Академический Документы
Профессиональный Документы
Культура Документы
II. Production of 1,4-butanediol from Maleic Anhydride via Dimethyl Maleate Hydrogenation Process
The synthesis is made up of three major stages. First is the production of maleic anhydride by vapor phase
oxidation of a hydrocarbon feedstock, in this case, n-butane, followed by the esterification of maleic
anhydride using methanol vapor to form dimethyl maleate, and finally, the hydrogenation of dimethyl
maleate forming 1,4-butanediol and other byproducts.
For the production of maleic anhydride, n-butane is supplied at a pressure of from 1 to 3 bar and at a
temperature of 400 C to a partial oxidation plantwhich is also supplied with air from another line.The partial
oxidation reactor is operated at an air:n-butane feed ratio of 20:1. The reaction is catalyzed using vanadium
pentoxide. The hot vaporous product stream recovered from partial oxidation is cooled by external cooling
against boiler feed water to raise steam and then against cooling water to reduce its temperature to 138 C.
This contains 2.9% w/w maleic anhydride, 5.8% w/w water, 1.3% w/w carbon dioxide, 1.0% w/w carbon
monoxide, 0.01% w/w acetic acid, 0.01% w/w acrylic acid, 15.7% w/w oxygen, and the balance essentially
comprising nitrogen and other inert gases. The following reaction takes place:
7
C 4 H 10 + O2=C 2 H 2 (CO )2 O+4 H 2 O
2
n-butane
Maleic anhydride
This stream is then supplied to the bottom of a column which is divided by a bubble cap plate into a lower
sectionand an upper section. The lower sectionof the columnis provided with a number of washing trays
where the vaporous feed stream passes up against a downflowing spray of dimethyl phthalate vapor which
is supplied at a temperature of about 68 C via spray nozzles positioned at the top of the lower section. The
bottoms product, which is a liquid stream, comprises a solution of approximately 22% w/w maleic anhydride
and 0.04% w/w acrylic acid in dimethyl phthalate. While the off gas from the lower sectionof the
columnpasses up through bubble cap plateinto the upper sectionof column. The upper section of the
column is also provided with a number of washing trays where the off gas containing some dimethyl
phthalate vapor passes up against a downflowingstream of di-n-butyl phthalate sprayed through nozzles
placed at the top part of the uppersectionin order to scrub dimethyl phthalate out of this off gas. A solution
of dimethyl phthalate in di-n-butyl phthalate collects in the bottom part of upper sectionand is removed from
the column in a side draw. The scrubbed gas exits upper sectionof the column through mist eliminator and
is purged from the plant where it can be passed to a waste burner.
The solution of maleic anhydride in dimethyl phthalate obtained as bottoms products from the previous
column is then supplied to the top of a column reactorfor esterification. The reactor comprises a number of
esterification trays mounted one above the other, each containing a charge of a solid esterification catalyst,
such as Amberlyst 16 resin or DPT1 ion exchange resin, and each having a vapor upcomer for upflowing
vapor and a liquid downcomer to permit liquid to flow down the column from one esterification tray to the
next lower one. The column reactor is operated at a temperature of from about 110 C to about 125 C and
at a pressure of from about 1 bar to about 3 bar.The residence time in the column reactoris about 3 hours.
Normally the temperature on the top tray will be somewhat higher (e.g. about 125 C) than that on the
lowermost tray(e.g. about 115 C). Methanol vapor is supplied to near the bottom of the column reactor
while water of esterification is removed in the vapor stream exiting the column reactor as the tops product.
The esterification reaction that takes place is:
CH
2 COOCH
Dimethyl maleate
The bottoms productfrom the column reactor is a solution containing about 250 g/l dimethyl maleate in
dimethyl phthalate. The solution is sent to near the top of a stripping columnoperated at a temperature of
170 C and a pressure of 885 psia (61.02 bar). The column has a number of distillation trays above the
point of injection of the dimethyl maleate solution in order to reduce carryover of dimethyl phthalate in the
overhead stream. The solution of dimethyl maleate in dimethyl phthalate flows down through
packingagainst an upflowing stream of hydrogen supplied at near the bottom of the stripping column. The
stripped dimethyl phthalate obtained as bottoms product is sent as recycle to a line combining with fresh
dimethyl phthalate solvent supplied to the first column while a purge stream of the recycled solvent can be
taken into another line.
The tops product from the stripping column is a near saturated vapor mixture stream comprising dimethyl
maleate in hydrogen, with a hydrogen:dimethyl maleate molar ratio of about 320:1. This vapor mixture
stream is at a temperature of from about 180 C to about 195 C and at a pressure of 62 bar. It is mixed
with hot hydrogen supplied at a temperature of from about 180 C to about 195 C to yield a vaporous
stream with a hydrogen:dimethyl maleate molar ratio of about 350:1 and is at least about 5 C above its
dew point. This vaporous mixture passes onwards to the hydrogenation plantwhich includes an adiabatic
reactor packed with a reduced copper-based catalyst, for example, a reduced copper chromite catalyst,
and operated at an inlet temperature of 173 C, an inlet pressure of 885 psia (61.02 bar), and an exit
temperature of 190 C. The dimethyl maleate feed rate corresponds to a liquid hourly space velocity of 0.5
h1.
CH
2 COOCH
HOOC
Dimethyl maleate
1,4-butanediol
The plant also includes a purification section in which the crude hydrogenation product mixture is distilled in
several stages to yield pure 1,4-butanediol. Other streams include -butyrolactone stream and
tetrahydrofuran stream.
This chemical process begins with two feedstocks: hydrogen gas and bio-succinic acid. The hydrogen gas
will be obtained from a pipeline at 150 atm and will be used in molar excess inside the reactor. The plant
will require 63,000 metric tonnes of bio-succinic acid per year to meet the proposed plant capacity. First the
bio-succinic acid feed is pumped up to 150 atm to match the hydrogen gas feed, and then it is mixed with
the hydrogen gas prior to being sent into heat exchanger for heating. The heat exchanger brings the two
feeds up to 110oC and sends them to the jacketed packed bed reactor.
The hydrogenation reaction occurs inside of the reactor thanks to the packed catalyst bed. The catalyst
used is 0.4% Fe, 1.9% Na, 2.66% Ag, 2.66% Pd, 10.0% Re on 1.5mm carbon support. With this catalyst,
BDO is produced with over 90% selectivity and minimal side reactions of THF and GBL (Bhattacharyya and
Manila, 2011). The reaction has an operating pressure of 2000-4000 psi and internal reactor temperature of
165C. This temperature allows for about 99.7% conversion of succinic acid (Bhattacharyya and Manila,
2011). Due to the exothermic nature of the reaction, a cooling jacket is required which utilizes downstream
cold streams to cool the internal bed to maintain the desired reaction temperature.
The effluent of the reactor is sent back to heat exchanger as the hot stream. After exiting heat exchanger,
the reactor product stream is sent to a secondary exchanger, where utility cooling water is used to reduce
the temperature to an acceptable temperature prior to sending it to a pressure let-down valve. At this point
the pressure of the stream is taken from 150 atm to 1 atm. This large pressure drop allows for the stream to
split into its vapor and liquid portions in a gas-liquid separator. The vapor stream of the gas liquid separator
is primarily hydrogen gas and sent to a flare for disposal. The liquid effluent is at approximately 45oC
leaving the separator and is therefore pumped to the reactor jacket for the reaction cooling mentioned
previously. After running through the reactor jacket, the stream enters the separation processes.
The first distillation column is a 10 stage column whose primary purpose is separating the THF from the
product feed. Due to THFs lower boiling point, the byproduct comes off of the top of the column with mostly
water. This distillate is sent to the plant's THF waste storage tank that has the capacity of two weeks. The
bottoms of the column is sent to the subsequent distillation column that separates the BDO from the GBL
and water. The relatively close boiling points of BDO and GBL, 235oC and 204oC, respectively, create a
difficult separation that requires a 15 stage column. The distillate of the column is approximately 23% GBL
with balance water. This stream is sent to a storage tank with similar sizing parameters as the THF storage
tank. The bottom stream is the final 99.5wt% BDO product. This stream is sent to the final product tank.
Reference/s:
Tuck, M. W., Eastland, P. H., Hiles, A. G., & Reed, G. (2001, August 14). United
States of America Patent No. US6274743 B1. Retrieved November 21, 2015,
from http://www.google.com/patents/US6274743