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US10065902

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MAIMULTAMINHA OUTLOOK TOTHE TI MINI
US010065902B2
(12) United States Patent
( 10) Patent No.: US 10 , 065 ,902 B2
(45 ) Date of Patent:
Koma
(54 ) BUTADIENE PRODUCTION SYSTEM AND
Sep. 4 , 2018
( 71 ) Applicant: SEKISUI CHEMICAL CO ., LTD .,
(58 ) Field of Classification Search
CPC ..... B01J 23/6562 ; B01J 23 /80 ; C07C 1/ 2076 ;
C07C 2521/08 ; C07C 2523 /80 ; C07C
29/ 151; C07C 29/ 36 ; C07C 45/ 49
Osaka (JP )
( 72 ) Inventor: Satoshi Koma, Tokyo ( JP )
(56 )
BUTADIENE PRODUCTION METHOD
(73) Assignee : SEKISUI CHEMICAL CO ., LTD .,
Osaka ( JP )
Subject to any disclaimer , the term of this
patent is extended or adjusted under 35
U .S .C . 154 (b ) by 0 days.
( * ) Notice :
(21) Appl. No.:
(22 ) PCT Filed :
15 /531, 120
Jan . 13 , 2016
(86 ) PCT No.:
PCT/JP2016 /050820
(30 )
Nov . 23, 2017
Foreign Application Priority Data
Jan . 13, 2015 (JP ) ............................ 2015 -004461
2012 /0071697 Al
2013 /02 10096 AL
3 /2012 Ichikawa
8 /2013 Schultz et al.
FOREIGN PATENT DOCUMENTS
5 / 2013
102424359
CN
JP
2011 - 57869
3 / 2011
(Continued )
OTHER PUBLICATIONS
( PCT) Application No. PCT/JP2016 /050820 .
(Continued )
Primary Examiner — Sharon Pregler
(74 ) Attorney, Agent, or Firm — Wenderoth , Lind &
Ponack , L . L .P .
ABSTRACT
(57)
A butadiene production system and a butadiene production
method are provided in which the yield is high and envi
ronmental load can be reduced . The butadiene production
system ( 1 ) includes: a gas preparation device ( 10 ) that heats
raw materials to prepare a mixed gas including hydrogen
and carbon monoxide ; an ethanol production device ( 12 )
that is provided downstream of the gas preparation device
(51) Int . Cl.
CO7C 1 / 20
C10K 3 /00
(52 ) U . S . CI.
???
References Cited
U .S . PATENT DOCUMENTS
International Search Report dated Mar. 8, 2016 in International
$ 371 (c) (1 ),
May 26 , 2017
(2 ) Date :
(87 ) PCT Pub . No.: WO2016 /114299
PCT Pub . Date : Jul. 21, 2016
Prior Publication Data
(65)
US 2017 /0334805 A1
See application file for complete search history.
( 10 ) and brings the mixed gas into contact with a first
(2006 . 01)
( 2006 .01)
(Continued )
catalyst to obtain ethanol; a butadiene production device
( 16 ) that is provided downstream of the ethanol production
device (12 ) and brings the ethanol into contact with a second
catalyst to obtain butadiene; and return means ( 18 ) for
C07C 1 /20 ( 2013 . 01) ; C07C 29 / 151
(2013.01); CIOJ 3 /72 (2013.01); CIOK 3/00
( 2013 .01); CIOJ 2300 /0946 (2013.01)
returning hydrogen , ethylene , and the like, which are pro
duced as by -products in the butadiene production device
(Continued )
.
24
22
+ 24a
10
41
20
44 46
oy
US 10,Page
065 ,2902 B2
(16 ), to the gas preparation device ( 10 ). In addition , in the
tem ( 1 ) is used .
butadiene production method, the butadiene production sys
18 Claims, 2 Drawing Sheets
(51) Int. Ci.
C10J 3 / 72
C07C 29 / 151
(56)
( 2006 .01)
(2006 . 01)
References Cited
FOREIGN PATENT DOCUMENTS
JP
WO
WO
WO
WO
WO
WO
WO
2012 - 1441
2013 - 121939
2013 -199461
2010 /092819
2012 /058508
2012 /087949
2013 /081779
2013 / 125389
2014 /031246
2014 /049158
1 / 2012
6 / 2013
10 / 2013
8 / 2010
5 /2012
6 /2012
6 / 2013
8 / 2013
2 /2014
4 / 2014
OTHER PUBLICATIONS
Extended European Search Report dated Jun . 1, 2018 in European
Application No. 16737370 .3 .
U . S . Patent
Sep . 4 , 2018
Sheet 1 of 2
US 10 ,065,902 B2
I . 1
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124
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44 46
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2
U . S . Patent
Sep . 4 , 2018
Sheet 2 of 2
US 10 ,065,902 B2
FIG . 2
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46
US 10 , 065,902 B2
downstream of the gasification furnace and reform hydro
BUTADIENE PRODUCTION SYSTEM AND
BUTADIENE PRODUCTION METHOD
carbon in the mixed gas into hydrogen and carbon monox
ide.
It is preferable that the return means be means for
5 returning at least a portion of the gas other than butadiene to
The present invention relates to a butadiene production the reforming furnace.
A butadiene production method according to the present
system and a butadiene production method .
Priority is claimed on Japanese Patent Application No. invention includes : a gas preparation step of heating raw
2015 -4461, filed on Jan . 13 , 2015, the content of which is materials to prepare a mixed gas including hydrogen and
10 carbon monoxide ; an ethanol production step of bringing the
incorporated herein by reference .
mixed gas into contact with a first catalyst to obtain ethanol;
a butadiene production step of bringing the ethanol into
BACKGROUND ART
TECHNICAL FIELD
contact with a second catalyst to obtain butadiene ; and a
Butadiene such as 1 , 3 -butadiene is used as a raw material
return step of returning at least a portion of the gas other than
butadiene is purified from a C4 fraction which is produced
preparation step .
It is preferable that the gas preparation step include a
of styrene -butadiene rubber ( SBR ) or the like. In general, 15 butadiene from the butadiene production step to the gas
as a by -product when ethylene is synthesized from petro
leum .
gasification operation and a reforming operation , that, in the
However, recently, bioethanol synthesized from a bio
gasification operation , solid raw materials be thermally
mass -derived raw material has attracted attention as an 20 decomposed to produce the mixed gas including hydrogen
alternative raw material to petroleum . For example , PTL 1
and carbon monoxide , and that, in the reforming operation ,
discloses a method of producing butadiene from ethanol
hydrocarbon in the mixed gas be reformed into hydrogen
and carbon monoxide .
It is preferable that the return step be a step of returning
using a catalyst.
However, in the method of obtaining butadiene from
ethanol using the catalyst as in PTL 1, the yield is not 25 at least a portion of the gas other than butadiene to the
industrially sufficiently high . In addition , when butadiene is reforming operation.
industrially produced , it is important to reduce a load on the
Advantageous Effects of Invention
global environment as much as possible.
CITATION LIST
Patent Literature
[PTL 1 ] PCT International Publication No. WO2013 /
125389
30
In the butadiene production system according to the
present invention , the yield of butadiene is high , and envi
ronmental load can be reduced.
In the butadiene production method according to the
present invention , butadiene can be produced with a high
35 yield , and environmental load can be reduced .
SUMMARY OF INVENTION
BRIEF DESCRIPTION OF DRAWINGS
FIG . 1 is a schematic diagram showing an example of a
Technical Problem
40 butadiene production system according to the present inven
An object of the present invention is to provide a buta - tion .
diene production system and a butadiene production method
FIG . 2 is a schematic diagram showing another example
in which the yield is high and environmental load can be of the butadiene production system according to the present
invention .
reduced .
45
Solution to Problem
A butadiene production system (apparatus) according to
DESCRIPTION OF EMBODIMENTS
The definitions of the following terms are applied to this
the present invention includes : a gas preparation device that
specification and claims.
heats raw materials to prepare a mixed gas including hydro - 50 The meaning of “ returning at least a portion of the gas
gen and carbon monoxide ; an ethanol production device that other than butadiene to the gas preparation device ” includes
is provided downstream of the gas preparation device and
a configuration of returning at least a portion of the gas other
brings the mixed gas into contact with a first catalyst to
than butadiene such that the temperature of the mixed gas
obtain ethanol; a butadiene production device that is pro -
emitted from the gas preparation device is held at a tem
production device to the gas preparation device .
H2. For example, a configuration is included in which , in the
vided downstream of the ethanol production device and 55 perature ( for example , 1000° C . to 1200° C .) at which
brings the ethanol into contact with a second catalyst to
carbon monoxide is synthesized from the returned gas due to
obtain butadiene ; and return means for returning at least a
an equilibrium reaction represented by CO2+ H , A CO + H2O
portion of the gas other than butadiene from the butadiene
or a reaction represented by C , H ,, + nH20 - > CO + (m / 2 + n )
It is preferable that the return means include a pipe 60 pipe connected to the reforming furnace of the gas prepa
through which the butadiene production device and the gas
ration device , hydrogen is returned to a portion where the
preparation device are connected .
temperature of the mixed gas is held at a temperature at
gasification furnace and a reforming furnace, that the gas -
carbon monoxide side such that carbon dioxide in the pipe
It is preferable that the gas preparation device include a
which the equilibrium reaction is sufficiently shifted to the
ification furnace thermally decompose solid raw materials to 65 is converted into carbon monoxide. In addition , another
produce the mixed gas including hydrogen and carbon
monoxide, and that the reforming furnace be provided
configuration is included in which , in the pipe connected to
the reforming furnace of the gas preparation device, ethylene
US 10 ,065 ,902 B2
is returned to a portion where carbon monoxide is synthe sized from hydrocarbon in the mixed gas due to the reaction
such that ethylene in the pipe is converted into carbon
butadiene production device 16 are connected to each other
through a pipe included in the return means 18 .
The gas preparation device 10 heats raw materials to
configuration of returning at least a portion of the gas other
The gasification furnace 20 thermally decomposes solid
prepare a mixed gas including hydrogen and carbon mon
monoxide .
The meaning of “ returning at least a portion of the gas 5 oxide at an arbitrary ratio , and includes the gasification
other than butadiene to the gas preparation step ” includes a
furnace 20 and the reforming furnace 22 .
than butadiene to a step where the temperature of the mixed raw materials such as biomass , organic waste ( for example ,
gas heated in the gas preparation step is held at a temperature
waste plastic, waste paper, or waste cloth ), or coal to
at which carbon monoxide is synthesized due to the equi- 10 produce a mixed gas including hydrogen and carbon mon
librium reaction or a reaction of synthesizing carbon monoxide from hydrocarbon . The same can be applied to the
meaning of “ returning at least a portion of the gas other than
oxide . As the gasification furnace 20 , for example , a furnace
that can produce themixed gas by firing a portion of biomass
or organic waste in the presence of oxygen so as to be
thermally oxidized can be adopted . As the gasification
butadiene to the reforming operation ” .
" Raw materials ” are organic materials from which the 15 furnace , a fluidized bed type gasification furnace is prefer
mixed gas including hydrogen and carbon monoxide is able . The fluidized bed type gasification furnace is prefer
obtained by heating, and include both of solid raw materials
able from the viewpoint that it is not likely to be affected by
such as biomass or organic waste and raw material gases the forms of the raw materials and the viewpoint that the
amount of auxiliary fuel used is small .
such as natural gas or waste gas .
“ CO conversion ratio ” refers to a percentage of the 20
number of moles of carbon monoxide consumed by a
reaction to the number of moles of carbon monoxide in the
The reforming furnace 22 hydrocarbon in the mixed gas
reacts with water so as be reformed into hydrogen and
carbon monoxide. In the reforming furnace 22, the concen
tration of carbon monoxide in themixed gas produced from
mixed gas .
“ Selection ratio ” refers to a percentage of the number of the gasification furnace 20 is increased such that a ratio
moles of carbon monoxide converted into a specific com - 25 between hydrogen and carbon monoxide is adjusted to a
pound to the number of moles of carbon monoxide con - desired value . For example , a ratio H , /CO of hydrogen to
sumed in the mixed gas.
carbon monoxide is adjusted to higher than 0 /1 and 2 / 1 or
lower.
As the reforming furnace 22 , for example , a cylindrical
First Embodiment
30 member which can heat the mixed gas in the presence of
water vapor at a temperature higher than a temperature for
(Butadiene Production System )
In a butadiene production system according to the present the thermal decomposition in the gasification furnace 20 can
invention , raw materials are heated to prepare a mixed gas
including hydrogen and carbon monoxide , ethanol is
be adopted .
It is preferable that the pipe 41 be formed of a material
obtained from the mixed gas , and butadiene is produced 35 which is inert with the mixed gas and, for example , be
from the ethanol. Hereinafter, an example of the butadiene
formed of a stainless steel pipe.
production system according to the present invention will be
In the gas preparation device 10 , the solid raw materials
are thermally decomposed in the gasification furnace 20 to
described .
As shown in FIG . 1 , a butadiene production system i produce the mixed gas including hydrogen and carbon
according to the embodiment includes : a gas preparation 40 monoxide, and hydrocarbon in the mixed gas reacts with
device 10 ; an ethanol production device 12 that is provided
water in the reforming furnace 22 to be reformed into a
downstream of the gas preparation device 10 ; a purification
mixed gas having a higher carbon monoxide concentration .
device 14 that is provided downstream of the ethanol
production device 12 ; a butadiene production device 16 that
As in the case of the pipe 41, it is preferable that the pipe
42 be formed of a material which is inert with the mixed gas
is provided downstream of the purification device 14 ; and 45 and , for example , be formed of a stainless steel pipe .
return means 18 for returning at least a portion of the gas
It is preferable that a gas purifier be provided in the pipe
other than butadiene from the butadiene production device
42 . By providing the gas purifier in the pipe 42 , impurities
reaction pipe 24 and a gas - liquid separator 26 that is
provided downstream of the reaction pipe 24 .
or the like can be adopted . Examples of the wet method
16 to the gas preparation device 10 . The gas preparation
in the mixed gas such as tar, sulfur , nitrogen , chlorine , or
device 10 includes a gasification furnace 20 and a reforming water can be removed .
furnace 22 that is provided downstream of the gasification 50 As the gas purifier, for example , various well-known gas
furnace 20 . The butadiene production device 16 includes a purifiers of the related art using a wet method , a dry method ,
The gasification furnace 20 and the reforming furnace 22
include a sodium hydroxidemethod , an ammonia absorption
method , a lime- plaster method , and a magnesium hydroxide
are connected to each other through a pipe 41. The reforming 55 method . Examples of the dry method include an absorption
furnace 22 and the ethanol production device 12 are con nected to each other through a pipe 42 . The ethanol produc -
method such as pressure swing absorption (PSA ) and an
electron beam method .
tion device 12 and the purification device 14 are connected
to each other through a pipe 43. An exhaust pipe 44 is
In the pipe 42 , a cooler for reducing the temperature of the
mixed gas may be provided . By providing the cooler in the
connected to the purification device 14 . The purification 60 pipe 42 , it is easy to sufficiently reduce the temperature of
device 14 and the reaction pipe 24 of the butadiene produc
tion device 16 are connected to each other through a pipe 45 .
The reaction pipe 24 and the gas- liquid separator 26 are
the mixed gas supplied to the ethanol production device 12.
In addition , by rapidly cooling the mixed gas using the
cooler, the shift of equilibrium may be prevented , and the
connected to each other through a pipe 46 . A pipe 47 is
concentration of carbon monoxide can be maintained at a
connected to the gas - liquid separator 26 .
65 high level.
In this example , the reforming furnace 22 of the gas
In the pipe 42 , a gas disperser which saturates liquid such
preparation device 10 and the gas-liquid separator 26 of the as water with the mixed gas by aeration or the like may be
US 10 ,065, 902 B2
provided such that the liquid saturated with the mixed gas is
supplied to the ethanol production device 12 .
The ethanol production device 12 brings the mixed gas,
It is preferable that the pipe 45 be formed of a material
which is inert with ethanol and, for example , be formed of
a stainless steel pipe .
which has been supplied from the gas preparation device 10 ,
In the pipe 45 , a heating device 28 which heats liquid
into contact with a first catalyst to obtain ethanol. In the 5 ethanol to be gasified is provided . As a result, ethanol in the
ethanol production device 12 according to the embodiment,
gasified state is supplied to the butadiene production device
a microorganism capable of ethanol fermentation using
carbon monoxide as a substrate is used as the first catalyst.
example
heating. device 28 heats ethanol to 90
C16..toFor150°
C . to, bethegasified
heating device 28 is not particularly limited as long
In the ethanol production device 12 , by bringing the 10 as itTheheats
ethanolto be gasified . For example , a well-known
mixed gas into contact with the first catalyst, a primary heating device
can be adopted . As a material of the heating
product including ethanol is obtained .
device
28
,
a
material
which is inert with ethanol is prefer
The ethanol production device 12 is not particularly able .
limited as long as it can produce ethanolby ethanol fermen
The butadiene production device 16 brings ethanol into
tation using
using aa microorganism
For example
example ,, aa well
well--known
known 15 contact
microorganism .. For
with a second catalyst to obtain butadiene. The
bioreactor can be adopted . Examples of the bioreactor butadiene production device 16 includes: the reaction pipe
include a continuously stirred tank reactor, an immobilized 24 in which ethanol is brought into contact with a second
cell reactor, a trickle bed reactor, a bubble column, a gas lift
catalyst to obtain butadiene; and the gas -liquid separator 26
fermenter , a membrane reactor ( for example , a hollow fiber
that separates butadiene from a secondary product including
20 butadiene and by -products (hydrogen , ethylene , and the like )
obtained in the reaction pipe 24 . The butadiene production
material which is inert with the mixed gas and ethanol is device 16 may further include a well -known device , for
membrane reactor ), and a static mixer.
As a material of the ethanol production device 12 , a
example , a gas flow rate control portion that regulates the
As the microorganism used as the first catalyst, a wellflow rate such as mass flow rate of gas.
known microorganism capable of ethanol fermentation in 25 The reaction pipe 24 is filled with the second catalyst to
preferable .
which carbon monoxide is used as a substrate can be
adopted . For example , microorganisms described in Pub lished Japanese Translation No. 2011 -500100 of the PCT
form a reactor bed 24a . It is preferable that the reaction pipe
butadiene, hydrogen , ethylene , and the like. In addition , it is
International Publication and Published Japanese Transla
preferable that the reaction pipe 24 have a shape that can
24 be formed of a material which is inert with ethanol,
tion No. 2013 -532481 of the PCT International Publication 30 endure heating at about 200° C . to 600° C . or pressing at
can be used . Specifically , for example , genus Clostridium
about 10 MPa . As the reaction pipe 24 , for example , a
(for example , Clostridium ljungdahlii or Clostridium substantially circular stainless steel member is used .
autoethanogenum ) can be used .
The reactor bed 24a may be any one of a fixed bed , a
As the microorganism used as the first catalyst, one kind moving bed , a fluidized bed , and the like .
may be used alone, or two or more kinds may be used . The 35 The second catalyst is not particularly limited as long as
amount of the first catalyst used is not particularly limited
butadiene can be synthesized from ethanol using it . As the
and can be appropriately determined depending on the kind
second catalyst , for example, a catalyst including an oxide of
of the microorganism in a typical range in which the
a metal belonging to Group 4 to Group 13 in the periodic
microorganism can be sufficiently cultured .
table and magnesium oxide is used . In the second catalyst,
The microorganism capable of ethanol fermentation in 40 it is preferable that the metal belonging to Group 4 to Group
which carbon monoxide is used as a substrate may be used
13 in the periodic table be bonded to magnesium oxide
in combination with a microorganism other than the above -
through one or more selected from magnesia and silica .
Preferable examples of the second catalyst include a
described microorganism .
It is preferable that the pipe 43 be formed of a material catalyst in which tantalum oxide is bonded through magne
which is inert with the primary product including ethanol 45 sia and silica ( Ta , 0 /MgO /SiO , (mass ratio = 2 / 83 / 15 ), refer
and the like and, for example, be formed of a stainless steel to PCT International Publication No. WO2013/ 125389) .
pipe .
The second catalyst is produced using a well-known
In the pipe 43, a pressure control portion which controls method .
the internal pressure of the ethanol production device 12
Examples of a method of producing the second catalyst
may be provided . By the pressure control portion increasing 50 include a method including: dispersing a sol of a catalyst
the internal pressure of the ethanol production device 12 to metal in a sol of one or more selected from magnesia and
be higher than the atmospheric pressure , the amount of
silica to obtain a catalyst sol; and firing the catalyst sol.
hydrogen and carbon monoxide in the mixed gas which is
It is preferable that the pipe 46 and the pipe 47 be formed
dissolved in the liquid is increased , and the yield of ethanol of a material which is inert with butadiene, hydrogen ,
is increased . The internal pressure of the ethanol production 55 ethylene, and the like and , for example, be formed of a
device 12 is controlled to be, for example, 0 to 1 MPa.
stainless steel pipe.
The purification device 14 removes materials (for
In the embodiment, the pipe 46 includes a pressure control
example , by -products , water, unreacted mixed gas , a culture
portion 30 . The pressure control portion 30 is not particu
medium , or a catalyst) other than ethanol from the primary
larly limited as long as it can adjust the internal pressure of
product . Examples of the purification device 14 include a 60 the reaction pipe 24 to an arbitrary value . For example , a
distillation device , a gas -liquid separator, a solid -liquid
separator, and a combination thereof.
The materials removed by the purification device 14 are
exhausted through the exhaust pipe 44 . It is preferable that
well-known pressure valve is used .
As the gas -liquid separator 26 , a well - known gas - liquid
separator formed of a material which is inert with butadiene,
hydrogen , ethylene , and the like can be adopted .
the exhaust pipe 44 be formed of a material which is inert 65 In the gas -liquid separator 26 , butadiene is separated by
with the materials removed by the purification device 14
liquefying butadiene in a state where by - products including
and, for example , be formed of a stainless steel pipe .
hydrogen , ethylene , and the like are gaseous. The separated
US 10 , 065 , 902 B2
and purified butadiene is collected in a storage tank or the
other than butadiene from the butadiene production device
by - product such as hydrogen or ethylene ) are separated from
each other. Butadiene is collected through the pipe 47 . The
gas other than butadiene may include unreacted gas .
The gas other than butadiene including hydrogen , ethyl
includes a pipe through which the gas -liquid separator 26 of
returned to the reforming furnace 22 of the gas preparation
the butadiene production device 16 and the reforming fur-
device 10 by the return means 18 . In the reforming furnace
and the like and, for example, be formed of a stainless steel
pipe .
hydrocarbon such as ethylene due to the reaction represented
pipe of the return means 18 .
Optionally, a valve , a pump,or the like is connected to the
by C „ Hm + nH20 -> CO + (m /2 + n )HZ.
The butadiene production system 1 includes the return
ylene) present in the gas phase of the gas - liquid separator 26
reaction by converting it into carbon monoxide using hydro
is returned to the reforming furnace 22. For example , a
gen which is produced by the butadiene production device
like ( not shown ) through the pipe 47 .
The return means 18 returns at least a portion of the gas
16 to the gas preparation device 10 . The return means 18 5 ene, and the like which are produced as by -products is
nace 22 of the gas preparation device 10 are connected .
22 , carbon dioxide present around the periphery is converted
It is preferable that the pipe of the return means 18 be into carbon monoxide using the returned hydrogen due to
formed of a material which is inert with hydrogen , ethylene , 10 the equilibrium reaction represented by CO , + H , CO +
H2O . In addition , carbon monoxide is synthesized from
In this example , the entire portion of the gas other than 15 means 18 . Therefore , carbon dioxide present in the gas
butadiene ( including by - products such as hydrogen or eth preparation device 10 can be used for an ethanol production
separation membrane may be provided in the pipe of the
16 as a by -product. In addition , typically, hydrocarbon such
return means 18 such that hydrogen and ethylene are sepa - 20 as ethylene which is exhausted as carbon dioxide can be
rated from the gas other than butadiene and then are
used for an ethanol production reaction by converting it into
returned .
A configuration of returning at least hydrogen in the gas
carbon monoxide due to an oxidation reaction . As a result,
the amountof carbon dioxide exhausted can be reduced, and
other than butadiene is advantageous from the viewpoint
thus environmental load can be reduced .
that carbon dioxide, which is not used in the related art, can 25 In addition , in a configuration of returning at least hydro
be used by converting it into carbon monoxide . A configu gen in the gas other than butadiene, carbon dioxide , which
ration of returning the entire portion of the gas other than
butadiene is more advantageous from the viewpoint that the
separation costs are not required and the viewpoint that the
is not used in the related art, can be used as a raw material
for an ethanol production reaction by converting it into
carbon monoxide . Therefore , butadiene can be obtained with
yield of ethanol can be further improved by reusing both 30 a higher yield as compared to a case where hydrogen is not
returned .
A position of the reforming furnace 22 to which the pipe
(Butadiene Production Method )
of the return means 18 is connected is not particularly
Hereinafter, a method of producing the butadiene produc
hydrogen and hydrocarbon such as ethylene.
limited as long as carbon dioxide in the reforming furnace 22
tion system 1 will be described as an example of a butadiene
reaction and hydrocarbon is converted into carbon monox -
butadiene production method according to the embodiment
is converted into carbon monoxide due to the equilibrium 35 production method according to the present invention . The
ide. For example , in a case where the reforming furnace 22
is a cylindrical member, the pipe of the return means 18 may
includes a gas preparation step , an ethanol production step ,
a butadiene production step , and a return step described
be connected to a portion of the cylindrical body close to a
below .
center of the cylindrical body, or to a portion of the cylin drical body close to a gas exhaust port (close to the ethanol
production device 12 ).
In the butadiene production system 1, the solid raw
prepare a mixed gas including hydrogen and carbon mon
oxide
Ethanol production step : a step of bringing the mixed gas
into contact with a first catalyst to obtain ethanol
nace 20 of the gas preparation device 10 to produce the
into contact with a second catalyst to obtain butadiene
gas supply port ( close to the gasification furnace 20 ), to the 40
materials are thermally decomposed in the gasification fur - 45
Gas preparation step : a step of heating raw materials to
Butadiene production step : a step of bringing the ethanol
mixed gas including hydrogen and carbon monoxide . The
Return step : a step of returning at least a portion of the gas
mixed gas is supplied to the reforming furnace 22 through
other than butadiene from the butadiene production step to
the pipe 41 , and hydrocarbon in the mixed gas reacts with
the gas preparation step .
water in the reforming furnace 22 to be reformed into a 50 <Gas Preparation Step >
mixed gas having a higher carbon monoxide concentration .
The gas preparation step according to the embodiment
The reformed mixed gas is supplied from the reforming
includes a gasification operation and a reforming operation ,
pipe 42 and brought into contact with the first catalyst to
mally decomposed to produce the mixed gas including
furnace 22 to the ethanol production device 12 through the
in the gasification operation , solid raw materials are ther
react with the first catalyst such that a liquid primary product 55 hydrogen and carbon monoxide , and in the reforming opera
including ethanol is obtained . The primary product is sup - tion , hydrocarbon in the mixed gas is reformed into hydro
plied to the purification device 14 through the pipe 43 and gen and carbon monoxide by causing it to react with water.
is purified . The purified primary product which is gasified by
the heating device 28 is supplied to the reaction pipe 24 of
In the gasification operation , in the gasification furnace 20
of the gas preparation device 10 , a portion of the crushed
the butadiene production device 16 through the pipe 45 . 60 solid raw materials such as biomass, organic waste (for
Ethanol in the gaseous primary product supplied to the
example , waste plastic , waste paper, or waste cloth ), or coal
reaction pipe 24 is brought into contact with the second
is fired in the presence of oxygen . As a result, the solid raw
catalyst to react with the second catalyst such that a gaseous materials are thermally decomposed and gasified to produce
the mixed gas including hydrogen and carbon monoxide.
and the like is obtained . The secondary product is supplied 65 A temperature for the thermal decomposition of the solid
secondary product including butadiene , hydrogen , ethylene ,
to the gas-liquid separator 26 through the pipe 46 , and the
liquid butadiene and the gas other than butadiene (including
raw materials in the gasification operation is not particularly
limited as long as it is a temperature at which the mixed gas
US 10 , 065 , 902 B2
10
including hydrogen and carbon monoxide is produced . The
temperature for the thermal decomposition is preferably
200° C . to 1000° C . and more preferably 500° C . to 800° C .
In a case where the temperature for the thermal decompo
The temperature of the mixed gas supplied to the ethanol
production device 12 is preferably decreased to 30° C . to 50°
C . and is more preferably decreased to 35º C . to 40° C . In
a case where the temperature of the mixed gas supplied is in
sition is lower than the lower limit value , substantially no 5 the above - described range, a decrease in activity or extinc
solid raw materials are gasified , and the object cannot be tion of the microorganism caused by heat is easily inhibited .
is preferable that the supply amount of the mixed gas to
achieved . In a case where the temperature for the thermal theIt ethanol
production device 12 be adjusted such that
decomposition is higher than the upper limit value, the hydrogen
and
monoxide are saturated in the liquid
proportion of the solid raw materials to be fired to increase 10 such as water. carbon
In
a
case
the supply amount of the
the temperature increases, and the proportions of hydrogen mixed gas is as describedwhere
above
,
ethanol can be produced
and carbon monoxide in the mixed gas decrease .
efficiently .
In the reforming operation , in the reforming furnace 22 , more
temperature in the ethanol production device
hydrocarbon in the mixed gas which is supplied from the 12 Ais reaction
preferably
30° C . to 45° C . and more preferably 35° C .
gasification furnace 20 through the pipe 41 is caused
react 1515 toto 40°
ed toto reacl
40° CC . InIn aa cas
case where the reaction temperature is in the
with water. As a result , hydrocarbon is reformed into hydro above - described range , ethanol can be produced more effi
gen and carbon monoxide, the concentration of carbon ciently.
monoxide is increased , and thus a mixed gas having a
An internal pressure ( reaction pressure ) of the ethanol
desired ratio between hydrogen and carbon monoxide is production device 12 is preferably 0 to 1 MPa, more
obtained .
20 preferably 0 . 2 to 0 .8 MPa , and still more preferably 0 .4 to
A temperature for heating themixed gas in the reforming
operation is higher than the temperature for the thermal
decomposition in the gasification operation and is preferably
0 .6 MPa . In a case where the reaction pressure is the lower
limit value or higher, hydrogen and carbon monoxide in the
mixed gas are likely to be dissolved in the reaction solution ,
1000° C . to 2000° C . and more preferably 1000° C . to 1500°
and ethanol can be produced more efficiently . In a case
C . In a case where the heating temperature is the lower limit 25 where the reaction pressure is the upper limit value or lower,
value or higher, the reaction sufficiently proceeds, and the high -pressure resistance is unnecessary , and environmental
concentration of carbon monoxide can be increased . In a
case where the heating temperature is the upper limit value
or lower, the material of the reforming furnace is not
load can be reduced .
The primary product including ethanol obtained in the
ethanol production device 12 is supplied to the purification
necessarily heat- resistant, and thus environmental load can 30 device 14 through the pipe 43 and is purified by distillation ,
gas - liquid separation , and the like to remove materials other
be reduced .
The total proportion of hydrogen and carbon monoxide in
than ethanol. Next, the purified primary product which is
the mixed gas prepared in the gas preparation step is
preferably 50 vol % or higher, more preferably 80 vol % or
heated to be gasified by the heating device 28 is supplied to
the butadiene production device 16 through the pipe 45 .
increased . The upper limit value of the total proportion of
hydrogen and carbon monoxide in the mixed gas is 100 vol
is brought into contact with the second catalyst of the reactor
bed 24a . As a result, the secondary product including
ide (hereinafter, also referred to as “ the ratio HZ/CO ” ) in the
the embodiment is gaseous.
higher , and still more preferably 90 vol % or higher . As the 35 < Butadiene Production Step >
total proportion of hydrogen and carbon monoxide
The primary product including ethanol is supplied to the
increases, the synthesis efficiency of ethanol can be easily reaction pipe 24 of the butadiene production device 16 and
%.
40 butadiene is obtained due to the reaction represented by the
A volume ratio represented by hydrogen /carbon monox following formula ( 1 ) . The secondary product according to
mixed gas prepared in the gas preparation step is preferably
(1 )
2C2H5OH - C4H7 +H2+ 2H20
higher than 0 / 1 and 2 /1 or lower, more preferably higher
than 0 / 1 and 1/ 1 or lower, and still more preferably higher 45 The temperature ( reaction temperature ) at which the pri
than 0 /1 and 1 /2 or lower. In a case where the ratio H , /CO
m ary product is brought into contact with the second cata
is in the above- described range , the synthesis efficiency of
ethanol can be easily increased .
Themixed gas may include not only hydrogen and carbon
lyst, that is, the temperature of the reactor bed 24a is
preferably 300° C . to 500° C . and more preferably 350° C .
prens
to 450° C . In a case where the reaction temperature is the
monoxide but also methane, ethane, ethylene, nitrogen , 50 lower limit value or higher , the catalyst reaction speed is
carbon dioxide, water, and the like.
sufficiently increased , and butadiene can be produced more
from the reforming furnace 22 of the gas preparation device
efficiently . In a case where the reaction temperature is the
upper limit value or lower, deterioration in the second
catalyst is likely to be inhibited .
In the ethanol production device 12 , the microorganism as
product is brought into contact with the second catalyst , that
water, a culture medium , and the like , and an environment
example , normal pressure to 1 MPa .
< Ethanol Production Step >
Themixed gas whose temperature is decreased is supplied
10 to the ethanol production device 12 through the pipe 42 . 55
the first catalyst is present in a reaction solution including
is adjusted so as to be capable of ethanol fermentation in
The pressure ( reaction pressure ) at which the primary
is, the internal pressure of the reaction pipe 24 is, for
The proportion of ethanol in the primary product supplied
which the microorganism is used . The mixed gas supplied to 60 in the butadiene production step is preferably 70 mass % or
the ethanol production device 12 is brought into contact with
the microorganism as the first catalyst such that the primary
higher and more preferably 90 mass % or higher. In a case
where the proportion of ethanol is the lower limit value or
product including ethanol is obtained by ethanol fermenta - higher, the synthesis efficiency of butadiene can be further
increased .
In the embodiment, the primary product is a mixture of 65 A space velocity of the primary product in the reactor bed
liquid (for example , ethanol or water ) and gas (for example ,
24a in terms of values measured under standard conditions
is preferably 100 to 50000 UL -catalyst/hr, more preferably
unreacted mixed gas ).
tion .
US 10 ,065, 902 B2
12
200 to 10000 L /L -catalyst/hr, and still more preferably 300
In a case where the entire portion of the gas other than
to 5000 UL -catalyst/hr. The space velocity is appropriately butadiene after gas - liquid separation is returned , it is pref
adjusted in consideration of the reaction pressure , the reac
erable that the amount of the gas other than butadiene
tion temperature, and the composition of the primary prod
returned be determined after appropriately adjusting a ratio
uct.
5 between hydrocarbon such as ethylene and water vapor in
Next, the secondary product is supplied from the reaction the mixed gas . By adjusting the amount of the gas other than
pipe 24 to the gas- liquid separator 26 through the pipe 46 , butadiene returned to control the reaction , the amount of
the temperature is decreased, and the liquid butadiene and carbon dioxide is reduced , and environmental load can be
the gas other than butadiene ( including by- product such as easily reduced . In addition , butadiene can be easily produced
hydrogen or ethylene ) are separated from each other. Buta - 10 with a high yield . In addition , instead of adjusting the
diene is collected in a storage tank or the like (not shown )
amount of the gas other than butadiene returned , the amount
through the pipe 47.
of water vapor added in the gas preparation step may be
adjusted .
< Return Step >
The gas other than butadiene (for example, hydrogen or 15 As described above, in the butadiene production method
ethylene) is returned from the butadiene production step to
according to the embodiment, the gas other than butadiene
the reforming operation . Specifically, the gas other than ( for example, hydrogen or ethylene ) is returned from the
butadiene (for example, hydrogen or ethylene ) which is butadiene production step to the gas preparation step . As a
separated from butadiene by the gas - liquid separator 26 is result , carbon dioxide present around the periphery in the
returned to the reforming furnace 22 of the gas preparation 20 gas preparation step is converted into carbon monoxide
device 10 . By returning the gas other than butadiene to the using hydrogen included in the gas . In addition , hydrocarbon
reforming operation in a high - temperature environment,
such as ethylene is caused to react with water vapor present
sented by CO , + H , A CO +H2O . In addition , carbon monox ide is synthesized from hydrocarbon such as ethylene due to
amount of carbon dioxide exhausted including the amountof
carbon dioxide produced from the by - products of the buta
the reaction represented by C „ Hm +nH2O -> CO + (m / 2 + n )
diene production step (for example , carbon dioxide pro
carbon dioxide present around the periphery in the reform - around the periphery in the gas preparation step to produce
ing operation is converted into carbon monoxide using
carbon monoxide , and the produced carbon monoxide can
hydrogen in the gas due to the equilibrium reaction repre - 25 be used in the ethanol production step . As a result , the
H ,. As a result, the mixed gas which is rich in carbon
duced by oxidation of hydrocarbon such as ethylene) can be
monoxide is supplied to the ethanol production device 12 . 30 reduced . Thus, environmental load can be reduced . In addi
In the return step , the entire portion of the gas other than tion , by returning at least hydrogen in the gas other than
butadiene (for example , hydrogen or ethylene ) may be butadiene , carbon dioxide, which is not used in the related
returned to the gas preparation step , or only hydrogen or
art, can be used as a raw material for an ethanol production
ethylene which is separated from the gas other than butadireaction by converting it into carbon monoxide. Therefore ,
ene may be returned to the gas preparation step. A configu - 35 butadiene can also be obtained with a higher yield as
ration of returning at least hydrogen in the gas other than
butadiene is advantageous from the viewpoint that carbon
dioxide , which is not used in the related art , can be used by
compared to a case where hydrogen is not returned .
In addition , in the embodiment, the microorganism , which
is used as the first catalyst and performs ethanol fermenta
converting it into carbon monoxide . In addition , a configu-
tion in which carbon monoxide is used as a substrate , can use
butadiene to the gas preparation step is more advantageous
result, in a configuration of using the microorganism as the
ration of returning the entire portion of the gas other than 40 water in the reaction solution as a hydrogen source. As a
from the viewpoints of the costs and the yield ofbutadiene .
first catalyst, even in a case where the gas other than
For example , in a case where hydrocarbon such as eth -
butadiene is returned from the butadiene production step to
ylene which may be included in the gas other than butadiene
the gas preparation step so as to increase the concentration
is returned together with hydrogen , the concentration of 45 of carbon monoxide in the mixed gas, the amount of
carbon monoxide in the mixed gas is further increased not hydrogen required for the ethanol fermentation is likely to
only due to the equilibrium reaction using hydrogen but also be sufficient, and the synthesis efficiency of ethanol is
due to the reaction represented by C „Hm + nH2O = CO + ( m / particularly high .
2 + n ) H , using hydrocarbon such as ethylene. Therefore , the
synthesis efficiency of ethanol is increased , and thus the 50
Second Embodiment
yield of butadiene is increased . In addition , even in a case
where hydrocarbon such as ethylene is returned , the hydro
Hereinafter, a second embodiment of the butadiene pro
carbon is converted into carbon monoxide and then is
duction system and the butadiene production method
supplied to the ethanol production step . Therefore, an
according to the present invention will be described . In the
adverse effect of the hydrocarbon on the ethanol fermenta - 55 butadiene production system and the butadiene production
method according to the embodiment, a metal catalyst is
tion caused by the microorganism can be prevented .
In a case where hydrogen in the gas other than butadiene
is returned , it is preferable that the amount of hydrogen
returned be appropriately adjusted according to the amounts
used as the first catalyst. Within a range where the effects of
the present invention do not deteriorate, the metal catalyst
may be used in combination with themicroorganism capable
of carbon , hydrogen , and oxygen in the mixed gas . By 60 of ethanol fermentation in which carbon monoxide is used as
adjusting the amount of hydrogen returned to control the
equilibrium reaction , the amount of carbon dioxide is
a substrate .
(Butadiene Production System )
reduced , and environmental load can be easily reduced . In
FIG . 2 is a schematic diagram showing a butadiene
addition , butadiene can be easily produced with a high yield . production system 2 according to the embodiment. In FIG .
In addition , instead of adjusting the amount of hydrogen 65 2 , the same components as those in FIG . 1 will be repre
returned , the amount of oxygen added in the gas preparation
sented by the same reference numerals , and the description
step may be adjusted .
thereof will not be repeated .
US 10 , 065 , 902 B2
13
14
The butadiene production system 2 includes: the gas
Examples of the auxiliary active metal include titanium ,
preparation device 10 ; an ethanol production device 12A magnesium , and vanadium . By not only the hydrogenation
that is provided downstream of the gas preparation device active metal but also the auxiliary active metal being sup
10 ; a purification device 14A that is provided downstream of ported on the metal catalyst, the CO conversion ratio , the
the ethanol production device 12A ; a butadiene production 5 selection ratio of ethanol and acetaldehyde can be further
device 16 that is provided downstream of the purification improved .
device 14A ; and the return means 18 for returning at least a
As the metal catalyst, a rhodium catalyst having a com
portion of the gas other than butadiene from the butadiene
position represented by the following Formula (ml) is
production device 16 to the gas preparation device 10 .
preferable .
The reforming furnace 22 and the ethanol production 10
The ethanol production device 12A and the purification
(ml)
aRh.bMn.cMe'.dMe
In Formula (ml), Mel represents an alkali metal, Me?
the butadiene production device 16 are connected to each
sion ratio , a in Formula ml
( ) preferably represents 0 .053 to
device 12A are connected to each other through the pipe 42 .
device 14A are connected to each other through the pipe 43 . represents an auxiliary active metal, and a , b , c , and d
The exhaust pipe 44 is connected to the purification device represent molar fractions in which a + b + c + d = 1 .
14A . The purification device 14A and the reaction pipe 24 of 15 From the viewpoint of easily increasing the CO conver
other through the pipe 45 .
The ethanol production device 12A is filled with themetal
catalyst as the first catalyst to form a reactor bed 12a . It is
0 . 98 , more preferably 0 .24 to 0 . 8 , and still more preferably
0.32 to 0 .67 .
from the viewpoint of easily increasing the CO conver
preferable that the ethanol production device 12 A be formed 20 sion ratio , b in Formula (ml) preferably represents 0 . 0006 to
of a material which is inert with the mixed gas and ethanol.
0 .67 , more preferably 0 .033 to 0 .57 , and still more prefer
In addition , it is preferable that the ethanol production
device 12A have a shape that can endure heating at about
ably 0 .089 to 0 .44 .
From the viewpoint of easily increasing the CO conver
100° C . to 500° C . or pressing at about 10 MPa. As the
sion ratio , c in Formula (ml) preferably represents 0 .00056
ethanol production device 12A , for example, a substantially 25 to 0 .51, more preferably 0 .026 to 0 . 42 , and still more
preferably 0 .075 to 0 .33 .
circular stainless steel member is used .
The reactor bed 12a may be any one of a fixed bed , a
d may be 0 (that is , the auxiliary active metal is not
moving bed , a fluidized bed , and the like.
The mixed gas is supplied to the ethanol production
device 12A without any change from the gas state .
included ) and may be more than 0 (that is, the auxiliary
active metal is included ). In a case where the auxiliary active
30 metal is included , from the viewpoint of increasing the CO
Examples of the catalyst metal used in the metal catalyst
conversion ratio , d preferably represents 0 . 0026 to 0 . 94 ,
as the first catalyst include a hydrogenation -activemetal and
more preferably 0 .02 to 0 .48 , and stillmore preferably 0 .039
an aggregate of a hydrogenation - active metal and an auxil-
to 0 .25 .
As the metal catalyst, a rhodium catalyst may be used in
iary active metal described below .
In a case where ethanol is synthesized from a mixed gas 35 combination with a metal catalyst other than a rhodium
of hydrogen and carbon monoxide using the metal catalyst,
catalyst.
typically, a primary product including acetaldehyde or acetic
As the metal catalyst, a so -called supported catalyst in
acid is obtained in addition to ethanol due to the following which a catalyst metal is supported on a porous support is
preferable. In the case of the supported catalyst, a ratio
reactions (2 ) to (6 ).
40
between ethanol and acetaldehyde in a product can be easily
2H2+ 2C0 --CH3COOH
controlled .
A material of the porous support is not particularly
3H2+ 2C0 - CH3CHO +H2O
limited , and examples thereof include silica, zirconia, tita
nia , and magnesia . Among these , silica is preferable because
2H2+ CH2COOH - C2H5OH +H20
45 various products thereof having different specific surface
H4 + CH , CHO°C, H , OH
areas and different pore diameters are commercially avail
@
@
@
able .
4H2+ 2C0 - C,H ,OH +H20
(6)
The supported catalyst can be produced using a well
As the hydrogenation -activemetal, a well -knownmetal of known method of producing a supported catalyst of the
the related art in which ethanol can be synthesized from the 50 related art. Examples of the method include an impregnation
mixed gas can be adopted . Examples of the hydrogenation
active metal include : alkali metals such as lithium and
sodium ; elements belonging to Group 7 in the periodic table ,
method and an ion exchange method . Among these , an
impregnation method is preferable . In a case where the metal
catalyst is produced using an impregnation method, a metal
such as manganese and rhenium ; elements belonging to is more uniformly dispersed , and the contact efficiency
Group 8 in the periodic table, such as ruthenium ; elements 55 between the metal catalyst and the mixed gas is further
belonging to Group 9 in the periodic table , such as cobalt
and rhodium ; and elements belonging to Group 10 in the
periodic table , such as nickel and palladium .
Among these ,hydrogenation -active metals , one kind may
improved . Therefore, the CO conversion ratio and the selec
tion ratio of ethanol and acetaldehyde can be further
improved .
In the embodiment, the pipe 43 includes a pressure control
combination . As the hydrogenation -active metal, from the
larly limited as long as it can adjust the internal pressure of
be used alone , and two or more kinds may be used in 60 portion 32 . The pressure control portion 32 is not particu
viewpoints further improving the CO conversion ratio and
improving the selection ratio of ethanol, a combination of
rhodium , manganese , and lithium , a combination of ruthe -
the ethanol production device 12A to an arbitrary value. For
example , a well-known pressure valve is used .
The purification device 14A removes materials ( for
nium , rhenium , and sodium , or a combination of rhodium or 65 example, acetic acid , ethyl acetate , unreacted mixed gas, a
ruthenium , an alkali metal, and another hydrogenation
culture medium , or a catalyst ) other than ethanol and acet
active metal is preferable .
aldehyde from the primary product. By using the second
US 10 , 065 , 902 B2
15
catalyst in the butadiene production device 16 , butadiene
can be synthesized from ethanol and acetaldehyde .
Examples of the purification device 14A include a device
including a separation membrane . Examples of the separa -
16
preferably 1.5 / 1 to 2.5 to 1 . In a case where the ratio HZ/CO
is in the above-described range , the yield of ethanol can be
easily increased .
Themixed gas may include not only hydrogen and carbon
tion membrane include an acidic gas -containing gas treat- 5 monoxide but also methane , ethane, ethylene, nitrogen ,
ment separation membrane described in PCT International carbon dioxide , water , and the like.
Publication No. WO2014 /080670 and a porous support <Ethanol Production Step >
zeolite membrane composite described in PCT International
The mixed gas is supplied from the reforming furnace 22
Publication No . WO2013 / 125661.
of
the
preparation device 10 to the ethanol production
In the butadiene production system 2 , as in the case of the 10 device gas
12A
through the pipe 42 . The mixed gas supplied to
butadiene production system 1, the mixed gas is prepared in the ethanol production
device 12 is brought into contact with
the gas preparation device 10 .
the
metal
catalyst
as
the
catalyst such that the primary
The mixed gas is supplied from the reforming furnace 22 product including ethanolfirst
and
acetaldehyde is obtained .
to the ethanol production device 12A through the pipe 42 15. In the embodiment, the primary
product is gaseous.
and brought into contact with the first catalyst to react with 15 The temperature ( reaction temperature
) at which the
the first catalyst such that a gaseous primary product includ
ing ethanol and acetaldehyde is obtained . The primary
mixed gas is brought into contact with the metal catalyst as
pipe 45 .
In a case where the reaction temperature is the lower limit
product is supplied to the purification device 14A through the first catalyst, that is , the temperature of the reactor bed
the pipe 43 and is purified . The reformed primary product is 12a is preferably 150° C . to 450° C ., more preferably 200°
supplied to the butadiene production device 16 through the 20 C . to 400° C ., and still more preferably 250° C . to 350° C .
In the butadiene production device 16 , as in the case of the
value or higher, the catalyst reaction speed is sufficiently
butadiene production system 1 , a gaseous secondary product increased , and ethanol can be produced more efficiently . In
including butadiene , hydrogen , ethylene, and the like is
a case where the reaction temperature is the upper limit
obtained and the liquid butadiene and the gas other than 25 value or lower, the selection ratio of ethanol can be
butadiene ( for example, hydrogen or ethylene) are separated increased.
fromTheeach
other. Butadiene is collected through the pipe 47.
The pressure (reaction pressure ) at which the mixed gas is
gas other than butadiene (for example , hydrogen or brought into contact with the metal catalyst as the first
ethylene ) is returned to the reforming furnace 22 of the gas
, that is, the internal pressure of the ethanol produc
preparation device 10 by the return means 18 . In the 30 catalyst
tion
device
is preferably 0.5 to 10 MPa, more preferably
reforming furnace 22 , carbon dioxide present around the 1 to 7 .5 MPa12A
,
and
more preferably 2 to 5 MPa . In a case
periphery is converted into carbon monoxide using hydro where the reactionstillpressure
is the lower limit value or
gen in the returned gas other than butadiene due to the higher, the catalyst reaction speed
increased ,
equilibrium reaction represented by CO2+ H , CO + H20the. 3 and ethanol can be produced moreis sufficiently
efficiently
.
In a case
In addition , the concentration of carbon monoxide in the 35 and
mixed gas is further increased due to the reaction repre
sented by CH +nH , 0 - > CO + ( m / 2 + n )H , using hydrocar-
bon such as ethylene .
In the butadiene production system 2 . as in the case of the
where the reaction pressure is the upper limit value or lower ,
the selection ratio of ethanol can be increased.
A space velocity of the mixed gas in the reactor bed 12a
( a value obtained by dividing the supply amount of gas per
butadiene production system 1, carbon dioxide present in the 40 unit timeby the amount of the catalyst ( in terms of volume))
gas preparation device 10 can be used for an ethanol
production reaction by converting it into carbon monoxide
using hydrogen which is produced by the butadiene produc tion device 16 as a by -product. In addition, hydrocarbon
in terms of values measured under standard conditions is
preferably 10 to 100000 L /L -catalyst /hr, more preferably
1000 to 50000 L /L -catalyst/hr, and still more preferably
3000 to 20000 L /L -catalyst /hr. The space velocity is appro
such as ethylene is caused to react with water vapor present 45 priately adjusted in consideration of the reaction pressure ,
in the gas preparation device 10 to produce carbon monox - the reaction temperature , and the composition of the mixed
ide, and the produced carbon monoxide can be used in the
gas as a raw material.
ethanol production reaction . Therefore , environmental load
A molar ratio represented by ethanol/acetaldehyde ( here
can be reduced , and butadiene can be obtained with a higher
inafter, also referred to as " ratio EtOH / AcH ” ) in the primary
yield as compared to a case where hydrogen , ethylene , and 50 pro
product according to the embodiment is preferably 1 /5 to
the like which are produced in the butadiene production
5 / 1. In a case where the ratio EtOH /AcH is in the above
device as by- products are not returned .
described
range , the synthesis efficiency of butadiene can be
(Butadiene Production Method)
further increased .
Hereinafter, a butadiene production method using the
above - described butadiene production system 2 will be 55 The ratio EtOH /AcH in the primary product can be easily
described . As in the case of the butadiene production system
1 , the butadiene production method according to the
embodiment includes a gas preparation step , an ethanol
production step , a butadiene production step , and a return
adjusted by combining the composition of the metal catalyst ,
preparation step according to the embodiment is preferably
purified primary product is supplied to the butadiene pro
1 /2 to 4 / 1, more preferably 1/1 to 3 /1 , and still more
duction device 16 through the pipe 45 .
the average pore diameter of the support of the metal
catalyst, the reaction temperature , the reaction pressure , and
the like. For example , in a case where the reaction tempera
60 ture is increased , the selection ratio of ethanol is increased ,
step described below .
and the ratio EtOH / AcH is increased .
< Gas Preparation Step >
The gas preparation step according to the embodiment is
The primary product including ethanol obtained in the
performed using the same method as in the butadiene ethanol production device 12A is supplied to the purification
production system 1 .
device 14A through the pipe 43 and is purified to remove
A ratio H / CO in the mixed gas prepared in the gas 65 materials other than ethanol and acetaldehyde . Next, the
US 10 , 065 , 902 B2
18
gas preparation device may include a gasification -reforming
The butadiene production step and the return step accord - furnace including both functions of the gasification furnace
reforming furnace .
ing to the embodiment are performed using the samemethod andThethereturn
means included in the butadiene production
as in the butadiene production system 1 .
according to the present invention may be means for
In the butadiene production method according to thee 55 system
SYS
storing hydrogen or by -products including hydrogen
embodiment, as in the first embodiment,hydrogen , ethylene, obtained
the butadiene production device in a storage
and the like which are produced in the butadiene production tank or from
the like and returning the stored hydrogen or
step as by -products are returned . As a result, carbon dioxide by-products to the gas preparation device using various
< Butadiene Production Step and Return Step >
present around the periphery in the gas preparation step is kinds of transport means such as transport using a vehicle .
converted into carbon monoxide using hydrogen included in " However, from the viewpoint of reducing energy loss, it is
the gas. In addition , hydrocarbon such as ethylene is caused
preferable that the return means be return means using a
to react with water vapor present around the periphery in the pipeThe. butadiene production method according to the present
gas preparation step to produce carbon monoxide, and the
invention is not limited to the method using the above
produced carbon monoxide can be used in the ethanol 15 described
butadiene production system 1 or 2 .
In the butadiene production method according to the
reduced , and butadiene can be obtained with a high yield . present invention , the gas other than butadiene may be
As described above, in the butadiene production system
returned from the butadiene production step to the gasifica
and the butadiene production method according to the
tion operation . The gas preparation step may include only
present invention , butadiene can be produced with a high 20 the reforming operation without including the gasification
operation. In the gas preparation step , the gasification opera
yield , and environmental load can be reduced .
production step . Therefore , environmental load can be
In the present invention , as the first catalyst, the micro
tion and the reforming operation may be performed at the
organism capable of ethanol fermentation in which carbon same
time.
Hereinafter, the present invention will be described in
monoxide is used as a substrate is more preferable than the
est, 2525 detail using Examples. However, the present invention is not
metal catalyst. In the metal catalyst used as the first catalyst
to the following description .
the efficiency of the ethanol production reaction is high limited
[
Component
Analysis ]
under conditions where the proportion of hydrogen is higher
The amounts of butadiene, hydrogen , and ethylene in a
than that of carbon monoxide . On the other hand , in addi -
tion, in the embodiment, the microorganism which performs
secondary product obtained in each example were measured
by gas chromatography.
ethanol fermentation in which carbon monoxide is used as a 30
Example 1
substrate can use water in the reaction solution as a hydrogen
source. Therefore, at least ethanol can be more efficiently
Butadiene was produced using the butadiene production
synthesized from hydrogen in the mixed gas rather than
system
1 shown in FIG . 1 .
from carbon monoxide. Thus, the configuration of using the 35as Specifically
, 400 g /hr of a simulated waste simulating an
microorganism as the first catalyst is particularly advanta
geous in the present invention in which the concentration of
carbon monoxide in the mixed gas is increased using hydro
gen which is produced as a by-product during the production
of butadiene.
industrial waste ( combustible content: 76 % , ash content :
9 % , water content: 15 % , amount of heat: 4000 kcal/kg ) was
gasified in the gasification furnace 20 , and a water vapor
reforming reaction was performed in the reforming furnace
40 22 . As a result, 625 NL /hr of a mixed gas was obtained . 2
The butadiene production system according to the present g /hr of hydrogen and 12 g /hr of ethylene , which were
invention is not limited to the above -described butadiene
produced as by -products from the gas- liquid separator 26 of
the butadiene production device 16 , were returned to the
production system 1 or 2 .
For example , in the butadiene production system accord - reforming furnace 22 .
dienerfor
ing to the present invention , the gas other than butadiene
( for 48
45 Themixed gas was supplied to a reaction solution includ
ing an inorganic salt in the ethanol production device 12, and
example , hydrogen or ethylene) may be returned from the
113 g /hr of ethanol was obtained using a microorganism
gas-liquid separator of the butadiene production device to
the gasification furnace of the gas preparation device , or the
gas other than butadiene may be returned to a pipe between
catalyst reaction . As the microorganism as the first catalyst,
genus Clostridium was used . In the ethanol production
gen and hydrocarbon such as ethylene in the returned gas
other than butadiene , the gas other than butadiene may be
returned to a portion of the pipe, which is provided down
ethanol production device 12 was purified by a distiller as
the purification device 14 , was gasified , and was supplied to
the butadiene production device 16 . As a result , the second
12 , the reaction temperature was 37° C ., and the
the gasification furnace and the reforming furnace . Within a 50u device
reaction pressure was 0 .6 MPa .
range where carbon monoxide can be produced from hydro
The primary product including ethanol obtained in the
stream of the reforming furnace , where the temperature of 55 ary product including butadiene was obtained . As the second
the mixed gas emitted from the reforming furnace is suffi
ciently held to be high .
catalyst, a tantalum catalyst was used . In the reaction pipe
24 , the reaction temperature was 420° C . and the reaction
The gas preparation device included in the butadiene pressure was 0 . 1 MPa, and the supply amount of the gasified
production system according to the present invention is not primary product was 113 g /hr.
particularly limited as long as it can heat the raw materials 60 In the butadiene production device 16 , 53 g /hr of buta
to produce the mixed gas including hydrogen and carbon
diene , 2 g /hr of hydrogen, and 14 g /hr of ethylene were
monoxide . For example , the gas preparation device may
include only the reforming furnace without including the
gasification furnace , in which raw material gases such as
natural gas or waste gas emitted from a factory are heated 65
obtained . The yield of butadiene was 90 % .
Comparative Example 1
and reformed in the reforming furnace so as to prepare the
Butadiene was produced using the same method as in
mixed gas including hydrogen and carbon monoxide . The
Example 1 , except that hydrogen and ethylene which were
US 10 ,065, 902 B2
20
19
produced as by-products in the butadiene production device
a return step of returning a gas excluding the butadiene
16 were not returned to the reforming furnace 22. In the
reforming furnace 22 , 615 NL /hr of a mixed gas was
obtained . In the ethanol production device 12 , 100 g /hr of
ethanol was obtained .
from the butadiene production step to the gas prepara
tion step ; and
an ethanol production step of converting carbon dioxide
present in the gas preparation step into carbon monox
obtained . The yield of butadiene was 80 % .
6 . The method according to claim 5 ,
wherein the gas preparation step comprises a gasification
In the butadiene production device 16 , 47 g/hr of buta
diene, 2 g /hr of hydrogen , and 12 g/hr of ethylene were
REFERENCE SIGNS LIST
ide .
10
10
thermally decomposed to produce the mixed gas com
prising hydrogen and carbon monoxide, and
1 , 2 : BUTADIENE PRODUCTION SYSTEM
10 : GAS PREPARATION DEVICE
12 , 12A : ETHANOL PRODUCTION DEVICE
14, 14A : PURIFICATION DEVICE
16 : BUTADIENE PRODUCTION DEVICE
18 : RETURN MEANS
in the reforming operation , hydrocarbon in the mixed gas
15
is reformed into hydrogen and carbon monoxide .
7 . The method according to claim 6 ,
wherein the return step returns the gas excluding the
butadiene to the reforming operation .
8 . The butadiene production system according to claim 2 ,
20 : GASIFICATION FURNACE
22 : REFORMING FURNACE
24 : REACTION PIPE
26 : GAS -LIQUID SEPARATOR
operation and a reforming operation ,
in the gasification operation , solid raw materials are
20
41 to 43, 45 to 47 : PIPE
44 : EXHAUST PIPE
25
wherein the gas preparation device comprises a gasifica
tion furnace and a reforming furnace ,
the gasification furnace thermally decomposes solid raw
materials to produce the mixed gas comprising hydro
gen and carbon monoxide, and
the reforming furnace is provided downstream of the
gasification furnace and reforms hydrocarbon in the
The invention claimed is :
1 . A butadiene production system , comprising :
mixed gas into hydrogen and carbon monoxide .
9 . The butadiene production system according to claim 8 ,
wherein the return means is means for returning the gas
a gas preparation device that heats raw materials to
prepare a mixed gas comprising hydrogen and carbon
30
excluding the butadiene to the reforming furnace.
monoxide;
an ethanol production device that is provided downstream
10 . The butadiene production system according to claim
of the gas preparation device and brings themixed gas 1 ,
wherein the return means is configured to return the gas
into contact with a first catalyst to obtain ethanol;
excluding the butadiene and comprising a hydrogen
a butadiene production device that is provided down
stream of the ethanol production device and brings the 35
ethanol into contact with a second catalyst to obtain
device .
11 . The butadiene production system according to claim
10 ,
butadiene;
a return means for returning a gas excluding the butadiene
from the butadiene production device to the gas prepa 40
carbon dioxide present in the gas preparation device is
ration device ; and
converted into carbon monoxide through an ethanol
production reaction .
2 . The butadiene production system according to claim 1,
wherein the return means comprises a pipe through which 45
the butadiene production device and the gas preparation
device are connected .
3 . The butadiene production system according to claim 1,
wherein the gas preparation device comprises a gasifica tion furnace and a reforming furnace ,
by - product generated in the butadiene production
50
wherein the return means comprises a pipe through which
the butadiene production device and the gas preparation
device are connected .
12 . The butadiene production system according to claim
10 ,
wherein the gas preparation device comprises a gasifica
tion furnace and a reforming furnace ,
the gasification furnace thermally decomposes solid raw
materials to produce the mixed gas comprising hydro
gen and carbon monoxide , and
the reforming furnace is provided downstream of the
gasification furnace and reforms hydrocarbon in the
the gasification furnace thermally decomposes solid raw
mixed gas into hydrogen and carbon monoxide.
materials to produce the mixed gas comprising hydro
13 . The butadiene production system according to claim
12,
gen and carbon monoxide, and
the reforming furnace is provided downstream of the
wherein the return means is configured to return the gas
gasification furnace and reforms hydrocarbon in the 55
excluding the butadiene and comprising the hydrogen
by -product to the reforming furnace .
mixed gas into hydrogen and carbon monoxide.
4 . The butadiene production system according to claim 3 ,
14 . The method according to claim 5 ,
wherein the return means is means for returning the gas
wherein the gas excluding the butadiene returned in the
excluding the butadiene to the reforming furnace .
return step to the gas preparation step comprises a
5 . A method of producing butadiene, comprising :
60
hydrogen by - product generated in the butadiene pro
a gas preparation step of heating raw materials to prepare
duction step .
a mixed gas comprising hydrogen and carbon monox
15 . The method according to claim 14 ,
wherein the gas preparation step comprises a gasification
ide ;
an ethanol production step ofbringing the mixed gas into
contact with a first catalyst to obtain ethanol;
a butadiene production step of bringing the ethanol into
contact with a second catalyst to obtain butadiene ;
65
operation and a reforming operation ,
in the gasification operation , solid raw materials are
thermally decomposed to produce the mixed gas com
prising hydrogen and carbon monoxide, and
US 10 , 065 , 902 B2
21
in the reforming operation , hydrocarbon in the mixed gas
is reformed into hydrogen and carbon monoxide .
16 . The method according to claim 15 ,
wherein the return step returns the gas excluding the
butadiene and comprising the hydrogen by -product to 5
the reforming operation .
17 . The butadiene production system according to claim
11 ,
wherein the gas preparation device comprises a gasifica
tion furnace and a reforming furnace ,
10
the gasification furnace thermally decomposes solid raw
materials to produce the mixed gas comprising hydro
gen and carbon monoxide, and
the reforming furnace is provided downstream of the
gasification furnace and reforms hydrocarbon in the 15
mixed gas into hydrogen and carbon monoxide .
18 . The butadiene production system according to claim
17,
wherein the return means is means for returning the gas
excluding the butadiene and comprising the hydrogen 20
by -product to the reforming furnace .
*
*
*
*
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