U.S. patent application number 14/922775 was filed with the patent office on 2016-04-28 for device and process for producing undecylenic acid methyl ester using methyl ricinoleate as raw material.
This patent application is currently assigned to ZHEJIANG UNIVERSITY OF TECHNOLOGY. The applicant listed for this patent is Zhejiang University of Technology. Invention is credited to Ying DUAN, Ruchao GONG, Jianbing JI, Meizhen LU, Yong NIE, Shangzhi YU.
Application Number | 20160115114 14/922775 |
Document ID | / |
Family ID | 52497832 |
Filed Date | 2016-04-28 |
United States Patent
Application |
20160115114 |
Kind Code |
A1 |
NIE; Yong ; et al. |
April 28, 2016 |
Device and process for producing undecylenic acid methyl ester
using methyl ricinoleate as raw material
Abstract
A device and a process for producing undecylenic acid methyl
ester using methyl ricinoleate as raw material are provided. The
device comprises a feed pump, a raw material pre-heater, a
microwave catalytic reactor, a microwave generator, a temperature
controller and an infrared sensor, a condenser, a product tank and
a discharge pump. The feed pump is connected with the raw material
pre-heater, which is connected with the inlet of the microwave
catalytic reactor. The outlet of the microwave catalytic reactor is
connected with the condenser, which is connected to the product
tank and the discharge pump. The microwave catalytic reactor is
located in the microwave generator, which is connected with the
temperature controller and the infrared sensor. The process is as
follows: high-purity methyl ricinoleate, used as the raw material,
is converted to methyl undecene and heptaldehyde by
microwave-assisted pyrolysis process, followed by isolation and
purification to produce methyl undecene.
Inventors: |
NIE; Yong; (Hangzhou,
CN) ; DUAN; Ying; (Hangzhou, CN) ; GONG;
Ruchao; (Hangzhou, CN) ; YU; Shangzhi;
(Hangzhou, CN) ; LU; Meizhen; (Hangzhou, CN)
; JI; Jianbing; (Hangzhou, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Zhejiang University of Technology |
Hangzhou |
|
CN |
|
|
Assignee: |
ZHEJIANG UNIVERSITY OF
TECHNOLOGY
Hangzhou
CN
|
Family ID: |
52497832 |
Appl. No.: |
14/922775 |
Filed: |
October 26, 2015 |
Current U.S.
Class: |
554/127 ;
422/109 |
Current CPC
Class: |
B01J 2208/00442
20130101; Y02P 20/123 20151101; B01J 2219/0801 20130101; B01J
2219/0871 20130101; C07C 67/333 20130101; B01J 8/0285 20130101;
B01J 2208/00176 20130101; B01J 2219/1215 20130101; B01J 2219/1245
20130101; B01J 2219/0869 20130101; B01J 2208/0053 20130101; B01J
2219/0892 20130101; Y02P 20/10 20151101; B01J 19/126 20130101; C07C
67/333 20130101; C07C 69/533 20130101 |
International
Class: |
C07C 67/333 20060101
C07C067/333; B01J 19/12 20060101 B01J019/12 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 27, 2014 |
CN |
2014 105 851 58.X |
Claims
1. Device for producing undecylenic acid methyl ester using methyl
ricinoleate as raw material, comprising: a feed pump, a raw
material pre-heater, a microwave catalysis reactor, a microwave
generator, a temperature controller and an infrared sensor, a
condenser, a product tank and a discharge pump; wherein the feed
pump is connected with the material pre-heater, which is connected
to an inlet of the microwave catalytic reactor; wherein an outlet
of the microwave catalytic reactor is connected with the condenser,
which is connected to an upper port of the product tank; wherein a
lower port of the product tank is connected to the discharge pump;
wherein the microwave catalytic reactor is arranged in the
microwave generator, which is connected with the temperature
controller and the infrared sensor.
2. The device according to claim 1, wherein the inlet and the
outlet of the microwave catalytic reactor are arranged in the upper
or side portion of the microwave catalytic reactor.
3. The device according to claim 1, wherein the microwave catalytic
reactor is made of glass, ceramics or other wave-transparent
material that can withstand high temperature.
4. The device according to claim 1, wherein a layer of microwave
absorbing material is arranged inside the microwave catalytic
reactor.
5. The device according to claim 4, and the microwave absorbing
material comprises any one of silicon carbide, activated carbon,
Fe/Co/Ni loaded alumina and zeolites.
6. The device according to claim 1, wherein the microwave catalytic
reactor is arranged inside the microwave generator.
7. The device according to claim 6, wherein the microwave generator
is connected with a feed inlet, a product outlet and a temperature
measurement port arranged on the top or the side of the microwave
generator.
8. The device according to claim 1, wherein the microwave generator
is connected with the temperature controller, the infrared sensor,
and a paperless recorder.
9. A process for producing undecylenic acid methyl ester using
methyl ricinoleate as raw material and employing the device of
claim 1, the processing comprising the steps as follows: 1) setting
a cracking reaction temperature of the microwave generator, and
turning on the microwave generator to start a heating process; 2)
inputting into the device a methyl ricinoleate of high purity using
the feed pump, regulating a flow rate of the methyl ricinoleate
using a flow meter and heating the methyl ricinoleate using the raw
material pre-heater; 3) at the set temperature and in the microwave
catalytic reactor, cracking the methyl ricinoleate of high quality
into methyl undecene and heptaldehyde gases, and conveying the
methyl undecene and heptaldehyde gases into the condenser via the
outlet pipe; and 4) forming a liquid product by condensing the
methyl undecene and heptaldehyde gases using the condenser,
conveying the liquid product into the product tank and pumping the
liquid product into a distillation unit using the feed pump, and
purifying the liquid product to obtain the undecylenic acid methyl
ester.
10. The process of claim 9, further comprising the step of
subjecting raw methyl ricinoleate to transesterification and
distillation to provide the methyl ricinoleate of high purity.
11. The process according to claim 9, wherein the temperature of
the cracking reaction is between 400 and 600 degree centigrade.
12. The process according to claim 9, wherein the pyrolysis system
is under atmospheric pressure or negative pressure.
13. The process according to claim 12, further comprising a step of
venting the product tank or connecting it to a vacuum so as to
provide the atmospheric pressure or negative pressure for the
pyrolysis system.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority to Chinese Patent
Application CN201410585158.X filed on Oct. 27, 2014.
TECHNICAL FIELD
[0002] The present invention relates to the field of lipid chemical
production technology, and particularly, to a device and a process
for producing undecylenic acid methyl ester using methyl
ricinoleate as raw material.
BACKGROUND
[0003] By means of saponification and acidification, undecylenic
acid methyl ester can be obtained from undecylenic acid.
Undecylenic acid has extensive applications. Particularly, after
bromide and ammonolysis undecylenic acid can become aminoundecanoic
acid, which can be polymerized to form tonylon-11 (PA11). PA11 has
several advantages: it has a low water absorption rate, is good in
oil resistance, can well withstand low temperature, and is easy
processing, etc. PA11 has been widely used in automotive industry,
military industry, electrical and electronic devices, sports
equipment, food industry, medical devices, and so on. Undecylenic
acid is used in large quantities in manufacturing flavors and
fragrances. Musk T, which is made of undecylenic acid and has
strong musk fragrance, is the raw material for the remixing of the
three main synthetic flavors including the daily-use flavor. In
addition, undecylenic acid also has a wide range of applications in
medicine and surfactant.
[0004] Currently, the production methods of undecylenic acid mainly
include direct pyrolysis of castor oil and pyrolysis of methyl
ricinoleate. The method of direct pyrolysis of castor oil has some
shortcomings such as high boiling point, high viscosity of castor
oil and high pyrolysis temperature. The direct pyrolysis of castor
oil in lead bath was once used in China to produce undecylenic
acid, with the reaction temperature of higher than 600 degrees
centigrade. Further issues with this process include serious coking
and pollution, as well as low product yield. Since the 1980s, the
direct catalytic cracking method has been studied; however, it
still requires a temperature higher than 550 degrees centigrade and
also has the issues of high cost of catalyst and low reusing rate.
The method for producing undecylenic acid used by the French
company ATO is to crack methyl esterified castor oil under high
temperature, and method has already been industrialized. The
technology of producing nylon-11 from undecylenic acid is
monopolized by ATO. However, it also has the issues of high
cracking temperature and easy coking, and the yield is only about
30%. In Chinese Patent CN101289383A, an electric heater tower's
cracking furnace was provided to directly crack castor oil at the
cracking temperature of 500.about.600 degrees centigrade. It needs
superheated steam of 500.about.600 degrees centigrade, and the
method has issues of high energy consumption, low productivity, low
yield, and high equipment requirement.
[0005] Microwave heating is widely used in drying because of its
unique advantages: the process of microwave heating does not need
direct contact to heat supply, or other intermediate conversion
processes. A microwave absorbing material can be directly and
quickly heated through absorption of microwave. Microwave heating
can save electricity by up to 30.about.50% compared to conventional
heating methods. The process of producing undecylenic acid methyl
ester by pyrolysis of methyl ricinoleate under microwave heating
has not been reported before.
SUMMARY
[0006] This invention intends to overcome the deficiencies of the
known techniques and provides a device and a process for producing
undecylenic acid methyl ester using methyl ricinoleate as raw
material. The device and the process have advantages of low energy
consumption, high product yield, and less coking. After
transesterification and vacuum distillation, castor oil can be
converted into methyl ricinoleate of good fluidity and high purity.
Using a microwave pyrolysis system, methyl ricinoleate can be
quickly cracked to undecylenic acid methyl ester; then, isolation
and purification processes are used to obtain high-purity
undecylenic acid methyl ester.
[0007] The objective of the present invention is achieved by the
following technical scheme. The device for producing undecylenic
acid methyl ester using methyl ricinoleate as raw material
comprises: a feed pump, a raw material pre-heater, a microwave
catalytic reactor, a microwave generator, a temperature controller
and an infrared sensor, a condenser, a product tank and a discharge
pump. The feed pump is connected with the raw material pre-heater,
which is connected with the inlet of the microwave catalytic
reactor. The outlet of the microwave catalytic reactor is connected
with the condenser, which is connected with the product tank and
the discharge pump. The microwave catalytic reactor mentioned above
is located in the microwave generator, which is connected with the
temperature controller and the infrared sensor.
[0008] Preferably, the microwave catalytic reactor is designed with
an inlet and an outlet. The inlet and the outlet are arranged in
the upper or side portion of the reactor. In addition, the
microwave catalytic reactor can be made of glass, ceramics or any
other wave-transparent material that can stand high
temperature.
[0009] Preferably, inside the microwave catalytic reactor is
arranged a layer of microwave absorbing material. The microwave
absorbing material may be silicon carbide, activated carbon,
Fe/Co/Ni loaded alumina or zeolites, etc.
[0010] Preferably, the microwave catalytic reactor is arranged
inside the microwave generator, and the microwave generator is
connected with a feed inlet, a product outlet and a temperature
measurement port. The feed inlet, product outlet and temperature
measurement port are arranged on the top or the side of the
microwave generator.
[0011] Preferably, the microwave generator is connected with the
temperature controller, the infrared sensor and a paperless
recorder.
[0012] The present invention also provides a process for producing
undecylenic acid methyl ester using methyl ricinoleate as raw
material, with specific steps as follows: [0013] 1. Set a cracking
reaction temperature of the microwave generator and turn on the
microwave generator to start a heating process; [0014] 2. Input
into a device as mentioned above a methyl ricinoleate of high
purity using the feed pump of the device, regulating a flow rate of
the methyl ricinoleate using a flow meter and heating the
methylricinoleate using the raw material pre-heater; the methyl
ricinoleate of high purity may be obtained by subjecting raw methyl
ricinoleate to transesterification and distillation; [0015] 3. At
the set temperature and in the microwave catalytic reactor of the
device, methyl ricinoleate is quickly cracked into methyl undecene
and heptaldehyde gases; the methyl undecene and heptaldehyde gases
are conveyed into the condenser via the outlet pipe; and forming a
liquid product by condensing the methyl undecene and heptaldehyde
gases using the condenser, conveying the liquid product into the
product tank and pumping the liquid product into a distillation
unit using the feed pump, and purifying the liquid product to
obtain the undecylenic acid methyl ester.
[0016] Preferably, the temperature of the cracking reaction is
between 400 and 600 degrees centigrade.
[0017] Preferably, the pyrolysis system is under atmospheric
pressure or negative pressure. This may be achieved by venting the
product tank or connecting it to a vacuum.
[0018] The beneficial effects of the present invention are as
follows: 1. The process of microwave heating does not need direct
contact to heat supply and other intermediate conversion process;
microwave absorbing material can be directly and quickly heated
through absorption of microwave; microwave heating can save
electricity by up to 30.about.50% compared to conventional heating
methods. The present invention uses microwave generating device and
microwave absorbing catalytic material, leading to a uniform
heating process which can reduce energy consumption and carbon
deposition. 2. Compared to other high-temperature pyrolytic devices
and processes, the present invention eliminates lead pollution,
shortens reaction time, improves reaction efficiency, and increases
product yield.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 shows a diagram showing a device and a process
according to the present invention.
[0020] FIG. 2 presents a gas chromatography-mass spectrometer
(GC-MS) total ion chromatogram of raw material and products in
microwave-assisted cracking of methyl ricinoleate at high
temperature.
EXPLANATION OF THE REFERENCE SIGNS
[0021] 1-1: feed pump [0022] 2: raw material pre-heater [0023] 3:
microwave catalysis reactor [0024] 6-1: microwave generator [0025]
6-2: temperature controller [0026] 6-3: infrared sensor [0027] 6-4:
condenser [0028] 5: product tank [0029] 1--discharge pump
PREFERRED EMBODIMENTS
[0030] A detailed description of a preferred embodiment of this
invention is presented as follows.
[0031] As shown in FIG. 1, the device for producing undecylenic
acid methyl ester using methyl ricinoleate as raw material
comprises, among other parts, a feed pump (1-1), a raw material
pre-heater (2), a microwave catalysis reactor (3), a microwave
generator (6-1), a temperature controller (6-2) and an infrared
sensor (6-3), a condenser (4), a product tank (5) and a discharge
pump (1-2). The feed pump (1-1) is connected with the material
pre-heater (2), which is connected to the inlet of the microwave
catalytic reactor (3). The outlet of the microwave catalytic
reactor (3) is connected with the condenser (4), which is connected
to the upper port of the product tank (5). The lower port of the
product tank (5) is then connected to the discharge pump (1-2). The
microwave catalytic reactor (3) is placed in the microwave
generator (6-1), which is connected with the temperature controller
(6-2) and infrared sensor (6-3), and also a paperless recorder if
necessary.
[0032] The microwave catalytic reactor (3) mentioned above has an
inlet and an outlet, which are located on the top or the side of
the microwave catalytic reactor (3). The microwave catalytic
reactor (3) can be made of glass, ceramics or other
wave-transparent material that can withstand high temperature.
Inside the microwave catalytic reactor (3) is a layer of microwave
absorbing material, which can be silicon carbide, activated carbon,
Fe/Co/Ni loaded alumina or zeolites. The microwave catalytic
reactor (3) is arranged inside the microwave generator (6-1), and
the microwave generator (6-1) is connected with a feed inlet, a
product outlet and a temperature measurement port. The feed inlet,
the product outlet and the temperature measurement port are
arranged on the top or the side of the microwave generator
(6-1).
[0033] A process for producing undecylenic acid methyl ester using
methyl ricinoleate as raw material comprises the specific steps as
follows: [0034] 1. Set a cracking reaction temperature of the
microwave generator (6-1) at 400.about.600 degrees centigrade and
turn on the microwave generator (6-1) to start the heating process;
[0035] 2. Input into a device as mentioned above a methyl
ricinoleate of high purity using the feed pump (1-1), regulating a
flow rate of the methyl ricinoleate using a flow meter and heating
the methyl ricinoleate using the raw material pre-heater (2); the
methyl ricinoleate of high purity may be obtained by subjecting raw
methyl ricinoleate to transesterification and distillation; [0036]
3. At the set temperature and in the microwave catalytic reactor of
the device, methyl ricinoleate is quickly cracked into methyl
undecene and heptaldehyde gases; the methyl undecene and
heptaldehyde gases are conveyed into the condenser (4) via the
outlet pipe; and forming a liquid product by condensing the methyl
undecene and heptaldehyde gases using the condenser, conveying the
liquid product into the product tank (5) and pumping the liquid
product into a distillation unit using the feed pump (1-2), and
purifying the liquid product to obtain the undecylenic acid methyl
ester.
[0037] As an embodiment of the invention: at 60 degrees centigrade,
castor oil is mixed with an alkali solution of methanol to start
the transesterification reaction. After 1 hour, the oil phase
obtained from layering is washed with water until its pH=7. Then,
rotary evaporation is performed to remove the methanol and the
trace water, to obtain crude methyl ester containing 87% (by
weight) of methylricinoleate. The crude methyl ester is then
distilled at the reduced pressure of 100 PaA and reflux ratio of 5,
during which temperature at the bottom of the distillation device
is controlled at 190.about.210 degrees centigrade and the
temperature at the top of the distillation device is controlled at
about 170 degrees centigrade. The purity of the methylricinoleate
obtained is higher than 99%, and the methylricinoleate obtained is
used as the feedstock, or the raw material, for the subsequent
microwave pyrolysis.
[0038] Silicon carbide is input to the microwave catalytic reactor
(3), and the temperature of the microwave generator (6-1) is set at
500 degrees centigrade. The feed tube N is connected to the import
port E of the microwave catalytic reactor (3) and the outlet tube O
is connected to the export port F of the microwave catalytic
reactor (3). The export F is then connected with the condenser (4),
on which the ports J and I are the import and export of freezing
water, respectively. The microwave generator (6-1) is turned on to
make the microwave absorbing material in the microwave catalytic
reactor (3) reach the set temperature and stabilize for a period of
time. The raw material (high-purity methyl ricinoleate) is pumped
by the feed pump (1-1), the flow rate of the raw material is
measured or regulated by the flow meter, the raw material is heated
by the raw material pre-heater (2), and then enters the microwave
catalytic reactor via the inlet 3E thereof, and is cracked in the
microwave catalytic reactor. On the raw material pre-heater, port
2A, B, C, and D are the feed port, discharge port, outlet of heat
transfer oil, inlet of heat transfer oil, respectively. At the set
temperature, the raw material is quickly cracked into methyl
undecene and heptaldehyde gases, which flow through the outlet F
into port 4G of the condenser. The methyl undecene and heptaldehyde
gases are condensed in the condense to form a liquid, which flows
out of the condenser through port H and enters the product tank
through port K. Port L of the product tank can be vented or
vacuumed or connected to a vacuum to provide a negative pressure
for the pyrolysis system. The pyrolysis system may be under
atmospheric pressure or negative pressure. This may be achieved by
venting the product tank or connecting it to a vacuum. The liquid
is pumped into a downstream distillation unit by the feed pump
(1-2), and isolation and purification processes can be carried out
on the liquid to obtain high-purity methyl undecene, and
saponification and acidification processes may follow to finally
obtain the undecylenic acid. Results of the embodiment are as
follows: the liquid yield is 90.5%; the yield of the undecylenic
acid is 70.2%; and selectivity of the undecylenic acid is 80.5%. By
comparison, the yield is only 34.about.38% in the electrical
heating process as reported by Chinese patent CN101289383A, and the
yield in the melting lead process is only 30.about.32%. Compared
with these processes, the yield of undecylenic acid in the present
invention can be at least doubled.
[0039] It can be understood that as for technical staff in the
present field, equivalent replacements or changes to the technical
scheme or inventive concept in the present invention should be
protected according to the claims in the present invention.
* * * * *