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Production of
Saddam Firas Sami
Fathi Mohammed
Amer Ahmad
Butadiene from
n-Butane Guided by
2018 /2019
Production of Butadiene
from n-Butane
TIKRIT'S UNIVERSITY
COLLEGE OF ENGINEERING
1
CONTENTS :
CHAPTER 1: INTRODUCTION
2
1.11 PROCESS DESCRIPTION …………………………….……………………………………………………. 39
3
4.3 REACTOR DESIGN ……...……………………………………………….…………….……...…….……. 114
4
CHAPTER 1
INTRODUCTION
5
INTRODUCTION
6
The region seeing the strongest performance has been Asia due to increased
production of finished goods in the electronics, automobile and tire sectors. The
major source of butadiene is as a by-product in the steam cracking of naphtha and
gas oil to make ethylene and propylene. The butadiene is extracted from the C4
cracker stream using extractive distillation. Butadiene is a colorless, non-corrosive
liquefied gas with a mild aromatic or gasoline-like odor. Butadiene is both explosive
and flammable because of its low flash point. [Anonymous, (February 2009),
Butadiene CAS No: 106-99-0] [10]
1.2 HISTORY:-
1,3-Butadiene was discovered in the nineteenth century and its use in the
development of rubber-like polymers was explored during the early 1900s (Grub
and Loser 2005; Sun and Writers 2002).
Large volume production of 1,3-butadiene in the United States began during World
War II.
The Russian chemist Sergei Vasilyevich Lebedev was the first to polymerize
butadiene in 1910. [1][5]
In 1926, he invented a process for manufacturing butadiene from ethanol, and in
1928, developed a method for producing polybutadiene using sodium as a catalyst.
There are two sources of butadiene in world: Extractive distillation from Crude C4
stream produced as a co-product of ethylene production, and “on-purpose”
production by dehydrogenation of n-Butane or 1-Butenes. Leading licensors of
technology for Butadiene are Shell, BASF and Nippon-Zeon. [1]
E.CAVENTOU was the first author in isolating the butadiene by means of pyrolysis
for amyl alcohol.
7
M.BERTHELOT produced it by passing a mixture of acetylene and ethylene through
a red-hot iron tube.
In 1885, G.CIAMICIAN and P.MAGNAGHI elucidated the structure of butadiene.
H.E.ARMSTRONG and A.K.MILLER, in 1886, discovered butadiene in the products
obtained on cracking of petroleum.
In 1910, S.LEBEDEW discovered that butadiene forms as a rubber like polymers,
practical interest in this compound and its derivatives developed.
Butadiene was product on a large scale in Germany prior to World War II and in the
USA during the war. Simultaneously, methods were developed for manufacture of
useful butadiene polymers. [5]
After the war, K.ZIEGLER and G.NATTA, worked on polymerization with
organometallic catalytic agents and they got better quality of rubber. [5]
Production of 3.1 billion pounds (1.4 x 109 kg) according to United States
International Trade Commission USITC. [1]
Although this is not very different from production in 1971. It represents significant
rebound from the low production in the mid-1980s. [1]
1.3 BACKGROUND:-
1,3-Butadiene is a simple conjugated diene. It is an important industrial chemical
used as a monomer in the production of synthetic rubber. When the word
butadiene is used, most of the time it refers to 1,3-butadiene. [Sun, H.P. Wristers,
J.P. (1992).]
The name butadiene can also refer to the isomer, 1,2-butadiene, which is a
cumulated diene. However, this allene is difficult to prepare and has no industrial
significance.
8
In the United States, Western Europe, and Japan, butadiene is produced as a
byproduct of the steam cracking process used to produce ethylene and other
olefins. When mixed with steam and briefly heated to very high temperatures
(often over 900 °C), aliphatic hydrocarbons give up hydrogen to produce a complex
mixture of unsaturated hydrocarbons, including butadiene. The quantity of
butadiene produced depends on the hydrocarbons used as feed. Light feeds, such
as ethane, give primarily ethylene when cracked, but heavier favor the formation
of heavier olefins, butadiene, and aromatic hydrocarbons.
Butadiene is typically isolated from the other four-carbon hydrocarbons produced
in steam cracking by extraction into a polar aprotic solvent such as acetonitrile or
dimethylformamide, from which it is then stripped by distillation.
Butadiene can also be produced by the catalytic dehydrogenation of normal
butane. The first such commercial plant, producing 65,000 tons per year of
butadiene, began operations in 1957 in Houston, Texas. [7]
In other parts of the world, including Eastern Europe, China, and India, butadiene
is also produced from ethanol. While not competitive with steam cracking for
producing large volumes of butadiene, lower capital costs make production from
ethanol a viable option for smaller-capacity plants. Two processes are in use.
In the single-step process developed by Sergei Lebedev, ethanol is converted to
butadiene, hydrogen, and water at 400–450 °C, over any of a variety of metal oxide
catalysts. [1]
This process was the basis for the Soviet Union's synthetic rubber industry during
and after World War II, and it remains in limited use in Russia and other parts of
Eastern Europe. [1]
9
In the other, two-step process, developed by the Russian chemist Ivan
Ostromislensky, ethanol is oxidized to acetaldehyde, which reacts with additional
ethanol over a tantalum-promoted porous silica catalyst at 325–350 0 C to yield
butadiene. [Beychok, M.R. and Brack, W.J, June 1957][10]
Biethylene
Buta-1,3-diene
Butadiene
Divinyl
Erythrene
Vinylethylene
1,3-Butadiene [10]
10
water and polymerizes readily, particularly if oxygen is present, slightly soluble in
methanol and ethanol, and soluble in organic solvents like diethyl ether, benzene,
and carbon tetrachloride. [1]
1,2-butadiene is much less studied. It is a flammable gas at ambient conditions. The
conjugation of the double bonds makes it more thermodynamically stable than
molecule with two isolated single bonds. [5]
[5]
The double-bond length in 1,3-butadiene is 0.134 nm, and the single-bond, 0.148
nm Since normal carbon-carbon single bonds are 0.154 nm, this indicates the
extent of double-bond character in the middle single-bond. Upon complexing with
metal carbonyl moieties like Fe(CO)3, the two terminal bonds lengthen to 0.141 nm,
and the middle bond shortens even more to 0.145 nm. [1]
11
Table 1 Physical properties of Butadiene [1][2]
PROPERTIES VALUES
12
Molecular formula C4H6 , CH2==0.134nm==CH--0.148nm--CH==0.134nm==CH2
Butadiene has two conjugated double bonds and, therefore, can take part in
numerous reactions, which includes 1,2- and 1,4- additions with itself
(polymerization) and with other reagents, linear dimerization and dimerization,
and ring formation.
Polymerization by means of 1,2- and 1,4- addition is the most important butadiene
reaction. On 1,2-addition, astatic polymers, in which the vinyl group has an
arbitrary steric position, can also be formed. The manufacture of chloroprene
(chlorinated hydrocarbons) requires the chlorination of butadiene followed by
isomerization and alkaline dehydrochlorination.
In the production of adipic-acid according to a BASF procedure, butadiene reacts
with carbon monoxide and methanol in two steps under different reaction
conditions. At a higher temperature, approximately 1850C, and at a lower pressure
13
pentene acid ester 5 reacts again with carbon monoxide and methanol to give
adipic acid dimethyl ester. Hydrolysis then leads to the formation of adipic acid.
Butadiene undergoes hydroformylation to give valeric aldehyde.
In the production of hexamethylenediamine, hydrogen cyanide reacts with
butadiene in two steps and the adiponitrile thus obtained is hydrogenated to give
the diamine. Butadiene also reacts in several ways to give 1,4-butanediol. [1]
Linear dimerization and dimerization: Butadiene forms linear dimers or trimmers
in the presence of Ni, Co, Pd, or Fe catalysts. Dimerization of butadiene and
simultaneous reaction with carbon monoxide and alcohol leads to the synthesis of
pelargonic acid, which is a starting material in production of heat-resistant
lubricants.
Cyclization, Diels-Alder Reaction: The Diels-Alder reaction is one of the best-known
reactions of butadiene. Usually, a dienophile, i.e., an olefin with an activated
double bond, reacts with butadiene forming a cyclohexane ring. This addition
reaction, which is exclusively a 1,4-addition, can also take place with a second
molecule of butadiene as the dienophile component, forming 4-vinylcyclohexene
1.Vinylcyclohexene, when subjected to dehydrogenation or oxidation, gives
styrene. In the synthesis of anthraquinone, butadiene undergoes a Diels-Alder
reaction with naphthaquinone to give tetrahydroanthraquinone, which in turn is
oxidized to anthraquinone.
14
Butadiene readily undergoes a 1,4-addition with sulfur dioxide forming a cyclic
sulfone, 2.5-dihydrothiophene-1,1-dioxide. This compound is converted into
sulfolan, a heat-stable and highly polar solvent, on catalytic hydrogenation.
Formation of Complexes: Butadiene reacts with numerous metal compounds to
form complexes, e.g., with Cu(I) salts, which are used in the extraction of butadiene
from C4-hydrocarbon mixtures. Complexes with iron, nickel, cobalt, palladium, and
platinum are also well known. [4][10]
1.7 APPLICATIONS:-
The 1,3-butadiene is the simplest member of the series of conjugated dienes, which
contain the structure C=C−C=C, the C being carbon. The wide variety of chemical
reactions peculiar to this system makes butadiene important in chemical synthesis.
Under the influence of catalysts, butadiene molecules combine with each other or
with other reactive molecules, as acrylonitrile or styrene, to form elastic, rubberlike
materials. In uncatalyzed reactions with reactive unsaturated compounds, such as
maleic anhydride, butadiene undergoes the Diels-Alder reaction, forming
cyclohexene derivatives. Butadiene is attacked by the numerous substances that
react with ordinary olefins, but the reactions often involve both double bonds (e.g.,
addition of chlorine yields both 3,4-dichloro-1-butene and 1,4-dichloro-2-butene).
At atmospheric conditions, 1,3-butadiene exists as a colourless gas, but it is
liquefied either by cooling to -4.4° C (24.1° F) or by compressing to 2.8 atmospheres
at 25°C. [Kirshenbaum, I. (1978)]
Nearly all (96%) of the butadiene produced globally is as a co-product of the steam
cracking of naphtha and gas oil to make ethylene and propylene. After ethylene
and propylene are extracted from the cracker, a “C4 stream” is separated from the
15
process which contains predominately hydrocarbons containing four carbon
atoms, e.g. butadiene and butenes.
Up to 50% of the produced volume of butadiene is taken up by SBR and
polybutadiene. These applications are forecast to lead the demand in the near
future, as they are both set to lavishly develop through 2017; Butadiene is used to
manufacture rubber for tires, hoses, gaskets, paints and adhesives. It is also used
in the production of nylon clothing, carpets and engineering plastic parts
1,3-Butadiene is a major product of the petrochemical industry. Elastomers
consume the bulk of 1,3-Butadiene led by the manufacture of styrene - butadiene
rubber SBR. [3][1]
Its simple chemical structure combined with its low molecular weight and high
chemical reactivity makes it a very useful building block in the synthesis of other
materials.
[10]
Table 2 Use Patterns for 1,3-Butadiene in the US, 1996
16
Butadiene is used primarily as a monomer in the production of a wide range of
polymers and copolymers. It is also used as an intermediate in the production of
several chemicals.
A. Polymer Usage:-
As illustrated in Table 1.1, the largest single use of ABS resins are butadiene
(approximately 30%) is in the production of SBR. Produced by the
polymerization of styrene and butadiene, the primary use of SBR is in tires
and tire products. This material also is use in adhesives and sealants, coatings
for wire and cable and many other rubber articles such as shoe soles. In
addition, it could been used as a chewing gum base. [10]
SBLs comprise about 13% of the butadiene end-use in the U.S. Latex; in
general, can been described as a stable aqueous dispersion, which contains
17
discrete polymer particles of approximately 0.05 to 5 micrometers in
diameter. SBL applications include foam rubber (carpet backing, cushions,
pads, sponges, etc.), adhesives (floorings, tiles, road and roofing, etc.),
sealants and paper coatings. [10]
18
ethylene/butylene and styrene form SEBS block copolymers. End uses for
these thermoplastic materials include asphalt extenders, lubricating oil
additives, adhesives, automotive applications, food and other types of
packaging, medical devices, footwear, toys, disposable dinnerware and
polymer modification such as impact modifiers. [10]
7. Methyl Methacrylate-Butadiene-Styrene (MMBS):
2. Chloroprene:
Chloroprene is formed by chlorinating butadiene. This material is then
polymerized to produce neoprene. Neoprene rubber is a multipurpose
19
material that accounts for about 3% of the butadiene usage. It is used in
applications that include gloves, coatings, adhesives, binders, sealants,
tires, belts, hoses, faucet washers and footwear. [10]
3. Other Chemical Intermediate Uses:
Butadiene also is used in the production of 1,4-hexadiene, sulfolane and
1,5,9-cyclodecatriene. 1,4-hexadiene is primarily used as the monomer
for ethylene-propylene terpolymer (EPDM); sulfolane is an extraction
solvent, and the 1,5,9-cyclodecatriene is used in the production of nylon
fibers and resins.
In summary, 1,3-butadiene has developed into an extremely versatile and
significant industrial chemical ,Figure 1provides an overview of
1,3Butadiene
20
1.8 PROSPECTS OF COMMERCIAL MARKETS:
The single largest use for butadiene is in the production of synthetic elastomers
including styrene-butadiene rubber (SBR) and polybutadiene rubber, both of which
are consumed in the manufacture of tires. Other elastomer applications include
nitrile rubber hoses, mechanical belts, carpet backing, footwear, and neoprene
products. Butadiene is also copolymerized into plastics, the largest-volume being
acrylonitrile-butadiene-styrene (ABS) resins, which are used in various applications.
Because of the global nature of butadiene production and its diverse applications,
the following pie chart shows world consumption of butadiene:
Figure 2
21
It is impacted by various dynamics including changes in the production of ethylene,
fluctuations in energy markets, and general economic cycles.
Since the late 1990s, growing demand for elastomers and other polymers in Asia
has led to an increase in butadiene demand; however, the demand for natural
rubber is still strong and maintains some downward pressure on commodity
synthetic rubbers.
In regions where downstream markets are still developing, such as the Middle East
and Asia, demand growth will be robust. Continued economic and demand growth
in China will secure the country’s position as the world’s largest producer and
consumer of butadiene. In the more mature markets of North America, Western
Europe, and Japan, growth will be much slower or even declining over the forecast
period. With the rapid development in China, Asia has emerged as the world’s most
active butadiene market, with new capacity being built close to naphtha-fed steam
crackers and downstream derivatives production expanding rapidly. Analysts
anticipate that automobile sales in emerging markets will double or possibly triple
over the next 10–15 years, driven by the expanding middle and upper classes. Given
the current economic conditions, however, companies will continue to exercise
caution in planning and executing new capacity buildup, particularly with instability
in both naphtha and butadiene pricing.
ABS resin production is the largest nonrubber market and the third-largest
individual end use for butadiene, accounting for nearly 14% of total global
consumption in 2017. Used in various home and office appliances, personal
electronics, and automotive components, global demand will likely improve at a
rate of 4–5% annually on end-market growth. Demand in SB copolymer latexes
(used in paper products and carpet backing) and adiponitrile (which is
predominantly converted into hexamethylenediamine [HMDA] and used to
produce nylon 66 fibers and resins) will experience 1–2% growth annually.
Consumption for other applications, particularly styrenic block copolymer
elastomers, which are consumed in footwear, asphalt, and adhesives/sealants, is
likely to increase as a result of both improved demand in developing regions and
producers and investors looking to improve their return on investment through
greater diversification of product offerings.
23
And old studies say according to CMAI (25 March 1999 18:32pm), global butadiene
demand is expected to grow at just under 3.5%/year through 2012, slightly above
the average of 3.2%/year growth of the past five years. Demand in India will be the
largest, growing nearly 15%/year for the next five years. Demand in Asia is expected
to exceed 5%/year, although demand in some countries, primarily China, will be at
more than 10%, analysts say. Demand in North America and Western Europe is
expected to rise at less than 1%.
Most of the capacity will be added in Asia, particularly China, which will account for
nearly 75% of new capacity, added before 2012. Operating rates in Asia are
expected to be strong at 85%-90%, while operating rates in Europe will be highest,
at about 90%, analysts say. Operating rates in North America are expected to hover
in the 70% range, they say. Table 2.3 shows the butadiene producer and production
rate in Asia. Notice that in Malaysia, there is only 100,000 mt /year production
totally.
24
Yanshan Petrochemical 113
Others 395
Total 1508
India Reliance Industries 150
Others 172
Total 322
Japan Japan Synthetic Rubber 268
Chiba Butadiene 177
Nippon Zeon 150
Okayama Butadiene 140
Tobu Butadiene 130
Tonen General 105
Nippon Petrochemicals 70
Total 1040
Korea Yeochon Naphtha Cracking Centre 218
Korea Kumho Petrochemical 205
LG Chemical 145
Lotte Daesan Petrochemical 109
Samsung Petrochemicals 99
LG Daesan Petrochemical 98
SK Corp. 72
SK Energy 72
Total 1018
Malaysia Titan Petchem 100
Total 100
Singapore 60
Total 60
Taiwan Formosa Petrochemical 373
Chinese Petroleum 173
Total 546
25
Thailand Bangkok Synthetics 140
IRPC5 65
Total 205
Average: 149.96875
26
The objective of the acetylene hydrogenation section is to hydrogenate C4
acetylenes that could otherwise contaminate the butadiene product. This is
achieved using a liquid phase reactor system. Butadiene-dimers and
trimmers formed in the reactor are removed via distillation in the green oil
column located just downstream of the reactor. The green oil column
overhead stream is fed to the extractive distillation section. The function of
the extractive distillation section is to separate the C4 hydrocarbon stream
into a butane/isobutene/transbutene-2 stream (C4 Raffinate 1) and a
butadiene/cis-butene-2 stream via extractive distillation and solvent
stripping. The green oil column overhead stream is vaporized then fed to the
lower portion of the extraction column where the vapors are counter
currently contacted with the aqueous methoxy-proprionitrile
(MOPN)/furfural solvent which are fed into the top of the column. Butane
and the less soluble butenes are concentrated and removed in the overhead
stream
The butadiene/cis-butene-2 rich solvent from the bottom of the extraction
column are fed to the extract stripper column, where butadiene, cis-butene-
2 and acetylenes (ppm level) are stripped overhead. The extract stripper
column overhead stream is used to feed the butadiene purification column
where butadiene is concentrated in the overhead product. Then the
remaining butene-2 and heavier components are drawn from the bottom of
the column and recycled to the olefins plant cracking furnaces. The purpose
of the solvent purification section is to remove impurities from the lean
solvent. The system consists of two evaporators, a stripping column and a
solvent settling drum which are used to remove furfural-butadiene polymer,
27
acrylonitrile-butadiene codimer, and vinylcyclohexene compounds.
[Anonymous, (2002),Butadiene product Stewardship Guidance Manual]
The large-scale industrial production of butadiene from acetylene has been
carried out in Germany using two processes. These methods are no longer
used as the production of acetylene requires a large amount of energy and
is very expensive. As show in fig.3 [8][10]
Figure 3
28
C. Butadiene Production via Catalytic Dehydrogenation of n-
Butane and n-Butene (the Houdry process):
29
C4 concentrate is produced to be fed to a butadiene extraction system for
the recovery of high purity butadiene.
Figure 4 CATADIENE PROCESS PLANT
30
D. Butadiene Production via Oxidative Dehydrogenation of n-
Butenes (the Oxo-D or O-X-D process):
31
rise.[Anonymous, (2002),Butadiene product Stewardship Guidance
Manual]
The reactor effluent is cooled and the C4 components are recovered in
an Absorber/degasser/stripper column combination. The lean oil flows
from the bottom of the stripper back to the absorber, with a small
amount passing through a solvent purification area. Crude butadiene is
stripped from the oil, recovered in the overhead of the stripper, and then
it is sent to a purification system to recover the butadiene product.
[Anonymous, (2002), Butadiene product Stewardship Guidance Manual]
Figure 5
32
from the equilibrium. The addition of oxygen causes the oxidation of
hydrogen to water.
C4H8 + 1/2O2 C4H6 + H2O
The addition of oxygen to the dehydrogenation reaction of butane is not
meaningful because at the high temperatures required,oxygen reacts
with the reaction products, giving rise to undesired byproducts. Fig.4
&5[8][10]
Figure 6 [4]
33
F. Butadiene Production Via Steam Cracking of Paraffinic
Hydrocarbons :
Figure 7
The indicated feed stocks (ethane, propane, butane, naphtha and gas oil)
are fed to a pyrolysis (steam cracking) furnace where they are combined
with steam and heated to temperatures between approximately 1450-1525
°F (790-830 °C). Within this temperature range, the feedstock molecules
34
"crack" to product hydrogen, ethylene, propylene, butadiene, benzene,
toluene and other important olefins plant co-products. After the pyrolysis
reaction is quenched, the rest of the plant separates the desired products
into streams that meet the various product specifications. Process steps
include distillation, compression, process gas drying, hydrogenation (of
acetylenes), and heat transfer. The focus of this review is 1,3-butadiene;
however, since butadiene is created in the olefins plant pyrolysis furnace,
and is present in the crude butadiene product stream at concentrations up
to approximately 75 wt%, the olefins plant process and the crude butadiene
stream are addressed in this publication to a limited degree.[ Anonymous,
(2002),Butadiene product Stewardship Guidance Manual]
While some olefins plant designs will accommodate any of the listed feed
stocks, many olefins plants process only Natural Gas Liquids (NGLs) such as
ethane, propane and sometimes butane. The mixes of feed stocks, the
conditions at which the feed stocks are cracked, and the physical plant
design, ultimately determine the amount of each product produced, and for
some of the streams, the chemical composition of the stream. Olefins plants
generally produce crude butadiene streams that contain very few C3 and C5
components, as shown by the analysis found in Table 1.1. The composition
of the crude butadiene stream also can be altered via recycle blending of
various product streams. For example, when finished butadiene streams
(99+ wt% pure) do not meet commercial specifications, they are often
combined with crude butadiene streams in order to recover the butadiene.
In this situation, the resulting stream may not fall into the example range.
Generally, crude butadiene is stored as a liquid under pressure in a pressure
35
products sphere.[Anonymous, (2002),Butadiene product Stewardship
Guidance Manual]
Steam cracking is a complex, highly endothermic pyrolysis reaction. The
main cracking feed stock is ethane, which yields only a little C4 hydrocarbons
and is thus not suitable as a route to butadiene.
Catalytic
Steam
Dehydrogenation Oxidative
The plant Cracking of
of n-Butane and n- Dehydrogenation
Paraffinic
Butene (the of n-Butenes
Hydrocarbons
Houdry process)
Reaction
exothermic exothermic exothermic
(exo/endo)
Yield % of
2-16% 30% - 50% 70-90%
butadiene
36
Ethane,
propane,
n-butane/n-
Raw material butane, n-Butenes
Butenes
naphtha,
gas oil
bismuth
catalysts --- chromium/alumina
molybdate
Among the choices for implementing the production of butadiene (polymer grade)
from C4 fractions, we have chosen to do a coupling of catalytic dehydrogenation of
n-butane and n-butene (the Houdry process) and oxidative dehydrogenation of n-
butene (the Oxo-D or O-X-D process).
We have chosen this route because the coupling of the non oxidative catalytic
dehydrogenation with the oxidative dehydrogenation of the n-butenes formed
provides a very much higher yield of butadiene based on n-butane used. The non
oxidative dehydrogenation can also be operated in a gentler manner. This coupling
process features particularly effective utilization of the raw materials.
Thus, losses of the n-butane raw material are minimized by recycling unconverted
n-butane into the dehydrogenation. The isomerization of 2-butene to 1-butene also
yield 1-butene as the product of value. So because of the coupling process method,
we get 1-butene as our byproduct after butadiene as a major production.
For our by product, 1-butene is a linear alpha olefin (alkene), produced either by
separation from crude C4 refinery streams or from the reaction of ethylene. It is
distilled to give a very high purity product.[ Anonymous, (2007),Butadiene Market
Demand]
37
Butene-1 can be produced directly from C4 cracking and also by extraction from
C4's mixtures out of ethylene crackers. It is used as a copolymer in polyethylene
alkylates gasoline, polybutenes, butadiene; as intermediates for C4 and C5
aldehydes, alcohols and other derivatives; and in the production of maleic
unhydride by catalytic oxidation.
Demand for 1-butene also has a big contribution in chemical area, like Japan’s
chemical markets for 1-butenes will grow strongly and for isobutylene very slowly
during 2007–2012. Since August 2004, 1-butene demand for propylene production
via butylene metathesis quadrupled to 2007, but will slow over the forecast
period.[ Anonymous, (2007),Butadiene Market Demand]
While for application for 1-butene is used in the manufacture of a variety of other
chemical products. It fills an important role in the production of materials such as
linear low density polyethylene (LLDPE). The co-polymerisation of ethylene and 1-
butene produces a form of polyethylene that is more flexible and more resilient. 1-
butene can also help to create a more versatile range of polypropylene resins. It is
also used in the production of polybutene, butylene oxide and in the C4 solvents
secondary butyl alcohol (SBA) and methyl ethyl ketone (MEK).
If a high yield of Butadiene is required, the Houdry Catadiene process has proven
most economic .we will not use others methods of production because of these
reasons:
38
Oxidative Dehydrogenation of n-Butene : At the high temp. required ,
oxygen reacts with the reaction products ,giving rise to undesired
products.
Oxidative Dehydrogenation of n-Butene with halogen : Has the
disadvantage of causing serious corrosion problems in the plant.
Steam cracking : Is a complex,highly endothermic pyrolysis reaction.
DEHYDROGENATION OF BUTANE:
CHEMICAL REACTIONS:
39
the combustion of carbon deposit on the catalyst during the regenerative period.
The temperature of reaction at the start of the make period is 6500C, dropping to
5500C at the end before switching to regeneration. The pressure is low, 6-9 bar, to
force the reaction to the right. [1]
The product gases are oil-quenched, compressed, cooled and separated from the
light ends and hydrogen by absorption in naphtha following by stripping. The
overhead is fractionated to yield crude butadiene at the top, which is purified by
(1) absorption using cuprous ammonium acetate (CAA), (2) extractive distillation
with furfural, (3) azeotropic distillation with ammonia. [2]
The more common absorption process involves contact of the close-boiling
butadienebutene fraction with lean CAA solution, which dissolves butadiene. A
desorption step at higher temperature is followed by distillation, compression, and
liquefaction of butadiene to give 98-99% product purity. Mono-olefins may be
required. Ammonia is recovered in the distillation tower by water addition; it is
then separated as substantially anhydrous NH3 by fractionation. [1] [10]
Butane may be catalytically dehydrogenated directly to butadiene in one-step
process. Some butylenes are formed and may be either recycled or used aviation
gasoline manufacture. [3]
Fresh butane feed and recycle gases are preheated to 650°C and then passed into
a fixed-bed reactor. The reactor is a horizontal steel shell lined with ceramic tile
and filled with a chromia-alumina catalyst held at 600 to 620°C at 6 in. (15 cm) Hg
absolute pressure. At a space velocity of 1 to 1.5 volumes charge/unit volume of
supported catalyst per hour, the reactor may be held "on stream" for 8 to 10 min
before the temperature drops to 600°C. The preheated feed is then shifted to
another reactor that has just been brought to temperature. The catalyst in the first-
40
mentioned reactor is now covered with carbon and ready regeneration. It is first
vacuum-purged to remove hydrocarbons, and then regenerated in situ with
preheated air. Burning of the carbon on the catalyst heats the fused alumina
catalyst support to reaction temperature. The heat capacity of the alumina is
sufficient to sustain the dehydrogenation reaction during the 8 to 10 min it will be
on stream. After regeneration the reactor is steam-purged. Accordingly, a
minimum of three reactors is required in parallel: 1one on stream, 2one being
regenerated, 3and one being steam-purged and having necessary valve changes
made. [3]
Most plants have five or more reactors. The reactor effluent is oil- quenched,
stripped of light ends and heavy materials, and fractionated to produce a C4 cut for
extraction. Either ammonium acetate or furfural may be used as the extraction
medium. Yield of butadiene is 11 to 11.5 wt % per pass . The butane - butylene
fraction may be used in aviation gasoline manufacture or recycled to the reactor.
In the latter case, the ultimate total yield of butadiene is 50 to 60 wt %. [3]
A newer and growing process is the two-stage dehydrogenation process in the first
stage of which n-butenes are produced as above or by a similar process from a 98
% n-butane feed; in the second stage oxidative dehydrogenation is used to convert
the butenes to butadiene. In the second stage a compressed air-steam mixture is
heated, mixed with the butene feed ( typically containing 90 % butene by weight,
5 % butanes, 1 % butadiene, 2 % C5+ and small amounts of C3s isobutene, and
acetylenes) and passed over an oxidative dehydrogenation catalyst in a continuous
reactor. A single recovery and purification line is fed b three parallel reactors. The
effluent is quenched, cooled, washed, and recovered in an oil absorber. C4
components are recovered, and the butadiene is extracted and purified. The
41
important feature of this process is the fuel saving; oxidative dehydrogenation is
exothermic and thus requires much less energy than other dehydrogenation
processes. [3]
42
stream which is butadiene. To this end, C4 product gas stream is contacted in an
extraction zone with an extractant, preferably an N-methyl-2pyrrolidone
(NMP)/water mixture. Suitable extractants are butyrolactone, nitriles such as
acetonitrile, propionitrile, methoxypropionitrile, ketones such as acetone, furfural,
N-alkyl-substituted cyclic amides (lactams) such as N-alkylpyrrolidones, especially
NMP. In general, alkyl-substituted lower aliphatic amides or N-alkylsubstituted
cyclic arnides are used.[ Anonymous, (1996),Process of Butadiene production] [10]
The effects of the solvents used will be taken into consideration in the comparison
for the separation of C4 product to butadiene.
43
Toxic and flammable.
Acetonitrile (ACN) It is metabolized into hydrogen
cyanide and thiocyanate
It is noticed that all types of solvents used are hazardous and toxic. MOPN and ACN
are unfavorable in terms of environmental friendly, as both of these solvents will
metabolize into hydrogen cyanide (HCN), which causes threat to not only human
health, but also environment. Thus, NMP is the most acceptable solvent to be used
in the process as it causes least harm to the environment.[10]
Therefore Extractive distillation process by using aqueous n-methyl-2-pyrrolidone
(NMP) is the most environmental friendly method to be used as the solvent (NMP)
causes less harm to the environment and provides the process with a safer mode
due to the high autoignitable temperature.[10]
1.13 SOLVENT PROPERTIES:
Table 7
properties value
Chemical formula C5H9NO
Mole weight 99.13
Boiling point 202 - 204 °C
44
H-2 M-1 H-1 R-1,2,3 H-3 T-1 T-2 H-4 H-6 M-2 T-3
Air heater Recycle mixer Feed hater Fixed bed reactor Quench tower absorber striper Striper heater Heat integral point Mixer setller CAA striper
H-2 V-8
P-17 P-3 P-4 P-5
P-13
V-1 V-2 V-3
V-7
P-25
H-6
P-1 P-2
P-24
H-1 T-2 P-26
M-1 H-3 P-21
P-19
P-20
45
T-1 H-4 P-27
P-18
R-1 R-2 R-3
P-18 P-26
V-4 V-5 V-6
P-6 P-7 P-8
M-2 P-27
P-14 P-15
P-16 P-16A
P-29
E-13
P-25 P-31
P-33
Figure 8 DEHYDROGENATION OF n-BUTANE to product Butadiene [9]
P-28 T-3
S-2
P-35 P-34 P-32
P-30
S-1
C-2 T-4
C-1
1.14 RAW MATRIAL PROPERTIES (n-BUTANE):
The main feed supplied to the plant is crude C4 which mainly consisted of butanes
(also called normal butane or n-butane). According to Wikipedia (2018), butane is
the unbranched alkane with four carbon atoms, CH3CH2CH2CH3. Butane is also used
as a collective term for n-butane together with its only other isomer, isobutane
(also called methylpropane), CH (CH3)3. Figure shows the molecular structure of n-
butane and isobutane. [1]
Figure : Molecular structure of (a) n-butane and (b) isobutane Butanes are highly flammable, colorless,
easily liquefied gases. The properties of butane as feed are given in Table.
PROPERTIES VALUES
46
CHAPTER 2
MATERIALS BALANCE
47
MATERIALS BALANCE
2.1 INTRODUCTION:
The basis is how much we need from the Butadiene within one year in the market,
the amount needed for each hour need to be known operation day are assumed
300 days with 65 days shutdown and the plant operation 24 hours per day,
according to the previous economic study, we need about 100000 metric tons of
butadiene per year, from which we will launch for other accounts.
100000 𝑡𝑜𝑛 1 𝑦𝑒𝑎𝑟 1000 𝑘𝑔
𝑘𝑔 𝑏𝑢𝑡𝑎𝑑𝑖𝑒𝑛𝑒 = | | = 231.481 𝑘𝑔/𝑚𝑖𝑛
𝑦𝑒𝑎𝑟 432000 𝑚𝑖𝑛 1 𝑡𝑜𝑛
take 1 min of operation
N. mole butadiene = 231.481 / 54 = 4.2866 kmol
Assumptions:
The processes follow the law of conservation of mass where:
Material out = Material in + Generation – Consumption – Accumulation
Steady-state condition in all equipment
Pure reactants are used
No leakage in pipes and vessel in the system.
All stream flow rate is in unit kg/min.
Catalyst used in reactor does not contribute in mass.
The entire components in the system behave as ideal condition.
The total input of any substance to a pump, valve or mixer is assumed
equal to the total output of the substance where no reaction occurs in that
device.
48
Table 8 Components formulas and Molecular Weigh
2.2 REACTOR:
49
Stoichiometric treatment:
No. mole of butane react = (1/1) mole of butene product in reaction 1
No. mole of butane react = (1/1) mole of hydrogen product in reaction 1
No. mole of butadiene produced = (1/1) mole of butene react in reaction 2
No. mole of butadiene produced = (1/1) mole of hydrogen produced in reaction 2
To find conversion of reaction 2 must find no. mole unreacted of butane
No. mole of butene react = 4.2866 mole
Unreacted of n-butane reaction I = 8.929125 – 7.1443
= 1.784825 mole
Unreacted of butene reaction II = 7.1443 - 4.2866
= 2.8577 mole
Butadiene produced in reaction II = 4.2866 * 54
= 231.476 kg
Butene unreacted in reaction II = 2.8577 mole * 56
= 160.0312 kg
Butane feed to reactor = 8.929125 mole * 58
= 517.88925 kg
Butane unreacted in reaction I = 1.784825 mole * 58
= 103.52 kg
H2 produced in reactions I = 7.1443 * (1/1) = 7.1443 mole
H2 produced in reactions II = 4.2866 * (1/1) = 4.2866 mole
Total H2 produced = 11.4309 mole *2
= 22.8618 kg
Total input = 517.88925 kg
Total output = 103.52 + 231.476 + 160.0312 + 22.8618
= 517.889 kg
Input Output
material
kg % kg %
C4H10 517.889 100 103.52 19.98887
C4H8 0 0 160.0312 30.90072
C4H6 0 0 231.476 44.69613
H2 0 0 22.861 4.414273
NMP 0 0 0 0
CAA 0 0 0 0
Total 517.889 517.8882
50
Figure 9 Reactor
Input Output
Reactor
2.3 ABSORBER:
Moles of inert gas (H2) entering absorber through gas mixture
(Gm) = 11.4309 mole
Moles of solute = 1.784825 + 2.8577 + 4.2866
= 8.929 mole
Y1= Mole ratio of solute to inert in the entering gas mixture
8.929
= 11.4309 = 0.7811
99 % of solute be removed in the absorber [9][2]
∴ Y2 = Mole ratio of solute to inert in the leaving gas mixture
= 1 * 10−2 * Y1
= 0.01 * 0.7811
= 0.007811
Mole ratio of solute to solvent (N-Methyl-2-pyrrolidone (NMP)[10]) entering the
absorber X2 = 0 (as pure naphtha is used)
Let Lm be pure solvent used & X1 be mole ratio of solute to solvent leaving the
absorber
51
Over all Material balance for solute in the absorber:
Lm (X1 – X2) = Gm (Y1 – Y2)
For minimum solvent rate, (Lm) min, X1 = X1*
Equilibrium relationship from data paper [18]
∴ X1* = 0.26628 for Y1 = 0.7811
(Lm) min (0.26628 – 0) = 11.4309 (0.7811– 0.007811)
(Lm) min = 33.194 mole
Let actual solvent rate be 1.4 times the minimum solvent rate
∴ Lm = 1.1 *(Lm) min = 1.1 * 33.194 = 36.514 mole * Mwt of NMP = 99 [16]
= 36.514 * 99 = 3614.92 kg of NMP
Lm (X1 – X2) = Gm (Y1 – Y2)
36.514 (X1 – 0) = 11.4309 (0.7811– 0.007811)
X1 = 0.242 = solute / solvent
Solute = 0.242 * 36.514 = 8.84 mole solute in solvent
Insoluble = 8.929 - 8.84 = 0.089 mole so neglect
H2 unabsorbed 22.8618 * 0.99 = 22.6331 kg
H2 absorbed = 22.8618 – 22.6331 = 0.22 kg
52
Figure 10 ABSORBER
H2 = 22.6331 kg
Output Input
C4H10 = 103.52 kg
C4H8 = 160.0312 kg
C4H6 = 231.476 kg
C4H10 = 103.52 kg H2 = 0.22 kg
C4H8 = 160.0312 kg NMP = 3614.92kg
C4H6 = 231.476 kg
H2 = 22.861 kg
Absorber
2.4 STRIPPER:
All NMP be removed in the stripper [10]
Because small amount of H2 and Light ends,they are not taken into account, as
they are negligible. 3614.92 kg of NMP in liq. Stream. Fig.11
53
Figure 11 STRIPPER
Total = 495.2559 kg
Output
Stripper
54
Figure 122 MIXER SETTLER
CAA Butane
CAA = 495.2559 kg C4H10 = 103.52 kg
MIXER
Crude Butadiene Butadiene
C4H10 = 103.52 kg
SETTLER
CAA = 495.2559 kg
C4H8 = 160.0312 kg C4H8 = 160.0312 kg
C4H6 = 231.476 kg
C4H6 = 231.476 kg
Total = 495.2559 kg
Now we return to the reactor, the amount of material entering the reactor (n-
butane) is the initial operating state, after we separated the n-butane non-
reacted now we return to the stream Feed the reactor and this will enter Butane in
a smaller amount
Material balance in the mixer before the reactor :
Feed to mixer = Feed to reactor – recycle
= 517.88925 – 103.52 = 414.36925 kg
Amount of n-Butane is feed to the factory
2.6 STRIPPER:
All CAA be removed in the stripper [9]
Material balance around stripper: fig. 13
55
Figure 13 STRIPPER
Butadiene
C4H8 = 160.0312 kg
C4H6 = 231.476 kg
56
Figure 14 AZEOTROPIC DISTILLATION TOWER
Ammonia Butene
NH3 = 78.30144 kg C4H8 = 160.0312 kg
AZEOTROPIC
Butadiene DISTILLATION
C4H8 = 160.0312 kg TOWER Butadiene
C4H6 = 231.476 kg
NH3 = 78.3014 kg
Total = 391.5072 kg
C4H6 = 231.476 kg
Water Butadiene
H2O = 61.9555 kg C4H6 = 231.476 kg
butadiene
purifier
Butadiene Ammonia solution
NH3 = 78.3014 kg NH3 = 78.3014 kg
C4H6 = 231.476 kg H2O = 61.9555 kg
57
2.9 Material balance in the NH3 Still :
Figure 16 NH3 Still
Water
H2O = 61.9555 kg
Ammonia solution
Ammonia
NH3 = 78.3014 kg
Still Ammonia
H2O = 61.9555 kg NH3 = 78.3014 kg
INPUT OUTPUT
material
kg % kg %
C4H10 414.3694 8.882895 0 0
C4H8 0 0 160.0312 3.43078
C4H6 0 0 231.476 4.962427
H2 0 0 22.6331 0.485213
NMP 3614.92 77.49355 3614.92 77.49735
CAA 495.255 10.61685 495.255 10.61737
NH3 78.30144 1.678559 78.30144 1.678641
H2O 61.9555 1.328149 61.9555 1.328214
Total 4664.80134 4664.57224
58
Figure 17 OVERALL MATERIAL BALANCE
Butadiene
C4H6 = 231.476 kg
Butane CAA
C4H10 = 414.3694 kg CAA = 495.2555 kg
Water
CAA H2O = 61.9555 kg
CAA = 495.2555 kg OVERALL Ammonia
Water
MATERIAL NH3 = 78.30144 kg
NMP
H2O = 61.9555 kg BALANCE NMP = 3614.92 kg
Butene
Ammonia C4H8 = 160.0312 kg
NH3 = 78.30144 kg
Hydrogen
NMP
NMP = 3614.92 kg H2 = 22.6331 kg
59
CHAPTER 3
ENERGY BALANCE
60
ENERGY BALANCE
3.1 PREHEATER:
The fuel gas will entering of temp. 9000C and leaving at temp. 2000C to heating
butane to temp. 6500C . [2]
Table 9 Required data for preheater [2]
Steam = 259.376 kg
Inlet Temp = 1000C
C4H10 : 517.88925 kg
Inlet Temp = 6500C
C4H10 : 517.88925 kg
Inlet Temp = 250C
water = 259.376 kg
Inlet Temp = 1000C
61
3.2 REACTOR:
Table 10 Required data for reactor [15][14]
C4H10 8.92912 -125.6 From [2] C4H10 1.7848 -125.6 From [2]
Assumption
Isothermal reactor
Steady-state
Datum temp: 250C = 2980k
63
Figure 13 REACTOR
P-11
Air = 1005.59 kg
Temp in = 127 0C
Temp in = 650 0C
Temp out = 650 0C
Input Output
Reactor
Air = 1005.59 kg
P-14
Temp in = 50 0C
64
3.3 AIR BURNER:
Air burners is device used to heating air by burn fuel oil (Acetylene) so we calculate
the amount of fuel gas we need
Q fuel gas = Q air
(ΔHc° kJ/kg * m kg) fuel gas = (m * cp * ΔT) air
Figure 14 BURNER
Air = 1005.6 kg
Temp in = 25 0C
P-2
P-1
Air = 1005.6 kg
Temp in = 127 0C
65
3.4 WASTE HEAT BOILER;
P-4
water = 605.65 kg
Temp out = 15 0C
Air = 1005.6 kg
Temp in = 50 0C Air = 1005.6 kg
P-1
Temp out = 25 0C P-2
water = 605.65 kg
Temp out = 25 0C
P-3
66
3.5 QUENCH TOWER:
Required data Cold fluid (sat. water) Hot fluid (product from reactor)
Mass , (Kg) 444.836 517.889
Specific heat, (kJ/Kg.K) 2256.4 [14] (kJ/Kg) Like reactor (kJ)
Outlet temp. , (0C) 100 sat. vap. 25
Inlet temp. , (0C) 100 sat. liq. 650
Temp. difference ∆𝑻 , (0C) 275 625
ΔE = Δm(H + 𝑃𝐸 + 𝐾𝐸 ) − 𝑄 − 𝑤
ΔE = 0 , 𝑤 & 𝑃𝐸 & 𝐾𝐸 = 0
Δ𝐻 = 𝑄 = 𝑚 𝑐𝑝 Δ𝑡
Q cold fluid = Q hot fluid
∑(m Cp ΔT)cold fluid =∑(m Cp ΔT)hot fluid
m x 2257.4 = [(210066.65) + (349246.33) + (259207.3) + (185208.94)]
m = 444.6395 kg ∴ Mass of sat. liq. Water at 100˚c = 444.64 kg
Figure 16 QUENCH TOWER
P-1
E-2
Sat.Vap. = 444.64 kg
Temp in = 100 0C
P-3
3.6 Absorber:
ΔE = Δm(H + 𝑃𝐸 + 𝐾𝐸 ) − 𝑄 − 𝑤
There is no change in temp. in Absorber
H=0 , PE=0 , KE=0 , Q=0 , W=0
67
3.7 HEAT EXCHANGER:
68
3.8 HEAT EXCHANGER:
Figure 18 H-4
P-21 P-21
H-4
Sat. vap. = 14.55368 kg
Temp. = 100 C
P-27
69
CHAPTER 4
DESIGN
70
D E S I G N
We will make a design for one of them and Kern's method will used, and its will be
E-1, where the total feed will introduced to the first shell , the total feed is equal to
517.889 kg/min, but we make our design with respect to second not minute so its
equal to 8.6314 kg/sec.
4.1.1 Specification:
The aim of this heat exchanger is to heat the feed from 25⁰C to 175⁰C and this
system operate under high-pressure equal 50 bar, so all the material in liquid
phase.
The feed is pure n-Butane at 25⁰C and 50 bar, the n-butane physical properties at
these conditions is show in table below. [20]
Properties Value
Mass flow rate 8.6314 kg/sec
Mwt 58
Molar flow rate 0.15 mole/sec
Density 580 kg/m3
Specific Heat 2.4 kj/kg.K
71
Thermal Conductivity 0.107 W/m.K
Thermal Diffusivity 7.069 * 10-8
Dynamic Viscosity 1.8 *10-4 Pa.s
Prandtl Number 3.880
72
73
4.1.3 Heat Duty:
448
𝑞 = 0.15 ∫298 9.487 + 33.13 ∗ 10−2 ∗ 𝑇 − 1.108 ∗ 10−4 ∗ 𝑇 2 − 2.822 ∗ 10−9 ∗
𝑇 3 𝑑𝑇 = 2638.95 kJ/sec = 2638.95kw [2]
Saturated steam and saturated liquid at 50 bar 264⁰C from steam table.
4.1.5 Configuration:
74
C4H10 175⁰C
C4H10 25⁰C
25⁰C
75
4.1.7 Calculate correction factor:
225 − 25
𝑅= = 𝑖𝑛𝑓𝑖𝑛𝑖𝑡𝑦
250 − 250
As tube side fluid inlet and out let at the same temperature so we can't calculate
the correction factor so we will take it as F = 0.9 [2]
To ensure that the n-Butane don’t vaporize inside the heat exchanger, we will
calculate the vaporization temperature for Butane at 40 bar by using Antione
equation.
From [2]
ANTA = 15.6782
ANTB = 2154.9
ANTC = -34.42
Tmin = 17⁰C
Tmax = 288⁰C
Antione equation.
𝐴𝑁𝑇𝐵
𝑙𝑛(𝑃𝑚𝑚𝐻𝑔) = 𝐴𝑁𝑇𝐴 −
𝑇 0 𝐾 + 𝐴𝑁𝑇𝐶
2154.9
𝑙𝑛(30002.47) = 15.6782 −
𝑇 0 𝐾 − 34.42
Shell and tube, heaters, hot fluid steam, cold fluid organic solvent.
77
4.1.10 Calculate schedule number:
𝑃𝑠 × 1000
𝑠𝑐ℎ =
𝜑𝑠
50 × 1000
𝑠𝑐ℎ = = 142.85 ≅ 160 𝑠𝑡𝑎𝑛𝑑𝑒𝑟𝑑
350
4.1.11 Choice of common tube:
Bundle diameter
𝑁𝑡 1/𝑛1
𝐷𝑏 = 𝑑𝑜𝑚𝑚 ( )
𝐾
80 1/ 2.207
𝐷𝑏𝑚𝑚 = 21.336 ( ) = 291.73 𝑚𝑚 = 0.292 𝑚
0.249
Shell diameter
79
4.1.15 Choice of common shell size:
80
Din = 14.438 inch = 0.3413252 m
Shell thickness = 1.781 inch = 0.0452374 m
Dout = Din + 2* shell thickness = 0.4318 m
81
82
83
4.1.16.2 Tube-side heat transfer coefficient:
𝑘𝑓 𝜇
ℎ = 𝑗𝑏 × × 𝑅𝑒 × 𝑃𝑟 0.33 × ( )0.14
𝑑 𝜇𝑤
0.14
0.04 0.33
18 ∗ 10−6
ℎ𝑖 = 0.0023 × × 321370.8 × 1.626 ×( )
0.0117856 18 ∗ 10−6
𝑤
ℎ𝑖 = 2315.99
𝑚2 𝐾
4.1.16.3 Shell-side heat transfer coefficient:
85
Equivalent diameter
1.1 1.1
𝐷𝑒𝑞 = (𝑃𝑡 2 − 0.917𝑑𝑜 2 ) = (0.026672 − 0.917 × 0.0213362 )
𝑑𝑜 0.021336
𝐷𝑒𝑞 = 0.011515 𝑚
Jh = 0.01
86
𝑘𝑓 𝜇
ℎ = 𝑗𝑏 × × 𝑅𝑒 × 𝑃𝑟 0.33 × ( )0.14
𝐷𝑒𝑞 𝜇𝑤
0.083 0.33
0.00009 0.14
ℎ𝑜 = 0.01 × × 3289.23 × 3.253 ×( )
0.011515 0.000109
𝑤
ℎ𝑜 = 341.99
𝑚2 𝐾
𝑑𝑜
1 1 1 𝑑𝑜 × ln( ) 1 1 𝑑𝑜
𝑑𝑖
= + + +( + )
𝑈𝑜 ℎ𝑜 ℎ𝑜𝑓 2 × 𝐾𝑤 ℎ𝑖 ℎ𝑖𝑓 𝑑𝑖
0.02133
1 1 1 0.0213 × ln( ) 1 1 0.02133
= + + 0.011785 +( + )
𝑈𝑜 342 5000 2 × 116 2315.99 5000 0.01178
Uo = 231.3477 W/m2 C
87
4.1.17 New heat transfer area (1st iteration):
We notes that the required heat transfer area is much bigger than our first
assumption so, its required area, but we need safety operation are so take 10%
safety factor:
Bundle diameter
𝑁𝑡
𝐷𝑏 = 𝑑𝑜𝑚𝑚 ( )1/𝑛1
𝐾
88
From Table 12.4 for two passes and triangular pitch
K1 = 0.249
N1 = 2.207
282 1/ 2.207
𝐷𝑏𝑚𝑚 = 21.336 ( ) = 516.31 𝑚𝑚 = 0.517 𝑚
0.249
89
From Figure 12.10, bundle diametrical clearance = 59 mm
Shell diameter
𝑘𝑓 𝜇
ℎ = 𝑗𝑏 × × 𝑅𝑒 × 𝑃𝑟 0.33 × ( )0.14
𝑑 𝜇𝑤
90
𝐶𝑝 × 𝜇 3.614 × 1000 × 18 ∗ 10−6
Pr = = = 1.626
𝑘𝑓 0.04
𝑙 4.88
= = 414.06
𝑑𝑖 0.0117856
We can find jb from chart 12.23
0.14
0.04 0.33
18 ∗ 10−6
ℎ𝑖 = 0.0018 × × 68589.787 × 1.626 ×( )
0.0117856 18 ∗ 10−6
𝑤
ℎ𝑖 = 492.7354
𝑚2 𝐾
4.1.20.3 Shell-side heat transfer coefficient:
91
Mass flow rate (Butane) = 8.6314 kg/sec
Equivalent diameter:
1.1 1.1
𝐷𝑒𝑞 = (𝑃𝑡 2 − 0.917𝑑𝑜 2 ) = (0.026672 − 0.917 × 0.0213362 )
𝑑𝑜 0.021336
𝐷𝑒𝑞 = 0.011515 𝑚
Jh = 0.013
92
𝐶𝑝 × 𝜇 3 × 1000 × 0.9 ∗ 10−4
Pr = = = 3.253
𝑘𝑓 0.083
𝑘𝑓 𝜇
ℎ = 𝑗𝑏 × × 𝑅𝑒 × 𝑃𝑟 0.33 × ( )0.14
𝐷𝑒𝑞 𝜇𝑤
0.083 0.33
0.000090 0.14
ℎ𝑜 = 0.013 × × 1964.4 × 3.253 ×( )
0.011515 0.000109
𝑤
ℎ𝑜 = 265.6392
𝑚2 𝐾
𝑑𝑜
1 1 1 𝑑𝑜 × ln( ) 1 1 𝑑𝑜
𝑑𝑖
= + + +( + )
𝑈𝑜 ℎ𝑜 ℎ𝑜𝑓 2 × 𝐾𝑤 ℎ𝑖 ℎ𝑖𝑓 𝑑𝑖
0.02133
1 1 1 0.0213 × ln( ) 1 1 0.02133
= + + 0.011785 +( + )
𝑈𝑜 266 5000 2 × 116 492.7354 5000 0.01178
Uo = 124.2114 W/m2 C
231.3477 − 124.2114
𝑒𝑟𝑟𝑜𝑟% = × 100 % = 46.34 %
231.3477
Therefore, we need other iteration.
93
4.1.21 New heat transfer area (2nd iteration):
We notes that the required heat transfer area is much bigger than our first
assumption so.
Bundle diameter
𝑁𝑡
𝐷𝑏 = 𝑑𝑜𝑚𝑚 ( )1/𝑛1
𝐾
94
476 1/ 2.207
𝐷𝑏𝑚𝑚 = 21.336 ( ) = 654.53 𝑚𝑚 = 0.655 𝑚
0.249
𝑘𝑓 𝜇
ℎ = 𝑗𝑏 × × 𝑅𝑒 × 𝑃𝑟 0.33 × ( )0.14
𝑑 𝜇𝑤
96
From chart jb = 0.0032
0.14
0.04 0.33
18 ∗ 10−6
ℎ𝑖 = 0.0032 × × 40635.126 × 1.626 ×( )
0.0117856 18 ∗ 10−6
𝑤
ℎ𝑖 = 518.96
𝑚2 𝐾
4.1.24.3 Shell-side heat transfer coefficient:
97
Equivalent diameter:
1.1 1.1
𝐷𝑒𝑞 = (𝑃𝑡 2 − 0.917𝑑𝑜 2 ) = (0.026672 − 0.917 × 0.0213362 )
𝑑𝑜 0.021336
𝐷𝑒𝑞 = 0.011515 𝑚
Jh = 0.015
98
𝑘𝑓 𝜇
ℎ = 𝑗𝑏 × × 𝑅𝑒 × 𝑃𝑟 0.33 × ( )0.14
𝐷𝑒𝑞 𝜇𝑤
0.083 0.33
0.000090 0.14
ℎ𝑜 = 0.015 × × 1575.8319 × 3.253 ×( )
0.011515 0.000109
𝑤
ℎ𝑜 = 245.77
𝑚2 𝐾
𝑑𝑜
1 1 1 𝑑𝑜 × ln( ) 1 1 𝑑𝑜
𝑑𝑖
= + + +( + )
𝑈𝑜 ℎ𝑜 ℎ𝑜𝑓 2 × 𝐾𝑤 ℎ𝑖 ℎ𝑖𝑓 𝑑𝑖
0.02133
1 1 1 0.0213 × ln( ) 1 1 0.02133
= + + 0.011785 +( + )
𝑈𝑜 246 5000 2 × 116 518.96 5000 0.01178
Uo = 122.33 W/m2 C
124.2114 − 122.33
𝑒𝑟𝑟𝑜𝑟% = × 100 % = 1.5 %
124.2114
Therefore, we not need other iteration.
99
4.1.25 New heat transfer area (3rd iteration):
We notes that the required heat transfer area is much bigger than our first
assumption so, its required area, but we need safety operation are so take 10%
safety factor:
Bundle diameter
𝑁𝑡
𝐷𝑏 = 𝑑𝑜𝑚𝑚 ( )1/𝑛1
𝐾
100
From Table 12.4 for two passes and triangular pitch
K1 = 0.249
N1 = 2.207
532 1/ 2.207
𝐷𝑏𝑚𝑚 = 21.336 ( ) = 688.364 𝑚𝑚 = 0.689 𝑚
0.249
101
From Figure 12.10, bundle diametrical clearance = 65 mm
Shell diameter
4.1.28.1 Tube-side:
𝑙 𝜇 −𝑚 𝜌 × 𝑢𝑡 ²
∆𝑃𝑡 = 𝑁𝑝 (8 × 𝑗𝑓 × × ( ) + 2.5) ×
𝑑𝑖 𝜇𝑤 2
102
For P>10 bar, the pressure drop acceptable for 0.1*P = 4 bar = 400 kPa, so the 2
kPa is very acceptable pressure drop.
4.1.28.2 Shell-side:
103
Mass flux, G = 8.6314 / 0.736 = 11.72744565 kg/m2 sec
Linear velocity.
𝑙 𝐷𝑠 𝜌 × 𝑢𝑡 ²
∆𝑃𝑡 = (8 × 𝑗𝑓 × × )×
𝑙𝑏 𝐷𝑒𝑞 2
104
For P>10 bar, the pressure drop acceptable for 0.1*P = 4 bar = 400 kPa, so the
0.158kPa is very acceptable pressure drop.
The materiel we will used to made the shell of our heat exchanger is carbon steel
with weld joint factor (J) of 0.85 and design stress (f) of 135 N/mm2 and corrosion
allowance (c) of 2 mm/year and density of 7800 kg/m3
Pdesign = 1.2*Poperating
= 1.2 *50 = 60 bar = 6 N/mm2
𝑝𝑑𝑒𝑠𝑖𝑔𝑛 × 𝐷𝑠𝑖
𝑒𝑠 = +𝑐
2 × 𝐽 × 𝑓 − 𝑝𝑑𝑒𝑠𝑖𝑔𝑛
6 × 0.754
𝑒𝑠 = + 0.002 = 0.02224 𝑚 = 22.24 𝑚𝑚
2 × 0.85 × 135 − 6
ec = 0.6*es = 13.345 mm
DSo = Dsi +2*es = 0.754 + 2 × 0.02224 = 0.79848 m
𝛑 𝛑
𝑉𝑚𝑒𝑡𝑎𝑙 = × 𝑙 × (𝐷𝑠𝑜 2 − 𝐷𝑠𝑖 2 ) + × (𝐷𝑐𝑜 3 − 𝐷𝑐𝑖 3 )
4 6
𝑉𝑚𝑒𝑡𝑎𝑙 = 0.289356 𝑚3
105
4.2- Packed-bed absorber design
4.2.1- Introduction
The packed-bed absorbers are the most common absorbers used for gas
removal. The absorbing liquid is dispersed over the packing material, which
provides a large surface area for gas-liquid contact. Packed beds are
classified according to the relative direction of gas-to-liquid flow into two
types. The first one is co-current while the second one the counter current
packed bed absorber. The most common packed-bed absorber is the
countercurrent-flow towe.
The main purpose of the packing material is to give a large surface area for
mass transfer. However, the specific packing selected depends on the
corrosiveness of the contaminants and scrubbing liquid, the size of the
absorber, the static pressure drop, and the cost. There are three common
types of packing material: Mesh, Ring, and Saddles. In our project Ceramic
Berl Saddles packed was selected since it is good liquid distribution ratio,
good corrosion resistance, most common with aqueous corrosive fluids and
Saddles are beast for redistributing liquids low cost. Also we use 2 inches
diameter packing.
106
ASSUMPTIONS:
Some assumptions and conditions were design calculation
based on:
1. G and L are representing the gas and liquid flow rates.
2. x and y are for the mole fraction of Methanol in liquid and
gas respectively.
3. Assuming the column is packed
107
4.2.3.1- Packed tower diameter
ψ = ρ water/ρL = 0.97087
μ = 1.686 *10-3 P and gc = 9.8 m/s2
108
(L/G) √ρG/ρL=(3614.92 / 22.8618)*√1.614/ 1030
= 6.26
109
From the figure, and using the flooding line: ε = 0.0035
Z = HOG * NOG
NOG = number of transfer units based on an overall gas-film
coefficient.
HOG = height of a transfer unit based on an overall gas-film
coefficient,m.
HOG=(Gs/KoG.a)
Gs=(G/A)
Gs=(0.0228618/0.544)=0.04202 Kmol/m^2*s
HoG=(0.04202/0.081)=0.52 m
111
For NOG calculation we need Gm and Lm and m
where
Gm = molar gas flow-rate per unit cross-sectional area
Lm = molar liquid flow-rate per unit cross-sectional area
m= is the slope of the equilibrium line
Gm = P22/ A = 1.4/0.544 = 2.5736
Lm = P21/A = 2.2/0.544 = 4.027
(y1-y2)=m(x1-x2)
(0.7811-0.007811)=m(0.242-0)
m =3.1954
mGm/Lm =3.1954*2.5736/4.027=2.042
y1/y2=0.7811/0.007811=100
Z = HOG * NOG
Z = 0.52 * 11.8
Z Packing =6.2 m
112
Z column= Z Packing * (D tower + 0.25)
Z column= 6.2 * (0.1.125+ 0.25)
Z column = 8.525
113
4.3 Design of fixed bed reactor
The catalytic dehydrogenation of n-butane is a two-step process;
initially going from n-butane to n-butenes and then to butadiene. Both
steps are endothermic. A major butane-based process is the Houdry
Catadiene process. In the Houdry process, n-butane is dehydrogenated
over chromium/alumina catalysts. The reactors normally operate at 50
atm and approximately 1100-1260 °F (600-680 °C). Nine or more reactors
can be used to simulate continuous operation: Which divide into three
group; the first three reactor is on-line, the second is being regenerated,
and the third is being purged prior to regeneration. Residence time for
feed in the reactor is approximately 5-15 minutes.
Catalyst : Cr2O3/Al2O3
Catalyst Size : 3 mm
114
C4H10=517.88925 Kg
Catalyst:Cr2O3/Al2O3
C4H10 = 103.52 kg
C4H8 = 160.0312 kg
C4H6 = 231.476 Kg
H2 = 22.861 kg
Total = 517.889 kg
Opearating Condition
= 650 C° = 923 K Temperature : To
Pressure : Po = 50 atm
115
Density= 38.3720 Kg/m³
ᴨ
A= D2
4
Where
116
D= diameter; m
Z= packing height; m
Select: (Z/D)= 5.0m; Maximum
Where:
ᴨ
Vc= D2*Z
4
D=2.184 m
Z=10.92 m
Total reactor volume, Vr
𝑉𝑐
= ∗ 100 = 75% (Ref.12)
𝑉𝑟
Or Vc=0.75 Vr
𝑉𝑐
Vr= =41.9888m3
0.75
Where
ᴨ
Vr= Dr2*H
4
117
ᴨ
41.9888= (2.184)2 * H
4
H=11.208 m
Results:
D=2.184 m
Z= 10.92 m
H= 11.208 m
Vc=31.4916 m3
Vr= 41.9888 m3
ᴨ
A= D2=3.7462 m²
4
118
Z H
119
4.3.2 Pressure drop calculation(∆P):-
1 1
Log(𝜇) = 𝐴 ∗ (( ) − ( )) (Ref.2)
𝑇 𝐵
A=265.84 B=160.20
𝑚𝑁𝑠
𝜇 = 0.056177
𝑚2
u= Ѵ˳/A
=4.4988/3.7462=1.200 m/min u
=0.02001 m/secu
∆𝑃 (1 − 0.3)2 0.056 ∗ 10−3 ∗ 0.02001 (1 − 0.3) 38.372 ∗ (0.02001)2
= 150 ∗ ∗ + 1.75 ∗ ∗
𝐿 0.33 (0.003)2 0.33 0.003
𝑃.𝐷
e= +𝑐 (Ref.2)
2𝑓𝐽−𝑃
where:-
120
D=shell diameter (mm)
f = maximum allowable working stress
J= weld efficiency factor
c = corrosion allowance (mm)
Data
P=5.57 N/mm2
D=2184 mm
J= maximum; = 0.85
f = 120 N/mm2; for c-steel from table 1.
c = 3 mm
121
5.57∗2184
e= +3
2∗120∗0.85−5.57
e= 643mm=6.43cm
2-Head thickness
𝑝𝑖∗𝐷𝑖
e= +𝑐 (Ref.2)
2𝐽𝑓−0.2∗𝑝𝑖
Where:-
e= head thickness (mm)
Pi=maximum working pressure [N/mm2]
Di=shell diameter (mm)
f= maximum allowable working stress [N/mm2]
J= weld efficiency factor
C=corrosion allowance (mm) = 3mm
5.57∗2184
e= +3
2∗134∗0.85−0.2∗5.57
e= 62mm=6.2cm
122
U=Overall Heat-Transfer Coefficient, W/m² C°
Q=78514.46 KJ
U=500 W/m² C° (Ref.2)
Tair=700 C°
Treact.=650 C°
Q=78514.46 KJ
U=500 W/m² C°
78514.46=500*A*(700-650)
A=3140.57 m²
123
CHAPTER 5
CONTROL
124
C O N T R O L
125
5.1 PREHEATER CONTROL:
We will design a control loops to control the n-Butane temperature that result
from the heat exchanger at 175 ⁰C by manipulated the amount of steam and
pressure at 50 bar by using selective compressor.
PC PIT PE
compressor
FE
E-1
126
Controller type:
PI-Controller
Control Valve:
127
5.2 ABSORBER CONTROL:
128
5.3 REACTOR CONTROL:
Product
T TI TI
E T C
Reactant
To Po
Heating Air
129
References:
131