U.S. patent application number 15/720103 was filed with the patent office on 2018-03-08 for catalyst for fixed bed aniline rectification residue recycling and preparation method.
The applicant listed for this patent is Wanhua Chemical Group Co., Ltd. Invention is credited to Shanjian Cao, Hao Chen, Zhongying Chen, Bingbo Hu, Qingmei Jiang, Yuan Li, Hua Mei, Zilin Ni, Jun Qu, Jinhong Song, Hui Wang, Zaigang Yang, Dewei Yu, Congying Zhang.
Application Number | 20180065916 15/720103 |
Document ID | / |
Family ID | 49821166 |
Filed Date | 2018-03-08 |
United States Patent
Application |
20180065916 |
Kind Code |
A1 |
Mei; Hua ; et al. |
March 8, 2018 |
CATALYST FOR FIXED BED ANILINE RECTIFICATION RESIDUE RECYCLING AND
PREPARATION METHOD
Abstract
The present invention relates to a catalyst for fixed bed
aniline rectification residue recycling and preparation method
thereof. Based on the total weight of the catalyst, the catalyst
comprises the following components in percentage by weight: 5-40%
of an active component, 2-30% of a first cocatalyst component,
10-30% of a second cocatalyst component and the balance of carrier,
wherein the active component is NiO; the first cocatalyst component
is one or more of Fe, Mo, Cr or Co oxide; and the second cocatalyst
component is one or more of La, Zr, Y or Ce oxide. The catalyst is
prepared through co-precipitation. The catalyst shows high activity
and stability in the waste liquid treatment process, and can still
maintain high rectification residue cracking rate after reaction of
200 hours.
Inventors: |
Mei; Hua; (Yantai, CN)
; Chen; Hao; (Yantai, CN) ; Yu; Dewei;
(Yantai, CN) ; Zhang; Congying; (Yantai, CN)
; Wang; Hui; (Yantai, CN) ; Li; Yuan;
(Yantai, CN) ; Chen; Zhongying; (Yantai, CN)
; Ni; Zilin; (Yantai, CN) ; Jiang; Qingmei;
(Yantai, CN) ; Cao; Shanjian; (Yantai, CN)
; Yang; Zaigang; (Yantai, CN) ; Qu; Jun;
(Yantai, CN) ; Song; Jinhong; (Yantai, CN)
; Hu; Bingbo; (Yantai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Wanhua Chemical Group Co., Ltd |
Yantai |
|
CN |
|
|
Family ID: |
49821166 |
Appl. No.: |
15/720103 |
Filed: |
September 29, 2017 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
14913853 |
Feb 23, 2016 |
|
|
|
PCT/CN14/73063 |
Mar 7, 2014 |
|
|
|
15720103 |
|
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 37/0236 20130101;
B01J 2523/3712 20130101; B01J 2523/847 20130101; B01J 37/031
20130101; C07C 211/35 20130101; B01J 23/866 20130101; B01J 2523/36
20130101; B01J 23/002 20130101; B01J 23/83 20130101; B01J 37/03
20130101; B01J 2523/845 20130101; B01J 2523/67 20130101; B01J
2523/48 20130101; B01J 2523/00 20130101; B01J 37/035 20130101; C07C
209/62 20130101; B01J 23/8871 20130101; B01J 2523/3706 20130101;
C07C 209/72 20130101; B01J 23/75 20130101; C07C 2601/14 20170501;
B01J 2523/68 20130101; B01J 2523/41 20130101; B01J 37/08 20130101;
C07C 209/72 20130101; C07C 211/35 20130101; B01J 2523/00 20130101;
B01J 2523/3706 20130101; B01J 2523/41 20130101; B01J 2523/842
20130101; B01J 2523/847 20130101; B01J 2523/00 20130101; B01J
2523/36 20130101; B01J 2523/41 20130101; B01J 2523/842 20130101;
B01J 2523/847 20130101; B01J 2523/00 20130101; B01J 2523/3712
20130101; B01J 2523/41 20130101; B01J 2523/845 20130101; B01J
2523/847 20130101; B01J 2523/00 20130101; B01J 2523/36 20130101;
B01J 2523/41 20130101; B01J 2523/845 20130101; B01J 2523/847
20130101; B01J 2523/00 20130101; B01J 2523/3712 20130101; B01J
2523/41 20130101; B01J 2523/48 20130101; B01J 2523/845 20130101;
B01J 2523/847 20130101; B01J 2523/00 20130101; B01J 2523/36
20130101; B01J 2523/41 20130101; B01J 2523/842 20130101; B01J
2523/845 20130101; B01J 2523/847 20130101; B01J 2523/00 20130101;
B01J 2523/36 20130101; B01J 2523/41 20130101; B01J 2523/68
20130101; B01J 2523/847 20130101; B01J 2523/00 20130101; B01J
2523/3712 20130101; B01J 2523/41 20130101; B01J 2523/67 20130101;
B01J 2523/847 20130101 |
International
Class: |
C07C 209/62 20060101
C07C209/62; B01J 37/03 20060101 B01J037/03; B01J 23/83 20060101
B01J023/83; C07C 209/72 20060101 C07C209/72; B01J 23/00 20060101
B01J023/00; B01J 23/86 20060101 B01J023/86; B01J 23/887 20060101
B01J023/887; B01J 37/08 20060101 B01J037/08; B01J 37/02 20060101
B01J037/02; B01J 23/75 20060101 B01J023/75; C07C 211/35 20060101
C07C211/35 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 3, 2013 |
CN |
2013103961006 |
Claims
1. A process of recycling aniline rectification residue, comprising
subjecting the aniline rectification residue to fixed bed
hydrogenation with a catalyst, wherein said catalyst comprises the
components described below based on the total weight of the
catalyst: 5-40 wt % of NiO as an active component, 2-30 wt % of one
or more selected from oxides of Fe, oxides of Mo, oxides of Cr and
oxides of Co as a first cocatalyst component, 10-30 wt % of one or
more selected from oxides of La, oxides of Zr, oxides of Y and
oxides of Ce as a second cocatalyst component, the remaining
portion being the support.
2. The process of claim 1, wherein said catalyst comprises the
components described below based on the total weight of the
catalyst: 15-30 wt % of NiO as the active component, 5-25 wt % of
one or more selected from oxides of Fe, oxides of Mo, oxides of Cr
and oxides of Co as the first cocatalyst component, 15-25 wt % of
one or more selected from oxides of La, oxides of Zr, oxides of Y
and oxides of Ce as the second cocatalyst component, the remaining
portion being the support.
3. The process of claim 1, wherein the support is SiO.sub.2.
4. The process of claim 1, wherein the aniline rectification
residue is treated by gas phase hydrogenation to obtain cyclohexyl
amine and dicyclohexyl amine, using monofunctional saturated
alcohol as the diluent, under the catalysis of the catalyst, at a
certain temperature and pressure.
5. The process of claim 4, wherein the monofunctional saturated
alcohol is ethanol or methanol.
6. The process of claim 4, wherein the monofunctional saturated
alcohol/aniline rectification residue in mass ratio of 0.1-0.7:1 is
introduced to a fixed bed reactor, wherein the liquid phase volume
space velocity is 0.6-1.5 h.sup.-1, the reaction pressure is 1-4
MPa, the reaction temperature is between 250-320.degree. C., and
the volume ratio of the hydrogen amount and the amount of aniline
rectification residue is 500-3000:1.
Description
RELATED APPLICATIONS
[0001] This application is a divisional and claims the benefit of
priority under 35 U.S.C. .sctn.120 of U.S. application Ser. No.
14/913,853, filed on Feb. 23, 2016, which is a National Stage Entry
under 35 U.S.C. .sctn.371 of International Patent Application No.
PCT/CN14/73063, filed on Mar. 7, 2014, which claims the benefit of
priority of Chinese Patent Application No. 201310396100.6, filed on
Sep. 3, 2013.
FIELD OF THE INVENTION
[0002] The present invention relates to the use of a catalyst for
fixed bed aniline rectification residue recycling.
BACKGROUND OF THE INVENTION
[0003] Aniline is a colorless, oily liquid with a strong odor and
toxicity. It is an important chemical intermediate, and thus is
widely used for producing rubber processing aids, dyes,
photographic chemicals, pharmaceuticals, pesticides, explosives,
polyurethanes and the like. The production methods of aniline
comprise phenol ammoniation, iron powder reduction and catalytic
hydrogenation of nitrobenzene.
[0004] Taking into account the source of raw materials, energy
consumption, environmental protection and so on, most manufacturers
use catalytic hydrogenation of nitrobenzene. The catalytic
hydrogenation may be divided into two processes, i.e., the fixed
bed gas phase hydrogenation and fluidized bed gas phase
hydrogenation according to the different forms of the reactor used.
The fixed bed gas phase hydrogenation has the advantages of simple
process, low maintenance cost, no need for separation of catalyst,
low reaction temperature, good product quality and the like, but
local overheating (hot spot) is prone to occur due to poor heat
transfer of the fixed bed, which leads to side reactions and
deactivation of the catalyst. Therefore, the activity cycle of the
catalyst is shortened. For the fluidized bed reactor, heat transfer
is good, such that local overheating may be avoided, side reactions
may be reduced and the service life of the catalyst may be
prolonged. The fluidized bed reactor has the disadvantages of
complicated operation, remarkable catalyst abrasion, and high
operation and maintenance costs. The liquid phase hydrogenation
comprises a gas phase reaction and a liquid phase reaction and
achieves easy reaction heat removal, and has the advantages of
simple equipment and low operation and maintenance costs, but the
cost of technology introduction is high.
[0005] Usually, aniline is produced by the liquid phase catalytic
hydrogenation process, wherein the raw material nitrobenzene is
desulfurized and decarbonized by an oxidation system, the
nitrobenzene and hydrogen gas are mixed and pretreated, and then
reacted in a fluidized bed reactor and the used catalyst is
recycled to the reactor for reuse. Since water is generated in the
reaction, the crude product obtained after reaction is refined by
extraction, the unreacted nitrobenzene is recovered, aniline is
obtained by rectification, and aniline rectification residue is
enriched in the rectification tower kettle. The aniline
rectification residue is primarily originated from the two aspects:
(1) a part of high boiling components is produced from nitrobenzene
due to the excess of hydrogen gas in the hydrogenation; (2)
cyclohexanone intermediate produced in the hydrogenation reaction
may be reacted with aniline to form Schiff base tar, which is black
viscous liquid with a pungent smell and contains a lot of aromatic
substances with negatively charged .pi.-electron system, such
as
##STR00001##
cyclohexyl aniline
##STR00002##
diphenyl amine
##STR00003##
1,2,3,4-tetrahydrocarbazole
##STR00004##
p-(phenylamino) aniline
##STR00005##
phenol, N-cyclohexyl-1,2-phenylenediamine
##STR00006##
2-phenyl aniline
##STR00007##
long chain alkanes and the like. These substances have higher
molecular weight, and if the molecules contain an amino group
(--NH.sub.2), two molecules containing such amino group will take
place deamination reaction, so as to form a large molecule
containing --NH--. These factors make aniline rectification residue
have high viscosity and poor fluidity, and thus difficult to be
reused. It is generally used for firewood material and waterproof
material. The amount of aniline rectification residue used for the
two uses is very small, based on the total amount of aniline
rectification residue. Therefore, most of the aniline rectification
residue, as waste liquid, is treated by incineration, but after
incineration, it will produce nitrogen oxides and lead to acid rain
and pollution environment, and further reduce the output of
agriculture and fisheries.
[0006] The technical problem to be solved by the present invention
is how to crack the aniline rectification residue sufficiently to
obtain a certain amount of high economic value of product, in order
to turn it from waste to treasure and reduce the pollution of the
environment as far as possible. At present, there is no effective
method for the utilization of aniline rectification residue.
SUMMARY OF THE INVENTION
[0007] It is an object of the present invention to provide a
catalyst for fixed bed aniline rectification residue recycling,
which can hydrocrack aniline rectification residue to break
molecular chains C--C, C--N of the high molecular weight substances
contained in the residue, to make the C.dbd.C molecular chains
saturated, to decrease their molecular weight, to reduce the
viscosity of the system, to enhance the fluidity, and also to
obtain useful substances such as cyclohexyl amine, dicyclohexyl
amine and the like such that the subsequent separation operation is
facilitated.
[0008] Another object of the present invention is to provide a
method of preparing the catalyst for fixed bed aniline
rectification residue recycling. Said method is simple, and the
prepared catalyst has good stability.
[0009] A yet another object of the present invention is to provide
the use of said catalyst for fixed bed aniline rectification
residue recycling.
[0010] The technical solution of the present invention used to
achieve the above-said object is described as below.
[0011] A catalyst for fixed bed aniline rectification residue
recycling, which comprises the components described below based on
the total weight of the catalyst:
5-40 wt % of NiO as an active component, 2-30 wt % of one or more
selected from oxides of Fe, oxides of Mo, oxides of Cr and oxides
of Co as a first cocatalyst component, 10-30 wt % of one or more
selected from oxides of La, oxides of Zr, oxides of Y and oxides of
Ce as a second cocatalyst component, the remaining portion being
the support.
[0012] In a preferable embodiment, based on the total weight of the
catalyst, it comprises the components described below:
15-30 wt % of NiO as the active component, 5-25 wt % of one or more
selected from oxides of Fe, oxides of Mo, oxides of Cr and oxides
of Co as the first cocatalyst component, 15-25 wt % of one or more
selected from oxides of La, oxides of Zr, oxides of Y and oxides of
Ce as the second cocatalyst component, the remaining portion being
the support.
[0013] In an embodiment of the catalyst of the present invention,
said support is SiO.sub.2.
[0014] A method of preparing the catalyst for fixed bed aniline
rectification residue recycling, which comprises:
A) dissolving nickel nitrate, the nitrates of the metals comprised
in the first and second cocatalyst components in water to form the
mixing solution of the metal nitrates, and adding dropwise the
mixing solution, alkali solution and aqueous sodium silicate
solution in a sedimentation tank separately or together in the
manner of parallel flow; or dissolving nickel nitrate, sodium
silicate, and the nitrates of the metals comprised in the first and
second cocatalyst components in water to form the mixing solution,
and adding dropwise the mixing solution and alkali solution in a
sedimentation tank separately or together in the manner of parallel
flow; or dissolving nickel nitrate, the nitrates of the metals
comprised in the first and second cocatalyst components in water to
form the mixing solution of the metal nitrates, and adding dropwise
the mixing solution and alkali solution containing dissolved sodium
silicate in a sedimentation tank separately or together in the
manner of parallel flow; and B) precipitating the mixture in the
sedimentation tank at controlling pH of 7-8, aging, filtering,
drying and calcining the resulting precipitate, and then molding
and pulverizing it.
[0015] When the first cocatalyst component comprises the oxide of
Mo, it is different from the above-said method in that the
precipitate of the components except Mo is immersed in ammonium
molybdate solution, and then calcinated, molded and pulverized.
[0016] In an embodiment of the preparation method of the present
invention, the concentration of the metal ions in said mixing
solution of metal nitrates is controlled at 0.3-5 mol/L.
[0017] In an embodiment of the preparation method of the present
invention, said alkali solution is aqueous Na.sub.2CO.sub.3
solution, aqueous NaOH solution or aqueous solution of ammonia, and
its concentration is 0.5-10 mol/L.
[0018] In an embodiment of the preparation method of the present
invention, the concentration of said aqueous sodium silicate
solution or the concentration of sodium silicate in alkali solution
is 0.1-1 mol/L.
[0019] In an embodiment of the preparation method of the present
invention, the temperature in the sedimentation tank is controlled
at 50-70.degree. C.
[0020] In an embodiment of the preparation method of the present
invention, the calcination temperature is between 300-700.degree.
C., and the calcination time is 4-6 h.
[0021] In an embodiment of the preparation method of the present
invention, said aging temperature is 60-80.degree. C., and the
aging time is 4-8 h; the drying temperature is 100-150.degree. C.,
and the drying time is 8-15 h.
[0022] In an embodiment of the preparation method of the present
invention, said molding comprises extrusion molding or compression
molding the calcinated catalyst, and the pulverization comprises
pulverizing the catalyst to 10-20 mesh.
[0023] The present invention additionally provides the use of the
above-said catalyst or the catalyst prepared by the above-said
method for aniline rectification residue recycling, wherein the
aniline rectification residue is treated by gas phase hydrogenation
to obtain cyclohexyl amine and dicyclohexyl amine, using
monofunctional saturated alcohol as the diluent, under the
catalysis of the catalyst, at a certain temperature and
pressure.
[0024] Said monofunctional saturated alcohol is ethanol or
methanol.
[0025] The monofunctional saturated alcohol/aniline rectification
residue in mass ratio of 0.1-0.7:1 is injected to a fixed bed
reactor with the catalyst loading capacity of 10 ml by a
micro-metering pump, and is completely evaporated at the upper end
of the reaction tube. The liquid phase volume space velocity is
0.6-1.5 h.sup.-1, the reaction pressure is 1-4 MPa, the reaction
temperature is between 250-320.degree. C., the volume ratio of the
hydrogen amount and the amount of aniline rectification residue is
500-3000:1, the hydrogen flow rate is 150-400 ml/min. Prior to
initiation of the reaction, the catalyst needs to be reduced, and
the reduction temperature and time are 350-500.degree. C. and 4 h,
respectively. The reducing gas is H.sub.2 (50 ml/min). When the
reduction is ended and the temperature drops to the reaction
temperature, the feeding and reaction is initiated, and the
resulting product is quantitatively analyzed by gas chromatograph.
The resulting catalyst has high activity and high selectivity,
based on the mass of the rectification residue, the cyclohexylamine
and dicyclohexylamine yields are up to 36.8% and 40% respectively,
and the catalyst has good stability and the product selectivity is
still not decreased after 200 h reaction.
[0026] The reaction of the aniline rectification residue processed
by the catalyst of the present invention belongs to hydrocracking.
By hydrocracking, the molecular chains C--C, C--N of the high
molecular weight substances contained in the aniline rectification
residue are broken, the molecular chains C.dbd.C are saturated, the
viscosity of the system is decreased, and small molecular
substances such as cyclohexyl amine, dicyclohexyl amine are
obtained, such that the subsequent separation operation is
facilitated. Furthermore, the catalyst of the present invention
will not cleave the ring of small molecules, and the reaction
principle may refer to the following reaction schemes:
##STR00008##
[0027] In the catalyst of the present invention, the components
have a synergic effect among them, so that the catalyst has high
activity and stability. Ni catalyst has good catalytic activity,
but is subjected to activity lowering due to the loss, sintering
and coking of the active constituents in a high temperature
reaction, and prone to sulfur poisoning. By changing the support
and adding the first and second cocatalyst components, the loss of
the active constituents may be reduced, and the degree of carbon
deposition and sintering may be alleviated, thereby enhance the
stability of the catalyst and prolong the service life of the
catalyst. Y has effects of regulating the catalyst surface acidity,
preventing carbon deposition and reducing ring opening reaction. Fe
has the role of stabilizing the catalyst, and Mo, Cr, Zr, Ce, La or
Co has the functions of reducing carbon deposition on the catalyst
and prolonging the life of the catalyst.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 is the gas chromatogram of the product of Example 1
of the present invention.
THE MODE OF CARRYING OUT THE INVENTION
[0029] The embodiments of the present invention are further
described with reference to the Examples. The present invention
should not be interpreted to be limited to these examples, rather
comprise all variations and modifications within the scope of the
claims.
[0030] The fixed bed reactor used in the Examples have a size of
length 100 cm and inner diameter 25 mm. The reaction product is
analyzed by Shimadzu GC-2014 gas chromatograph (hydrogen flame
ionization (FID) detector) using internal standard method. The
detection conditions are as follows: analytical column SE-30,
capillary column (.PHI.0.30 mm.times.30 m), the gasification
chamber 270.degree. C., the detector 270.degree. C. The column
temperature is 70.degree. C. and maintained for 1 min, and then
rise to 240.degree. C. at the rate of 40.degree. C./ min and
maintained for 5 min.
[0031] The aniline rectification residue used in the Examples is
from the aniline rectification units of Ningbo Wanhua Polyurethane
Co., Ltd.
Example 1
[0032] 16 g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 20 g of
ferric nitrate Fe(NO.sub.3).sub.39H.sub.2O and 11 g of lanthanum
nitrate La(NO.sub.3).sub.3 6H.sub.2O are weighed respectively, and
dissolved in 300 ml of distilled water, referred to as solution
A.
[0033] 15 mass % of aqueous ammonia solution (200 ml) is
formulated, referred to as solution B.
[0034] 17 g of sodium silicate (Na.sub.2SiO.sub.3) is weighed and
dissolved in 150 ml water, referred to as solution C.
[0035] Firstly, 100 ml water in a sedimentation tank is heated to
50.degree. C., and the solution A, B and C are added dropwise to
the sedimentation tank. In the preparation process, pH and the
precipitation temperature are maintained at 7.5 and 60.degree. C.
respectively. After the end of precipitation, the stirring speed
and precipitation temperature are kept unchanged, and the resulting
precipitate is aged for 4 h, filtered and washed to neutral.
Thereafter, the precipitate is placed in an oven of 110.degree. C.
and dried for 12 h. After the end of drying, the precipitate is
calcined under air atmosphere at 400.degree. C. for 4 h, and then
grinded, extrusion molded, pulverized and sieved to 10-20 mesh.
Finally, 20% NiO-20% Fe.sub.2O.sub.3/40% SiO.sub.2-20%
La.sub.2O.sub.3 is prepared.
[0036] 10 ml of the above-said catalyst is packed in a fixed bed
reactor, and reduced at 400.degree. C. After the reduction, the
temperature is lowered to the reaction temperature of 280.degree.
C., the system pressure is raised to 1.5 MPa, and the feeding is
initiated, wherein the mass ratio of ethanol and aniline
rectification residue is 0.2:1. Liquid phase space velocity is 0.7
h.sup.-1, and H.sub.2 flow rate is 200 ml/min. After 10 h reaction,
sampling is conducted for analysis, and cyclohexyl amine and
dicyclohexyl amine yields are 33.6% and 24%, respectively. After
200 h reaction, cyclohexyl amine and dicyclohexyl amine yields are
maintained at 31.2% and 24.6% respectively.
Example 2
[0037] 24g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 20 g of
ferric nitrate Fe(NO.sub.3).sub.39H.sub.2O and 7 g of yttrium
nitrate Y(NO.sub.3).sub.36H.sub.2O are weighed respectively, and
dissolved in 300 ml of distilled water, referred to as solution A.
0.7 mol/L of Na.sub.2CO.sub.3 solution is formulated, 17 g of
sodium silicate (Na.sub.2SiO.sub.3) is weighed and dissolved in 300
ml Na.sub.2CO.sub.3 solution, referred to as solution B.
[0038] Firstly, water in the sedimentation tank is heated to
70.degree. C., and the solution A and B are added dropwise to a
sedimentation tank in a parallel flow. In the preparation process,
pH and the precipitation temperature are maintained at 8 and
70.degree. C. respectively. After the end of precipitation, the
stirring speed and precipitation temperature are kept unchanged,
and the resulting precipitate is aged for 4 h, filtered and washed
to neutral. Thereafter, the precipitate is placed in an oven of
110.degree. C. and dried for 12 h. After the end of drying, the
precipitate is calcined under air atmosphere at 500.degree. C. for
4 h, and then grinded, compression molded, pulverized and sieved to
10-20 mesh. Finally, 30% NiO-20% Fe.sub.2O.sub.3/40% SiO.sub.2-10%
Y.sub.2O.sub.3 is prepared.
[0039] 10ml of the above-said catalyst is packed in a fixed bed
reactor, and reduced at 450.degree. C. After the reduction, the
temperature is lowered to the reaction temperature of 300.degree.
C., the system pressure is raised to 2 MPa, and the feeding is
initiated, wherein the mass ratio of ethanol and aniline
rectification residue is 0.2. Liquid phase space velocity is
0.7h.sup.-1, and H.sub.2 flow rate is 250ml/min. After 10 h
reaction, sampling is conducted for analysis, and cyclohexyl amine
and dicyclohexyl amine yields are 36.8% and 40%, respectively.
After 200 h reaction, cyclohexyl amine and dicyclohexyl amine
yields are maintained at 35.8% and 38.7% respectively.
Example 3
[0040] 20 g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 8 g of
cobalt nitrate Co(NO.sub.3).sub.26H.sub.2O and 15 g of cerium
nitrate Ce(NO.sub.3).sub.36H.sub.2O are weighed respectively, and
dissolved in 200 ml of distilled water, referred to as solution
A.
[0041] 1 mol/L of NaOH solution is formulated, 17 g of sodium
silicate (Na.sub.2SiO.sub.3) is dissolved in 200 ml NaOH solution,
referred to as solution B.
[0042] Firstly, the solution B is poured into a sedimentation tank
and heated to 70.degree. C., and the solution A is added dropwise
to the sedimentation tank slowly. In the meantime, the
precipitation temperature is maintained at 70.degree. C. After the
end of precipitation, the stirring speed and precipitation
temperature are kept unchanged, and the resulting precipitate is
aged for 4 h, filtered and washed to neutral. Thereafter, the
precipitate is placed in an oven of 110.degree. C. and dried for 12
h. After the end of drying, the precipitate is calcined under air
atmosphere at 550.degree. C. for 4 h, and then grinded, compression
molded, pulverized and sieved to 10-20 mesh. Finally, 24% NiO-10%
Co.sub.3O.sub.4/39% SiO.sub.2-27% CeO.sub.2 is prepared.
[0043] The evaluation of the catalyst is the same as that of
Example 2. Cyclohexyl amine and dicyclohexyl amine yields are 31.2%
and 33.2%, respectively. After 200 h reaction, cyclohexyl amine and
dicyclohexyl amine yields are maintained at 28% and 32.5%
respectively.
Example 4
[0044] 20 g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 17 g of
sodium silicate Na.sub.2SiO.sub.3, 8 g of cobalt nitrate
Co(NO.sub.3).sub.26H.sub.2O and 15 g of cerium nitrate
Ce(NO.sub.3).sub.36H.sub.2O are weighed respectively, and dissolved
in 200 ml of distilled water, referred to as solution A.
[0045] 15 mass % of aqueous ammonia solution (200 ml) is
formulated, referred to as solution B.
[0046] Firstly, the solution A is poured into a sedimentation tank
and heated to 70.degree. C., and the solution B is added dropwise
to the sedimentation tank slowly. In the meantime, the
precipitation temperature is maintained at 70.degree. C. After the
end of precipitation, the stirring speed and precipitation
temperature are kept unchanged, and the resulting precipitate is
aged for 4 h, filtered and washed to neutral. Thereafter, the
precipitate is placed in an oven of 110.degree. C. and dried for 12
h. After the end of drying, the precipitate is calcined under air
atmosphere at 600.degree. C. for 4 h, and then grinded, compression
molded, pulverized and sieved to 10-20 mesh. Finally, 20% NiO-10%
Co.sub.3O.sub.4/40% SiO.sub.2-30% CeO.sub.2 is prepared.
[0047] The evaluation of the catalyst is the same as that of
Example 2. Cyclohexyl amine and dicyclohexyl amine yields are 30.1%
and 23.7%, respectively. After 200 h reaction, cyclohexyl amine and
dicyclohexyl amine yields are maintained at 28.8% and 22.3%
respectively.
Example 5
[0048] 18 g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 18 g of
cobalt nitrate Co(NO.sub.3).sub.26H.sub.2O and 10 g of yttrium
nitrate Y(NO.sub.3).sub.36H.sub.2O are weighed respectively, and
dissolved in 200 ml of distilled water, referred to as solution
A.
[0049] 200 ml of 1 mol/L of Na.sub.2CO.sub.3 solution is
formulated, and therein 14.6 g of sodium silicate
(Na.sub.2SiO.sub.3) is dissolved, referred to as solution B.
[0050] Firstly, water in the sedimentation tank is heated to
70.degree. C., and the solution A and B are added dropwise to a
sedimentation tank in a parallel flow. In the preparation process,
pH and the precipitation temperature are maintained at 8 and
70.degree. C. , respectively. After the end of precipitation, the
stirring speed and precipitation temperature are kept unchanged,
and the resulting precipitate is aged for 4 h, filtered and washed
to neutral. Thereafter, the precipitate is placed in an oven of
110.degree. C. and dried for 12 h. After the end of drying, the
precipitate is calcined under air atmosphere at 500.degree. C. for
4 h, and then grinded, compression molded, pulverized and sieved to
10-20 mesh. Finally, 24% NiO-25% Co.sub.3O.sub.4/36% SiO.sub.2-15%
Y.sub.2O.sub.3 is prepared.
[0051] 10 ml of the above-said catalyst is packed in a fixed bed
reactor, and reduced at 500.degree. C. After the reduction, the
temperature is lowered to the reaction temperature of 280.degree.
C., the system pressure is raised to 2.5 MPa, and the feeding is
initiated, wherein the mass ratio of ethanol and aniline
rectification residue is 0.3. Liquid phase space velocity is 0.7
h.sup.-1, and H.sub.2 flow rate is 250 ml/min. After 10 h reaction,
sampling is conducted for analysis, and cyclohexyl amine and
dicyclohexyl amine yields are 37.2% and 41.5%, respectively. After
200 h reaction, cyclohexyl amine and dicyclohexyl amine yields are
maintained at 36.8% and 40.1% respectively.
Example 6
[0052] 18 g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 18 g of
cobalt nitrate Co(NO.sub.3).sub.26H.sub.2O, 3 g of zirconium
nitrate Zr(NO.sub.3).sub.45H.sub.2O, and 5 g of cerium nitrate
Ce(NO.sub.3).sub.36H.sub.2O are weighed respectively, and dissolved
in 200 ml of distilled water, referred to as solution A.
[0053] 200 ml of 1 mol/L of Na.sub.2CO.sub.3 solution is
formulated, and therein 14 g of sodium silicate (Na.sub.2SiO.sub.3)
is dissolved, referred to as solution B.
[0054] Firstly, water in the sedimentation tank is heated to
70.degree. C., and the solution A and B are added dropwise to a
sedimentation tank in a parallel flow. In the preparation process,
pH and the precipitation temperature are maintained at 8 and
70.degree. C. , respectively. After the end of precipitation, the
stirring speed and precipitation temperature are kept unchanged,
and the resulting precipitate is aged for 4 h, filtered and washed
to neutral. Thereafter, the precipitate is placed in an oven of
110.degree. C. and dried for 12 h. After the end of drying, the
precipitate is calcined under air atmosphere at 500.degree. C. for
4 h, and then grinded, compression molded, pulverized and sieved to
10-20 mesh. Finally, 24% NiO-25% Co.sub.3O.sub.4/36% SiO.sub.2-5%
ZrO.sub.2-10% CeO.sub.2 is prepared.
[0055] 10ml of the above-said catalyst is packed in a fixed bed
reactor, and reduced at 500.degree. C. After the reduction, the
temperature is lowered to the reaction temperature of 290.degree.
C., the system pressure is raised to 2.5 MPa, and the feeding is
initiated, wherein the mass ratio of ethanol and aniline
rectification residue is 0.4. Liquid phase space velocity is
0.7h.sup.-1, and H.sub.2 flow rate is 250 ml/min. After 10 h
reaction, sampling is conducted for analysis, and cyclohexyl amine
and dicyclohexyl amine yields are 32.5% and 33.7%, respectively.
After 200 h reaction, cyclohexyl amine and dicyclohexyl amine
yields are maintained at 31.7% and 32.1% respectively.
Example 7
[0056] 16 g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 11 g of
cobalt nitrate Co(NO.sub.3).sub.26H.sub.2O, 10 g of ferric nitrate
Fe(NO.sub.3).sub.39H.sub.2O and 10 g of yttrium nitrate
Y(NO.sub.3).sub.36H.sub.2O are weighed respectively, and dissolved
in 200 ml of distilled water, referred to as solution A.
[0057] 250 ml of 1 mol/L of Na.sub.2CO.sub.3 solution is
formulated, and therein 16 g of sodium silicate (Na.sub.2SiO.sub.3)
is dissolved, referred to as solution B.
[0058] Firstly, water in the sedimentation tank is heated to
70.degree. C., and the solution A and B are added dropwise to a
sedimentation tank in a parallel flow. In the preparation process,
pH and the precipitation temperature are maintained at 8 and
70.degree. C. , respectively. After the end of precipitation, the
stirring speed and precipitation temperature are kept unchanged,
and the resulting precipitate is aged for 4 h, filtered and washed
to neutral. Thereafter, the precipitate is placed in an oven of
110.degree. C. and dried for 12 h. After the end of drying, the
precipitate is calcined under air atmosphere at 500.degree. C. for
5 h, and then grinded, compression molded, pulverized and sieved to
10-20 mesh. Finally, 20% NiO-15% Co.sub.3O.sub.4-10%
Fe.sub.2O.sub.3/40% SiO.sub.2-15% Y.sub.2O.sub.3is prepared.
[0059] 10 ml of the above-said catalyst is packed in a fixed bed
reactor, and reduced at 500.degree. C. After the reduction, the
temperature is lowered to the reaction temperature of 300.degree.
C., the system pressure is raised to 2.5 MPa, and the feeding is
initiated, wherein the mass ratio of ethanol and aniline
rectification residue is 0.4. Liquid phase space velocity is
0.7h.sup.-1, and H.sub.2 flow rate is 250 ml/min. After 10 h
reaction, sampling is conducted for analysis, and cyclohexyl amine
and dicyclohexyl amine yields are 36.9% and 40.2%, respectively.
After 200 h reaction, cyclohexyl amine and dicyclohexyl amine
yields are maintained at 35.8% and 39.5% respectively.
Example 8
[0060] 24g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O and 14 g
of yttrium nitrate Y(NO.sub.3).sub.36H.sub.2O are weighed
respectively, and dissolved in 300 ml of distilled water, referred
to as solution A. 300 ml of 0.7 mol/L of Na.sub.2CO.sub.3 solution
is formulated, and 17 g of sodium silicate (Na.sub.2SiO.sub.3) is
weighed and dissolved in the Na.sub.2CO.sub.3 solution, referred to
as solution B.
[0061] Firstly, water in the sedimentation tank is heated to
70.degree. C., and the solution A and B are added dropwise to a
sedimentation tank in a parallel flow. In the preparation process,
pH and the precipitation temperature are maintained at 8 and
70.degree. C. , respectively. After the end of precipitation, the
stirring speed and precipitation temperature are kept unchanged,
and the resulting precipitate is aged for 4 h, filtered and washed
to neutral. Thereafter, the precipitate is placed in an oven of
110.degree. C. and dried for 12 h. After the end of drying, the
resulting catalyst is immersed in ammonium molybdate
((NH.sub.4).sub.6Mo.sub.7O.sub.24 4H.sub.2O) solution for 5 h,
calcined under air atmosphere at 500.degree. C. for 4 h, and then
grinded, compression molded, pulverized and sieved to 10-20 mesh.
Finally, 30% NiO-10% MoO.sub.3/40% SiO.sub.2-20% Y.sub.2O.sub.3 is
prepared.
[0062] 10 ml of the above-said catalyst is packed in a fixed bed
reactor, and reduced at 450.degree. C. After the reduction, the
temperature is lowered to the reaction temperature of 300.degree.
C., the system pressure is raised to 2 MPa, and the feeding is
initiated, wherein the mass ratio of ethanol and aniline
rectification residue is 0.2. Liquid phase space velocity is
0.7h.sup.-1, and H.sub.2 flow rate is 250 ml/min. After 10 h
reaction, sampling is conducted for analysis, and cyclohexyl amine
and dicyclohexyl amine yields are 38.8% and 36.7%, respectively.
After 200 h reaction, cyclohexyl amine and dicyclohexyl amine
yields are maintained at 36.2% and 34.5% respectively.
Example 9
[0063] 20g of nickel nitrate Ni(NO.sub.3).sub.26H.sub.2O, 17 g of
sodium silicate Na.sub.2SiO.sub.3, 8 g of chromium nitrate
Cr(NO.sub.3).sub.39H.sub.2O and 15 g of cerium nitrate
Ce(NO.sub.3).sub.36H.sub.2O are weighed respectively, and dissolved
in 200 ml of distilled water, referred to as solution A.
[0064] 20mass % of aqueous ammonia solution (150ml) is formulated,
referred to as solution B.
[0065] Firstly, the solution A is poured into a sedimentation tank
and heated to 70.degree. C., and the solution B is added dropwise
to the sedimentation tank slowly. In the meantime, the
precipitation temperature is maintained at 70.degree. C. After the
end of precipitation, the stirring speed and precipitation
temperature are kept unchanged, and the resulting precipitate is
aged for 4 h, filtered and washed to neutral. Thereafter, the
precipitate is placed in an oven of 110.degree. C. and dried for 12
h. After the end of drying, the precipitate is calcined under air
atmosphere at 600.degree. C. for 3 h, and then grinded, compression
molded, pulverized and sieved to 10-20 mesh. Finally, 24.5%
NiO-7.2% Cr.sub.2O.sub.3/39.9% SiO.sub.2-28.4% CeO.sub.2 is
prepared.
[0066] The evaluation of the catalyst is the same as that of
Example 2. Cyclohexyl amine and dicyclohexyl amine yields are 28.3%
and 20.7%, respectively. After 200 h reaction, cyclohexyl amine and
dicyclohexyl amine yields are maintained at 25.8% and 18.4%
respectively.
* * * * *