives after the obligatory
historical introduction an overview about the last century including current distillation innovation. An extensive description will be given in a book chapter, which will appear soon
[12]. In addition, many old books and further material has
been digitalized and is available online to inspire new studies.

From Stone to Middle Ages

The development of early distillation devices is illustrated in

Fig. 1 for the period from early civilizations to the dawn of
modern ages [3]. The Sumerian began around 3500 BC to apply evaporating and condensing a liquid to refine a substance
for extracting essential oils from herbs. Many of the pots and

[1]

Prof. Dr.-Ing. Norbert Kockmann

TU Dortmund, Biochemical and Chemical Engineering Faculty
(BCI), Apparatus Design, Emil-Figge-Strae 68, 44227 Dortmund,
Germany.
E-Mail: [email protected]

English version of DOI: 10.1002/cite.201300092

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Figure 1. Development of early distillation equipment from

neolithicum to the beginning of the modern age, according to
[3, 8].

stills shown on the right side were found in excavations 250 km

north of Bagdad, Iraq [2].
The liquid in the still evaporates by gentle heating from below and condenses at the colder cap (distillation). Droplets are
running down to be collected in the ring, where organic material such as leaves and herbs are extracted by the liquid (extraction). Typical dimension of the earthenware pot are approximately 50 cm in diameter and 25 to 50 cm in height. Besides
herbs and perfumes, asphalt and wood tar were distilled, often
for spiritual services [13]. Hence, priests and temple servants
used such apparatus and kept their recipes secret. In Egypt,
essential oils and elixirs from herbs were distilled depicted on
the papyrus Ebers (1550 BC) on medical issues [13].
Pliny and Dioscorides described the top right device to be
used on ships producing drinking water from sea water by
heating it up [10] as depicted in Fig. 1 top. Water evaporates by
sun radiation and condenses in a wet wool fleece. Similar to
this a Mongolian still works with a collecting cup centrally
within the still body [3]. Fermented horse milk was heated and
distilled to karakumyss. The amount of cooling water determines the content of alcohol in the product.
From 300 BC under the Ptolemaic regime, Alexandria in
Egypt evolved to the scientific center of the antique world. The
city with university and library served as mediator between
eastern and western civilization until 600 AD. In the 1st century AD the School of Alchemists formed which systematically
collected and developed the contemporary chemical knowledge.

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In the course of developments, the simple earthen ware pots

with rim were supplemented with a tubular connection
through which the condensate could exit continuously. Capacity and performance are increased and different fractions can
be taken separately. The rim moves into the lid, hence, the hot
still is thermically separated from the cold dephlegmator and
alembic. The elements are connected and sealed by wet lime,
clay, wool, and other natural fibers. A beautiful glass distillation
helmet, the alembic, from Alexandria (500800 AD) is shown
on the top of Fig. 1 [3]. Major products were medical products,
herbal essential oils, perfumes, light oils, and also tar as viscous
residue for construction and ship building purposes.
The Alexandrian period was followed by the early Arab period from 7001200 AD without any larger disturbances. The
Arabs adopted the technology of the Alexandrian and Syrian
chemists, mainly for the production of perfume, rose water and
oil, and medical substances. Two major centers were important
for the technology conservation, Bagdad in the east and Cordoba in the west. In South Europe, Salerno with its medical
school, Venice with its trade connections and glass blowing art,
and the Moorish cities in Spain played an important role. Here,
traditional books were translated from Arabic to Latin. Typical
examples from the richly illustrated books are shown in Fig. 2,
depicting the investigation and teaching in medical schools.
Additionally, Eastern knowledge and skills were brought to
Europe the Crusades.

Figure 2. Medieval book miniatures from the medical school of

Salerno The Articella. Left: a physician holding a flask with liquid,
possibly comparing it to pictures or descriptions in a book; right:
a physician displaying a flask to a student. Courtesy of the
National Library of Medicine.

In Europe, alcohol was one of the major products due to its

use for drinking, disinfection, and preparation of medical substances. Albert the Great (Albertus Magnus, 11931280 in
Cologne) worked on the distillation of wine and other spirits.
He considered distillation as the most important method in
alchemy: the alchemist requires two or three rooms exclusively devoted to sublimations, solutions and distillations [4].
Around 1300 AD the distillation processes were classified in
two methods: per ascensum (ascending) and per descensum
(descending). Both methods and descriptions were kept into
the 18th century, but the latter is now rarely applied. It was
mainly used for the dry distillation of solid substances such as
woods, barks and herbs. The ascending method follows the vapor path and is realized in nearly all current processes.

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the top left corner and in the opposite corner another still
alembic and a young man are shown. The Rosenhut, an invention of the medieval ages, is a conical head for the still to
improve cooling and vapor guidance. In the top right corner,
a man is drinking from a small bottle, as is the deer in the middle. The lower part of the illustration shows a garden with
many different plants, harvested by two women and a man,
probably the farmer with a hoe in his hand. In the lower right
part the young man with a floral wreath in his hair, similar to
the wreath of young women, harvesting is operating the distillation vessel. While heating with his right hand, he is testing
the temperature of the upper part of the cucurbit with the fingertips of the left hand. The title page illustrates the two major
products of distillation: drinking alcohol and medical applications.
As early as 1555, Conrad Gesner described a multistep distillation for higher purity [20]. Georg Agricola described in his
famous book De Re Metallica [21] in 1556 the distillation and
concentration of mineral acids such as sulfuric or nitric acid.
These were used for ore processing and metal separation and
purification. Due to the large amounts needed, the stills were
arranged in parallel around the heating source, also called
Fauler Heinz (lazy Henry) in German. The first steam heating
was used by Claude Dariot (153394), and nearly
200 years later Jean Pissonier (1770) described the
first counter-current flow cooling [10].
The 17th and 18th century were characterized by
the installation of complete laboratories for chemical studies and the large-scale production of
alcohol, medical substances, perfumes, or mineral
acids, see Fig. 4. In 1595, Andreas Libau (Libavius)
described in Latin the general setup of a chemical
laboratory [22]. He distinguished the rooms according to their functions and chemical operations
and already used a tube system for tapped water.
He also categorized the distillation equipment according to the heating, cooling, and the vapor flow
direction, i.e., ascending or descending.
Robert Boyle (16261692), often called the father
of modern chemistry, conducted systematic distillation experiments. He distilled alcohol with fragments of acetic acid over several days and found
that the liquid at the end had a higher content in
acid than the starting material. He worked under
vacuum and elevated pressure conditions. Johann
Kunckel von Lwenstern, a glassmaker, apothecary,
and experimental chemist, described in his book
Laboratorium Chymicum (1716) [25] the current
knowledge of lab chemistry. From his intensive
knowledge of different materials and processes, he
preferred glass equipment in the laboratory, which
is dominant until today.
The Industrial Revolution was led by the mechanical textile industry with its high demand for
sulfuric acid as bleaching agent. The acid was produced with stills from platinum [26]. Concurrently,
the production rate of drinking alcohol increased
driven by sugar cane farming and rum demand. In
Figure 3. Title page of Brunschwygks book on the Art of Distillation [17], displaythe British colonies The Society of Rectifying Distiling an herb garden with two stills.
The invention of printed books with movable letters at the
end of the 15th century AD led to a wider distribution of
knowledge and further promotion of inventions. Besides effective and rapid multiplication and distribution of knowledge,
local languages such as French, English, or German were supported and dominated science and technology. Now, more people could read and understand the new methods to work on
the equipment and recipes. People with more technical background had the chance to come into contact with the traditional knowledge from monasteries and noble courts. Main
authors on distillation were Michael Puff von Schrick (1487)
[16], Hieronymus Brunschwygk (1500) [17], Philip Ulsted
(1526) [18], and Walter Ryff (1545) [19]. In these books equipment and design details as well as many recipes were given to
produce a multitude of distilled waters from plants and animals.
Apparently, many pharmacists and apothecaries used the advanced methods of distillation to concentrate herb extracts or
to mix alcohol with other ingredients. They placed their apparatus directly in the herb gardens, as can be seen on the title
page from Brunschwygk [17], see Fig. 3.
Two different distillation set-ups are shown in the corners: a
Rosenhut still with a man filling an empty flask is depicted in

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Figure 4. Standardized distillation still with air-cooled alembic.

Left: John French (1651) [23]; right: Johann Elsholtz (1674) [24]
showing the laboratory setup.

lers [27] played a major role for the development and spreading
of this technology.

Science, Engineers, and

Industrialization

At the end of the 18th century, French scientists leading the

way in pure chemistry, but English scientist were ahead in
commercial-technical chemistry [28]. At the chemical world
exhibition in 1862, England was indisputable the world leader
in chemical industry, but by 1893 world exhibition in Chicago,
Germany had taken over. One reason was the unification of
Germany in 1870/71 that pooled its intellectual forces and allowed for easier exchange of goods and information. The exchange of goods and information got easier. Another reason
was the strength of German universities in chemical research
and the high standard of engineering schools for science-based
innovation.
At the beginning of the 19th century Napoleon offered a
prize for sugar beet production and fermentation to gain independence from British imports of sugar and alcohol. A series of
patents on distillation equipment was issued from 1801 to 1818
[4]. Jean-douard Adam developed a discontinuous apparatus
for fractionating distillation, which was further developed to
include a device for partial condensation by Isaac Brard. Their
work realized two principles: (i) the enrichment of a low boiling component in the rising vapor and (ii) the enrichment of
the vapor by partial condensation and reflux into the still. Both
principles combined led to the continuously working distillation patented by Jean-Baptiste Cellier-Blumenthal (17681840)
in 1813, 200 years ago. In Fig. 5, this distillation column is illustrated. The upper part of the column contains bubble-cap
trays, while the lower part is structured by conical metal caps,
which also serve for contacting vapor and liquid. This setup is
base for all further development in the following 60 years in

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Figure 5. Continuously working distillation column for wine by

Cellier-Blumenthal, patented 1813 [10]. The arrangement consists of two vessels, the stripping region with conical metal
sheets, the enrichment section, partial condenser (dephlegmator), and water cooled condenser [29].

France and also influenced the constructions in both Germany

and England.
Many details of the Cellier column were improved in the following years. In 1817 Charles Derosne (17801846) also built a
continuously working distillation column and brought it to industrial maturity [4]. His economic and technical success also
relied on other industrial products, such as sugar plants, locomotives, and other railway equipment. In 1822 Anthony Perrier got a patent on baffles as tray construction in a whiskey
distillery to enhance the contact between vapor and liquid
phase. They are similar to current bubble-tray caps and inserts.
Aeneas Coffey developed perforated trays as sieve structures
for the vapor-liquid contact in 1830. Sieve plate columns had a
distance of 6 in (15 cm) or more [5]. They were primarily developed for higher viscous liquids, which was not successful.
Today sieve trays are used for nonfoaming, low viscous liquids
such as liquefied air separation columns. Higher viscous liquids
could successfully be separated by a bubble-cap trays column
patented in 1854 by Henri Champonnois.
Nearly at the same time as Cellier, Heinrich Pistorius (1777
1858) patented in Germany his distillation plant in 1817 for
alcohol from fermented potato mash, see Fig. 6. Brandy from
fermented potatoes became very popular in Germany in the
beginning of the 19th century. The Pistorius still was widely
used in Germany until 1870 and produced liquors with 60 to
80 % in alcohol content. The unit consists of two stills with
manual stirrer and two conical distributors in the column,
which allow only for a low separation performance.

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Figure 6. Two-vessel-still by Heinrich Pistorius, German patent of

in small alcohol distilleries.

Pierre Savalle (17911864) was an early co-worker of Cellier

and made his first experiments in a sugar refinery. Together
with his son Francois Dsir Savalle (born 1838) he designed
new equipment and improved many details of the cooling and
heating systems [31]. The throughput became 78 times higher
than in the Cellier column [4]. The simple continuously working apparatus from Savalle was especially used for alcohol production from cane-sugar. In his book from 1873 [31] Savalle
observed that more than 16 000 distilleries are working in Germany, but only 700 in France. The production of 100 L alcohol
from wine needs 40 kg of coal. The Savalle columns contain typically 30 trays and reflux two-thirds of the total distillate. Savalle described the rectification of methyl alcohol and the fractionation of crude benzene in two columns at BASF [4] in
Ludwigshafen, Germany. Another pupil of Cellier was AugustePierre Dubrunfaut, who also improved the Cellier column. He
designed and built columns with diameter of 80100 cm with a
daily yield of 200 to 4800 L alcohol (9294 %). His book on distillation [32] is still one of the best sources for the distillation
development [4]. His columns influenced German companies
such as Heckmann and others [4], and gave input for engineers
such as Eugen Hausbrand, who will be described later.
The second product besides alcohol, by which the innovation
in distillation is guided in the 19th century, was waste from the
coal and coke industry. In the late 18th century dry distilled
coal (coke) was used for the first time for iron production and
smelting. Coke gases were found to burn with a bright flame
for private and public lighting. In 1826 gas lighting was introduced in Berlin, after London in 1807 and Paris in 1822. The
gas had to be washed in absorbers before feeding into the pipelines. The washing fluid contained ammonia, benzene, phenol,
and other aromatic compounds as valuable goods, which had
to be stripped off. Coal tar was the highly viscous byproduct in
gas plant for lightening and coke. In 1822, the first industrial
tar distillation plant was built in Britain [33]. In 1823, Friedlieb
Runge discovered phenol and aniline in the coal tar and laid
the foundation of tar chemistry. The valuable side products
were separated by washing, absorption, and distillation at the
white side of coking plants. The first absorption and distillation

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equipment was made from wood with

stacked wooden internals [34]. Other materials were dumped and unstructured stones
or lumps of coke and iron or steel for
higher stability of the outer construction
and vessel. Ammonia distillation towers
and benzene washers looked similar to alcohol plants, see Fig. 7.
In 1842 the first tar distillation in Germany was started in Offenbach near Frankfurt. Julius Rtgers built a plant in Erkner
near Berlin in 1860 [33], followed by other
plants in Dresden, Katowice, Vienna, Munich, and Rauxel. The tar was primarily
used to impregnate and waterproof railway
sleepers, telegraph poles, and other wooden
construction material. The high boiling
1817 [30], often used
fraction or residue was used for street
pavement. In 1867 Georg Lunge wrote a
comprehensive book on coal tar distillation
[35], where he described his experience from tar distillation
plants in England and Germany. Regarded as the father of technical chemistry, he brought practical knowledge into the aca-

Figure 7. Ammonia distillation tower with a combination of

dephlegmator and bubble-tray column, tall column with conical
contactors, and right column with bubble-cap trays [30].

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demic circuits as professor in Zrich, discussing quantitative

methods to design distillation plants and related cost calculations. His contribution opened the British technology to continental Europe and inspired for new ideas. Also the young
petroleum industry benefitted from these developments. Lunge
already described the concept of unit operations before it was
coined by Arthur D. Little in 1915. Phenol chemistry needs
high purity components and, hence, tall separation columns
were constructed of up to 60 m in height. This development demanded for better construction material, enhanced gas-liquid
contacting internals, and improved calculation procedures.
In the beginning of the 20th century, coal tar distillation was
established for the production of raw materials for the chemical
industry [36]. Both discontinuous and continuous processes
were developed, although the latter is quite complex due to the
high viscosity of tar and pitch. The invention of Frederic Lennard was pathbreaking, with German patents in 1889 and
1891, consisting of a long, heated tube for gas generation with
a typical throughput of 100150 t d1. In 1913, Fritz Raschig
patented in Germany rings with 25 mm height and diameter
made from glass, porcelain, copper, iron, or other resistive material [5]. They exhibited a lower pressure loss and better mass
transfer characteristics and could be setup in an arranged packing [28]. In 1914, a Raschig plant was started in Linz am Rhein
at Walter Feld GmbH consisting of three tube bundle heat
exchangers and two columns. For the medium fraction, the column was equipped with bubble-cap trays, while the vacuum
column had a Raschig ring filling for light oil and naphtha separation [34].
With increasing steel and coal production, the oxygen demand was also increasing, similarly to the increasing nitrogen
demand in chemistry. After the liquefaction of air by Carl von
Linde in 1895, the separation of oxygen and nitrogen became
important. Raoul Pictet developed his oxygen apparatus in
1899 with a special rectifying arrangement [37] and heat recovery in the column. The Linde oxygen column from 1902 is
filled with glass beads, wherein nitrogen rich vapor streams up,
while the oxygen rich liquid trickles down to the column reboiler. The liquid oxygen is partially evaporated and leaves the column over a siphon with a purity of 99 %. Distillation columns
with dumped glass beads of 4 mm in diameter were already
tested by Walther Hempel 1881 for lab applications, before in
1890 Robert Ilges used porcelain balls with 12 in (2550 mm)
in diameter in columns [5]. He also developed a temperature
controlled apparatus, which was then very popular in small distilleries. In 1903, Georges Claude, founder of the French company lAir Liquide, presented an oxygen column with only one
single heat exchanger. The column internals were bubble-cap
trays with downcomers for the liquid on top of the heat
exchanger section [37]. In 1907 Linde further improved his
oxygen column with medium and low pressure column and
presumably already sieve trays.

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Scientific Understanding and Process

Integration

At the beginning of the 20th century, the number of production

from distillation is increasing together with the multitude of
equipment designs. Devices and internals are built by small
and medium enterprises such as Heckmann [38, 39] or Montz
[40] guided by genius engineers. Eugen Hausbrand (1845
1922) was chief engineer and director at Heckmann and was
already mentioned in the tradition of Cellier and his pupils. He
is regarded as one of the first process engineers [38], who published first quantitative calculations for rectification and distillation [39]. In his famous monograph [39], he discussed heat
and mass flow diagrams in rectification columns similar to
Sankey-diagrams of today. Hausbrand was director of the
Heckmann Company for over 40 years. He practiced the method of discussion to evaluate new technical systems, comparable
to HAZOP (hazards and operability studies) methods of today.
Further publications of him dealt with heat and mass transfer
of process equipment, continued later by Wilhelm Nuelt.
Simple calculations for batch distillation were performed by
Rayleigh in 1902 [5] with material balance and simplification
of the relative volatility. He applied also Henrys and Raoults
law and compared his results with test data. Hausbrand initiated further work on distillation, e.g. Robinson in 1922 [41],
Walker, Lewis, and McAdams in 1923 [42], von Rechenberg in
1923 [43], or Mariller in1925 [44]. In 1925 Thiele and McCabe
[45] published a simple graphical method to determine the
performance and number of separation steps in columns with
binary mixtures. Thormann already integrated this method in
his textbook [46] from 1927 and described tray columns,
dumped packing, binary and ternary mixtures as well as some
properties of binary mixtures. The last chapter of his book
deals with the equipment of alcohol distillation, the best understood system at that time. Other distillation systems were probably still under secrecy (air separation, aromatics, hydrocarbons etc.) or used equipment comparable to that of alcohol
distillation.
To compare the different column types, Thomas Chilton and
Allan Colburn proposed a method of the height equivalent to a
theoretical plate reaching vapor-liquid-equilibrium (HETP) for
packed columns in distillation and absorption in the 1935 [47].
Later, Colburn defined the Murphree tray efficiency, which indicates the relative vapor concentration compared to the equilibrium and is a good measure of the efficacy of the mass transfer over a tray. In 1942, the methods of distillation and
rectification were standardized in Germany in DIN 7052 [48].
In 1929 Emil Kirschbaum started his work at the chair of
process engineering in Karlruhe and later published his famous
textbook on distillation [48]. Based on this work, Reinhard Billet in Bochum worked on optimization studies in distillation,
especially in vacuum columns [49]. He worked with several
companies to optimize structured packing and fluid distributors. Ernst-Ulrich Schlnder in Karlsruhe combined extraction
and adsorption with distillation in his textbook [50] and
worked on the heat and mass transfer and integration in columns. His pupil Jerzy Makowiak wrote the textbook on structured packing [51] and their transport characteristics. In 1960

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the textbook on Transport Phenomena by Byron Bird, Warren

Stewart, and Edwin Lightfoot [52] was a landmark and shifted
the view from unit operations to more fundamental processes
of mass and heat transfer. Based on the unit operation concept,
Schembecker, Gorak and Schmidt-Traub developed the conceptual design concept [1] with view on fundamental transport
processes and their combinations on different levels.
Mixtures with close boiling point and isotope separation demand for many separation steps, hence a tall column with intensive mass transfer. Internals from wire mesh and structured
metal sheets were firstly proposed by Walter Podbielnak in
1931 [53]. The Atomic Energy Research Establishment in Harwell, UK, developed in the 1930s a special column internal
called Spraypak filling for heavy water concentration [28]. The
packing is made from stretched or expanded metal, see Fig. 8.
It showed good characteristics for high duty loading for gas
and liquid phase and can be operated with two- to threefold
gas velocity compared to bubble-cap trays. Metal mesh could
reach approximately two theoretical stages per meter.
The second development line of structured packing was the
Stedman Column in 1935 from Knolls Atomic Power Laboratory, General Electric Company, for isotope separation [54].
The packing is fabricated of Monel wire cloth, which is
punched, embossed, and welded to form a series of cells. Another type of structured metal sheet packing, the multiple-cell
triangular pyramid type, was patented by Stedman in 1936
[55]. The triangular packing type exhibits low pressure drop
and hold-up and performs with HETP values of 1.52 in (38
50 mm) and 2.53.3 in (6384 mm) for column diameters of
1.56 in (38152 mm) and 12 in to 11 ft (3003400 mm) diameter, respectively. Applications were low boiling paraffin hydrocarbons (C1 to C7 fraction), which were separated in vacuum columns. The development of structured packing was
guided by smaller companies such as Montz [40], Koch,
Glitsch, Khni, or Sulzer [56]. They take up the demand of the
larger industrial companies and developed specialized solutions
in gas-liquid-contacting, which they could offer to further customers.
Further momentum came from the combination of different
separation technology with distillation for complex separation
tasks or higher yield and efficiency. In extractive distillation
early work was done from 1945 to 1960 [57] to overcome azeotropic limits or to increase the purity. A well-known example is
the separation of toluene and methylcyclohexane [58]. The

selection of the additional solvent is the crucial part during

process design [59]. A list of 32 candidates is given in [57] with
their activity coefficients. The first application of reactive distillation was published in 1948 by the Othmer group [60] on the
esterification of dibutyl phthalate from butanol and phthalic
acid. An illustrative example published in 1984 is the integrated
reactive-extractive distillation of methylacetate from methanol
and acetic acid, which overcomes the chemical equilibrium as
well as azeotropes [61, 62]. Conceptually, the column can be
treated as four heat-integrated distillation columns (one with
the reaction) stacked on top of each other, see Fig. 9. The reactive distillation scheme has been widely discussed from 1995 to
2003, including [63] or [64]. Catalytic active packing such as
Katapak was developed since 1999 and play an important role
in process development.
Focusing on energy consumption significant interest was put
on thermally coupled systems and dividing wall columns for
ternary or more mixtures. A fractionator with vapor side
stream and side-cut rectifier, also known as Petlyuk tower, was
discussed by Stupin and Lockhart in 1972 [66]. The dividing
wall column is topologically equivalent to the fully thermally
coupled system that was first patented in 1933 to produce three
pure products from a single column [67]. One of the first industrial applications was the side rectifier configuration for air
separation and argon production. The fully thermally coupled
system is 30 to 50 % less in energy consumption than any other
ternary column configuration [68, 69], depending on the feed
composition and volatility of the components. Although invented long ago, dividing wall columns and fully thermally
coupled distillation systems were not implemented in practice
until the late 1980s [70]. All the multicomponent thermally
coupled configurations have a corresponding dividing wall column equivalent. Gerd Kaibel has shown in 1987 [71] several
examples of columns with multiple dividing walls, separating
three, four, and six components. In 2005, there were about 60
dividing wall columns in operation; 42 are owned by BASF
[72], where the first was set up in 1985 in Ludwigshafen, Germany.
Further improvements in distillation concern the estimation
and determination of vapor-liquid equilibrium properties [73],
graphical treatment of separation tasks [74], or the establishment of independent research institutes [75, 76], which are outwith the scope of this paper.

Figure 8. Left: Spraypak filling of an absorption/distillation column [28]; right:

column packing made from metal sheets according to the Stedman patent from
1936 [5].

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What Will the Next Innovation

Cycle Bring?

Due to the long innovation cycle in process industries, owing to high investment costs, innovation is
slowly and only partially transferred to practice.
The overall goal is the increasing separation power
per unit volume with better understanding of the
physics of mass transfer processes, while decreasing
the equipment cost [56]. Optimization of the gas
and liquid flows in future packing geometry will be
of high importance assisted by numerical simulation, such as computational fluid dynamics, CFD.
Distributors will have more streamlined forms to

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Figure 9. Integrated reactive-extractive distillation column to produce methylacetate. Left: column with feed positions, middle: concentration profile; right: temperature profile, adapted from [65].

increase capacity and robustness as well as to reduce plugging

and maldistribution. The inlet pressure drop of packing was
minimized and further improvement of mass transfer could be
measured [56].
A general trend is the emerging of multifunctional packing
and their application in combined systems, like catalytic distillation. Still, better understanding of the catalytic performance
and reaction together with the distillation process is necessary
[1]. Combined processes are often performed in separate
equipment, such as hybrid separation processes made from
rectification and melt crystallization to purify close boiling
mixtures [77]. Membrane separation was integrated in a distillation column [78]. Another interesting combination is the vacuum distillation with biocatalytic active packing by Li in 2012
[79]. Microbial biofilms are grown on the structure surface and
employed for ethylene glycol conversion to aldehydes. Another
trend is the use of alternative solvents such as ionic liquids.
In Fig. 10, the separation performance of dumped and structured packing is displayed from 1900 with rocks and Raschig
rings over Berl and Intalox saddles to more complex structured
Nutter rings and Sulzer structured packing in 1990 [80]. Dur-

Figure 10. Development of the packing performance (HTU value) over last 110 years, adapted from [80].

www.ChemBioEngRev.de

ing the last 110 years, a doubling in efficiency took nearly

50 years. With miniaturized internal structures, an increase of
separation performance is described with the square symbols.
Now, only 15 years are necessary for doubling the separation
performance. Most of the data were obtained in very tiny
equipment in the millimeter range [81], from which the results
are hard to scale up to pilot or even production scale. The combination of microchannel flow and a centrifugal field leads to
highest performance in Fig. 10, displayed with circular points.
The other two circles represent experimental data from the
group of Wang in 2011 [82] and Jordan MacInnes and coworkers from rotating spiral microchannel distillation in 2010
[83]. The performance values were calculated in comparison to
conventional structured packing given in the work.
The successful innovation path leads over smart combination, composition, increasing or diminishing, synthesis of different, novel elements as well as application in new areas. Rotating internals were already used in absorption and distillation
columns for better mass transfer in coke tar processing [29].
With this multitude of possibilities, the conceptual design of
distillation systems will become more important [84] and can
serve as a guide through topographic methods selecting optimum configurations. Large companies as user and small companies as flexible suppliers work closely together with academia
and research institutes to push equipment development on
technology platforms and its applications
Distillation accompanies mankind since the early civilizations and distilled products influenced their cultural development. Today, distillation is the most important separation step
in chemical and biochemical processes. Many brilliant minds
worked on the development of processes and apparatus until
today. Nevertheless, new combinations and more advanced
equipment still require research and development. This article
illustrates the main development steps over the last centuries,
from which new inspirations can be drawn for future innovation cycles.
The author has declared no conflict of interests.

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Norbert Kockmann studied

mechanical engineering at TU
Munich and obtained his PhD
on the fouling in heat exchangers from the University of
Bremen. Starting in 1997, he
worked for Messer Griesheim,
Krefeld, as project manager in
plant construction until joining IMTEK at the University
of Freiburg in 2001, where he
established the micro process
engineering group and habilitated in 2007. Joining Lonza
AG, Visp, as head of laboratory for continuous reaction engineering, he developed micro reactors and processes for
pharma production. In April 2011, Norbert Kockmann was
appointed the Bayer endowed chair in Equipment Design at
the TU Dortmund and works on small-scale modular devices and process intensification.

References
[1] Integrated Reaction and Separation Operations (Eds:
H. Schmidt-Traub,A. Gorak), Springer, Berlin 2006.
[2] E. Blass Jr., T. Liebl, M. Hberl Jr., Chem. Ing. Tech. 1997, 69,
431437.
[3] J. Needham, H. Ping-Y, L. Gwei-Djen, N. Sivin, Science and
Civilisation in China: Chemistry and Chemical Technology, Pt.
4: Spagyrical, Discovery and Invention: Apparatus, Theories
and Gifts, 5th ed., Cambridge University Press, Cambridge
1980.
[4] R. J. Forbes, A Short History of the Art of Distillation, Brill,
Leiden 1970 (reprint from 1948).
[5] R. H. Perry, Perrys Chemical Engineers Handbook, 3th ed.,
McGraw-Hill, New York 1950, 655.
[6] L. Deibele, Dissertation, TU Mnchen 1992.
[7] L. Deibele, Chem. Ing. Tech. 1991, 63, 458470.
[8] L. Deibele, Chem. Ing. Tech. 1994, 66, 809818.
[9] A. Bittel, Chem. Ing. Tech. 1959, 31, 365378.
[10] E. Krell, in Historia scientiae naturalis (Eds: E. H. W. Giebeler,K. A. Rosenbauer), GIT-Verlag, Darmstadt 1982.
[11] A. J. V. Underwood, Trans. Inst. Chem. Eng. 1935, 13, 3465.
[12] Destillation (Ed: A. Gorak), Elsevier, Amsterdam 2014.
[13] M. Levey, Chemistry and Chemical Technology in Ancient Mesopotamia, Elsevier, Amsterdam 1959.
[14] H. Schelenz, Zur Geschichte der pharmazeutischen Destilliergerte, Miltiz, Leipzig, 1911.
[15] www.nlm.nih.gov/hmd/medieval/articella.html (accessed 04
June 2012).
[16] M. Puff von Schrick, Von den ausgebrannten Wassern, Augsburg, 1481. urn:nbn:de:bvb:12-bsb00013339-9
[17] H. Brunschwygk, Das Buch der rechten Kunst zu distillieren,
Strassburg, 1500. urn:nbn:de:bvb:12-bsb00031146-3
[18] P. Ulsted, Coelum philosophorum, Strassburg, 1526. urn:nbn:
de:bvb:12-bsb00029475-2

www.ChemBioEngRev.de

[19] W. H. Ryff, Das new gro Distillier-Buch, wolgegrndter knstlicher Distillation, Frankfurt/Main 1545. urn:nbn:de:bvb:12bsb00029508-6
[20] C. Gesner, Thesaurus Euonymi Philiatri, Ein kstlicher Schatz
usw. Zrich 1555. urn:nbn:de:bvb:12-bsb00020905-4
[21] G. Agricola, De Re Metallica, Libri XII, Marix-Verlag, Wiesbaden 2007.
[22] A. Libavius, Praxis alchimiae, Alchymia, Frankfurt 1606. urn:
nbn:de:bvb:12-bsb10073209-2
[23] J. French, Art of Distillation, London 1651.
[24] J. S. Elsholtz, Destillatoria Curiosa, Berlin 1674. urn:nbn:de:
bvb:12-bsb10072415-6
[25] J. Kunckel von Lwenstern, Laboratorium Chymicum, Heyl,
Hamburg 1716. urn:nbn:de:bvb:12-bsb10073115-6
[26] A. Clow, N. L. Clow, in Wissenschaft und Technik im 18. Jahrhundert, (Ed: A. E. Musson), Suhrkamp Verlag, Frankfurt
1977.
[27] F. W. Gibbs, in Wissenschaft und Technik im 18. Jahrhundert
(Ed: A. E. Musson), Suhrkamp Verlag, Frankfurt 1977.
[28] F. A. Henglein, Grundri der Chemischen Technik, 11th ed.,
Verlag Chemie, Weinheim 1963.
[29] F. M. Ress, Geschichte der Kokereitechnik, Verlag Glckauf,
Essen 1957.
[30] P. Berdelle-Hilge, Es ist alles viel lter Die Verfahrenstechniken im 19. Jahrhundert, Fa. Philipp Hilge, Bodenheim 1987.
[31] D. Savalle, Progrs rcents de la distillation, Masson, Paris
1873.
[32] A. P. Dubrunfaut, Trait complet de lart de la distillation, 2nd
ed., Bruxelles 1825.
[33] G.-P. Blmer, G. Collin, H. Hke, in Ullmanns Encyclopedia
of Industrial Chemistry, Wiley-VCH, Weinheim 2011.
[34] Kokerei, in Ullmans Enzyklopdie der technischen Chemie, 7th
ed., Urban & Schwarzenberg, Berlin 1919, 89.
[35] G. Lunge, Die Destillation des Steinkohlentheers und die Verarbeitung der damit zusammenhngenden Produkte, Vieweg,
Braunschweig 1867. urn:nbn:de:bvb:12-bsb10305222-0
[36] Steinkohlenteer, in Ullmanns Enzyklopdie der technischen
Chemie, 10th ed., Urban & Schwarzenberg, Berlin 1922.
[37] L. Kolbe, Flssige Luft, Barth, Leipzig 1920.
[38] G. Buchheim, R. Sonnemann, Lebensbilder von Ingenieurwissenschaftlern, VEB Fachbuchverlag, Leipzig 1989.
[39] E. Hausbrand, Die Wirkungsweise der Rektificir- und DestillirApparate mit Hlfe einfacher mathematischer Betrachtungen,
1st ed., Springer, Berlin 1893.
[40] S. Gabele, F. Simon, 100 Jahre Julius Montz GmbH Eine Unternehmenschronik, Julius Montz GmbH, Hilden 2011.
[41] C. S. Robinson, Elements of Fractional Distillation, McGrawHill, New York 1922.
[42] W. H. Walker, W. K. Lewis, W. H. McAdams, Principles of
Chemical Engineering, McGraw-Hill, New York 1923.
[43] C. von Rechenberg, Einfache und fraktionierte Destillation in
Theorie und Praxis, Leipzig 1923.
[44] C. Mariller, Distillation et rectification des liquids industriels,
Paris 1925.
[45] W. L. McCabe, E. W. Thiele, Ind. Eng. Chem. 1925, 17, 605
611.
[46] K. Thormann, Destillieren und Rektifizieren, Spamer, Leipzig
1928.

2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemBioEng Rev 2014, 1, No. 1, 4049

48

[47] T. H. Chilton, A. P. Colburn, Ind. Eng. Chem. 1935, 27, 255

260.
[48] E. Kirschbaum, Destillier- und Rektifiziertechnik, 3rd ed.,
Springer, Berlin 1969.
[49] R. Billet, Optimierung in der Rektifiziertechnik unter besonderer Bercksichtigung der Vakuumrektifikation, Bibliographisches Institut, Mannheim 1967.
[50] E. U. Schlnder, F. Thurner, Destillation, Absorption, Extraktion, Thieme Verlag, Stuttgart 1986.
[51] J. Mackowiak, Fluiddynamik von Fllkrperkolonnen und
Packungen, 2nd ed., Springer, Berlin 2003.
[52] R. B. Bird, W. E. Stewart, E. N. Lightfoot, Transport Phenomena, John Wiley & Sons, New York 1960.
[53] W. Podbielniak, Ind. Eng. Chem. Anal. Ed. 1931, 3, 177188.
[54] D. F. Stedman, US Patent 2 227 164, 1939.
[55] D. F. Stedman, US Patent 2 047 444, 1935.
[56] L. Spiegel, W. Meier, Chem. Eng. Res. Des. 2003, 81, 3947.
[57] B. D. Smith, B. Block, K. C. D. Hickman, Distillation, in Perrys Chemical Engineers Handbook (Eds: R. H. Perry, C. H.
Chilton), 5th ed., McGraw-Hill, New York 1973, Ch. 13.
[58] J. R. Fair, D. E. Steinmeyer, W. R. Penney, J. A. Brink, LiquidGas Systems, in Perrys Chemical Engineers Handbook (Eds:
R. H. Perry, C. H. Chilton), 5th ed., McGraw-Hill, New York
1973, Ch. 18.
[59] J. D. Seader, J. J. Siirola, S. D. Barnicki, Distillation, in Perrys
Chemical Engineers Handbook (Eds: R. H. Perry, D. W.
Green), 7th ed., McGraw-Hill, New York 1997, Ch. 13.
[60] S. Berman, A. A. Melnychuk, D. F. Othmer, Ind Eng. Chem.
1948, 40, 2139.
[61] V. H. Agreda, L. R. Partin, US Patent 4 435 595, 1984.
[62] V. H. Agreda, L. R. Partin, W. H. Heise, Chem. Eng. Prog.
1990, 86 (2), 40.
[63] B. Bessling, J.-M. Lning, A. Ohligschlger, G. Schembecker,
K. Sundmacher, Chem. Eng. Technol. 1998, 21, 393400.
[64] R. S. Huss, F. Chen, M. F. Malone, M. F. Doherty, Comput.
Chem. Eng. 2003, 27, 1855.
[65] J. Krafczyk, J. Gmehling, Chem. Ing. Tech. 1994, 66, 1372
1375.

www.ChemBioEngRev.de

[66]
[67]
[68]
[69]
[70]

[71]
[72]
[73]

[74]
[75]
[76]

[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]

W. J. Stupin, F. J. Lockhart, Chem. Eng. Prog. 1972, 88, 7172.

D. A. Monro, US Patent 2 134 882, 1933.
R. Agrawal, Z. T. Fidkowski, US Patent 6 106 674, 1998.
R. Agrawal, Z. T. Fidkowski, AIChE J. 1999, 45, 485496.
M. F. Doherty, Z. T. Fidkowski, M. F. Malone, R. Taylor,
Distillation, in Perrys Chemical Engineers Handbook (Eds:
R. H. Perry, D. W. Green), 8th ed., McGraw-Hill, New York
2008, Ch. 13.
G. Kaibel, Chem. Eng. Technol. 1987, 10, 9298.
N. Asprion, G. Kaibel, Chem. Eng. Process. 2010, 49, 139
146.
U. Onken, W. Arlt, Recommended Test Mixtures for Distillation Columns, 2nd ed., Institution of Chemical Engineers,
Rugby, UK 1990.
M. F. Doherty, J. D. Perkins, Chem. Eng. Sci. 1978, 33, 281.
Fractionating Institute, www.fri.org, (accessed on 14 November 2012).
Separations Research Program, University of Texas at Austin,
uts.cc.utexas.edu/~utsrp/index.html (accessed on 04 November 2012).
J. Micovic, T. Beierling, P. Lutze, G. Sadowski, A. Grak,
Chem. Ing. Tech. 2012, 84, 20352047.
Z. Oluji, M. Behrens, L. Sun, J. de Graauw, J. Membrane Sci.
2010, 350, 1931.
X. Z. Li, PhD thesis, University of New South Wales, Australia
2012.
E. Cussler, 7th Int. Congr. of Chemical Engineering, Glasgow,
July 2005.
A. Ziogas, G. Kolb, H.-J. Kost Jr., V. Hessel, Chem. Ing. Tech.
2011, 83, 465478.
G. Q. Wang, Z. C. Xu, J. B. Ji, Chem. Eng. Res. Des. 2011, 89,
14341442.
J. M. MacInnes, J. Ortiz-Osorio, P. J. Jordan, G. H. Priestman,
R. W. K. Allen Jr., Chem. Eng. J. 2010, 159, 159169.
H. Z. Kister, P. M. Mathias, D. E. Steinmeyer, W. R. Penney,
B. B. Crocker, J. R. Fair, in Perrys Chemical Engineers Handbook (Eds: R. H. Perry, D. W. Green), 8th ed., McGraw-Hill,
New York 2008, Ch. 14.

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