Amines catalysis using group VIB metal-containing condensation catalysts

33 Pages·2013·3 MB·English

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USO05|225600A
United States Patent [191 [11] Patent Number: 5,225,600
King et al. [45] Date of Patent: * Jul. 6, 1993
[54] AMINES CATALYSIS USING GROUP VIB 4,316,841 2/1982 Ford et al. ................. .. 260/239 BC
METAL-CONTAINING CONDENSATION 4,324,917 4/1982 McConnell ..... .. 564/479
4,362,886 12/1982 Ford et a1. 564/479
CATALYSTS '
4,394,524 7/1983 Ford et a1. 564/479
[75] Inventors: Stephen W. King, Scott Depot; 4,399,308 8/1983 Ford et a1. 564/479
Arthur R. Doumaux, Jr., Charleston; 4,448,997 5/1984 Brennan ...... .. 564/479
David J. Schreck, Cross Lanes, all of 4,463,193 7/1984 Johnson et a1. 564/479
W. Va. 4,503,253 3/1985 Ford et a1. 564/479
4,521,600 6/1985 Wells et a1. 544/352
[73] Assignee: Union Carbide Chemicals & Plastics 4,524,143 6/1985 Vanderpool .. 502/208
Technology Corporation, Danbury, 4,540,822 9/1985 Vanderpool 564/479
Conn. 4,547,591 10/1985 Brennan et a1. .. 564/479
4,550,209 10/1985 Unvert et al. 564/479
[ ‘ ] Notice: The portion of the term of this patent 4,552,961 11/1985 Herdle ........ .. 544/402
subsequent to Aug. 26, 2009 has been 4,555,582 11/1985 Vanderpool .. 564/479
disclaimed. 4,560,798 12/1985 Ford et a1. ..... .. 564/503
4,578,517 3/1986 Johnson et al. ................... .. 564/479
[21] Appl. No.: 934,901 (List continued on next page.)
[22] Filed: Aug. 26, 1992
FOREIGN PATENT DOCUMENTS
Related US. Application Data 0312253 10/1988 European Pat. Off. .
0290960 11/1988 European Pat. Off. .
[63] Continuation of Ser. No. 742,731, Aug. 6, 1991, aban
375355 6/1990 European Pat. Off. .
doned, which is a continuation of Ser. No. 390,708,
78945 5/1985 Japan .
Aug. 8, 1989, abandoned.
236752 10/1986 Japan .
[51] Int. Cl.5 ................. .. C07C 209/ 16; C07C 209/22 236753 10/1986 Japan .
6323744 l/1988 Japan .
[52] US. Cl. .................................. .. 564/480; 544/359;
303964 12/1988 Japan .
544/401; 544/402; 502/308; 502/309; 564/470;
211246 8/1990 Japan.
564/479; 564/503; 564/505; 564/ 506; 564/507;
2147896 10/1984 United Kingdom .
564/508; 564/511; 564/512 9003963 4/1990 World Int. Prop. 0. .
[58] Field of Search ............. .. 564/480, 470, 479, 503,
Primary Examiner-Richard L. Raymond
564/505, 506, 507, 508, 511, 512; 544/359, 401,
Assistant Examiner-Scott C. Rand
402; 502/308, 309
Attorney, Agent, or Firm-R. M. Allen
[56] References Cited
[57] ABSTRACT
U.S. PATENT DOCUMENTS
This invention relates to a process for making amines by
1,875,746 9/1932 Martin et al. ..................... .. 564/480 condensing an amino compound in the presence of a
2,073,671 4/1931 Andrews .... .. 260/127 Group VIB metal-containing condensation catalyst.
2,389,500 11/1945 Goshom ........ .. 260/585 This invention also relates to an alkyleneamines produc
2,467,205 4/ 1949 Gresham et al. 260/268
ers composition rich in triethylenetetramine (TETA),
2,529,923 11/1950 Dickey et al. 564/480
tetraethylenepentarnine (T EPA) and pentaethylenehex
3,128,311 4/1964 Shirley et al. 564/480
4,036,881 7/1977 Brennan et a1. . 260/583 P amine (PEI-1A). '
4,044,053 8/1977 Brennan et a1. . . 260/583 P
4,206,150 6/1980 Slaugh . . . . . . . . . . . . . . . . . . . . .. 564/480
4,301,036 11/1981 Childress et a1. 252/458
4,314,083 2/1982 Ford et al. . . . . . . . . . . . . . .. 564/479
4,316,840 2/1982 Ford et a1. 260/239 BC 35 Claims, No Drawings
5,225,600
Page 2
Us. PATENT DOCUMENTS 4,625,030 11/1986 Best ................................... .. 564/480
4,578,518 3/1986 Vanderpool et a1. ............. .. 564/479 4,647,701 3/1987 Gibson ...... .. .. 564/480
4,578,519 3/1986 Larken er a1. ....... .. 564/479 4,683,335 7/1987 Knifton et a1. . 564/480
4,584,405 4/1986 Vanderpool ........ .. 564/479 4,698,427 10/1987 Vanderpool 544/404
4,584,406 4/1986 Vanderpool et a1. . 564/479 4,720,588 1/ 1988 Turcotte et al. 564/479
4,588,842 5/1986 Vanderpool .... .. 564/479 4,774,218 9/1988 Shimasaki et a1. . 502/202
4,605,770 8/1986 Ford et a1. ...... .. 564/479 4,806,517 2/1989 Vanderpool et a1. .. 502/208
4,609,761 9/1986 Watts, Jr. et a1. . 564/479 4,833,248 5/1989 Shimasaki et a1. 546/184
4,612,397 9/1986 Renken ........ .. 564/479 4,841,061 6/1989 Shimasaki et a1. . _. 546/184
4,617,418 10/1986 Ford et a1. ........................ .. 564/479 4,922,024 5/ 1990 Bowman et a1. .................. .. 564/480
5,225,600
1 2
trimetaphosphoric acid, primary ammonium phos
AMINES CATALYSTS USING GROUP VIB phate, secondary ammonium phosphate, normal am
METAL-CONTAINING CONDENSATION monium phosphate, ammonium metaphosphate, sec
CATALYSTS ondary ammonium pyrophosphate, normal ammo
5 nium pyrophosphate, aluminum phosphate, alumi
This application is a continuation of prior U.S. appli num acid phosphate and mixtures of two or more of
cation Ser. No. 07/742,731 Filing Date Aug. 6, 1991, such materials.”
now abandoned, which is a continuation of application whereas U.S. Pat. No. 2,467,205 describes one of the
Ser. No. 07/390,708 Aug. 8, 1989, now abandoned. preferred catalysts as “basic aluminum phosphate”.
10 U.S. Pat. No. 2,454,404 describes the “catalytic deam
RELATED APPLICATIONS ination of alkylene polyamines” by reacting diethylene
U.S. patent application Ser. No. 136,615, ?led Dec. triamine (DETA) vapor over solid catalysts such as
22, 1987, commonly assigned. activated alumina, bauxite, certain aluminum silicates
The following are related, commonly assigned appli such as kaolin and oxides of thorium, titanium and zir
cations, ?led on an even date herewith: U.S. patent conium.
application Ser. No. 390,829, U.S. patent application U.S. Pat. Nos. 2,073,671 and 2,467,205 demonstrate a
Ser. No. 390,709; U.S. patent application Ser. No. common experience in using aluminum phosphate as a
390,714; U.S. patent application Ser. No. 309,828; and condensation catalyst to produce aliphatic amines, and
U.S. patent application Ser. No 390,706; all incorpo U.S. Pat. Nos. 2,454,404 and 2,467,205 contemplate the
rated herein by reference. 20 other solid catalysts for deamination of amines to make
heterocyclic noncyclic amines. In general, the reaction
BRIEF SUMMARY OF THE INVENTION
conditions under which deamination to effect cycliza
1. Technical Field tion occurs are more severe than those employed for
This invention relates to a process for making amines condensation to generate noncyclic molecules, all other
by condensing an amino compound in the presence of a 25 factors being comparable.
Group VIB metal-containing condensation catalyst. U.S. Pat. Nos. 4,540,822, 4,584,406 and 4,588,842
This invention also relates to an alkyleneamines pro depict the use of Group IVB metal oxides as supports
ducers composition rich in higher polyalkylene poly for phosphorus catalysts used to effect the condensation
amines such as triethylenetetramine (TETA), tetrae of amino compounds with alkanolamines.
thylenepentamine (TEPA) and pentaethylenehexamine 30 U.S. Pat. No. 4,683,335 describes the use of tungsto
(PEl-lA). phosphoric acid, molybdophosphoric acid or mixtures
2. Background of the Invention deposited on titania as catalysts for the condensation of
There is a substantial body of literature directed to amines and alkanolamines to make polyalkylenepolya
the use of various acid catalysts to effect intramolecular mines.
and intermolecular condensation of amino compounds. 35 U.S. Pat. Nos. 4,314,083, 4,316,840, 4,362,886 and
U.S. Pat. No. 2,073,671 and U.S. Pat. No. 2,467,205 4,394,524 disclose the use of certain metal sulfates as
constitute early prior work on the use of acid condensa useful catalysts for the condensation of alkanolamine
tion catalysts to condense amino compounds. U.S. Pat. and an amino compound. No distinction is made be
No. 2,073,671 discusses, in a general fashion, the cata tween the sulfur compounds in respect to catalytic effi
lytic intermolecular condensation of alcohols and cacy. Sulfuric acid is as good as any metal sulfate, and
amines or ammonia using the same phosphate catalysts all metal sulfates are treated as equivalents. At column 8
later favored by U.S. Pat. No. 2,467,205 for the intramo of US. Pat. No. 4,314,083, it is noted that boron sulfate
lecular condensation of amines. The two patents are not “gave extremely high selectivity at a low level” of
in harmony over the use of other materials as catalysts. EDA. However, selectivity in general was shown to
To illustrate this point, U.S. Pat. No. 2,073,671 states: 45 increase with an increase of EDA relative to MBA in
“Alumina, thoria, blue oxide of tungsten, titania, the feed. The only specific metal sulfates disclosed in
chromic oxide, blue oxide of molybdenum and zirco the patents are antimony sulfate, beryllium sulfate, iron
nia have been mentioned in the literature for use as sulfate and aluminum sulfate.
catalysts in carrying out these reactions but their In the typical case of the manufacture of alkylenea
effectiveness is so low that no practical application 50 mines, mixtures with other alkyleneamines (including a
has been made of their use.” variety of polyalkylenepolyamines and cyclic al~
whereas U.S. Pat. No. 2,467,205 in describing the self kylenepolyamines) are formed. The same holds true
condensation of ethylenediamine (EDA) under vapor when the object of the process is to produce polyalk
phase conditions, to initially produce ethyleneamines, ylenepolyamines whether acyclic or cyclic, in that a
but after recycle, eventually generates piperazine 55 variety of amino compounds are also formed. Each of
through multistep condensation reactions, followed by these cyclic and acyclic alkyleneamines can be isolated
deamination, recommends “dehydration catalysts” from the mixture.
which are thereafter characterized as The acid catalyzed condensation reaction involving
“silica gel, titania gel, alumina, thoria, boron phos the reaction of an alkanolamine with an amino com
phate, aluminum phosphate, and the like.” pound in the presence of an acidic catalyst is believed to
U.S. Pat. No. 2,073,671 describes the condensation proceed through the mechanism of esterifying free sur
catalyst in the following terms: face hydroxyl groups on the acid catalyst with the alka
“ . . a heated catalyst or contact mass containing nolamine and/or by protonating the alkanolamine in the
phosphorus and especially one or more of the oxygen presence of the acid catalyst, followed by loss of water
acids of phosphorus, their anhydrides, their poly 65 and amine condensation of the ester or the hydrated
mers, and their salts; for example, orthophosphoric species, as the case may be, to form the alkyleneamine.
acid, metaphosphoric acid, pyrophosphoric acid, Illustrative prior art directed primarily to the cyclic
phosphorous pentoxide, dimetaphosphoric acid, polyalkylenepolyamines (heterocyclic polyamines), but
5,225,600
3 4
not necessarily limited to the aforementioned acid con labeling it so, see U.S. Pat. No. 2,467,205, supra. The
densation reaction, are: U.S. Pat. Nos. 2,937,176, acid catalysts are phosphorus compounds and the reac
2,977,363, 2,977,364, 2,985,658, 3,056,788, 3,231,573, tion is carried out in the liquid phase. The trend in this
3,167,555, 3,242,183, 3,297,701, 3,172,891, 3,369,019, catalyst direction was early set as demonstrated by U.S.
3,342,820, 3,956,329, 4,017,494, 4,092,316, 4,182,864, Pat. Nos. 2,073,671 and 2,467,205, supra. A modi?ca
4,405,784 and 4,514,567; European Patent Applications tion of this route includes the addition of ammonia to
0 069 322, O 111 928 and O 158 319; East German Patent the reaction, see, for example, U.S. Pat. No. 4,394,524
No. 206,896; Japanese Patent Publication No. and U.S. Pat. No. 4,463,193 for the purpose of convert
51-141895; and French Patent No. 1,381,243. The evo ing alkanolamine such as MBA in situ to alkylene amine
lution of the art to the use of the acid catalyzed conden such as EDA by reaction with ammonia, and the EDA
sation reaction to generate acyclic alkyleneamines, par is in situ reacted with MEA according to the process of
ticularly acyclic polyalkylenepolyamines, as the pre U.S. Pat. No. 4,036,881 to form alkyleneamines.
dominant products stemmed from the initial disclosure A summary of the prior art employing acid catalysts
in U.S. Pat. No. 4,036,881, though earlier patent litera for making alkyleneamines is set forth in Table 1 below.
ture fairly well characterized such an effect without 15
TABLE 1
CITATION CATALYST TYPE REACTANTS
U.S. Pat. No. 2,467,205 Silica gel, titania gel, alumina, Vapor phase condensation of
thoria, aluminum phosphate. EDA over a fixed bed of the
Preferred catalyst is basic catalyst, multipass process
aluminum phosphate. shifts from polyethylene
polyarnines with the first few
cycles.
U.S. Pat. No. 4,036,881 Phosphorus containing substances Alkanolamine and alkylene
selected from the group consisting amine in liquid phase
of acidic metal phosphates, reaction.
phosphoric acid compounds and
their anhydrides, phosphorus acid
compounds and their anhydrides,
alkyl or aryl phosphate esters,
alkyl or aryl phosphite esters,
alkyl or aryl substituted
phosphorous and phosphoric acids
wherein said alkyl groups have
from 1 to about 8 carbon atoms and
said aryl groups have from 6 to
about 20 carbon atoms. alkali
metal monosalts of phosphoric
acid. the thioanalogs of the fore
going. and mixtures of the above.
U.S. Pat. No. 4,044,053 Phosphorus containing substances Alkanepolyols and alkylene
selected from the group consisting amine in liquid phase
of acidic metal phosphates, reaction.
phosphoric acid compounds and
their anhydrides, phosphorus
acid compounds and their
anhydridcs, alkyl or aryl
phosphate esters, alkyl or aryl
phosphite esters, alkyl or aryl
substituted phosphorous acids and
phosphoric acids wherein said
alkyl groups have from 1 to about
8 carbon atoms and said aryl
groups have from 6 to about 20
carbon atoms, alkali metal mono
salts of phosphoric acid and
mixtures of the above.
U.S. Pat. No. 4,314,083 Salt of a nitrogen or sulfur con Alkanolamine and an
taining substance or the corresponding alkyleneamine in liquid
acid. phase reaction.
U.S. Pat. No. 4,316,840 Metal nitrates and sulfates Reforming linear polyamines.
including zirconium sulfate.
U.S. Pat. No. 4,316,841 Phosphate, preferably boron Reforming linear polyamines.
phosphate.
U.S. Pat. No. 4,324,917 Phosphorous-containing cation Alkanolamine and an alkylene
exchange resin. , amine in liquid phase
reaction.
U.S. Pat. No. 4,362,886 Arsenic, antimony or bismuth Alltanolamine and an alltylene
containing compounds. Antimony amine in liquid phase
sulfate speci?cally disclosed. reaction.
U.S. Pat. No. 4,399,308 Lewis acid halide. Alkanolamine and an alkylene
amine in liquid phase
reaction.
U.S. Pat. No. 4,394,524 Phosphorus-containing substance Ammonia, alkanolamine and an
or salt of a sulfur-containing alkyleneamine in liquid phase
substance, or the corresponding reaction.
acid.
U.S. Pat. No. 4,448,997 Reacts alumina with phosphoric EDA with MEA.
acid, adds ammonium hydroxide.
5,225,600
TABLE l-continued
CITATION CATALYST TYPE REACTANTS
U.S. Pat. No. 4,463,193 Group 11113 metal acid phosphate. Ammonia, alkanolamine and
an alkyleneamine.
U.S. Pat. No. 4,503,253 Supported phosphoric acid. Ammonia, alkanolamine and
an alkyleneamine.
U.S. Pat. No. 4,521,600 Select hydrogen phosphates and Alkanolamine and an alkylene
pyrophosphates. amine.
U.S. Pat. No. 4,524,143 Phosphorus impregnated onto Alkanolamine and an alkylene
zirconium silicate support. amine.
U.S. Pat. No. 4,540,822 Phosphorus compound deposited Alkanolamine and an alkylene
on a Group IVB metal oxide amine, regenerates the
support. catalyst with Oz-containing
gas.
U.S. Pat. No. 4,547,591 Silica-alumina alone or in An ethyleneamine and an
combination with an acidic alkanolamine; ethyleneamines;
phosphorus cocatalyst. or ammonia and an alkanol
amine.
U.S. Pat. No. 4,550,209 An intercalatively catalytically EDA and MEA.
active tetravalent zirconium
polymeric reaction product of an
organo phosphonic acid or an
ester thereof with a compound of
tetravalent zirconium reactive
therewith.
U.S. Pat. No. 4,552,961 Phosphorus amide compound. Alkyleneamine and alkanolamine
and/or alkylene glycol.
U.S. Pat. No. 4.555.582 Phosphorus chemically bonded to MEA and EDA.
a zirconium silicate support.
U.S. Pat. No. 4,560,798 Rare earth metal or strontium MEA.
acid phosphate.
U.S. Pat. No. 4,578,517 Group 111B metal acid phosphate. Ammonia or p-/svamine
and alkanolamine.
U.S. Pat. No. 4,578,518 Thermally activated, calcined, MBA and EDA.
pelleted titania containing
titanium triphosphate. . . the
titania that was used was . . .
anatase." (Col. 9, lines 18-19).
U.S. Pat. No. 4,578,519 Thermally activated. calcined, MBA and EDA with optional
pelleted titania with chemically recycle of DETA.
bonded phosphorus derived from
polyphosphoric acid.
U.S. Pat, No. 4.584,405 Activated carbon, optionally MBA and EDA.
treated to incorporate phosphorus.
Activated carbon may be washed
with strong mineral acid to
remove impurities followed by
water wash. Optional treatment
follows.
U.S. Pat. No. 4,584,406 Pelleted Group IVB metal oxide MBA and EDA.
with chemically bonded phosphorus
derived from phosphoryl chloride
or bromide.
U.S. Pat. No. 4,588,842 Thermally activated pelleted MEA and EDA.
Group lVB metal oxide with
chemically bonded phosphorus.
U.S. Pat. No. 4,605,770 Group 11A or 11113 metal acid Alkanolamine and an
phosphate. alkyleneamine "in liquid
phase".
U.S. Pat. No. 4,609,761 Thermally activated pelleted MBA and EDA.
titania with chemically bonded
phosphorus.
U.S. Pat. No. 4,612,397 Thermally activated pelleted MEA and EDA,
titania with chemically bonded
phosphorus.
U.S. Pat. No. 4,617,418 Acid catalysts, mentions “beryl- Ammonia, alkanolamine and
lium sulfate". an alkyleneamine "under
vapor phase conditions".
Japanese Patent Variety of phosphorus and metal Ammonia, alkanolamine and
Application phosphates including Group IVB ethyleneamine, with ammonia/
#l983-185,87l, phosphates. alkanolamine molar ratio
Publication greater than 11.
#l985-78,945
U.S. Pat. No. 4,683,335 Tungstophosphorie acid, molybdo Claims reaction of MEA and
phosphoric acid or mixtures EDA, but discloses self
deposited on titania. Examples condensation reaction of
2~7 characterize titania surface EDA and DETA.
areas of 51, 60 and 120 rnZ/gm.
Japanese Patent Group IVB metal oxide with Ammonia and MEA.
Application bonded phosphorus.
#1985-078,391,
Publication
# 1986236752
5,225,600
7 8
TABLE l-continued
CITATION CATALYST TYPE REACTANTS
Japanese Patent Group IVB metal oxide with Ammonia and MEA.
Application bonded phosphorus.
#l985-078,392,
Publication
#l986-236,753
U.S. Pat. No. 4,698,427 Titania having phosphorus Diethanolamine and/or
thermally chemically bonded hydroxyethyldiethylene
to the surface thereof in the tn'amine in EDA.
form of phosphate bonds.
U.S. Pat. No. 4,806,517 Pelleted Group IVB metal oxide MEA and EDA.
with phosphorus thermally
chemically bonded to the
surface thereof.
The market demand for higher polyalkylene poly amines, by such condensation reactions utilizing one or
amines such as TETA, TEPA and PEHA has been more oxides of tungsten as the condensation catalyst.
progressively increasing in recent years. These higher The invention further relates to a continuously gener
polyalkylene polyamines are desirable co-products with ated alkyleneamines producers composition compris
DETA. It would be desirable to satisfy the existing ing, based on 100 percent of the weight of the composi
demand from a cost standpoint by modifying slightly tion and exclusive of any water and/or ammonia pres
the commercial processes directed to the manufacture ent,
of DETA from the reaction of MBA and EDA or other a) greater than about 3.0 weight percent of the combi
suitable starting raw materials such as DETA and nation of TETA and TEPA,
AEEA, to the production of TETA, TEPA and PEHA 25 b) greater than about 0.1 weight percent of TEPA,
as major products. c) greater than about 3.0 weight percent of TETA,
It would be desirable to have continuously produced d) less than about 90.0 weight percent of DETA
compositions, generated by the reaction of MBA and and/or EDA,
EDA or other suitable starting raw materials such as e) less than about 90.0 weight percent of MBA and
DETA and AEEA over a ?xed bed of a condensation /or AEEA,
catalyst under commercial conditions, that are rich in f) less than about 12.5 weight percent of the combina
TETA, TEPA and PEHA, and that are not dispropora tion of PIP and AEP,
tionately high in PIP and other cyclics. g) less than about 15.0 weight percent of other polyal
It would be very bene?cial to have a process which kylene polyamines,
increases one’s ability to generate the manufacture of 35 h) a TETA+TAEA to PIP+AEP+PEEDA+DA
desirable higher polyalkylene polyamine products such EP+DPE weight ratio of greater than about 0.5,
as TETA, TEPA and PEHA without generating large i) a TEPA+AETAEA to PIP+AEP+PEEDA+
amounts of cyclic alkylenepolyamine products. In addi DAEP + DPE + AEPEEDA + iAEPEEDA + A
tion, it would also be desirable to have a process with EDAEP+AEDPE+BPEA weight ratio of
raw material ?exibility which provides the potential to greater than about 0.5,
control congener distribution, linear to cyclic selectiv j) a TETA to TAEA weight ratio of greater than
ity and linear to branched selectivity of the higher poly about 4.0, and
alkylene polyamines products. As used herein, conge k) a TEPA to AETAEA weight ratio of greater than
ner distribution refers to polyalkylene polyamines con about 1.0.
taining the same number of nitrogen atoms but not nec 45 As used herein, the term “amino compound” em
essarily having the same molecular weight or structure. braces ammonia and any compound containing nitrogen
The above features are provided by this invention. to which is bonded an active hydrogen. Also, for pur
poses of this invention, the term “oxide” embraces ox
SUMMARY OF THE INVENTION
ides, hydroxides and/or mixtures thereof.
This invention relates in general to a process of mak 50 For purposes of this invention, the chemical elements
ing amines which comprises condensing an amino com are identified in accordance with the Periodic Table of
pound in the presence of a Group VIB metal-containing the Elements, CAS version, Handbook of Chemistry
condensation catalyst. The Group VIB metal-contain; and Physics, 67th Ed., 1986-87, inside cover. Also, for
ing condensation catalysts used herein contain sufficient purposes of this invention, Group IIIB metal oxides
residual bound hydroxyl groups or other groupings 55 embraces the lanthanides. and actinides.
which renders catalyst formation possible by loss of
DETAILED DESCRIPTION
water or its chemical equivalent such as ammonium
hydroxide. The higher polyalkylene polyamines such as TETA,
More particularly, this invention relates to a process TEPA and PEHA are very useful commercial products
of making amines by the (i) intramolecular condensation 60 for a variety of applications including fuel oil additives,
of an amino compound to an amine having a lower corrosion inhibitors, fabric softeners, fungicides and
molecular weight or (ii) the intermolecular condensa others. As indicated above, there is lacking a commer
tion of an amino compound with one or more of another cial process for the manufacture of enhanced quantities
amino compound or a compound containing an alco of TETA, TEPA and PEHA especially as signi?cant
holic hydroxyl group using certain Group VIB metal 65 products of reaction. There is thus a need for the ability
containing substances as the condensation catalyst. A to commercially generate larger production quantities
preferred process involves the manufacture of al of TETA, TEPA and PEHA and that is the direction of
kyleneamines, most desirably higher polyalkylene poly this invention. The process of this invention provides
5,225,600
9 1,0
for the reaction of MBA and DETA or other suitable taining substances encompassed within the scope of this
starting raw materials such as EDA and AEEA to pro invention possessing ionic character and/or ion ex
duce in a continuous manner a reaction product mix change capacity exhibit desired catalytic activity and
ture, termed herein an “alkyleneamines producers com provide desired product selectivity. While the reaction
position”, in which TETA, TEPA and PEHA are prin mixture may initially include one or more Group VIB
cipal products of the reaction. metal-containing substances other than Group VIB
The process of this invention is distinctive insofar as metal-containing substances possessing ionic character
it achieves the generation of high concentrations of and/or ion exchange capacity, it is believed to be desir
TETA, TEPA and PEHA in a manner which can be able that such Group VIB metal-containing substances
suitably employed in a commercial process, particularly possessing ionic character and/or ion exchange capac
a continuous process, for the manufacture of alkylenea
ity be formed in situ in order to provide desired cata
mines. In particular, the process of this invention allows lytic activity and product selectivity. In such instances,
the production of TETA, TEPA and PEHA in rela
the catalyst preparation conditions or reaction condi
tively high yields without generating large amounts of
tions should allow for the formation of Group VIB
cyclic polyalkylene polyamine products. The process 5 metal-containing substances possessing ionic character
this invention provides starting raw material ?exibility
and/or ion exchange capacity. Mixtures of Group VIB
thereby allowing the potential to control congener dis
metal-containing substances possessing ionic character
tribution, linear to cyclic selectivity and linear to
and/or ion exchange capacity with Group VIB metal
branched selectivity of the higher polyalkylene poly
containing substances having other than ionic character
amine products. 20
and/or ion exchange capacity are believed to exhibit
As indicated above, this invention relates to a process
desired catalytic activity and provide desired product
of making amines which comprises condensing an
selectivity.
amino compound in the presence of a Group VIB met
In accordance with this invention, Group VIB metal
al-containing condensation catalyst.
containing substances can be utilized as condensation
As also indicated above, this invention relates to a 25
catalysts in amines processes. Suitable Group VIB met
continuously generated alkyleneamines producers com
position comprising, based on 100 percent of the weight al-containing substances which are useful as condensa
tion catalysts herein include, for example, one or more
of the composition and exclusive of any water and/or
ammonia present, oxides of tungsten, chromium, molybdenum or mixtures
a) greater than about 3.0 weight percent of the combi 30 thereof. A tungsten-containing substance such as one or
nation of TETA and TEPA, more oxides of tungsten or tungsten metal impregnated
b) greater than about 0.1 weight percent of TEPA, onto a support are preferred condensation catalysts for
c) greater than about 3.0 weight percent of TETA, use in this invention.
d) less than about 90.0 weight percent of DETA The Group VIB metal-containing condensation cata
and/or EDA, 35 lysts can be prepared by conventional methods known
e) less than about 90.0 weight percent of MBA and in the art.
/ or AEEA, The level of activity of the Group VIB metal-con
f) less than about 12.5 weight percent of the combina taining condensation catalyst of the invention is that
tion of PIP and AEP, level which of itself makes the catalyst at least as active
g) less than about 15.0 weight percent of other polyal 40 in the condensation of amines as, for example, is phos
kylene polyamines, phoric acid on an equivalent basis. Preferably, sup
h) a TETA-i-TAEA to PIP+AEP+PEEDA +DA ported Group VIB metal-containing condensation cata
EP+DPE weight ratio of greater than about 0.5, lysts should have a surface area greater than about 70
i) a TEPA+AETAEA to PIP+AEP+PEEDA+~ mZ/gm to as high as about 260 mZ/gm or greater de
DAEP + DPE + AEPEEDA + iAEPEEDA + A 45 pending upon which metal oxide described below that is
EDAEP+AEDPE+BPEA weight ratio of employed. In the case of Group VIB metal-containing
greater than about 0.5, substances in association with titanium oxides, the sur
j) a TETA to TAEA weight ratio of greater than face area should be greater than about 140 mz/grn to as
about 4.0, and high as about 260 m2/ gm, more preferably, greater than
k) a TEPA to AETAEA weight ratio of greater than 50 about 160 mZ/gm to as high as about 260 mZ/gm, deter
about 1.0. mined according to the single point N2 method. In the
The alkyleneamines producers composition of this case of Group VIB metal-containing substances in asso
invention can be subjected to conventional separations ciation with zirconia oxides, the surface area should be
techniques for recovering the individual components of greater than about 70 mZ/gm to as high as about 150
the composition. Such techniques are well known in the 55 m2/ gm, more preferably, greater than about 90 mZ/g m
art and include, for example, distillation. to as high as about 135 mZ/gm, determined according to
This invention contemplates the catalyzed condensa the single point N1 method. It is appreciated that the
tion by (i) intramolecular condensation of an amino metal oxides described below which can be used in
compound to an amine having a lower molecular association with the Group VIB metal-containing con
weight, and (ii) intermolecular condensation of an densation catalyst and the performance moderators
amino compound with one or more of another amino described below can affect the surface area of the
compound or a compound containing an alcohol hy Group VIB metal-containing condensation catalyst.
droxyl group to an amine having a lower, same or While surface areas described above may be preferred,
higher molecular weight than the reactants, in the pres for purposes of this invention, the surface area of the
ence of a Group VIB metal-containing condensation 65 Group VIB metal-containing condensation catalyst
catalyst.
should be sufficient to contribute to product selectivity,
While not wishing to be bound to any particular catalytic activity and/or mechanical or dimensional
theory, it is believed that those Group VIB metal-con strength of the catalyst.
5,225,600
11
The Group VIB metal-containing condenation cata
lysts useful in this invention can be associated with one
or more metal oxides. Preferred metal oxides are am
photeric or slightly acidic or slightly basic. Illustrative
of such metal oxides which may be utilized in associa
tion with the Group VIB metal-containing condensa
tion catalyst include, for example, one or more of the
following: Group IA metal oxides, Group lIA metal
oxides, Group IIIB metal oxides (including lanthanides
and actinides), Group VB metal oxides, other Group
VIB metal oxides, Group VIIB metal oxides, Group
VIII metal oxides, Group 18 metal oxides, Group IIB
metal oxides, Group IIIA metal oxides, Group IVA
metal oxides, Group VA metal oxides, Group VIA
metal oxides and Group IVB metal oxides or mixtures
thereof. Preferred metal oxides which may be utilized in
association with the Group VIB metal-containg con
densation catalyst include, for example, one or more HfO2—TiO2, and the like. Other suitable mixed metal
oxides of beryllium, scandium, yttrium, terbium, dys oxide catalysts embraced within the scope of this inven
prosium, holmium, erbium, thulium, ytterbium, lute 20 tion are disclosed by Tanabe et al., Bulletin of the
tium, titanium, zirconium, hafnium, vanadium, niobium, Chemical Society of Japan, Vol. 47(5), pp. 1064-1066
tantalum, tungsten, iron, cobalt, zinc, silver, aluminum, (1974).
gallium, indium, silicon, germanium, tin, lead, arsenic, The metal oxides described herein which can be used
antimony and bismuth. in association with the Group VIB metal-containing
Group IVA and IVB metal oxides such as silica, 25 condensation catalyst may contribute to product selec
titanium dioxide and zirconium dioxide are preferred tivity and/or catalytic activity of the reaction and/or
for use in this invention. For mixed metal oxides in stability of the catalyst. The catalyst structure can com
which at least one of the metals is titanium, suitable prise from about 0 to about 90 percent or greater by
metals in association with titanium may include, for weight of the metal oxide, preferably from about 0 to
example, one or more of the following: Group IIIB about 75 percent by weight of the metal oxide, and
metals such as scandium, yttrium and lanthanum includ more preferably from about 0 to about 50 percent by
ing the lanthanides, Group VB metals such as niobium weight of the metal oxide, the remainder being the
and tantalum, other Group VIB metals such as chro weight of the Group VIB metal-containing condensa
mium, molybdenum and tungsten, Group VIII metals tion catalyst. For mixed metal oxides containing titania,
such as iron, cobalt and nickel, Group IIB metals such 35 higher concentrations of titania can provide very desir
as zinc and cadmium, Group IIIA metals such as boron, able product selectivities including acyclic to cyclic
aluminum, gallium and indium, Group IVA metals such selectivities and linear to branched selectivities of
as silicon, germanium, tin and lead, Group VA metals higher polyalkylene polyamine products. As discussed
such as arsenic, antimony and bismuth, and Group IVB hereinafter, the Group VIB metal-containing condensa
metals such as zirconium and hafnium. For mixed metal tion catalyst of this invention may also contain sup
oxides in which at least one of the metals is zirconium, port(s), binding agent(s) or other additives to stabilize
suitable metals in association with zirconium may in or otherwise help in the manufacture of the catalyst.
clude, for example, one or more of the following: Though the Group VIB metal-containing condensa
Group IVA metals such as silicon, germanium, tin and tion catalyst of the invention provides sufficient activity
lead, Group VB metals such as niobium and tantalum, 45 to effect the condensation reaction, certain combina
and other Group VIB metals such as chromium, molyb tions of reactants and/or product formation may be
denum and tungsten. The virtue of these metal oxides is bene?ted by treating the catalyst with a catalyst moder
that they demonstrate higher mechanical strength than ator, hereinafter termed “performance moderator.”
the Group VIB metal-containing substance per se and Catalyst moderators are widely used to control the
can contribute to product selectivity and catalytic activ 50 performance of catalysts in areas of selectivity to cer
ity. tain products and the repression of a catalyst’s procliv
Illustrative of mixed metal oxides which may be used ity to generate a broad range of reaction products. A
in association with the Group VIB metal-containing range of suitable materials may impact the Group VIB
condensation catalyst include, for example, Ti metal-containing condensation catalysts of this inven
Oz-SiOz, Ti02~A12030, TiO2—Cd0, TiO2--Bi203, 55 tion in the variety of reaction products. The perfor
TiOz-SbzOs, TiOz-SnOz, Ti02—ZI'O2, TiO2--BeO, mance moderator may be any material which impacts
TiOg-MgO, TiOg-CaO, TiOz-SIO, TiOz-ZHO, the Group VIB metal-containing condensation cata
TiO1——Ga2O3, TiO2——YzO3, TiO2—La203, Ti lyst’s selection of reaction products or which changes
O2—-M0O3, TiO2—Mn2O3, TiO2—Fe2O3, Ti the proportion of any one or more of the reaction prod—
Og-CO3O4, TiOg-WO3, TiOz-Vz05, TiC2—CrzO3, ucts which the Group VIB metal-containing condensa
TiO2—Th0z, TiO2—Na2O, TiO2—BaO, TiOg-CaO, tion catalyst generates at comparable processing condi
TiO2—HfO2, TiOz-LizO, TiO2—Nb2O5, Ti tions. In addition to contributing to product selectivity,
Oz—Ta2O5, TiO2—Gd203, TiO2—LU203, TiOz-Yb the performance moderator may be any material which
203, TiO2—CeO2, 1101-80203, TiO2-—PbO, TiO contributes to catalytic activity and/or catalyst stability
z-NiO, TiOz-CUO, TiO2—CoO, TiO2—_B2O3, 65 (mechanical or dimensional strength).
Zl'Oz-SiOz, ZrO2—Al203, ZrO2-—'SnO, ZI'O2—.PbO, An illustrative performance moderator is a mineral
ZrO2—Nb2O5, ZrO2—Ta2O5, ZrO2—Cr2O3, ZrO;—- acid or a compound derived from a mineral acid. Suit
MOO3, ZrO2—wO3, ZI'Or-TiOz, ZrQ2—HfO2, Ti able for use as performance moderators are one or more
5,225,600
13 14
phosphoric acid or a salt of phosphoric acid, hydrogen Na2(NH4)2P207, C?(NH4)2P2O7, MgHzPzov,
?uoride, hydro?uoric acid or a ?uoride salt, sulfuric Mg(NH4)2P2O7 and the like. Illustrative of metallic
acid or a salt of sulfuric acid, and the like. The modera polyphosphate performance moderators which may be
tor may also be organic esters of phosphoric acid or a utilized in this invention include, for example, NaSr2.
salt of phosphoric acid, hydrogen fluoride organic com P3010, Nacazpsoio, NaNizpsolo, NasPsoio, KsP301o,
plexes, hydro?uoric acid organic complexes or a ?uo NasMgPsoio, NaacuPsoto, Cus(P3010)2.Na3ZnP3010.
ride salt organic complexes, organic esters of sulfuric Na3CdP3O10, Na6Pb(P3O10)2, Na3COP3010, K3COP
acid or a salt of sulfuric acid, and the like. Suitable salts 3010, NaaNiPsoto, K2(NH4)3P3010, Ca(NH4)2P30i0,
of phosphoric acid include sodium dihydrogen phos La(NH4)2P3O10, NaMgH2P3O10 and the like. Illustra~
phate, disodium hydrogen phosphate, sodium phos tive of metallic metaphosphate performance moderators
phate and the like. Other illustrative performance mod which may be utilized in this invention include, for
erators include the metal oxides described above which example, Na3P3O9, K3P309, Ag3P3O9, Na4P4O12,
can be used in association with the Group VIB metal K4P4012, N112HP309, Na4-Mg(P309)2, NasrPsos,
containing condensation catalyst and also metallic phos NaCaP3O9, NaBaP309, KBaP3O9, Ca3(P3O9)2, Ba(P
phates and polyphosphates which may or may not have 15 309)2, Na2Ni2(Ps09)2, NuNi(P309)2, NMCO(P309)2.
a cyclic structure and which may or may not have a Na4Cd(P3O9)2 and the like. Illustrative of metallic ultra
condensed structure. I phosphate performance moderators which may be uti
The metallic phosphates and polyphosphates are pre lized in this invention include, for example, CaP4O11,
ferred performance moderators for use in this invention. Ca2P6017,NasP1o029, NaePsoza, Nazcal’aon, N821’
The metallic phosphate and polyphosphate perfor 20 4O11, NaBaP7O1g, NazPgozl, K4P6O17 and the like. The
mance moderators may or may not have a cyclic struc preferred metallic phosphate and polyphosphate perfor
ture and may or may not have a condensed structure. mance moderators for use in this invention include
Suitable metallic phosphates having a cyclic structure Group IA metal metaphosphates, Group IA metal dihy
or an acyclic structure are disclosed in U.S. patent ap drogen orthophosphates and Group IA metal dihydro
plication Ser. No. 390,706, ?led on an even date here 25 gen pyrophosphates, more preferably , Na3P3O9,
with and incorporated herein by reference. Suitable NaI-I2PO4 and Na2H2P2O7. Other suitable metallic
metallic polyphosphates having a condensed structure phosphate and polyphosphate performance moderators
are disclosed in U.S. patent application Ser. No. which are embraced within the scope of this invention
390,709, ?led on an even date herewith and incorpo are disclosed by Van Wazer, J. R., Phosphorus and Its
rated herein by reference. Compounds, Vol. 1, Interscience Publishers, Inc., New
Suitable metallic phosphate and polyphosphate per York (1958).
formance moderators can include, for example, metallic The metal oxides described hereinabove which can
orthophosphates (P04 -3), metallic pyrophosphates be used in association with the Group VIB metal-con
(P207 *4), metallic polyphosphates (including tripoly tainiing condensation catalyst can also be used as per
phosphates (P3010 "5), tetrapolyphosphates (P4013 -6), 35 formance moderators in accordance with this invention.
pentapolyphosphates (P5016 *7) and higher polyphos The metal oxides can contribute to product selectivity,
phates), metallic metaphosphates (including trimeta catalytic activity and/or catalyst stability (mechanical
phosphates (P309 -3), tetrametaphosphates (P4012 “4) strength).
and other lower and higher metaphosphates) and metal A variety of conventional phosphorus-containing
lic ultraphosphates (condensed phosphates containing substances may be suitable for use as performance mod
more P205 than corresponds to the metaphosphate erators in this invention. The conventional substances
structure). Corresponding metallic metaphosphimates, should be capable of functioning as a performance mod
metallic phosphoramidates and metallic amido- and erator. Illustrative of conventional phosphorus-contain
imidophosphates of the above may also be used as per ing substances may include, for example, those dis
formance moderators in accordance with this invention. closed in U.S. Pat. No. 4,036,881, U.S. Pat. No.
Suitable metals which can be incorporated into the 4,806,517, U.S. Pat. No. 4,617,418, U.S. Pat. No.
metallic phosphate and polyphosphate performance 4,720,588, U.S. Pat. No. 4,394,524, U.S. Pat. No.
moderators include, for example, Group IA metals, 4,540,822, U.S. Pat. No. 4,588,842, U.S. Pat. No.
Group IIA metals, Group IIIB metals, Group IVB 4,605,770, U.S. Pat. No. 4,683,335, U.S. Pat. No.
metals, Group VB metals, Group VIB metals, Group 50 4,316,841, U.S. Pat. No. 4,463,193, U.S. Pat. No.
VIIB metals, Group VIII metals, Group IB metals, 4,503,253, U.S. Pat. No. 4,560,798 and U.S. Pat. No.
Group IIB metals, Group IIIA metals, Group IVA
4,578,517. '
metals, Group VA metals, Group VIA metals and mix Suitable conventional phosphorus-containing sub
tures thereof. stances which may be employed as performance moder
Illustrative of metallic orthophosphate performance 55 ators in this invention include acidic metal phosphates,
moderators which may be utilized in this invention phosphoric acid compounds and their anhydrides, phos
include, for example, NaI-I2PO4, KI-I2PO4, RbH2PO4, phorous acid compounds and their anhydrides, alkyl or
LiI-I2PO4, MgHPO4, CaI'IPO4, YPO4, CePO4, LaPO4, aryl phosphate esters, alkyl or aryl phosphite esters,
ThPO4, MnPOa, FCPO4, BPO4, AlPO4, BiPO4, alkyl or aryl substituted phosphorous acids and phos
ME(H2PO4)2, Ba(H2P04)2, Mg(NH4)2P04, C80’! phoric acids, alkali metal monosalts of phosphoric acid,
2PO4)2, La(I-I2PO4)3 and the like. Illustrative of metallic the thioanalogs of the foregoing, and mixtures of any of
pyrophosphate performance moderators which may be the above.
utilized in this invention include, for example, Na2I-I2 The amount of the performance moderator of the
P207, K2H2P207, Ca2P207, Mg2P207, KMnPzov, mineral acid type used with the Group VIB metal—con
AgMnP207, BaMnPzO7, NaMnP2O7, KCrP2O7, NaCr 65 taining condensation catalyst of the invention is not
P207, Na4P2O7, K4P207, Na3HP2O7, NaH3P2O7, SiP narrowly critical. Generally, the amount does not ex
207, NrPz07, NaeFez(Pz0v)s, NasFe4(P2O7)s, Nae ceed 25 weight percent of the weight of the catalyst. As
C11(P207)2, Na32Cui4(P207)15, Na4Cui8(P207)s, a rule, it is desirable to use at least 0.01 weight percent
5,225,600
15
16 .
of the weight of the catalyst. Preferably, the amount of oxides to form oxide powders which can thereafter be
performance moderator, when used, will range from blended and compressed with the Group VIB metal
about 0.2 to about 10 weight percent of the weight of containing substance to form pellets and larger struc
the catalyst. Most preferably, the amount of perfor tures of the metal oxide-containing condensation cata
mance moderator, when used, will range from about 0.5 lyst of this invention. The one or more metal oxides
to about 5 weight percent of the weight of the catalyst. which can be used in association with the Group VIB
The amount of performance moderator other than metal-containing condensation catalyst in accordance
the mineral acid type used with the Group VIB metal with this invention can be provided from metal salts
containing condensation catalyst is not narrowly criti
which can be heated to form the metal oxide. It is appre
cal. Generally, the amount does not exceed 90 weight ciated that the performance moderator can be incorpo
percent of the weight of the catalyst. The amount of rated into the molecular bonding configuration of the
performance moderator can range from about 0 to metal oxide-containing condensation catalyst by con
about 90 or greater weight percent of the weight of the
ventional procedures known in the art.
catalyst, preferably from about 0 to about 75 weight
The Group VIB metal-containing condensation cata
percent of the weight of the catalyst, and more perfera 15 lysts in association with one or more metal oxides prior
bly from about 0 to about 50 weight percent of the
to the optional treatment of the performance moderator
weight of the catalyst. Most preferably, the amount of
may be prepared in a wide variety of ways. For exam
performance moderator, when used, will range from
ple, one or more metal oxides may be provided as a
about 0.5 to about 25 weight percent of the weight of
partial condensate on a support, such as a silica or alpha,
the catalyst. 20
beta or gamma alumina, silicon carbide, and the like,
This invention also embraces the use of vicinal di(
and then condensed by heating to effect polymerization
hetero)alkylene organometalates in the preparation of
to the desired oxide form. The metal oxide(s) may be
amines. Suitable vicinal di(hetero)-alkylene or
condensed from hydrolyzable monomers to the desired
ganometalates are disclosed in US. patent application
oxide, indeed, to form an oxide powder which can
Ser. No. 390,828, ?led on an even date herewith and 25
incorporated herein by reference. thereafter be compressed in the presence of a Group
VIB metal-containing substance to form pellets and
The performance moderator can be provided to the
Group VIB metal-containing condensation catalyst by larger structures of the metal oxide-containing conden
sation catalyst of the invention. A blend of the powder
conventional procedures known in the art. For exam
and Group VIB metal-containing substance can be
ple, the performance moderator can be provided to the 30
catalyst by impregnating particles or monolithic struc made into a shapeable paste which can be extruded and
tures comprising the Group VIB metal-containing con cut into pellets according to conventional procedures.
densation catalyst with liquid comprising the perfor The extrudate may thereafter be ?red to cure the Group
mance moderator. This is a well known procedure in VIB metal-containing substance and ?x the structure.
the art for incorporating additives to a solid support 35 The cut extrudate may be blended with a support mate
material. The Group VIB metal-containing condensa rial such as those characterized above, and the blend
tion catalyst of the invention may be utilized as solid fired to fuse the metal oxide-containing catalyst to the
powders or as fused, bonded or compressed solid pel support.
lets, or larger structures in association with the one or In a preferred embodiment of this invention, a high
more metal oxides, or as coated, fused, bonded or com 40 surface area silica or titania can be slurried with an
pressed solid pellets, or larger structures, composited aqueous solution of ammonium metatungstate, ex
with one or more support materials, in association with truded, and calcined at a temperature of about 400° C.
one or more metal oxides. These solid structures may be A preferred catalyst structure comprises one or more
treated with the performance moderator by mixing a oxides of tungsten or tungsten metal in association with
liquid body of the performance moderator with the 45 a Group IVA or IVB metal oxide having a surface area
solid structure. For example, the Group VIB metal-con of at least a 140 mZ/gm which may or may not be
taining condensation catalyst solids may be slurried in bonded to a support material. The term “support,” as
the performance moderator, drained, washed and suc used herein and in the claims, means a solid structure
tioned to remove excess performance moderator, and which does not adversely affect the catalytic properties
then dried with heat to remove any volatiles accompa of the catalyst and is at least as stable as the catalyst to
nying the performance moderator. The drying tempera the reaction medium. The support can function as an
ture chosen will depend on the nature of the volatiles to amine condensation catalyst independent of the Group
be removed. Usually, the time/temperature for effect VIB metal-containing substance, although it may have
ing drying will be below the conditions for effecting lower catalytic activity to the reaction. The support
dehydration to remove bound water from the metal 55 may act in concert with the catalyst to moderate the
oxide in association with the Group VIB metal-contain reaction. Some supports may contribute to the selectiv
ing condensation catalyst. Normally the drying temper ity of the reaction. The catalyst structure can comprise
ature will be greater than about 120° C. and below from about 2 to about 60 percent by weight or greater
about 600° C. depending on the thermal stability of the of the support, more preferably from about 10 to about
catalyst. The drying time will generally go down as the 60 50 percent by weight of the support, the remainder
drying temperature rises and vice versus, and may ex being the weight of the metal oxide(s) and Group VIB
tend from 5 seconds to about 24 hours. metal-containing substance. Included in the weight of
Alternatively, the performance moderator can be the support is the weight of any binding agent such as
provided to the catalyst at the time of preparing the phosphates, sulfates, silicates, fluorides, and the like,
Group VIB metal-containing condensation catalyst in 65 and any other additive provided to stabilize or other
association with one or more metal oxides. For exam wise help in the manufacture of the catalyst. The sup
ple, one or more metal oxides may be condensed from port may be particles as large or larger than the catalyst
their respective hydrolyzable monomers to the desired component and “glued” to the catalytic Group VIB