U.S. patent application number 13/496339 was filed with the patent office on 2013-02-28 for catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin.
This patent application is currently assigned to ARKEMA FRANCE. The applicant listed for this patent is Jean-Francois Devaux, Jean-Luc Dubois, Yasuhiro Magatani, Kimito Okumura. Invention is credited to Jean-Francois Devaux, Jean-Luc Dubois, Yasuhiro Magatani, Kimito Okumura.
Application Number | 20130053595 13/496339 |
Document ID | / |
Family ID | 42173600 |
Filed Date | 2013-02-28 |
United States Patent
Application |
20130053595 |
Kind Code |
A1 |
Magatani; Yasuhiro ; et
al. |
February 28, 2013 |
CATALYST AND PROCESS FOR PREPARING ACROLEIN AND/OR ACRYLIC ACID BY
DEHYDRATION REACTION OF GLYCERIN
Abstract
A catalyst composition comprising at least an heteropolyacid
deposited on a porous titania carrier. A catalyst composition
comprising at least an heteropolyacid in which protons in the
heteropolyacid may be partially exchanged by at least one cation
selected from elements belonging to Group 1 to Group 16 of the
Periodic Table of Elements that have been deposited on a porous
titania carrier. A method for preparing the catalyst composition,
comprising impregnating a titania carrier with a solution of at
least one metal selected from elements belonging to the Group 1 to
Group 16 of the Periodic Table of Elements or onium, drying and
firing the resulting solid mixture, secondly impregnating the
resulting solid mixture with a solution of heteropolyacid, drying,
and firing the resulting solid mixture. A process for preparing
acrolein and acrylic acid by dehydration of glycerin, carried out
in the presence of the catalyst.
Inventors: |
Magatani; Yasuhiro;
(SanyoOnoda-shi, JP) ; Okumura; Kimito;
(SanyoOnoda-shi, JP) ; Dubois; Jean-Luc; (Millery,
FR) ; Devaux; Jean-Francois; (Soucieu En Jarrest,
FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Magatani; Yasuhiro
Okumura; Kimito
Dubois; Jean-Luc
Devaux; Jean-Francois |
SanyoOnoda-shi
SanyoOnoda-shi
Millery
Soucieu En Jarrest |
|
JP
JP
FR
FR |
|
|
Assignee: |
ARKEMA FRANCE
Colombes
FR
NIPPON KAYAKU KABUSHIKI KAISHA
Chiyoda-ku, Tokyo
JP
|
Family ID: |
42173600 |
Appl. No.: |
13/496339 |
Filed: |
September 18, 2009 |
PCT Filed: |
September 18, 2009 |
PCT NO: |
PCT/JP2009/067115 |
371 Date: |
November 5, 2012 |
Current U.S.
Class: |
558/315 ;
502/210; 502/242; 502/350; 562/532; 568/471; 568/486 |
Current CPC
Class: |
B01J 23/002 20130101;
G01N 33/6893 20130101; G01N 2333/705 20130101; B01J 2523/00
20130101; B01J 37/0205 20130101; B01J 21/12 20130101; C07K 14/78
20130101; B01J 23/30 20130101; B01J 21/063 20130101; C07C 51/235
20130101; C07C 45/002 20130101; G01N 33/6887 20130101; C07C 45/52
20130101; C07C 253/26 20130101; B01J 27/188 20130101; C07C 51/252
20130101; C07C 45/52 20130101; C07C 47/22 20130101; C07C 51/252
20130101; C07C 57/04 20130101; B01J 2523/00 20130101; B01J 2523/15
20130101; B01J 2523/51 20130101; B01J 2523/69 20130101; B01J
2523/00 20130101; B01J 2523/41 20130101; B01J 2523/69 20130101;
B01J 2523/00 20130101; B01J 2523/51 20130101; B01J 2523/69
20130101 |
Class at
Publication: |
558/315 ;
502/350; 502/210; 502/242; 568/486; 568/471; 562/532 |
International
Class: |
B01J 21/06 20060101
B01J021/06; B01J 23/30 20060101 B01J023/30; C07C 253/26 20060101
C07C253/26; C07C 45/37 20060101 C07C045/37; C07C 51/16 20060101
C07C051/16; B01J 27/188 20060101 B01J027/188; C07C 45/29 20060101
C07C045/29 |
Claims
1. A catalyst composition comprising at least an heteropolyacid in
which protons in the heteropolyacid may be partially exchanged by
at least one cation selected from elements belonging to Group 1 to
Group 16 of the Periodic Table of Elements that have been deposited
on a porous titania carrier.
2. The catalyst composition of claim 1, in which said porous
titania carrier is covered at least partially by a compound
represented by the formula (I):
H.sub.aA.sub.b[X.sub.1Y.sub.cZ.sub.dO.sub.e].nH.sub.2O (I) in which
H is hydrogen, A is more than one cation selected from elements
belonging to Group 1 to Group 16 of the Periodic Table of Elements
except hydrogen, X is P or Si, Y is more than one element selected
from the group comprising W, Mo, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, In, Tl, Sn and Pb, Z is more than one element
selected from the group comprising W, Mo, Ti, Zr, V, Nb, Ta, Cr,
Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl, Sn and Pb, a, b, c, d and n
satisfying following ranges: 0.ltoreq.a<9 0.ltoreq.b.ltoreq.9,
preferably 0<b.ltoreq.9 0<c.ltoreq.12 and 0.ltoreq.d<12
n.gtoreq.0 and e is a number determined by the oxidation of the
elements.
3. The catalyst composition of claim 1, in which said titania
carrier comprises rutile or anatase or amorphous titanium
oxide.
4. The catalyst composition of claim 3, in which said titania
carrier comprises at least 80% anatase.
5. The catalyst composition of claim 1, in which said cation is at
least one alkali metal cation.
6. The catalyst composition of claim 5, in which said alkali metal
is cesium.
7. The catalyst composition of claim 2, in which said compound
contains at least one element selected from the group comprising W,
Mo and V.
8. A method for preparing a catalyst composition, comprising
impregnating a titania carrier with a solution of at least one
metal selected from elements belonging to the Group 1 to Group 16
of the Periodic Table of Elements or onium, drying and firing the
resulting solid mixture, secondly impregnating the resulting solid
mixture with a solution of heteropolyacid, drying, and firing the
resulting solid mixture.
9. A method for preparing a catalyst composition, comprising
impregnating a titania carrier with a solution of heteropolyacid,
drying and firing the resulting solid mixture, optionally secondly
impregnating the resulting impregnated carrier with a solution of
at least one metal selected from elements belonging to the Group 1
to Group 16 of the Periodic Table of Elements or onium, drying, and
firing the resulting solid mixture.
10. A method for preparing a catalyst composition prepared by more
than one cycle of impregnation and firing, in which each
impregnation is effected with a solution of an element of the group
1 to belonging to the Group 1 to Group 16 of the Periodic Table of
Elements or onium or with a solution containing more than one
element selected from the group comprising P, Si, W, Mo, Ti, Zr, V,
Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl, Sn, Pb, and in
which at least one impregnation is made with an acid precursor.
11. The method for preparing a catalyst composition of claim 8, in
which one impregnation is made with a phosphotungstic acid or
phosphotungstate solution.
12. The method for preparing a catalyst composition of claim 8, in
which one impregnation is made with a silicotungstic acid or
silicotungstate solution.
13. The method for preparing a catalyst composition of claim 8, in
which one impregnation is made with a cesium salt solution.
14. The method for preparing a catalyst composition of claim 8, in
which the impregnation is performed by techniques of pore volume
impregnation or excess solution impregnation.
15. The method for preparing a catalyst composition of claim 8, in
which the firing (calcination) is carried out under an atmosphere
of air, inert gas or a mixture of oxygen and inert gas, or under a
reduced gas.
16. The method for preparing a catalyst composition of claim 8, in
which firing (calcination) is effected at a temperature of 150 to
900.degree. C. for 0.5 to 10 hours.
17. A process for preparing acrolein by dehydration of glycerin,
carried out in the presence of a catalyst according to claim 1.
18. The process of claim 17 in which dehydration of glycerin is
effected in the presence of molecular oxygen.
19. The process of claim 17 in which dehydration of glycerin is
effected in the presence of a gas containing propylene.
20. The process of claim 17 carried out in a reactor of the plate
heat exchanger type or in a fixed bed reactor or in a fluidized bed
type reactor or in a circulating fluidized bed or in a moving
bed.
21. The process of claim 17, in which the resulting acrolein is
further oxidized to produce acrylic acid.
22. The process of claim 17, followed by second step of
ammoxidation of acrolein to acrylonitrile.
23. The process of claim 17, having an intermediate step of partial
condensation of water and heavy by-products issuing from the
dehydration step.
24. A catalyst composition comprising at least an heteropolyacid
deposited on a porous titania carrier.
25. The catalyst of claim 24 for preparing acrolein or acrylic acid
by dehydration of glycerin.
26. Use of the catalyst of claim 25 in a preparation of acrolein or
acrylic acid by dehydration of glycerin.
Description
TECHNICAL FIELD
[0001] This invention relates to a novel dehydration catalyst, in
particular to a dehydration catalyst for producing acrolein or
acrylic acid by catalytic dehydration of glycerin in gas phase or
liquid phase, to a method for preparing the catalyst and to a
process for producing acrolein and/or acrylic acid by using the
catalyst.
BACKGROUND ART
[0002] Glycerin is obtained in large amount as a byproduct when
bio-fuel is produced from bio resources that do not depend on
fossil resources, and research of new uses of glycerin is under
development.
[0003] We have proposed, in PCT/JP2009/057818 and
PCT/JP2009/057819, an improved dehydration catalyst comprising
mainly a compound in which protons in a heteropolyacid are
exchanged at least partially with at least one cation selected from
elements belonging to Group 1 to Group 16 of the Periodic Table of
Elements.
[0004] WO2007/058221 discloses a process for producing acrolein by
dehydration reaction of glycerin in gas-phase in the presence of
heteropolyacid used as a solid acid catalyst. The heteropolyacid is
those of Group 6 element such as tungstosilicic acid,
tungstophosphoric acid and phosphomolybdic acid. These
heteropolyacids are supported on bi-modal pore size distribution
silica carrier and produce acrolein at a yield of 86%. This
dehydration reaction of glycerin, however, is effected without
oxidation gas but using nitrogen stream as carrier gas, so that
deposition of carbon increase seriously and hence there is a
problem of deterioration in time of stability, activity and
selectivity of the catalysis.
[0005] Tsukuda et al. "Production of acrolein from glycerol over
silica-supported heteropoly acid" CATALYSIS COMMUNICATIONS, vol. 8,
no. 9, 21 Jul. 2007, pp 1349-1353, Chai et al., "Sustainable
production of acrolein: gas phase dehydration of glycerol over
12-tungstophosphoric acid supported on ZrO.sub.2 and SiO.sub.2",
GREEN CHEMISTRY, vol. 10, 2008, pp. 1087-1093, and Chai et al.,
"Sustainable production of acrolein: preparation and
characterization of zirconia-supported 12-tungstophosphoric acid
catalyst for gas phase dehydration of glycerol", APPLIED CATALYSIS
A: GENERAL, vol. 353, 2009, pp. 213-222 disclose that silica or
zirconia-supported heteropoly acid is effective as a catalyst for
dehydration of glycerol.
[0006] However, there is no usable catalyst in the industrial scale
at higher performance.
[0007] WO2007/058221 (Nippon Shokubai) discloses a process for
dehydrating polyhydric alcohols by using a catalyst containing an
element of group 6 (Cr, Mo, W), in particular, comprising a
heteropolyacid which can be supported on a carrier containing Al,
Si, Ti or Zr. Examples show the acrolein yield of 70% for
PW/Al.sub.2O.sub.3 70% for PW/ZrO.sub.2, 87% for SiW/SiO.sub.2 but
the conversion decreases from 100% to 70% in 8 hours.
[0008] U.S. patent No. 2009054538 (BATTELLE) discloses catalyst
composition comprising phosphotungstic or phosphomolybdic acid on
silica support and the acrolein yields obtained are not over 71%
with the catalysts.
[0009] U.S. Pat. No. 5,919,725 discloses a catalyst comprising
heteropoly salts and heteropolyacid salts deposited on a porous
support of silica, zirconia and titania. This catalyst is used for
aromatic alkylation such as alkylation of phenol with olefins but
there is no mention of glycerol dehydration.
[0010] U.S. Pat. No. 4,983,565 discloses a process for preparing a
catalyst composition by impregnating titania pellets with an
aqueous solution consisting of tungstosilicic acid or
molybdosilicic acid or their salts followed by drying and
calcination. The catalyst composition is prepared preferably by
impregnating a preformed pellet by immersing titania pellets in an
aqueous solution of the tungstosilicic acid or molybdosilicic acid,
for example. However, this patent teaches nothing about such a
feature defined in the present invention that protons in the
heteropolyacid are exchanged by at least one cation selected from
elements belonging to Group 1 to Group 16 of the Periodic Table of
Elements. Still more, this catalyst is used to prepare linear
polyethylenepolyamine but there is no mention in dehydration of
glycerol.
DISCLOSURE OF INVENTION
Technical Problems
[0011] Therefore, an object of this invention is to provide a novel
dehydration catalyst, in particular a dehydration catalyst for
producing acrolein or acrylic acid by catalytic dehydration of
glycerin in gas phase or liquid phase.
[0012] Another object of this invention is to provide a method for
preparing the catalyst and to a process for producing acrolein
and/or acrylic acid by using the catalyst.
[0013] Still another object of this invention is to provide a
process for producing acrolein and acrylic acid from glycerin that
is a material not derived from petroleum, at a high yield.
Technical Solution
[0014] A first subject of the present invention resides in a
catalyst composition comprising at least an heteropolyacid that has
been deposited on a porous titania carrier.
[0015] In a preferred embodiment, the catalyst composition of the
present invention comprises at least an heteropolyacid in which
protons in the heteropolyacid are exchanged at least partially by
at least one cation selected from elements belonging to Group 1 to
Group 16 of the Periodic Table of Elements that have been deposited
on a porous titania carrier.
[0016] Another subject of the present invention resides in a method
for preparing the catalyst composition comprising impregnating a
titania carrier with a solution of heteropolyacid, drying and
firing the resulting solid mixture, optionally secondly
impregnating the resulting impregnated carrier with a solution of
at least one metal selected from elements belonging to the Group 1
to Group 16 of the Periodic Table of Elements or onium, drying, and
firing the resulting solid mixture.
[0017] The catalyst composition according to the present invention
can be prepared also by the steps comprising impregnating a titania
carrier with a solution of at least one metal selected from
elements belonging to the Group 1 to Group 16 of the Periodic Table
of Elements or onium, drying and firing the resulting solid
mixture, secondly impregnating the resulting solid mixture with a
solution of heteropolyacid, drying, and firing the resulting solid
mixture. In a variation, more than two different elements can be
impregnated successively in the first impregnation step by using a
respective impregnation and calcination operation. The catalyst
composition according to the present invention can be prepared also
by the method comprising more than one cycle of impregnation and
firing, in which each impregnation is effected with a solution of
an element belonging to the Group 1 to Group 16 of the Periodic
Table of Elements or onium or with a solution containing more than
one element selected from the group comprising P, Si, W, Mo, Ti,
Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl, Sn, Pb, and
in which at least one impregnation is made with an acid
precursor.
[0018] Still other subject of the present invention resides in a
process for preparing acrolein by dehydration of glycerin, carried
out in the presence of the catalyst.
[0019] This invention has following features (1) to (21) taken
separately or in combination: [0020] (1) The porous titania carrier
is covered at least partially by a compound represented by the
formula (I):
[0020] H.sub.aA.sub.b[X.sub.1Y.sub.cZ.sub.dO.sub.e].nH.sub.2O
(I)
[0021] in which [0022] H is hydrogen, [0023] A is more than one
cation selected from elements belonging to Group 1 to Group 16 of
the Periodic Table of Elements except hydrogen, [0024] X is P or
Si, [0025] Y is more than one element selected from the group
comprising W, Mo, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn,
Ga, In, Tl, Sn and Pb, [0026] Z is more than one element selected
from the group comprising W, Mo, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, In, Tl, Sn and Pb, [0027] a, b, c, d and n
satisfying following ranges: [0028] 0.ltoreq.a<9 [0029]
0.ltoreq.b.ltoreq.9, preferably 0<b.ltoreq.9 [0030]
0<c.ltoreq.12 [0031] 0.ltoreq.d.ltoreq.12 and 0<c+d.ltoreq.12
[0032] n.gtoreq.0
[0033] and e is a number determined by the oxidation of the
elements. [0034] (2) The titania carrier comprises rutile or
anatase or amorphous titanium oxide. [0035] (3) The titania carrier
comprises at least 80% anatase. [0036] (4) The titania carrier has
a specific surface of 20 to 120 m.sup.2/g. [0037] (5) The cation is
at least one alkali metal cation. [0038] (6) The alkali metal is
cesium. [0039] (7) The compound contains at least one element
selected from the group comprising W, Mo and V. [0040] (8) In the
method for preparing the catalyst composition according to the
present invention, one impregnation is made with a phosphotungstic
acid or a phosphotungstate solution. [0041] (9) In the method for
preparing the catalyst composition according to the present
invention, one impregnation is made with a silicotungstic acid or a
silicotungstate solution. [0042] (10) In the method for preparing
the catalyst composition according to the present invention, one
impregnation is made with a cesium salt solution. [0043] (11) The
impregnation is performed by a technique of pore volume
impregnation or excess solution impregnation. [0044] (12) The
impregnation is performed in a fluidized bed or moving bed to
obtain a composition usable in a fluidized bed type reactor. [0045]
(13) The firing (calcination) is carried out under an atmosphere of
air, inert gas or a mixture of oxygen and inert gas, or under a
reduced gas such as H.sub.2. [0046] (14) The firing (calcination)
is effected at a temperature of 150 to 900.degree. C. for 0.5 to 10
hours, preferably at a temperature of 350 to 650.degree. C. [0047]
(15) The process for preparing acrolein by dehydration of glycerin
is carried out in the presence of the catalyst according to the
invention. [0048] (16) The process for preparing acrolein or
acrylic acid is effected in the presence of molecular oxygen, with
the conditions disclosed for example in WO 06/087083 or WO
06/114506. [0049] (17) The process for preparing acrolein or
acrylic acid is effected in the presence of a gas containing
propylene, as disclosed for example in WO 07/090,990 and WO
07/090,991, that is say to carry out the glycerol dehydration stage
beneath the propylene oxidation reactor of the conventional
process, taking benefit of the high temperature of the gas coming
out of that stage containing mainly acrolein and some remaining
propylene. [0050] (18) The process for preparing acrolein carried
out in a reactor of the plate heat exchanger type or in a fixed bed
reactor or in a fluidized bed type reactor or in a circulating
fluidized bed or in a moving bed. [0051] (19) The resulting
acrolein is further oxidized to produce acrylic acid. [0052] (20)
The process for preparing acrolein by dehydration of glycerin,
carried out in the presence of the catalyst is followed by a second
step of ammoxidation of acrolein to acrylonitrile, as described for
example in WO 08/113,927. [0053] (21) The process for preparing
acrolein by dehydration of glycerin, carried out in the presence of
the catalyst has an intermediate step of partial condensation of
water and heavy by-products issuing from the dehydration step, as
described for example in WO 08/087,315, dehydration of glycerin is
carried out under a pressure of 0.1 MPa to 0.5 MPa for an
intermediate step of partial condensation of water and heavy
by-products issuing from the dehydration step.
Advantageous Effect
[0054] The catalyst according to this invention have following
merits and advantages that are important in industrial uses: [0055]
(1) Acrolein and/or acrylic acid can be produced with higher yield.
[0056] (2) Deactivation of the catalyst is limited. [0057] (3) The
catalyst according to this invention can be regenerated at higher
temperature comparing to the catalyst having no support (or
carrier). [0058] (4) The catalyst according to this invention
maintains advantages of non-support catalyst. In fact, the
resistance to water is remarkably improved. On the contrary, in
case of the conventional heteropolyacid catalysts, deterioration or
deactivation of catalysts is serious in the glycerin dehydration
reaction in a gas phase reaction which is effected in the presence
of excess amount of water, such a reaction using as a material an
aqueous solution of glycerin at lower concentration, or in a liquid
phase in which water or lower alcohol is used as a reaction medium.
Still more, owing to the improvement in resistance to water, a
problem of corrosion of reactors that was observed when acid
catalyst was used can be also solved
BEST MODE FOR CARRYING OUT THE INVENTION
[0059] The heteropolyacid is known and has several structures such
as Keggin type, Dawson type and Anderson type and possess generally
such high molecular weight as 700 to 8,500. There are dimer complex
forms and those dimer complex are included in the present
invention.
[0060] The elements belonging to Group 1 to Group 16 of the
Periodic Table of Elements may be sodium, potassium, rubidium,
cesium, magnesium, calcium, strontium, barium, scandium, yttrium,
lanthanoid, titanium, zirconium, hafnium, chromium, manganese,
rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel,
palladium, platinum, copper, silver, gold, zinc, gallium, indium,
thallium, germanium, tin, lead, bismuth and tellurium. The onium
salts of heteropolyacid may be amine salts, ammonium salts,
phosphonium salts and sulfonium salts.
[0061] Ions of molybdenum and of tungsten form oxoacid in water and
the oxoacids polymerize to form the polyoxoacid of high molecular
weight. The polymerization may not be effected only with the same
kind of oxoacids but also with other kinds of oxoacids.
Heteropolyacid is a polyacid possessing polynuclear structure,
obtained by condensation of more than two kinds of oxoacids. An
atom which forms the center oxoacid is called as "hetero-atom",
while atoms forming oxoacids surrounding the center oxoacid and
obtained by the polymerization is called as "poly-atoms". The
hetero-atom may be silicon, phosphorus, arsenic, sulfur, iron,
cobalt, boron, aluminum, germanium, titanium, zirconium, cerium and
chromium. Among them, phosphorus and silicon are preferable. The
poly-atoms may be molybdenum, tungsten, vanadium, niobium and
tantalum. Among them, molybdenum and tungsten are preferable. The
heteropolyacids used in this invention to prepare a glycerin
dehydration catalyst may be tungstophosphoric acid, tungstosilicic
acid, phosphomolybdic acid and silico molybdic acid. The
heteropolyacid may be a mixed coordinate comprising the
hetero-atoms of phosphorus or silicon and the poly-atoms are mixed
coordinate of molybdenum and tungsten, or mixed coordinate of
tungsten and vanadium or mixed coordinate of vanadium and
molybdenum.
[0062] In a preferred embodiment, the glycerin dehydration catalyst
according to this invention comprises a compound in which at least
part of protons in the heteropolyacid are exchanged with at least
one cation of alkali metal.
[0063] The catalyst composition according to the present invention
used for producing acrolein and acrylic acid from glycerin contains
preferably at least one element selected from a group comprising W,
Mo and V.
[0064] In a preferred embodiment, the alkali metal is preferably
cesium and at least a part of protons in the heteropolyacid is
exchanged with cesium. It is also possible to exchange at least a
part of protons in the heteropolyacid with cesium and a part of
remaining protons in the heteropolyacid is exchanged at least
partially with at least one cation selected from elements belonging
to Group 1 to Group 16 of the Periodic Table of Elements. Acrolein
and acrylic acid can be produced at higher yield by using the
glycerin dehydration catalyst composition according to the present
invention. Resistance to water is increased by exchanging part of
protons contained in the heteropolyacid with cesium, so that the
life of catalyst is improved in comparison to heteropolyacid that
is inherently water-soluble.
[0065] An amount of the aqueous solution of mineral salt of
exchanging cation is determined in such a manner that an electric
charge of cation to be added is equal to or less than an electric
charge of the heteropolyanion. For example, when a cation with
charges of 1.sup.+ is added to a heteropolyanion with charges of
3.sup.-, the cation is added equal to or less than 3 equivalent to
the heteropolyanion, and when a cation with charges of 3.sup.+ is
added to a heteropolyanion with charges of 3.sup.-, the cation is
added equal to or less than 1 equivalent to the heteropolyanion.
When a plurality of cations are introduced, an amount of the cation
is determined in such a manner that the total electric charge of
the cations becomes equal to or less than an electric charge of the
heteropolyanion. If an amount of an aqueous solution of inorganic
salt or a proportion of the cation(s) to be exchanged with protons
become excessive, the activity of catalyst is spoiled or the yields
of acrolein and acrylic acid are lowered or the life of catalyst is
shortened.
[0066] In a variation, the glycerin dehydration catalyst according
to this invention contains further at least compound of elements
belonging to Group 1 to Group 16 of the Periodic Table of Element
in addition to the above compound. The compound of elements
belonging to Group 1 to Group 16 of the Periodic Table of Element
may be metal salts or onium salts. The metal salt may be salt of
tellurium, platinum, palladium, iron, zirconium, copper, cerium,
silver and aluminum. The onium salts may be amine salts, ammonium
salts, phosphonium salts and sulfonium salts. The metal salt or the
onium salt may be prepared from such materials as nitrates,
carbonate, sulfates, acetates, hydroxides, oxides and halides of
the metals or of onium but are not limited thereto. A proportion of
the metal salt is 0.0001 to 60% by weight, preferably 0.001 to 30%
by weight in term of the metal salts or the onium salt with respect
to the above compound.
[0067] As the mostly preferred dehydration catalyst of glycerin,
following composition that has been deposited on a porous titania
represented by the general formula (I) is mentioned:
H.sub.aA.sub.b[X.sub.1Y.sub.cZ.sub.dO.sub.e].nH.sub.2O (I)
in which
[0068] H is hydrogen,
[0069] A is at least one cation selected from elements belonging to
Group 1 to Group 16 of the Periodic Table of Elements except H
[0070] X is P or Si,
[0071] Y is at least one element selected from the group comprising
W, Mo, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl,
Sn and Pb,
[0072] Z is at least one element selected from the group comprising
W, Mo, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl,
Sn and Pb, and a, b, c and satisfying following ranges:
[0073] 0.ltoreq.a<9
[0074] 0.ltoreq.b.ltoreq.9, preferably 0<b.ltoreq.9
[0075] 0<c.ltoreq.12
[0076] 0.ltoreq.d<12 and
[0077] 0<c+d.ltoreq.12
[0078] e is a number determined by the oxidation of the elements
and n is any positive number.
[0079] In the present invention, the above-mentioned compound is
deposited on a titania carrier or support ("supported catalyst").
In this text, terms of carrier or support have the same
meaning.
[0080] An amount of the above-mentioned compound represented by the
formula (I) is 5 to 99.9% by weight, preferably 5 to 90% by weight
to the weight of the carrier.
[0081] The catalyst may have any shape and can be granule, powder
or monolith. In case of gas phase reactions, however, it is
preferable to mold the catalyst into a shape of monolith, sphere,
pellets, cylinder, hollow cylinder, bar or the like optionally with
adding a molding aid or the catalyst is shaped into these
configurations together with carrier and optional auxiliary agents.
A size of molded catalyst is for example 1 to 10 mm for a fixed bed
and less than 1 mm for a fluidized bed.
[0082] In case of a fluidized bed reactor for the process for
preparing acrolein, it is preferred to have a powder with
appropriate average particle size distribution namely between 40
and 300 .mu.m, preferably between 60 and 150 .mu.m.
[0083] The catalyst composition according to the present invention
can be prepared by successive impregnation of a carrier with a
solution of at least one metal selected from elements belonging to
the Group 1 to Group 16 of the Periodic Table of Elements or onium
and with a solution of heteropolyacid, and vice versa. The catalyst
can also be prepared by successive impregnation of a carrier with a
solution of heteropolyacid and with a solution of at least one
metal selected from elements belonging to the Group 1 to Group 16
of the Periodic Table of Elements or onium. After each
impregnation, the solid can be dried and fired as described below.
Impregnation can be performed by the known techniques of pore
volume impregnation or excess solution impregnation.
[0084] The catalyst composition can also be prepared by spay-drying
method with a spray-dryer.
[0085] In this text, wordings of "firing" or "calcination" are used
in the same meaning.
[0086] Namely, the catalyst composition according to the present
invention can be prepared by impregnating a preformed pellet or
porous titania carrier. For example, titania carrier is immersed in
an aqueous solution of at least one metal selected from elements
belonging to the Group 1 to Group 16 of the Periodic Table of
Elements or onium. The resulting solid mixture is then dried and
fired. In the present invention, the resulting solid mixture is
secondly impregnating with a solution of heteropolyacid. Then, the
resulting solid mixture is dried and fired to obtain an objective
catalyst.
[0087] The solution of at least one metal selected from elements
belonging to the Group 1 to Group 16 of the Periodic Table of
Elements or onium can be an aqueous solution of halide, hydroxide,
carbonate, acetate, nitrate, oxalate, phosphate or sulfate of metal
or onium.
[0088] Alternately, the catalyst composition according to the
present invention can be prepared by impregnating a titania carrier
firstly with a solution of heteropolyacid. For example, an aqueous
solution of heteropolyacid is prepared firstly. When the aqueous
solution of heteropolyacid is prepared, it is preferable to remove
waters contained in the heteropolyacid in a form of adsorptive
water and crystal water partially or totally under vacuum or
heat-drying. The resulting solid mixture is then dried and fired.
In the second impregnation, the resulting impregnated carrier is
impregnated with a solution of at least one metal selected from
elements belonging to the Group 1 to Group 16 of the Periodic Table
of Elements or onium, followed by drying and firing operations to
obtain an objective catalyst.
[0089] Or, the catalyst composition according to the present
invention can be prepared by the method comprising more than one
cycle of impregnation and firing. In this case, each impregnation
is effected with a solution of an element of the group 1 to
belonging to the Group 1 to Group 16 of the Periodic Table of
Elements or onium or with a solution containing more than one
element selected from the group comprising P, Si, W, Mo, Ti, Zr, V,
Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl, Sn, Pb, and at
least one impregnation is effected with an acid precursor. In a
variation, the catalyst composition according to the present
invention can be prepared by adding PW or Cs to titania powder
firstly and then, without drying and firing operations, Cs or PW is
added continuously.
[0090] Impregnation can be carried out at ambient temperature
(about 20.degree. C.). Higher temperatures of about 100.degree. C.
to about 150.degree. C. may be used, if desired. This treatment may
be continued, preferably with agitation, for about 0.1 to about 5
hours sufficient to permit the aqueous solution to penetrate the
pores of the titania carrier. Suitably, the amount of aqueous
solution of at least one metal selected from elements belonging to
the Group 1 to Group 16 of the Periodic Table of Elements or onium
and the heteropolyacid that is used should be adequate to permit
full immersion of the titania carriers.
[0091] At the end of the immersion step, the excess aqueous
solution can be evaporated from the treated titania carriers, or it
can be removed from the aqueous solution and permitted to dry in a
drying oven.
[0092] The exact nature of bonding of the catalyst composition
according to the present invention is not completely
understood.
[0093] The catalyst according to the present invention used in the
glycerin dehydration may be anhydrides or hydrates. In fact, they
can be used after pretreatment of firing and vacuum-drying or
without pretreatment.
[0094] The calcination can be carried out in air or under inert gas
such as nitrogen, helium and argon or under an atmosphere of mixed
gas of air and inert gas usually or under reduction gas such as
hydrogen or an atmosphere of mixed gas of hydrogen and inert gas in
a furnace such as muffle furnace, rotary kiln, fluidized bed
furnace. The furnace is not limited specially. The calcination can
be effected even in a reaction tube which is used for the glycerin
dehydration reaction. The firing temperature is usually 150 to
900.degree. C., preferably 200 to 800.degree. C. and more
preferably 350 to 650.degree. C. This can be determined by routine
experimentation for a particular catalyst. Temperatures above
900.degree. C. should be avoided. The calcination is continued
usually for 0.5 to 10 hours.
[0095] The dehydration reaction of glycerin according to this
invention can be carried out in gas phase or in liquid phase and
the gas phase is preferable. The gas phase reaction can be carried
out in a variety of reactors such as fixed bed, fluidized bed,
circulating fluidized bed and moving bed. Among them, the fixed bed
or the fluidized bed are preferable. Regeneration of the catalyst
can be effected outside the reactor. When the catalyst is taken out
of a reactor system for regeneration, the catalyst is burnt in air
or in oxygen-containing gas. In case of liquid phase reaction,
usual general reactors for liquid reactions for solid catalysts can
be used. Since the difference in boiling point between glycerin
(290.degree. C.) and acrolein and acrylic acid is big, the reaction
is effected preferably at relatively lower temperatures so as to
distil out acrolein continuously.
[0096] The reaction temperature for producing acrolein and acrylic
acid by dehydration of glycerin in gas phase is effected preferably
at a temperature of 200.degree. C. to 450.degree. C. If the
temperature is lower than 200.degree. C., the life of catalyst will
be shortened due to polymerization and carbonization of glycerin
and of reaction products because the boiling point of glycerin is
high. On the contrary, if the temperature exceeds 450.degree. C.,
the selectivity of acrolein and acrylic acid will be lowered due to
increment in parallel reactions and successive reactions.
Therefore, more preferable reaction temperature is 250.degree. C.
to 350.degree. C. The pressure is not limited specially but is
preferably lower than 5 atm and more preferably lower than 3 atm.
Under higher pressures, gasified glycerin will be re-liquefied and
deposition of carbon will be promoted by higher pressure so that
the life of catalyst will be shortened.
[0097] A feed rate of a material gas is preferably 500 to 10,000
h.sup.-1 in term of the space velocity of GHSV. The selectivity
will be lowered if the GHSV becomes lower than 500 h.sup.-1 due to
successive reactions. On the contrary, if the GHSV exceeds 10,000
h.sup.-1, the conversion will be lowered.
[0098] The reaction temperature of the liquid phase reaction is
preferably from 150.degree. C. to 350.degree. C. The selectivity
will be spoiled under lower temperatures although the conversion is
improved. The reaction pressure is not limited specially but the
reaction can be carried if necessary under a pressurized conditions
of 3 atm to 70 atm.
[0099] The material of glycerin is easily available in a form of
aqueous solution of glycerin. Concentration of the aqueous solution
of glycerin is from 5% to 90% by weight and more preferably 10% to
50% by weight. Too high concentration of glycerin will result in
such problems as production of glycerin ethers or undesirable
reaction between the resulting acrolein or acrylic acid and
material glycerin. Temperature which is necessary to gasify
glycerin is increased.
[0100] Now, the present invention will be explained in much detail
with referring several examples, but this invention should not be
limited to those described in following examples. In the following
Examples and Comparative Examples, % means mole %.
EXAMPLES
Example 1
CsPW/TiO.sub.2
[0101] 15 g of CsCO.sub.3 were dissolved in deionised water to
obtain an aqueous solution containing 7.6% of cesium carbonate.
10.2 g of this aqueous solution of cesium carbonate was sprayed
onto 25 g of TiO.sub.2 powder obtained by grinding anatase type
TiO.sub.2 pellets (ST31119 from Norpro Saint Gobain) to 35 to 48
mesh. The resulting powder was dried at 110.degree. C. for 2 hours
and then was fired in nitrogen atmosphere at 300.degree. C. for 3
hours to obtain Cs/TiO.sub.2.
[0102] 7.0 g of tungstophosphoric acid was dissolved in 11.1 g of
deionized water to obtain an aqueous solution of tungstophosphoric
acid. 15 g of the resulting 38.8% aqueous solution of
tungstophosphoric acid was then sprayed onto the above
Cs/TiO.sub.2. The resulting powder was then dried at 100.degree. C.
overnight and then was fired in nitrogen atmosphere at 400.degree.
C. for 3 hours to obtain a titania carrier supporting 20% of the
cesium tungstophosphate. This titania carrier was sieved to obtain
a particle size of 35 to 48 mesh.
[0103] The catalyst was evaluated in a fixed bed reactor operated
under ambient pressure in a fixed bed. Namely, 7 cc of the
resulting catalyst powder was packed in a quartz reaction tube
(diameter of 16 mm).
[0104] An aqueous solution of glycerin (a concentration of 28% by
weight) was fed to an evaporator at a flow rate of 26.9 g/hr
together with nitrogen (4.9 NL/hr) and with oxygen (1.2 NL/hr) at
280.degree. C. so that glycerin was gasified and the resulting
gasified glycerin was passed through the fixed catalyst bed. The
fixed catalyst bed was heated at a temperature of 275.degree. C.
Feed gas had a following composition in mol
%:glycerin:oxygen:nitrogen:water=5.7:3.9:14.1:76.1. GHSV was 4,530
h.sup.-1.
[0105] Products were condensed in a condenser and the collected
product was quantitative-analyzed by gas chromatographs (HP 6890
Agilent, FFAP column, FID detector, CP4900 Varian, Silicaplot and
Molecular Sieve 5 .ANG., TCD detectors). Proportions of products
were corrected in factors from the results of the gas chromatograph
to determine absolute amounts of products to calculate the
conversion (%) of material (the conversion of glycerin), the
selectivity of target substance (the selectivities of acrolein and
of acrylic acid) and the yield of target substance (the yields of
acrolein and of acrylic acid).
[0106] The conversion (%) of material, the selectivity of objective
substance and the yield of objective substance are determined by
following equations:
The conversion (%) of material=(a mole number of material reacted/a
mole number of material supplied).times.100
The selectivity (%) of objective substance=(a mole number of
objective substance obtained/a mole number of material
reacted).times.100
The yield (%) of objective substance=(a mole number of objective
substance obtained/a mole number of material fed).times.100
[0107] Result is shown in Table 1.
TABLE-US-00001 TABLE 1 Time on stream (h) 3 22 Glycerin conversion
(%) 93 61 Acrolein yield (%) 76 53 Acrolein selectivity (%) 81 87
Hydroxypropanone yield (%) 1.1 2.0 Acetaldehyde yield (%) 0.9 0.8
Propanaldehyde yield (%) 0.9 0.5 Acrylic acid yield (%) 0.8 0.9 CO
yield (%) 1.3 1.2 CO.sub.2 yield (%) 0.9 1.0
Example 2
CsPW/TiO.sub.2
[0108] 10 g of tungstophosphoric acid was dissolved in 150 ml of
deionized water to obtain an aqueous solution of tungstophosphoric
acid. 19.7 g of TiO.sub.2 powder obtained by grinding anatase type
TiO.sub.2 pellets (ST31119 from Norpro Saint Gobain--BET surface 39
m.sup.2/g) to 300 to 500 .mu.m and drying at 110.degree. C.
overnight was added in obtained aqueous solution of
tungstophosphoric acid, and then was mixed at room temperature for
2 hours. 2.26 g of 48.5% CsOH aqueous solution was diluted with 10
ml of deionized water. The resulting CsOH aqueous solution was
dropped in above white slurry of tungstophosphoric acid and
TiO.sub.2, mixing this white slurry. The resulting slurry was
evaporated at 60.degree. C. by use of rotary-evaporator. The
obtained powder was dried at 120.degree. C. for 10 hours and then
was calcined in air at 500.degree. C. for 3 hours to obtain a
titania carrier supporting 30% of Cs salt of tungstophosphoric
acid. The obtained powder was pressed to pellets and then was
sieved to obtain a particle size of 9 to 12 mesh, grinding above
pellets of CsPW/TiO.sub.2.
[0109] The catalyst was evaluated in a fixed bed reactor operated
under ambient pressure in a fixed bed. Namely, 10 cc of the
resulting catalyst granule was packed in a quartz reaction tube
(diameter of 20 mm).
An aqueous solution of glycerin (a concentration of 30% by weight)
was fed to an evaporator at a flow rate of 21 g/hr together with
nitrogen (3.7 NL/hr) and with oxygen (1.0 NL/hr) at 300.degree. C.
so that glycerin was gasified and the resulting gasified glycerin
was passed through the fixed catalyst bed. The fixed catalyst bed
was heated at a temperature of 300.degree. C. Feed gas had a
following composition in mol
%:glycerin:oxygen:nitrogen:water=6.3:4.0:14.9:74.8. GHSV was 2445
h.sup.-1.
[0110] The collection, analytical method and calculation of
products were the same way as Example 1.
TABLE-US-00002 TABLE 2 Time on stream (h) 2 21 Glycerin conversion
(%) 100 98 Acrolein yield (%) 78 78 Acrolein selectivity (%) 78 80
Hydroxypropanone yield (%) 0.0 0.4 Acetaldehyde yield (%) 2.1 3.5
Propanaldehyde yield (%) 0.1 0.4 Acrylic acid yield (%) 0.9 0.4 CO
yield (%) 5.3 3.5 CO.sub.2 yield (%) 3.1 2.1
Example 3
HPW/TiO.sub.2
[0111] 2.7 g of tungstophosphoric acid (Aldrich) was dissolved in
8.5 g of deionized water to obtain an aqueous solution of
tungstophosphoric acid. 7.6 g of the resulting aqueous solution was
then sprayed onto 15.4 g of TiO.sub.2 powder obtained by grinding
anatase type TiO.sub.2 pellets (ST31119 from Norpro Saint
Gobain--BET surface 39 m.sup.2/g) to 35 to 48 mesh. The resulting
powder was dried at 110.degree. C. for 2 hours and then was fired
in nitrogen atmosphere at 300.degree. C. for 3 hours. The resulting
powder was then dried at 100.degree. C. overnight and then was
fired in nitrogen atmosphere at 500.degree. C. for 3 hours to
obtain a titania carrier supporting 10% of tungstophosphoric acid.
This titania carrier was sieved to obtain a particle size of 35 to
48 mesh, having a BET surface of 35 m.sup.2/g.
[0112] Procedure of catalyst test was reproduced as in example 1.
Results are shown in table 3.
TABLE-US-00003 TABLE 3 Time on stream (h) 3 24 Glycerin conversion
(%) 100 81 Acrolein yield (%) 79 60 Acrolein selectivity (%) 79 74
Hydroxypropanone yield (%) 0.1 1.8 Acetaldehyde yield (%) 1.4 0.9
Propanaldehyde yield (%) 0.6 0.3 Acrylic acid yield (%) 0.3 0.9 CO
yield (%) 1.3 1.1 CO.sub.2 yield (%) 0.8 0.8
Example 4
HSiW/TiO.sub.2
[0113] 3.0 g of tungstosilicic acid (Aldrich) was dissolved in 11.1
g of deionized water to obtain an aqueous solution of
tungstosilicic acid. 11.8 g of the resulting aqueous solution was
then sprayed onto 25 g of TiO.sub.2 powder obtained by grinding
anatase type TiO.sub.2 pellets (ST31119 from Norpro Saint Gobain)
to 35 to 48 mesh. The resulting powder was dried at 110.degree. C.
for 2 hours and then was fired in nitrogen atmosphere at
300.degree. C. for 3 hours. The resulting powder was then dried at
100.degree. C. overnight and then was fired in nitrogen atmosphere
at 625.degree. C. for 3 hours to obtain a titania carrier
supporting 10% of silicotungstic acid. This titania carrier was
sieved to obtain a particle size of 35 to 48 mesh.
[0114] Procedure of catalyst test was reproduced as in example 1.
Results are shown in table 4.
TABLE-US-00004 TABLE 4 Time on stream (h) 3 24 Glycerin conversion
(%) 100 67 Acrolein yield (%) 79 55 Acrolein selectivity (%) 79 82
Hydroxypropanone yield (%) 1.5 2.4 Acetaldehyde yield (%) 0.9 0.8
Propanaldehyde yield (%) 1.1 0.8 Acrylic acid yield (%) 0.3 0.9 CO
yield (%) 1.0 1.1 CO.sub.2 yield (%) 0.7 0.8
[0115] These Examples reveal moreover that the supported catalyst
according to the present invention shows such advantages that
deactivation of the catalyst is limited and regeneration can be
done at higher temperature comparing to the catalyst having no
support, without spoiling great merits described in our previous
applications of PCT/JP2009/057818 and PCT/JP2009/057819.
Example 5 and Comparative Examples 6 to 8
[0116] Tungstophosphoric acid on silicon oxide or alumina was
prepared in the same manner as in example 3 with silicon oxide
SS61138 (251 m.sup.2/g) and SS61137 (161 m.sup.2/g) from Norpro
Saint Gobain and with aluminium oxide SA6578 from Norpro Saint
Gobain.
[0117] Those catalysts were tested along with catalyst of example 3
in the conditions described in the table 5 below.
TABLE-US-00005 TABLE 5 Example Comparative Example 5 6 7 8 Acid 10%
tungstophosphoric Catalyst support TiO.sub.2 SiO.sub.2 SiO.sub.2
Al.sub.2O.sub.3 ST31119 SS61138 SS61137 SA6578 Reactant ratios
2.8/1.7/14.3/81.2 glycerol/O2/N2/H2O GHSV (h-1) 5100 h.sup.-1 Oven
temperature 280.degree. C. Time on stream (h) 11 11 11 13 Acrolein
yield (%) 75% 10% 18% 18%
* * * * *