Note: Descriptions are shown in the official language in which they were submitted.
c~ q~35 ~O-Z- 0050/~2787
Preparatio~ of alkanolamine~ and use of the
reaction product as a motor fuel or lubricant additive
The present invention concerns a process for
preparing alkanolamines from epoxldes a~d the use of the
reaction product as motor fuel and lubricant additive.
The addition of the~e alkanolamines to motor fuels for
internal combu~tion engine~ and lubricant~ keep~ valve~
and carburetors clean.
The carburetor and inlet systems of gasoline
engines but also fuel injection systems in ga~oline and
diesel engines are increasingly subject to contamination
due to dust particle~ from the air, unburnt hydrocarbon
residues from the combustion space and the crankca~e
ventilation gases pas~ed into the carburetor.
The contamination alters the composition of the
fuel-air mixtuxe under idling and under low part-load
operating conditions in ~uch a way that the mixture
~ecomes richer, combustion becomes less complete and
again the proportion of unburnt or incompletely burnt
hydrocarbons in the exhaust gases becomes larger and fuel
consumption increa~es.
It i9 known that, to avoid theqe di~advantages,
fuel additive~ are used for keeping valves and carbure-
tors or injection sy~tem~ clean (cf. for example
M. Rossenbeck in Katalysatoren, Tenside, Mineraloladdi-
tive, ed-~. J. Falbe, U. Hasqerodt, p. ~23, G. Thieme
Verlag, Stuttgart, 1978).
Today there are two generation~ of 3uch detergent
additiveq, di~tingui~hed by their mode of action but al50
by their preferred ~ite of action.
The first generation of detergent additives could
only prevent the formation of deposit~ in the inlet
~y~tem but could not remove deposit~ already pre~ent,
wherea~ second generation additives c~n do both, keep
clean and clean up, owing to their excellent thermal
~tability, including in particular in high temperature
zone~, namely at the inlet valve3.
~r~ 3r3,~
- 2 - O.Z~ 0050/42787
At a molecular level, th~ struc-tural principle on
which rnotor fu~l detergents are bas~d can be generalised
as the ]inking of polar structures to usually relatively
high molecular weight, apolar o~ lipophilic radicals.
Representatives of second generation additives
are frequently products based on polyi~obutenes in the
apolar part of the molecule. Ad~itives of the polyiso-
butylamine type may be mentioned in particular. Polyiso-
butylamines are obtained from polyisobutenes in
essentially two ways. The first process involves a
chlorination of the basic polymeric structure and subse-
quent nucleophilic replacement by amino or preferably
ammonia. The disadvantage of this method is the use of
chlorine and the occurrence of chlorine- or chloride-
containing products, which are certainly no longer wanted
and should be avoided as far as possible (DE-A-21 29 461,
DE-A-22 45 918).
In the ~econd process, a reactive polyisobutene
is first carbonylated in an oxo process and then
reductively aminated in the presence of ~mmonia
(DE-A-36 11 230).
More favorable properties are obtained on using
alkanolamines.
DE 40 30 16~, not published prior to the date of
filing the present invention, discloses polyisobutyl-
aminoalcohols obtained by epoxidation of the correspond-
ing polyisobutenes and subsequent reaction with ammonia
or amlnes. The synthQ~i~ of the epoxide i~ acco~plished
by mean~ of known epoxidating agents (peracetic acid,
m-ohloroperbenzoic acid, hydroperoxides).
Under the conditions of the homo~eneous catalysis
de~cribed therein it is not entirely possible, in the
presence Of ~2~~ to avoid the formation of diols as a
result of hydrolysis of the epoxides. Moreover, the
yields are not as yet fully satisfactory.
The use of chlorine-cont~; n; ng Lewis acids as
homogeneous catalyst as described in DE-A-23 31 290
3r~ ~
- 3 - O.Z. 0050/42787
likewise has appreciable disadvant~ges~ The catalysts
have corrosive properties, their workup must take place
hydrolytically, and the salts formed theref rom have to be
disposed of in an environmentally sound manner. In addi-
tion, chlorinated hydrocarbons are formed a~ by-products.
It is an o~ject of the present invention to ma~e
available an improved process for preparing alkanolamines
in high purity.
We have found, surprisingly, that this object i~
achieved, and that the abovementioned disadvantages are
avoided, by a proces~ for preparing alkanolamines of the
formula I
Rl-- CH-- CH-- H2
R3-- N OH
R
l~ where
R1 and R2 are each independently of the other hydro~en or
an unsub~tituted or aryl-substituted saturated or un-
saturated aliphatic radical of from 25 to 350 carbon
atoms, with the proviso that at least one o~ the two
radicals n' and R2 i9 said alkyl radical and the total
numbex of carbon atoms in the radicals R~ and ~2 i~ from
25 to 350, and
R3 and R~ are each independently of the other hydrogen or
alkyl, hydroxyalkyl, aryl, aralkyl, alkaryl or aminoalkyl
radical~ which may be additionally substituted by further
hydroxyl- or amino-carrying alkyl radi~als, it being
possible for R3 and R4 together to form a heterocyclic
ring, which comprises reacting epoxides of the formula II
Rl - CH - CH - R2 II
o
whe~e R1 and R2 are each as defined above, with NH3 or
~ ~ L. 35 ~3
- 4 - O.ZO 005~/42787
amines of the formula III
R3
\ III
N-- H
R4~
where R3 and R4 are each a~ defined above, in the presence
of solid catalysts.
Preferably, R3 and R4 are each independently of
the other hydrogen, Cl-Cl0-alkyl, C5-C10-aryl, C7-C20-aral-
kyl, Cl-C8 hydroxyalkyl, C7-C20-alkylaryl or an aminoalkyl
radical of the formula IV
~ R5--NR6~ R7 IV
r~
wher~ R5 is C2-C5-alkylene and R6 and R7, which can be
identical or dffferent, are each hydrogen, Cl-C6-alkyl,
Cb-C10-aryl or Cl-ca-hydroxyalkyl~ and m i~ from 1 to 8,
and where R3 and R~ may to~ether form a heterocyclic ring.
By using ~olid (heterogeneous) cat~ly3ts such as
zeolites, SiO2 with a zeolite structure, phosphates
(including pho~phateq with a zeolite structure), phos-
phoric acid and/or boric acid on oxide~ of Al, Si, Ti,
Zx, Nb, oxide~ of the elements Fe, Co, Ni, Si, Al, Ti,
Zr, Nb, V, Mo, W, Cr or mixture~ thereof it i~ po3sible
to prepare the desired alkanolc~nines in an advantageou~
manner.
If the epoxide mixture used ~till contains water
in any proportion, then the use of zeolites and pho3-
phate3 with a ~eolite structure ha~ an additional
advantage. A~ well as acting catalytically they act a~
molecular sieves and can thu~ L~ ve water from the
reaction mixture. The formation of additional diols i8
prevented. In thi~ ca~e the cataly~ts therefore al80 act
as drier~.
In the alkanolamines of the formula I, Rl and R2
are each for example polymer chain~ of ethene/ propene,
isobutene or styrene-butadiene copolymers, depending on
2~ $ ~
- 5 - o.~. 0050/42787
the epoxide II used. The number of carbon atoms in the
radicals Rl ~nd R2 will fn each case vary from 25 to 350,
preferably from 40 to 200, in particular from 50 to 100.
The total number of carbon atoms in the radicals R1 and R2
is within the range from 25 to 350, prefera~ly from 40 to
200, in particular from 50 to 100, since R1 and R2 may
also be hydrogen. R3 and R~ are preferably each, depending
on the amine used or if NH3 was used, hydrogen, alkyl
radicals of from 1 to 10, in particular of from 1 to 6,
carbon atoms (linear, branched, eg. butyl, propyl,
i~obutyl), aryl of from 6 to 10 carbon atom~ (eg.
phenyl), aralkyl of from 7 to 20 carbon atoms ~eg.
benzyl), alkylaryl of ~rom 7 to 20, in particular of from
7 to 13, carbon atoms (eg. toluyl), aminoalkyl of the
above-indicated formula IV (eg. diethylenetriamine
radical, triethylenetetraamineethylene radical, poly-
ethylene:imine radical), hydroxyalkyl of from 1 to 8
carbon atoms (eg. ethanol radical, ethanolamine radical,
diethanolamine radical, aminoel;hylethanol~mine radical)
or cyclic ~mine derivatives (eg. morpholine radical).
The solid catalysts u3ed for the process of the
invention are for example zeolites, in particular acidic
zeolitic cataly3ts. Zeolite~ are~crystalline aluminosili-
cates which po~e~ a highly ordered ~tructure comprising
a rigid three~ n~ional network of SiO4 and ~lO~ tetra-
hedra joined together ~y common oxygen atoms. The ratio
of the Si and A1 atoms to oxygen i8 1: 2 (~ee Ull ~nn~
Encyclopadie d. t~chn. ~hemie, 4th edition, Volume 24,
page 575, 1983) a The electrovalence of the aluminum-
cont~;n;ng tetrahedra is balanced by the inclu~ion in the
crystal of cations, for example an alkali metal or
hydro~en ion. Cation exchanqe i9 po~ible. The spaces
between the tetrah~dra are occupied by water molecules
prior to dehydration by drying or calcination
Instead of aluminum ~he zeolite lattice may also
contain other elements such a~ B, Ga, Fe, Cr, Ti, V, As,
Sb, Bi or Be or mixture~ thereof, or the ~ilicon may be
2~ $~r3~
- 6 - O.Z. 0050/42787
repl~ced by a tetravalent element such a~ Ge~ Ti, Zr or
Hf .
According to their structure, zeolites are
divided into different groups (see Ullmanns Encyclopadie
S d. tech. Chemie, 4th edition, Volume 24, page 575,
1983). For instance, in the mordenite group the zeolite
structure is made up of chains and in the chabasite group
it is made up of layers of te-trahedra, whereas in the
faujasite group the tetrahedra are arranged in the form
of polyhedra, for example in the form o~ a cubooctahedron
composed of 4- or 6-membered rings. Depending on the
manner of linking of the cubooctahedron, which results in
voids and pores of different sizes, zeolites are classi-
fied as type A, L, X or Y.
Catalysts suitable for the process of the inven-
tion are zeolites of the mordenite group or narrow-pored
zeolites of the erionite or chabasite type or zeolite of
the faujasite type, eg. X-, Y- or L-zeolite3, and also
Beta zeolite. This group of zeolite~ also includes the
so-called "ultrastable" zeolitles of the faujasite type,
ie. dealuminated zeolites. Processes for preparing such
zeolites are desc~lbed for example in US Patent
4,512,961.
Of particular advantage are zeoliteQ of the
pentasil type (MFI structu3-e; G.T~ Kokotailo and
W.M. Meier, Spec. Publ. Chem. Soc. 33 (1980), 133). Their
common feature i~ the basic building block comprising a
five-membered ring composed of SiO~ tetrahedra. They ar~
characterized by a high SiO2/Al2O3 ratio and al~o by a
pcre size between that of the zeolites of type A and
those of type X or Y (cf. Ull ~nn~ Encyclopadie d. techn.
Chem., loc. cit.).
These 2eolites can have different chemical
compositions. The zeolites in question are aluminum
~ilicate, boron silicate, iron silica~e, beryllium
silicate, gallium silicate/ chromium silicate, arsenic
silicate, antimony silicate and bismuth silicate zeolites
s~
_ 7 . o.z. Q050/42787
or mixtures thereof and also aluminum germanate, boron
germanate, gallium germanate and iron germanate ~eolites
or mixtures thereof or titanium silicate zeolite~ such as
TS-l, ETS 4 and ETS 10.
Of particular suitability for the proce~s of the
invention are the aluminum silicate, boron silicate,
gallium ~ilicate and iron qilicate zeolites of the
pentasil type~
The aluminum silicate zeolike i9 prepared for
example from an aluminum compound, preferably Al(0~)3 or
Al~(S04)3, and a silicon component, preferably finely
divided silicon dioxide, in an aqueous amine ~olution, in
particular in polyamines such as 1,6-hexanediamine or
1,3-propanediamine or t~iethylen~tetraamine solution,
lS with or i.n particular without the addition of an alkali
or alkaline e~rth metal at from 100 to 220~C under
autogenous preqsure. Thi3 includes the iqotactic zeoliteq
of EP 34 727 and EP 46 504. The aluminoqilicate zeolites
! obtained have an SiO2/Al203 rat:io of from 10 to 40,000
d~pending on the choice of starting m~terials. Such
aluminosilicate zeolites can al.so be ~ynthesized in an
ethereal medium such as diethyleme glycol dimethyl ether,
in an alcoholic medium such as methanol or 1,4-butanediol
or in water.
The boro~ilicate zeolite i9 synthesized for
example at from 90 to 200~C under autogenous preqsure by
r~acting a bo~on compound, eg. H3B03, with a silicon
compound, preferably finely divided silicon dîoxide, in
an aqueouR amine solution, in particular in 1~6-hexane-
~i~mine or 1,3-propane~;~ ;ne or triethylenetetraamine
~olution, with and in particular without the addition of
an alkall or alkaline earth metal. Thi~ al30 includes the
isotactic zeoliteR of EP 34 727 and EP 46 5040 Such
borosilicate zeolite~ can likewi~e he prepared by carry-
ing out the reaction not in aqueou~ amine sollltion but in
an ethereal solution, for example in diethylene glycol
dimethyl ether, or in an alcoholic ~olution, for example
2~
- 8 ~ O.Z. 0050/~2~87
in 1,6-hexanediol.
The gallium ~ilicate zeolite of the penta8il type
is synthesized for example at from 90 to 200~C under
autogenous p~-essure hy reactinq a gallium compound for
ex~mple an alkali metal gallate, preferably sodium
gallate, or a gallium oxide or gallium halide or othér
suitable gallium ~alts, with the silicon compound, for
example alkali metal silicates, silica s015, silicic
esters or preferably finely divided silicon dioxide, in
an aqueous amine solution, for example primary, secondary
or tertiary amines or quaternary alkylammonium compounds,
in which case one or more amine functions can ~e pre~ent
in the molecule, ~or example in 1,6-diaminohexane 301u-
tion or in particular tetrapropylammonium hydroxide
solution, with or without the addition of an alkali or
alkaline earth metal. The preparation of zeolites in the
presence of the~e amine~ i~ described for example in
US-A-3 702 886 and DE-B-30 06 471.
~I The iron ~ilicate zeolite is obtained for example
~' 20 from an iron compound, preferab:ly Fe2( S04 ) 3, and a ~ilicon
compound, preferably finely divided silicon oxide, in an
aqueous amine ~olution, in particular 1,6-hexanediamine,
with or without the addition of an alkali or alkaline
earth metal at from 100 to 220~C under autogenous
pres~ure.
The usable high-~ilicon 2eolites ( SiO2/A1203 2 10 )
al~o include the so-called ~SM type~, zeolite Beta,
ferrierite, ~U-1, NU-l and sio~ with a zeolite tructure
(~ilicalite, a molecular ~ieve, a ~o called ~ilica
polymorph), ie. 5iO2 pha~e~ with a pentasil structure
whose parameter~ and a process for the preparation
thereof are de~cribe~ for example in US 4 061 724 and
al~o in EP-A-64 37~, EP-A~93 476 and EP-A-123 060.
The process of the invention can also be carried
out with so-called ultrastable zeolite~, for example of
the faujasite type or mordenite typeJ ie. dealuminated
Y-zeolite.~ or dealuminated mordenitel the preparation
~ r? ~ ~ r-
- - g - o.z.~5d~ 7
thereof is described for example in US-A-4 S12 961 and
also in H.~. Beyer and s. selenykajy~ Stud. Surf. sc.
Catal. 5 (lg80) 203-209 and also in I.M. Newsam, science,
~31 (1986), 1094.
SIt is similarly po~sible to use titanium sili-
cates with a pentasil ~tructure, for example TS-1,
described for example by B. Kraushaar and
I.H.C. von Haaff in Catalysis Letters 1 (1988), 81-89.
Similarly, the ETS molecular sieves such as ETS-4 and
10ETS-10 (US-A-4 853 202) can be used.
The preparation of the zeolite BETA i~ effected
according to US 4 391 4sa, ~pecifically according to
Examples 1 and 2 thereof.
The resulting aluminum silicate, gallium sili-
15cate, boron silicate, titanium silicate and iron silicate
zeolites or silicalites, after they have been isolated,
dried at f~om 100 to 160~C, preferably at 110~C, and
calcined at from 450 to 550~C, preferably at 500~C, can
be molded with a binder in a ratio of from 90:10 to
2040:60% by weight into extrudates or tablet~. Suitable
binders are various aluminum oxides, preferably ~oehmite,
amorphous aluminum silicate~ having an SiO2/Al203 ratio of
from 25:75 to 95:5, preferably 75:25, silicon dioxide,
preferably finely divided Al2O3, Tio2, ZrO2 and also clay.
25After molding, the extrudates or pellets are dried at
110~C over 16 h and calcined at 500~C for 16 h.
Advantageous cataly~t~ are also obtained on
molding the isolated zeolite~ such as the aluminum
silicate zeolite and the boron silicate zeolite directly
30after drying and not subjecting it to a calcination until
after molding. For instance, the a~-prepared aluminosili-
cata and borosilicate zeolites can al~o be u~ed in the
pure form, without binder, a~ extrudate~ or tablet~ t in
which case the extru~ion or peptization aids used being
35for example ethylcellulo~e, ~tearic acid, potato starch,
fo~mic acid, oxalic acid, acetic acid, nitric acid,
ammonia, amines, silicoe~ter~ and graphite or mixtures
2~ J~
- lO - O.Z. 0050/42787
thereof.
If the zeolite, on account of it~ manner of
preparation, is present not in the acidic H-form but, for
example in the Na-form, it can be completely or partially
S converted into the desired H-form by ion exchange, for
example with ammonium ion~, and sub-~equent calcination,
or by treatment with acids.
Should the zeolitic catalyst used according to
the invention undergo deactivation due to coking, it is
advisable to regenerate the zeolite by burning off the
coke deposi-t with air or with an air-N2 mixture at from
400 to 550~C, preferably at 500~C. Thi~ re~tores the
initial activity level of the zeolite.
By partial precoking it is possible to optimize
the selectivity of the catalyst in respect of the desired
reaction product.
To obtain the higheRt possible selectivity, a
high conversion and al~o long times on stream, it is
q advantageous to modify the zeolites. A ~uitable method o~
modifying the catalys-ts comprises for example doping the
molded or unmolded zeolite with metal salts by ion
exchange or impregnation. The metal~ u~ed are alkali
metals such as Li, C~ or K, alkaline earth metals such as
Mg, Ca or Sr, metals o~ main groups 3, 4 and 5 such as
Al, Ga, Ge, Sn~ Pb or Bi, trans:ition metals of ~ubgroup~
1 ~ 8 comprising Ti, Zr, V, Nb, Cr, Mo, W, Mn, Re, Fe,
Ru, O~, Co, Rh, Sx, Ni, Pd and Pt, or transition metals
Ruch as La, Ce, Pr, Nd, Fr, Yb and U.
Advantageously, the doping i-~ carried out by
introducing for example the molded zeolite into a riser
pipe and pa~sLng an aqueou~ or ammoniacal solution of a
halide or nitrate of one of the ab~v~ -ntioned metal~
through it at from 20 to 100~C. Such an ion exchange can
take place for example with the hydrogen r an~onium or
alkali metal form of the zeolite. Another way of applying
metal to the zeolite compri~e~ impregnating the zeolitic
material with, for example, a halide, nitrate or oxide of
r~
~ ll - O.Z. 0050/42787
one of the abovementioned metals in aqueou~, alcoholic or
ammoniacal solution. sOth ion exchange and impregnation
~re followed by ~ least a drying operation, alterna-
tively by another calcination.
A possible embodiment compri~es for example
clissolvinq Cu(NO3)2 x 3 ~2~ or Ni(NO3)z x 6 H2O or Ce(NO3)3
x 6 H2O or La(NO3)2 x 6 ~2~ or Cs2CO3 in water and impreg-
nating the molded or unmolded zeolite with the solution
for a certain period, for example 30 minute~. Any super-
natant solution is stripped of water in a rotary evapora-
tor. The impregnated zeolite is then dried at about 150~C
and calcined at about 550~C. This impregna-ting ~tep can
be carried out several times in succession until the
desired metal content is obtained.
It is also possible to prepare, for ~xample, an
aqueous Ni(NO3)2 solution or an ammoniacal Pd(NO3)2 solu-
tion and to suspend the pure ~ulverulent zeolite therein
at from 40 to 100~C by ~tirring for about 24 hours. After
filtration, drying at about 150~C and calcination at
about 500~C, the zeolitic material thus obtained can be
further processed with or withlout binders into extru-
dates, pellet~ or fluidizable material.
An ion exchange on the zeolite pre~ent in the
H-form or ammonium form or allcali metal form can be
carxied out by introducin~ the zeolite in extruded or
pellet fonm into a column and for example pa~ing an
aqueous Ni(NO3)2 ~olution or an ammoniacal Pd(NO3)2 ~olu-
tion through it at from 30 to 80~C in a recycle loop for
from 15 to 20 hour~. This i~ followed by washing out with
water, drying at about 150~C and calcination at about
550~C. With some metal-doped zeolite~, for example Pd-,
Cu- or Ni-doped zeolite~ an aftertreatment with hydrogen
i8 advantageou~.
A further method of modifying the zeolite com-
prise~ treating the zeolitic material, which may be in
molded or unmolded form, with an acid ~uch a~ hydro
chloric acid, hydrofluoric acid or phosphoric acid and/or
s~ 3r~
- 12 - O.Z. 0050t42787
steam, advantageously, for example, by treating the
zeolite in pulverulent form with 1 N phosphoric acid at
80~C for l hour and then washing with water, drying at
110~C for 16 hours and ~alcining at 500~C for 20 hours.
S Alternatively, before or a~ter being molded together with
the binder, the zeolite is treated for examplP at from 60
to 80~C with from 3 to 25% by weigh-t, in particular from
12 to 20% by weight, aqueous hydro~hloric acid for from
1 to 3 hours. A~terwards, the zeolite thus treated is
washed with water, dried and calcined at ~rom 400~C to
500~C.
In a special embodiment, the acid treatment
comprises treating the zeolitic material, before it is
molded, with hydrofluoric acid, generally in the fo~m of
from 0.001 N to 2 N, preferably from 0.05 N to 0.5 N,
hydrofluoric acid, at elevated temperatures, for example
by heating under re~lux for, in general, from 0.5 to 5,
preferably from 1 to 3, hours. After the zeolitic mater-
ial has ~een isolated, for example by filtering and
washing, it is advantageously dried, for example at from
100 to 160~C, and calcined, in general at from 450~C to
600~C. In a further preferred form of the acid treatment,
the zeolitic material, a~ter it has been molded tog~ther
with a binder, i8 treated at elevated temperatures,
advantageously at from 50 to ~O'IC, preferably at from 60
to 80~C, for from O.S to 5 hours with, preferably, from
12 to 20~ by weight of hydrochloric acid. The zeolitic
material is, in general, sub~equently washed, expediently
dri.ed at from 100 to 160~C and calcined at, in general,
from 450 to 600~C. An ~F treatment may also be followed
by an ~Cl treatment.
Alternatively zeolites can be modified by appli-
cation of pho~phoru~ compounds, such a~ trimethyl phos-
phate, trimethylphosphine or primary, secondary or
tertiary sodium phosphate. Of particular advantage is the
treatment with primary sodium phosphate. It comprises
impregnating the zeolite~ in extrudate, tablet or
- 13 - O.Z. 0050/~2787
fluidizable form with an aqueous NaH2P04 solution, drying
at 110~C and calcining ~t 500~C.
Further catalysts for the process of the inven-
tion are phosphates, in particul~r aluminum phosphate,
S silicon ~luminum phosphates, cerium phosphate, zirconium
phospha-tes, boron phosphate, iron phosphate or mixtures
thereof.
The ~luminum phosphate and silicon aluminum
phosphate catalysts used for the process of the invention
are in particular hydrothermally ~ynthesized substituted
and unsubstituted aluminum phosphates and silicon
alumin~lm phosphates.
The aluminum phosphate catalysts, structurally
related to the zeolites, are synthesized for the process
of the invention in particular un~er hydrothermal condi-
tions. They are silicon aluminum phosphates (SAPOs) or
aluminum phosphates (AlP04). The~e crystalline solids have
defined void and pore ~tructures and are structurally
related to the zeolites.
The preparation, properties and classification of
these solids on the basis of structure and chemical
composition are described in cletail in Pure and App.
Chem. 58 (1986), 1317-22, 1351-58.
The cry~tal structure~ known to date and the
numerous elemental modification~ now make up some 700
different combinations. The aluminopho~phate9 are desig-
nated by the ~ollowing acronyms: AlP04, SAP0, MeAP0,
MeAPS0, ElAP0 or ElAPS0. Here A or Al i8 ~luminum, S is
silicon, P is phosphorus and 0 i9 oxygen. Me is a metal
from Fe, Mg, Mn, Co and Zn and E1 denotes elements ~uch
as Be, Ga, Ge, Ti, As, B or Li. A hyphenated num~rical
~uffix denotes the cry~tal ~tructure of the phase in
que~tio~.
The hydrothermally synthesized alumlnum phos-
phates are for example AlP0-5, AlP0-9, AlP0-11, AlP0 12,
AlP0-14, AlP0-21, AlP0-25, AlP0-31, AlP0-33, AlP0-34,
AlP0-37 and AlP0-54. Syntheses of these compounds are
Z ~ $ 'L . ~
- 14 - O.Z. 0050/~2787
de~cribed in EP 132 709, US 4 310 440 and US 4 473 663.
For instance, AlPO~-S (APO-5) is synthesized by
homogeneously mixing orthophosphoric acid with pseudo-
boehmite (Catapal ss~) in wat~r, adding tetrapropyl-
ammonium hydroxide and reactinq at about 150~C under
autogenous pressure in an autoclave for from 20 to 60 h.
The AlPO4 i~ filtered off, dried at from 100 to 160~C and
calcined at from 450 to 550~C.
AlPO4-9 (APO-9) is likewise synthesized from
1 n orthophosphoric acid and pseudoboehmite, but in aqueou~
DABCO solution (1,4-diazabicyclo[2.2.2]octane) at about
200~C under autogenous pressure for from 200 to ~00 h.
The synthesis of AlPO4~21 (AP0-21) take~ place
from orthophosphoric acid and pseudoboehmite in aqueous
pyrrolidone solution at from 150 to 200~C under autogen-
ous pres~ure for from 50 to 200 h.
Synthese3 for MeAPOs are described in
US-A-4 544 143, EP-A-132 70~ and US-A-4 567 029 and for
ElAPO in US-A-4 500 651 and EP-A-2 158 976.
Preference for the proces~ of the invention is
given in particular to the silicon-containing alumino-
phosphateR (SAPO, MeAPSO or E~lAPSO) such a~ SAPO-ll,
SAP0-5, SAP0-20, SAPO-34, SAPO-37, SAPO-41 or SAPO-46~
Synthe~es of silicon aluminopho~phates are described
inter alia for SAPO in US-A 4 440 871 and EP-A-103 117,
for MeAPSO in ~P-A-158 348, EP-A-158 975 and
EP-A-161 491, and for ElAPSO in EP-A-159 624.
SAP08 are prepared by cry~tallization from
aqueous mixture at from 100 to 250~C under autogenous
pressure in the course of from 2 h to 2 weeks, the
reaction mixture comprising a silicon, an aluminum and a
pho~phoru~ component being reacted in aqueous organoamine
solution~ .
Suitable silicon aluminum phosphates are for
example ZYT-5, ZYT-6, ZYT-7, ZYT-9, ZYT-11 and ZYT-12
(J 5 9217-619).
SAP0-5 i~ o~tained for example by mixing SiO
- 15 - O. ~ . OQSO/42787
suspended in aqueou~ tetrapropylammonium hydroxide
solution with an aqueous ~u~pension of pseudohoe~mite and
orthophosphoric acid and subsequent reaction at from 150
! to 200~C for from 20 to 200 h under autogenous pressure
- 5 in a stirred autoclave. The powder i8 filtered off, dried
at from 110 to 160~C and calcined at from 450 to 550~C.
As phosphate cataly~ts it is also pos~ible to use
in the process precipitated al~minum phosphate~. Such an
aluminum phosphate i~ prepared for exampls by dissolving
92 g of diammonium hydrogenphosphate in 700 ml of water.
To this solution are added 260 g of Al(NO3)3 x H20 in
700 mi of water dropwise over 2 h. At the same time the
pH is maintained at 8 by the simultaneous addition of 25%
streng-th NH3 solution. The resulting precipitate is
subsequently stirred for 12 h, and then filtered o~f with
suction and washed. It is dried at 60~C for 16 h.
~oron pho~phates for the proce~s of the invention
can be prepared ~or example by mixing and kneading
concentrated boric acid and phosphoric acid and subse-
; 20 quent drying and calcination of the mixture in an inert
gas, air or steam atmosphere at from 250 to 650~C,
preferably at from 300 to 500~C.
CePO4 is obtained by precipitation of 5Z g of
Ce~NO3)3 x 6 H20 and 56 g o~ NaH2]?0~ x 6 ~2~- After filtra-
tion, the material i3 extruded, dried at 120~C and
calcined at 450~C. The catalyst contains 47.1% by weight
of Ce and 12.7~ by weight of P.
Suitable zirconium phosphates are commercially
available zirconium pho~phates, for example CSZ 100,
zirconium phosphate ~ilicates and zirconium phosphates
which will adsorb or have ad~orbed N~3.
Phosphoric a~id is applied for example to SiO2,
AlqO3r Tio2, ZrO2, Nb205 or pumice carrier~ by Lmpregnating
or spraying. A phosphoric acid-contA;ning catalyst can be
obtain~d for example by impregnating SiOz with ~3PO4 or
NaH2~PO4 or NazHPO4 solution and ~ubsequent drying or
calcination. However, phosphoric acid can also be sprayed
2.~ ..$ ~.'3
- 16 - O.z. 0050/427~7
tog~ther with silica gel in-to a prill tower, followed by
drying ~nd usually a calcination~ Pho~phoric acid c~n
also be sprayed onto the carrier material in an imprey-
nating mill.
Suitable untreated catalysts also include for
example metal oxides, in particular acidic oxide~ of the
elements Ti, Zr, Si, Al, Fe, Co, Ni, V, W, Mo, Nb and Cr.
They are titanium dioxide, zirconium dioxide, vanadium
oxides, niobium oxide~, chromium oxide~, molybdenum
oxides, tungsten oxides, etc. or mixtures thereof. Using
these catalysts the process of the invention will like-
wise give the desired products.
The catalysts described herein are alternatively
usable in the form of from 2 to 4 mm extrudates or as
tablets from 3 to 5 mm in diameter or as chips having
particle sizes of from 0.1 to 0.5 mm, or in a fluidizable
form. As solid catalysts they have the additional advan-
tage of being simple to separate from the reaction
mixture Eor reu3e.
The preferred polyisobutenes used have a mole-
cular weight of about 400 - 5000, preferably of from 800
to lS00. They are obtained in a conventional manner by
cationic polymer.ization of isobutene.
The epoxide~ II are prepared by mean~ of known
epoxidating agents (see DE 40 30 164~.
The reaction temperatures for the process of the
invention are in general from ~0~C to 600~C, preferably
from 50 to 500~C, in particular from 100 to 350~C.
The reaction timas can range from 30 min to
100 hourq~
It is preferred to car~y out the reaction in the
li~uid pha~e~ in particular by the suspension, downward-
flow or upward-flow proceduxe, at from 50 to 300~C,
preferably at from 100 to ~50~C, under a weight hourly
space velocity (W~SV) of from 100 h-~ to 0.5 h-1, prefer-
ably of from 60 h-' to 10 h-1.
Usable sol~ents are in general inert solvents,
- 17 - O. Z . 0050/427~3~
for example cyclohexane, toluene or petroleum e-ther. The
reaction autoclave i~ made for example of noncorrodable
stainless steel. The amount of catalyst used is in
general from 0.01 to 20% by weiqht, based on the epoxide
used.
Th~ proces~ i~ in general carried out at atmos-
pheric pressure or under superatmospheric pressure, ie.
at from 1 to 800 bar, preferably at from 50 to 500 bar,
in particular at from 150 to 350 bar. It can be carried
out sontinuously or batchwise.
Sparingly volatile or ~olid starting material~
are u~ed in dissolved form, for example in THF, toluene,
cyclohexane or petroleum ether solutionO Generally,
dilution of the starting mixture with such ~olvents or
with an inert gas such as N2 or Ar is possible.
The invention will now be more particularly
described by way of example~
Preparation of alkanolamines
~XAMPLES 1 TO 2 5
The reaction~ were carried out in the liquid
phase in an HC autoclave (300 ml) under isothermal
conditions. In detail the procedure adopted was a~
follows. 1 part by volume (50 g~ of polyisobutene epoxide
(molecular weight about 1000) was di~solved in 50 ml of
cyclohexane at room temperature and 1 g of solid ca-talyst
(see Table I) waB added; then the amount of NH3 shown in
Table I was injected and the reaction mixture was raised
to the temperature shown in Table I under autogenous
condition~. The autogenou~ pressure~ and al~o the reac-
tion times and yields of al~anolamines (GlA~I are also
shown in Table I. The reaction products were charac-
terized by dete ; n; ~q the usual numbers (hydrogenation
iodine number in accordance with DIN 53 241 Part 2 or
Ind. Chim. Belge 32 l1967), 134; amine number in accor-
dance with DIN 16 945 or DAB9 (see also ASTM D 2073-66);
epoxides in accordance with DIN 16 945 or DAB9, cf~ also
Hofmann and Stark: The Determination of ~poxide ~roups,
~' ~ ~L ~3r3~3
- 18 - O.Z. 0050/427~7
Per~c~non Press, Oxford, London, 1969; hydroxyl number in
accordanc~ with DIN 16 945 or DAB9, see also DIN 53 240
or AST~I D 2849-69).
TA~3LE I
S
Examples 1-25
Run Cat. Ratio Temp. Pres- Time Yield
No. epoxide/ [~t'] ~ure ~h~ [%]
NH3 [bar~ Gl~A based
on epoxide
1 A 1/4 150 137 60 46
2 A 1~4 200 300 60 76
3 A 1/4 250 402 60 62
4 s 1/2 50 20 20 31
s 1/2 100 56 20 31
6 s 1/2 150 110 20 35
7 s 1/2 200 155 20 52
8 C 1/2 100 56 20 31
9 C 1/2 150 110 20 45
C 1~2 200 155 20 53
11 D 1/2 50 14 21 17
12 D 1/4 200 270 21 47
13 ~ 1/2 50 15 20 21
14 E 1/4 200 2-l0 60 59
F 1/2 50 lt) 20 25
16 F 1/4 200 290 60 59
17 G 1/2 50 17 20 19
18 G 1/4 200 270 21 73
19 ~ 1/6 200 5~14 60 59
I 1/2 50 20 20 38
21 I 1/2 100 56 20 41
22 I 1/2 150 110 20 41
23 I 1/2 200 155 20 50
24 J 1/4 ~00 238 80 57
X 1/6 190 680 60 50
- O. z . ooso/a~27~7
EXAMPLES 2 6 - 2 8
The reactions were carrfed out in the liquid
pha~e under iF~othermal conditions in a stirred kettle
( 250 ml ) as describ~d in Example~ 1-25 . The reaction
5 products were ch~r~cteri2ed by determining the number~
m~ntioned. The starting material~ are polyisobutene
epoxide (molecular weight about 1000) and morpholine,
which are reacted to give the corresponding alcohol amine
(GlAAm) (see Table II).
TABLE II
Run Cat. Ratio T~mp. Pres- Time Yield
No. epoxideJ [~CJ sure [ h~ [%]
morpholine [barJ GlAAm*
26 A 1/4 102 1 10 14.4
27 A 1/4 102 1 60 57.2
28 A 1/4 102 1 72 71.5
* ba~ed on epoxide used
The catalysts used in the Examples were prepared
as follows:
Catalvst A
An alum:inosilicate zeolite of the pe.ntasil type
was prepared from 65 g o~ finely divided SiOz and 203 9
of Al2(SO~)3 x 18 ~2~ in 10 kg of an aqueou~ 1,6-hexane-
diamine solution (mixture 50:51J% by weight) in a stirred
autoclave under hydrothermal condition3 at 150~C and
autogenou~ pressure. After the crystalline reaction
pro~uct had been filtered off and washed, it wa~ dried at
110~C for 24 h and calcined at 500~C for 24 h. Thi~
aluminosilicate zeolite contained 92.8~ by weight of SiO2
and 4O2% by weight of Al2O3. This material i~ molded with
a molding aid into 2-mm extrudat~s, which are dried at
110~C fox 16 h and calcined at 500~C for 24 h.
Catalyst B
Catalyst ~ was prepared by molding a commercial
Na-Y ~eolite into 2-mm extrudates which were dried at
- ~0 - O.Z. 0050/~787
110~C for 16 h and calcined at 500~C for 16 h.
The extrudates were ion exchanged at 80~C with
20% stren~th NH4Cl solution (mass ratio 1:15). This was
followed by wa hing until chloride-free, drying at 110~C
and a 5 h calcination at 500~C. The Na content was 0.07~O.
Catalyst C
Catalyst C wa~ prepared by molding a commercial
Na-Y zeolite in powder form with pyrogenic silica (weight
ratio 80:20~ into 2-mm extrudate~, which were driPd at
110~C for 16 h and calcined at 500~C for 16 h.
The extrudates were ion exchanged at 80~C with
20% strength NH4Cl solution (mass ratio 1:15). This wa~
followed by washing until chloride-free, drying at 110~C
and a 5 h calcination at 500~C. The Na content was 0.07%.
Catalyst D
Catalyct D wa~ prepared by molding pseudoboehmite
with 2% ~f HCOO~ into 2-mm extrudate~, which were dried
at 110~C for 16 h and calcined at 500~C for 16 h.
Catal~st E
Commercial Tio2 (from Degussa)
Catalyst F
Commercial ZrO2 ~from Mel)
Catalvst G
~-A12O3 (BASF catalyst K 10)
Catal~st H
Cataly~t H was obtained by treating the extrud-
ates of ca-talyst A with 0.1 N ~F for 1 h, filtering,
wa~hing neutral, drying at 130~C' for 2 h and calcining at
540~C for 2 h~
Cakalyst I
Catalyst I wa~ prepared by molding catalyst A
with pyrogenic silica ~weight ratio 80:20) into 2-mm
extrudates which were dried at 110~C for 16 h and
calcined at 500~C ~or 16 h.
The extrudates were ion exchanged at 80~C with
20% strength NH4Cl ~olution (mass ratio 1:15~. This was
~ollowed hy washing until chloride-free, drying at 110~C
2~ 3~3
i
- 21 ~ O. ~ . 0050/~2787
and a 5 h c~lcination at 500~C.
Cataly~-t J
Commercial ZSM-5 zeolite (CBM 3020, from
Cont:eka ) .
Catalyst K
Cataly3t K wa~ prepared by moldin~ catalyst ~
with pyrogenic silica into 2-mm extrudates which were
dried at 110~C for 16 h and calcined at 500~C for 16 h.
The extrudates were ion exchanged at 80~C with
20% strength NH4Cl ~olution (ma~ ratio 1~ his was
followed ~y washing until chloride-free, drying at 110~C
and a 5 h calcinaticn at 500~C.
Appllcation testinq
The respective additive was added to the motor
. uel in a proportion of 800 ppm. The test was carried out
on two valve~ at a time of an Opel Kadett engine in
accordance with the CEC-F-02-T~79 standard. The additive
quality was as3e~sed by weighing the valve tappets. The
weight increase corre~pond6 to the amount of coke deposi-
B 20 ted at the valve inlet. The re~ultq are ~hown in Table
III.
TABLE III
Weight increase (mg)
Valve l Valve 2
Untreated fuel 440 564
Additive of run 3 86 15
Additive of run 1 35 15
Additive of run 18 13 35
