Note: Descriptions are shown in the official language in which they were submitted.
~ 0050/45700
~185~85
Crystalline ~ hates, their preparation and use
The invention relates to crystalline borophosphates of monovalent
5 and~or polyvalent cations, their preparation and use, for example
as ion Y~h~n7~rs and sorbents, as cer~mic materials ~or the
medical sector, preferably as catalysts.
There are snany known cry~talline inorganic solids oomprising
10 ol;j ~ or polymeric a~ion s~Lu~iLuLes built up of
corner-linked oxyger~ tetrahedra having metal or nonmetal atoms in
the center. These include, ~or example, the zeolites and aluminum
phosphate6 which are of considerable industrial; _ ~dn~.e as
catalysts, as ion ~yfh~n~ers and l~ r sieves. Exr3mple~ of
15 references which may be cited from the very _ _ scll~..sive
literature on this subject are: A. ~ 3ler, U. ~luller and
. R. Unger, "Synthetische Zeolithe und Al no~hosp~ste", Nachr.
Chem. Techn. Lab. 36, (1988) llo. 6, pp. 624--630.
20 For many industrial applications o~ these solids, the
three-~ ion?l periodic :iLL.I.~ u.e implied by the description
~crystalline" is of; _ L~ .e. For the purposes of the present
document, "crystalline~ is defined by the solids giving, on
irradiation with X--rays, an X-ray diffraction pattern having
25 discrete diffraction maxima.
Cry6talline ~;L~,~hov~hates compri~ing ol i; c or polymeric
boron--and phosphorus-containing anion aLL~ UL~3 are little
r; he~l in the prior art and their industrial use is not
30 described at all. The preparation of crystalline phases of the
composition 2 ~0.P205.B20~, where M is one of the alkaline earth
metals calcium, strontium or barium, by a hiyh ' _ ~LLuL~s
synthesis ha~ been puhl; ~d by 11. Bauer ~ Z . anorg. allg . Chem
34S,(1966), pp. 225--229, Z. anorg. allg. Chem. 337, (1965),
35 pp. 183--190 ) . Alternative k,Le~.~L~tive methods and the industrial
use of crystalline LaLv~ ates have not been known hitherto.
In a h~ al study of the ternary system Cao-B2o3-p2os~
P. ~ Lhy and T.J. Roc~cett (J. Am. Ceram. Soc. 57, (1974),
40 pp. S01--502 ) were able to obs~3rve only the ab.,~ ~ioned
2CaO.P20s.B203 as ~ole ternary phase at 900-C. J. ~iebertz ~nd
s. Stahr (Z. ~rist. 1~1, (1982), 135--137) ~I t.Lated the
existence of Zn3BP07 and ~g3BP07 and determined the lattice
constant~ o~ the~e solids.
0050~45700
~ 2185583
Amer. Mineral. 76, (1991), pp. 1400--1407 ~i~c7~s~s the ~tlW_~ULe
o~ the nineral lQneburgite whose composition can be 1 At~d in
terms of oxides a-
~
s 3HgO. 8203 P20s. 9EI20.
~he article cites a f urther mineral, seamanite, having the oxide
~ormula
6MnO. B2O3.P2Os 6H2O.
It i~ an cbject of the present invention to provide novelcry~tall}ne b~ ,yl~G;,~hates and to indicate alternative
~Lt~ r<~ive methods and also industrial ~ields of application.
Ne have found that this object is achieved by, in a first
_'i L, crystalline bol~r~n.~ t~e and a process for
preparing crystalline borophosphates of monovalent and/or
polyvalent cations of the general for~ula ( I )
X ~2/n y (B,Al)2OI P20s m E12 t~)
where
25 n is 1, 2 or 3 and C~IL ~=s~v.lds to the valence o~ the metal M,
y is from 0.1 to 50,
m i~ a number in the range from 0 to (2 + y),
x is selected such that ~-x ia in the range fro~ 0.1 to
6.(1 + y),
(13,Al) is boron and possibly ~ , with the proviso that the
molar boron content exceeds the molar aluminum content, and
M is one or nore cations of ~--valent metal3 or ammonium ions,
- which _ c~.c dissolving or V~p~n~ir~ a source o~ the metal or
40, i cations M, of borate ions, phosphate ions and, if
desired, of aluminum ions in a polar solvent and heating the
~olution or ~l-Qr na; ~ n in a pressure reactor under the duLoy~
pressure to a temperature between 100 C and the critical
t CI~ULe of the solvent, i~ de~ired holding this ~ 1 ULe
45 for a period of from one minute to 24 hours, cooling the mixture
again to a ~ ULe between the freezing point and the boiling
point o~ the solvent and isolating the solid ~rom the solvent.
oo50/45700 21~ 5
Examples of ~uitable polnr solvent1s are lower -hydLiC or
polyhydric alcohols such as methanol, ethanol, propanol, ethylene
glycol and the like, plus, in particular, water.
5 Metal cations M which can be used are ammonium ionC and also any
monovaleQ~, div~lent or trivalent caticn:j. Examples of monovalent
cations are the alkali metal cations and, in particular, sodium
and pota~sium ions. Furthermore, the monovalent ions o~ copper,
silver and gold are usef ul . Divalent cations which are pref erably
10 used are selected from the group consisting of zinc and alkaline
earth metal cations. ~iYalent transition met~l cations such as
the divalent cations of --n~ , iron, cobalt, nickel and the
platinum metal group can likewise be u~ed. Suitable trivalent
cations are, in particular, aluminum and trivalent transition
15 metal cations such as the trivalent cations of .ll~ , iron and
the lanthanides.
Suitable sources of these metal cations are tho~e ~ from
which the metal cation6 can be liberated in aqueous medium. These
20 are, in plrticular, the water-soluble salt~, preferably borates
and pho3phates, but also salts o~ further inorganic or organic
~cids, organic 1PYP' such as acetylacetonates and also oxides
and hydroxides. As sources of borate and pho~phate ions,
preference is given to using the COLLC-Y~ q acids. Their
25 ammoniu~ salts or salts of the metals ~ to be used can likewi~e
be employed. The sources of the metal or a~monium cations and of
the borate and phosphate ions are pref erably dissolved or
s ~L,~ ~^d in the polar solvent in the str~i~h1t -ic ratio given
by the formula (I). For the purposes of the present invention,
30 this means that the individual t~ have to be present in
such ratios that ,- _ ,lc of the formula (I) can be formed. It
is of course pos~ible to u~e individual ~ ts in a
s~oi--hi~ C-iC excess so that, after the reaction i8 complete,
the S~,.i,hi~ t.ic excess either remains in the solution or, as
35 an e,.l L ~nev.~D phase, contaminat~s the desired boL~ho,yhates of
the f ormula ( I ) .
The abov~'~~ hed pLoc~luLæ is suitable for preparing those
~- which only crystallize under hydrothermal conditions or
40 the AnAl r goll~ conditions in the case Or nonaqueous solvents .
E~owever, certain b~ ho~ ates of the general formula (~) can
also be obtained from a solution at below lOO-C. Accordingly, the
invention also provide a process for preparing crystalline
~vLv~ho~ ates of the general formula (I), wherein s~ t~ of
q5 sources o~ the metal or ammonium cations ~, of borate ions,
rh~y~te ions and, if de~ired, o~ aluminum ions are preferably
~ ~ nP~3 in the str~ hi L-lc ratio given by the formula (I) and
~ 0050/45700 2~8S~8~
the solid i~ precipit~t~d by ` ining the ~olutions, by mixlng
the solutions with lis;uids miscible therewi~ch and having lower
dielectric Cu~ tY, by tem~erature change and~or by
c~,nce~ ing the solution. Elere, what has l~een said above
5 applies to the sources of the metal or ammonium oations ~ and the
anionic ~ znt to the term "5to~h4~ LL~C ratio .
Under favorable condition~, the desired ~olids crystallize
directly from the solution on c i ~ golution~ of the
10 _ L~. If this i8 not the case, the crystallization of the
desired borophosphates can be carried out either by cv~ce~l-Lc~ing
the solution, for example by evaporating the solvent by
increa~ing the t _ ~uLæ, under reduced pressure or in the
presence of an agent which binds the solvent, ~or example water.
15 Alternatively, it i~ pos8ible to lower the solubility oS the
desired phases themselves, ~or exan~ple by changing the
temperature of the solution, generally by cooling, or by reducing
the dielectric constant of the solvent, for example by addition
of a liquid Illi-:rihl~ therewith and having a lower dielectric
20 constant, in particular of alcohols or ketones. AlternatiYely, it
i8 also possible to use supercritical gases such a~ Co2. These
individual measures f or accelerating the crystallization of the
bc, v~,ho~,~ilates of the formul~ ~I) can also be combined with one
another i~ desired.
FUL 1 h `~, the invention provides a process for preparing
crystalline borophosphates of the general formula tI), wherein a
gel comprising the cationic and anionic _ l s, preferably in
the 51~.i.-hi~ - 'O ratio given by the formula ~I), is prepared,
30 the gel is freed of solvent ant, if desired, dried and~or
sintered by action of microwaves or of thermal energy.
~he preparation of crystalline olids via a gel stage is well
known in the field of cera~ics. rhe preparation of the gel is
35 preferably carried out by Surther condensation of a sol, which i~
usually known a~ a 801--gel proce~. This process is generally
carried out starting Srom hydrolyzable ~L~U~ JL~ which are
dissolved in an organic medium and are hydrolyzed by additicn of
- water, which may be a~ d~ to form a sol. suitable P16:~UL~OL~
40 for this purpose are alkyls, acetylacetonates and pref2rably
a~lrrY;I ~ of the cationic components to be used. ~lowever, with a
suitable combination of the _ ~, the gel formation can
also be carri~d ou~ from a purely agueous phase. This is the
case, ~or example, when crystalline borophosph~tes containing
45 aluminum ion~ as trivalent cations ~ ~re erepared by neutrali2ing
a mixed boric acid and phosphoric acid solution with an aluminate
solution. ~urthermore, gels can be obtained by treating solution~
0050/45700
218~S85
containing boric acid and pbG,~.vL ic acid or solutions o esters
of these acids with alkali metal hydroxide solution.
It is known ~rom the chemistry o~ the zeolites and the aluminum
phosphates that the pore or channel a~Lu.~uL~ of the solids to be
prepared can be ;nfl~ n ed daring the synthesis by the presence
of templates in the reaction medium. Templates Are leC~
which, by p~ ~_tL-l_LuLing o~ the solution, of the gel and/or by
interaction with the growing crystal lattice, inf~ nre the
10 three~ nol S-LU ;~U~e~ of the latter. ~hese template
lec~ s are frequently ir.~;~,L~u~ lt.ed into the crystal lattice
and can subsequently be removed therefro~ by thermal degradation.
The crystal ~I.Lu.l.uLd of the crystalline bvLv~"l.vsL,hates of the
general formula (I~ can likewise be influenced by the presence of
15 template --lor~le~ in the reacticn medil~m, without these
neces~arily having to be incoL~LcLl.ed intc the solid. A~ter
isolation of the solid, template 1 ~CIll e6 can be removed, i~
desired, by drying or c~ ninq the solids after removal of the
solvent at, for example, frorn 100 to 600-C.
Suitab~e template 1 1~C~10Q are, in particular, primary,
seov,.daL~ or tertiary organic amineQ or pri~ary, se-v..dar~,
tertiary or guaternary organic ammonium ions or pho~rh~nium ions.
Examples ~re dimethyl ; ions, tdt ~I.y 1 ; ion~ and
25 t_e~L~ }~yl ~; ions, which can be used as water-soluble
salts, preferably as ~hl~ri~ s, bronides or hydroxides. r
ions having longer Alkyl chains, for exa~ple t~:~L~ Lv~
or tetrabutyl r- i salts and higher homologs thereof, zlre also
suitable as templates.
A ~lecond a~pect of the invention provides crystalline
bvLvyl.o.~hates of the general formula (I) wherein at lea~t on~ of
the ~ollowing conditions is fulfilled:
35 a) y i~ not equal to 1:
b ) the ' contain a proportion of aluminum in place cf
boron;
40 c) n is not egual to 2, ie. the metal M is not divalent;
d) x is less than 2, ie. the molar proportion of the metals M is
less than the molar pl-oz,~ v ~:, content;
45 e) ~2 is not Mg, Ca, Sr, Ba, Mn, Zn.
~ 0050~45700 218SS8S
The6e L.,~ G..~hates can also be desc~lbed by their SL~ LL~LC~1
characteristics. They comprise tetrahedral ~o~ and~or triangular
BO3, tetrahedral PO~ and, if desired, Al04 building blocks which
are li~ked at the corners to form linear and~or branched and/or
5 cyclic oligomeric polyanions or linear or branched catenated,
band, sheet or three-si -io- l polymeric polyanions.
FL~ference i~ given to those crystalline borophosphates whose
anlon S ~ LLU LuLe contains no alu~inutn. Preferred metal ion~ M
10 are ; , alkali metal or alkaline earth metal cation~
The invention urther provides a process for preparing the
ab.,~ 3_.ibed novel crystalline bvL~,~l.o~l,ate~, wherein mixtureD
of
a) boric acid and~or ~oric acid salts of the metal~ 1~ and
~) ~I.o,~l.c,.ic acid and/or a~monium pnosphates and/or phosph~tes
of the ~etal~ M and, if required,
c) oxides and/or hydroxides and/or carbonates and/or salts of
monocarboxylic or ~ v ~~ t~ ylic acids and/or enolate com-
plexe~ and/or Alk~ 8 of the metal~ M, i~ desired also of
Al,
are prepared, heated to from 700 to 1600-C, preferably frcm 900 to
lsOO C, lef~ at this i lltUL~ for at least 2 hours a~d cooled
to room t ~ ~u~e~ if desired pausing at t ~ between
reaction t , a-uL~= and room t ~ ,ULe. The b~. ,~l, ,Dt,hates
30 known in the literature were also prepared by such a erocess.
This process is preferably carried out using the 51~ ; LriC
ratio given by the formula (I) For the term sto;l h;~ LLiC
ratio~, what haDs been 5 aid abovê about the prepar~tion using
35 solvents again applies: it is of course ~ithin the scope of thOE
invention to deviate from the stoi~hi LLic mixing ratios given
by the general rorrGula ( I ) and to accept the resulting
C~.llt n~tion of the product~ of the invention with e7~La ~ S
phases or accept the necessity for their removal, ~or example by
40 selective ~licc~ ti~n~ For example, it c~n be advantageous to use
a.n excess o~ borates and~or phosphates which melt at least
partially under the reaction condition~ and thus act as solvents
or fluxes.
45 Where rêference has been made above under c) to carbonates and
carl~oxylic acid salt-c of the metal~ ~, these are not only the
neutral salts but also, i~ desired, basic or acid salts. I~ the
_ . , _ , _ . _ _ _ _ . _ _ _ _ _ _ _ _ _ _ _ . _ . _
0050~45700 21 8~585
.
metal~ M are used a~ caLL~ ,.,tain~ng _ _ ~ , t}le carbon or
the organic ~ t s are given of f as volatile ~ - ition
products under the sp~ifir~d reaction conditions. It is therefore
preferred to minimize the formation o~ such d- _-~ition
5 products by keepihg the proportion o~ the ~aLboll co~ ining
t in the c ~- of the metals M as small a-~ possible.
Aceordingly, prefe~Led carboxylio aeid3, enolate ~ or
.c are tho5e oontaining not more than 5 carbon atoms in
the moleeule. Preferred salts of ---rb~ylie or
10 ~ rlic acids are aecordingly the sAlts of ~ormic acid,
acetic acid, propionic acid, oxalic acid, citric acid or tartaric
acid. The preferred enolate i~ acetylacetonate, preerred
,.lk,-Yi~ are ethoxides and the vario~-s isomers of the propoxide~
and butoxides.
A further aspect of the invention is the use of crystalline
boLvyhG~yllates of the general formula (I) a~ eat~lysts for
reactions of _ ' having acidic hydrogen atoms and/or of
es~ters. For the purposes o the present invention,
20 having aoidic hydrogen atom3 include water and inorg~nic acids.
~owever, they are preferably organic ~ _ '~ having acidie
hydrogen atoms l~xamples are alcohols, carboxylic acidG and
primary or secondary amines- In particular, they are alcohols,
amines and carboxylic acid~ of fat-chemical origin. Such
25 c AC are those carboxylic acids which oeeur as _ _ ts of
natural ats and oils, and also the alcohols and amines whieh ean
be derived from these carbo~cylic acids. The lengths of the carbon
ehains of such carboxylie acids of fat-ehe3ical origin ~re
preferably in the range ~rom 8 to 24 earbon atoms. ~he carbon
30 chains, ~hich are preferably lineur, ean be s~uLated~
- a~uLat~d or polyunsaturated. ~urthermore, carboxylic aeids
of fat-ehemieal origin and alcohols or amines derived therefros
~lso include those obtainable by dimerization or polymerization
of sueh ~ubYtances. Examples of these are ~he dimeric aeids and
35 the Guerbet aleohol~. Carboxylic acids, alcohols and arnines of
f at-chemical origin are usually not pure substances, but have a
characteristic distribution pattern of the carbon chain lehgths
~r~ nr~ on the source o~ the vegetable or animal fat or oil.
40 Suitable reaction . ~ ts include not only orgahic alcohol~
andtor carboxylic acids, but also the esters obtainable tl~LeLL
by reaction with organic or inorganic acids or alcohols.
PL~fel~ ~ce i5 again given to using those esters in which either
the acid component or the alcohol ~ is of ra~ ica
~5 origin. These are again preferably those ester~ in which the
reaction c _ ~ i8 either inorganic or organic having a carbon
_ _ _ _ _ _ ,
0050t~5700 2 ~ ~5~85
chain lensth o~ 4 or less. æxamele2; are methyl esters o~ ratty
acids, fatty acid glycerides and fatty alcohol sulfates
The crystalline bol.",ho~!Lates of the general ~ormula ~I) can
5 catalyze reactions of _ ~ ~c having aoidio hydrogen atoms
and/or o4 e~ters with themselve~ or with reaction _ cs
which likewise belong to these groups of sub~tances. Eowever, the
boL-.pl~o~L l.ates are preferably u6ed as aatalysts 40r reactions in
which the _ having acidic hydrogen atoms and/or the
10 esters are reacted wiSh oxiranes. The unsubstituted oxirane is
known in the art as ethylene oxide. The oxiranes used can also be
alkyl-substituted. The simplest example o~ such a compound is
propylene oxide. The reaotion of fatty alcohols, a~inos and/or
carbooxylic acid3 and of esters oont~ining such ~ _ ~.. with
15 ethylene oxide and~or propylene oxide is a process carried out
industrially for producing nonionic surfactants. Dorr~ing on the
desired ~rP~ r, the stoi~hil ~LiC ratio of ethylene oxide
and/or eropylene oxide to the f at~ ical component can be
varied within wide limits in order to set the hydrophilicity or
20 I.~IL~ oLicity of the resultant ~.~L~a~e a~ ive, _~ in a
targeted manner.
The invention also provides for the use o~ crystalline
Lor.,l!ho.",hates of the general formula (I) as catalysts ~or
25 reactions of organic _ '- in which ~ aLL~ aLL~JQ bonds are
cleaved and/or formed. Industrially, such reactions play a role,
in particular, in the processing of petroleum. E~owever, the
aliphatic and/or aromatic llrl~ocaLL~JIls to be reacted can be
present not o~ly as _ - ~ ts of petroleu~, but also as
30 - _ -- ts of natural gas and/or of mixtures obtainable by
hydrogenation of ooal. Examples of such reactions are
p__L..I' 1.- r..~l cracking and/or reforming ~ o~c3ses, which are, in
chemical terD~s, principally chain cleavages or alkylation and/or
acylation reactions. Catalysts used for such reactions, which are
35 mostly carried out in oil ro4inorj~ are at pre~ent prinCirAlly
different type3 of zeol.ites. The use according to the invention
of the crystalline ~ ho ,~hates enables the selectivity of such
reactions to be infl~en~~od by means Or the specific distribution
of acidic and basio centers on the external and internal surfaces
40 of the solid. The b~,L~,~Lo,~hates also difrer from the zeolites in
their reduced tendency to c~rh~ni ~tion and sometimes by their
higher thermal stressability, which on the one hand makes
possible higher reaction t' _ a~L~3 and on the other hand makes
the regereration o_ the catalysts ea8ier when c~rh~ni~rati~r~
4S occurs.
0050~45700 21 8~85
~or use as catalysts, the products can, i~ desired, be converted
~y methods known per se into shaped bodies, ~or example pellets
The customary method3 for this purpose are known to thoDe skilled
in the art They include, for example, pelletiz~tion of moistened
S powder3 in ~.Ls~d~Ls with, ~h~ t drying, with it bei~g
possible to ca~ry out, i~ desired, a rounding step, ~or example
on a granulation pa~, between extrusion and drying. Shaped bodies
can also be obtained by introducing the product~, dry or
moistened, into molds and pressing them into shaped bodies under
10 the ~r~l iC~t~rln of pre~sure. ~his enablec higher ~L~= .DULe S to be
used and therel~ore more ~ y stable shaped bodie~ to be
obtained than is the case in the abv.. t ioned extrusion
proces~ .
15 If it is de~ired to increase the porosity o~ the 3haped bodies,
PVL_ ~,L.~.ing additives can be added during their production and
these additives are the~ removed by heating after removing the
shaped bodies from the mold. For example, a ~uitable additive for
this purpose is wood flour which burns leaving rirtually no
20 residue on heating the shaped bodies in an ~Yi~li7in~ gaq, for
example in air. Other pore formers which can be used are
.arLo~ate or ammonium hydrogen carbonate. On heating, these salt~
vaporize without leaving a residue.
25 A further a~pect o~ the invention is the use of crystalline
bvrophvz.yl.ates of the general formula (I) as cation D.~-h~ rS
A~ i~ also the case ~or the 2eolites, phase~ which are
particularly useful ~or thi~ purpose are those containing
monovalent metal ions M or ammonium ions.
~he invention also provides ~or the use of crystalline
bvLv~ ,"phates o~ the general formula tI) as sorbents for
inorganic or orgq~nic ~ec~ 6, in particular polar ~ ~lec~
The sorption can be carried out from a gaseous or liquid phase.
35 Examples of such sorption E~SVn~I;D~S are the removal of water ~rom
organic lictuids or the removal of organic impurities or of
inorganic gaqeous acid anhydrides ~rom air. With a Duitable pore
diameter, the crystalline borophosphates can have lr~c~ r sieve
properties similar to those of the known zeolites and ~-
ÇO ehosphates, ie. a particularly high binding capacity Sorl~c~ q of a certain si2e range.
The invention likewise provide_ ~or the use of the crystalline
bvLv~hvDpl~ates of the formula (I) as flame retardants, rheology
45 i _ v~ or fillers and pigments in paper or plastics.
oo50J45700 21 8~5 ~
Purthermore, the invention provldes for the us~ o~ crystalline
bv~aL)hGD~hates Or the general formula (I) as surgical implants,
in particular ~or tooth or ~one rerl~ t. This application
n~akes use of the high tissue compatibility of the crystalline
5 borophosphates which can, inter alia, be attributed to the
chemical similarity to oalcium phosphate. Pa~ticularly s~litable
f or thit purpose are those B-~L ~ oD~l.ates 0:~ the general
formula (I~ in which the cation M is an alkaline earth met~l
cation, in particular a calcium ion. Use can here be made of
10 implants which consist entirely of the bo~ L~h~ . Elowever,
it is also po~sible and even prererable in the case of implants
which are subjected to flexural stress to apply the
boL~,~ho .~haees aA a coating on i:nplants made of other, preferably
metallic, materials and thus to assist, for example, the growing
15 on o~ bone material. ~he coating can be applied in ~ull or in
part and may require certain sur~ace Dt~U~.~U'C,S~ for example
depre~sions, of the support material. For example, the support
material can have an v~ pv~ surface aL~ u ~" wherein in each
case the pore base is covered with crystalline ~or-,~l.os~hate.
20 Such DI~L~ ULI~3 having l~ ,yc.patite as coating material are
known ~rom DE~42 11 343.
Examples
25 A) Sy~ 3 by the sol-gel process
Example 1
Potassium bG~o~Lo ,~llate
30 P401o in ethanol ~molar ratio: 1:6) is reacted at ~O C with ~13BO~
and tetrapropylammonium bromide (TPA) in ethanol (molar ratio:
10:1:50) in a molar ratio of P:B - 1:1, heated to 90-C and
refluxed ~or 24 hours. Afte~ takin~ o~ halr the amount o~
tolvent, ROH flakes are added a little at a time until the pE~ is
35 7. During this PLO~ U' e, the solution becomes gel-like. I~fter
re~luxing for 4 hours, the product ~ormed is washed with EtOEI and
dried at 150 C, giving a finely cry3talline white product having a
particle size of 2--3 ~ he X--ray powder pattern shows
re~lections which can be a3signed eo no previously known phase.
40 According to EDX analyse~, the product comprises B, O, P and R.
~he product is sparingly soluble in water and l~tOEI.
0050/45700
11 2~8~5~S
X--ray powder eattern:
d(A) l:/Io
5 . 562 73
S 3. 734 60
3.517 100
3 . 356 92
2 . gl0 55
2.760 72
2. 170 38
Example 2
CalciusQ borophosphate
15 P~O~0 in ethanol ~molar ratio 1: 6 ~ is mixed with H3BO3 and
t,atL<~r~ l i bromide in ethanol ~molar ratio 10:1:50) in
amounts ~uch that the ~olar ratio of P:B = 3:1. The solution is
refluxed for 3 hours. ~rhe solution is then cooled to 70 C and
Ca(OH)2 powder is stirred in in an amount such th~t the molar
20 ratio of Ca:P = 1:1. This 3ixture is held at 150 C under
autogenou~ pressure for 10 hours in a stirring autoclave, then
cooled to room ~ Le, filtered, the ~olid is washed with
ethanol and dried at 110-C. Ele~ental analysis indicates a Ca:B:P
ratio of about 3:1:3. Part of the product was calcined at 500-C
25 for 5 hours.
Example 3
~a2 t B7P3Ols ] ~H2O
30 OP(OR)20E} having R = n--butyl and H3BO3 are reacted in a molar
ratio of 3 :1. The pa 0~ the resulting solution is adjusted to 7
using l~aOH !301ution and held at 90-C for 24 hour~. The produot
~ormed i~ filtered off, wa~hed with EtOH and dried at 150-C. The
X--ray powder pattern can be interpreted on the basis of the pha~
35 Na2tBI0Ol6l~4E~2O. According to EDX and AAS analyses, the product
has the ~ _ r;l~l formula Na2tB7P3OI9]-H2O. The product i8 readily
soluble in water, but sparingly soluble in EtOH.
X-ray powder pattern:
d(A) I/Io
5. 820 72
4 . gl7 17
4.029 31
3.861 100
3. 677 23
0050~4~700
218~585
12
3. 609 2~
3.370 12
3. 317 31
3.188 18 -
3.080 10
2.922 14
2.889 29
2.570 22
2.439 17
2.249 17
2.234 18
2. 157 12
2. 081 12
1 . 896 14
3 ) Syntheses f rom aqueous ~olution
~xample 4
31a2~B3,gPo,l(OH)3~gos~2] 3a20
~0
~is~ hydrogen phosphat~ (A) and sodium ~ .,La~e ~B) are
dissolved in ~rate~ ~C) at 70 C in a molar ratio of A:B:C z 5:2:180
and brought to a pE; o~ 8.5 using solid H3BO3. ~fter about 2 ~eeks,
crystal~ having a teLLeLh~l al habit were isolated. DSC
25 mea~uL~ - ~s up to 160-C ~how an endothermic effect ~t 142 C which
i~ aYsociated with a weight 10~18 of~ 16.27S ~water oontent of the
product: 18.45~). The X--ray powder pattern of the produot shows,
before the DSC measurement, clo~e si:~lilarity to that of
Na2~O7~5a2O ~;ncs~ n;te). Single-c~ystal X--ray studies show a
30 trigonal unit cell having a = 1113.5~2) p31 and c - 211g.9~5) pm
~rin~ nite a = 1109~3) pm, C - 2107~4) pm, space group = R32)-
The increase in the lattice ~ al.al Cg is here in ayL t with
the r~r1a~ ~ of B with ~V). 13DX analy~es of the single
crystAl showed the elements Na, B, O 2nd P. The Na:P ratio was
35 20 :1. Accordi~g to the analy~es the product hâs the empirical
f ormula Na2 [ E~3 gPo . 1 ~ OE~ ) 3 . 8s . 2 ] 3a20 -
C ~ Hydrothermal ~ynthesis
40 EYamP1e 5
Preparatiorl of luneburgite [ Mg3B2 ~ OH ) 6 ~ P0~ ) 2 ~ E~20 ) 6 ~
1.68 g o~ o i hydrogen rho~rh~te ~MgHPO~ ~ 3~2) and 0.2 gof boric acid (~olar ratio 3 :1 ) are weighed out. In addition,
45 0 17 g o~ t~t. c.hyl i hydroxide are added as template.
The starting materials are well triturated with one another and
placed in a Teflon âu~oclave ~Roth, volume 20 ml), then admixed
OOSO/45700
~ 218~8~
13
~ith 10 ml of Alkaline ~pE~ = 101 aqueouG potassium hydroxide
Yolution and held at 110 C for 6 days. The product ~ormed i~
washed with water and dried at 40 C, giving a finely crystalline
white eroduct. ~he reflection~ of the X--ray powder pattern can be
5 ~r1~in~-d by the pre~ence Or a two-phase mixture o~ r~9~n~qi
hydrogen phosphate (Mg~PO; f 3}120) and luneburgite
[ Mg3B2 ( OEI ~ 6 t P04 ) 2 ( H20 ) 6 ] . The proportion o~ lUneburgite is about40~ .
10 Exz~mple 6
Strontium borvL,l~os~l~ate
SrtO}~)2 is milled with boric acid in a molar ratio of 3:2 in a
ball mill. The mixture is i~ v~u~ed a little at a time while
15 stirring into such an amount of 10% strength by weight agueous
~ Vs~hv~-c acid solution that the molar ratio of Sr:B:P is 3:2:2.
The mixture is held at 130 C ~or 48 hours in an autoclave. It is
then cooled to room ~ _ aLul ., the product is ~iltered o~f ,
~ashed with vater and dried at 110 C. Part of the product wa~
20 r~lr~inr~ at 400 C.
13xample 7
Zin~ bGrv~lA .s~l.a~e
25 ZnO is milled with boric acid in a molar ratio of 3:1 in a bAll
mill. The mixture i5 il.-L.l~l- ed a little at a ti~e ~hile stirring
into such an amount of 10% strength by weight aqueous ~ .I.r., ~-
acid solution that the molar ratio of Zn:3:P is 3:1:3. The
mixture i8 held at 170-C for 24 hours in an autoclave. It is then
30 cooled ~o room I _ ~uLe, the product is filtered off, wAshed
with water and dried at llO-C. Part Or the product was calcined at
400-C.
Example 8
35 Nickel ~oLv!,~.v~hate
The PLVC~ L~ of Example 7 is repeated exactly, but using NiO in
place of ZnO.
40 D) High-~ rtu~e ~ynthesi~
Example 9
Ba $ ~ BP3012 1
45 A mixture of ~aC03. El3BO3 and (NEI,.)2~PO4 in a molar ratio o~ 2:1:3
was heated in a Pt crucible to 1300-C over a period of 4 hour~ and
left at this te~perature rOr 8 hours. The ~l _ r~l:u~e WaY lowered
~ 0050/45700 2~8~8~
14
to lOOO-C ~nd held for 24 hours; the mixture was then cooled to
room, _ ~t~L'~ over a period of 4 hours. The reaction product
comprised a vitreous matrix in which ~lor~5~ted ~L-IIVL' ' iG
pris~s of Ela3~BP3012] were embedded; according to X--ray powder
5 studies, Ela2[P207] had been formed as additicnal crystalline
by--product .
S~ ,LUL.'l analysi~ of Ba3[~P3012]: space group Ib~;
a - 2221.1~8), b = 1429.6(6), c = 710.2(4) pm; Z = 8;
lo DC~1C. = 4.1? gcm-3
The crystal SLLUI_LUL.2 - _- -C~C "in~inite one-~ n ~l~V anion
DLL~._LUl~S made up o E~0~ and P0~ tetrahedra linked via ccmmon
corners, The polymeric SLLU~ LUL~3 Or anion tetrahedra are ~ade up
s 0~ central guadruplet simple chains (~o~ and eo, alt~rnately); the
"rree" corners of the B0~ tetrahedra s~ultaneously belong to
~terminal~V Po~ tetrahedra, so that the overall result i8 ~two-fcld
open branched guadruplet simple chains".
20 The cry~tal ~LL~ ,ULe of 3a3~3P3012~ contains relatively large,
parallel channels running in the (001) direction, in which
channels the barium ions are positicned.
Sorption and desorption behavior
To determine the sorption and desorption behavior of selected
test substances, these were irst baked out at 110 C in a vacuum
drying oven. About 10 g of each o~ the sub6tances to be tested
were weighed into weighing bottles and distributed in a layer
30 about 3 mm deep on the bottcm of the weighing bottles. To test
the sorption behavior for vapors of liguids, dishes containing
~he liguids to be tested were stood on the ~ottom of desiccators
having a capacity of about 2 1 and the weighing bottles
containing the test substances were placed on the per~orated
35 plate of the de~iccators. Tho desiccators were then closed. In
order to test the sorption behavior ~or acid gases, the weighing
bottles contaLning the test substances were stood on the
3~CLL~, atc~ pl~tes of the desiccators, the gases to be sorbed were
inL~ olu- ed via a line and the desiccators were closed. After
40 ~tanding or 24 hours at room t~ .LULe~ the desiccators were
opened and the samples were L.h j~Jh~l, The weight increase of the
samples was ~A~--3~a~ as a percentage of the sDmple weight before
sorption. To test the desorption, the loaded samples were b~ked
out for 2 hours at llO-C in a vacuum drying oven The desorption
~5 determined by 1l igh;n7 the samples was ~ L~3 ~d a~ a
.
0050~45700 2~5~g5
percentage o~ the sorbed amount. ~he result~ are shown in
Table 1.
Table ~
Substance Product from Weight De~orption at 110 C
Example inorea~e
Water 1 15% 95~
2 12~ 98&
Acetone 1 179~ 10096
3 ~'~7nr~ in~ ) 8~ 1009
n P~vp~nol 3 ~ calcined) l
i-~?ropanol 3 calcined) 5~ 10o9
Ei2S gas 7 (1-nr:-1 ined) 8~6 45t
NO2 g~s 7 l~-n~ l r; ne~) s% 80&
SO2 gas 7 ~n~ ~1n~d) 13~ 70
Te~ting of the ion exchange behavior
To test the cation exchange properties of the products, a calcium
chloride solution having a calciu3 content equivalent to 500 ppm
25 f c~co3 wa5 prepared- Accurately weighed ~amples of about 0.1 g
were each aqded to 100 ml portions of the calcium chloride
solution, stirred at 25-C fo~ 30 minute~ and then filtered through
a me3brane filter having a pore opening of 0 . 2 llm. The calcium
content o~ the filtrate~ was determined by ~ l t~--i LLic
30 titration with EDTA and the calcium binding capacity of the t~st
substances, eYpres~ed in mg of CaO per gram of ~:.td~ , was
calculated from the residual hardne~s thu~ obtained.
Resultc: the products ~rom ~xamples 1 and 3 had a calcium binding
35 capacity o~ 35 mg/g and 63 mgtg reseectively.
Use as llc~ vy~ tion catalyst for ring closure reaction~
The test reaction employed ~as the ring closure reaction of
monoe~h~nt~ n~ to rorm ethylenimine with elimination of water
in the gas phase Tubes o~ stainless steel having an internal
diameter of 1.~ cm and a length of 20 cm were used as reaction
ves~el~. The tu~es were charged with the te~t D-~LD~ e~
comminuted to a particle :~ize o~ from l to 2 mm and were heated
S5 to 400 C in a tube furnace. During heating up, the tubes were
~lushed with nitrogen and this proceo~ was continued for
30 minutes a~ter the end Or the heating--up period. S~D6~-~ .,t1Y,
0050~45700 218S58~
5~ by volume of monoerh~nol~ ;ne were metered in~o the nitrogen
strea~ at a flow rate of about 5 l/min. 2he reaction mixture
leaving ~che reactor was analyzed by gas chromatography. Th~
catalytic yield in mol percent wa~ calcul~ted by means o~ the
5 quotient mole of ethylenimine rormed: mole of monoeth-n~l no
used .
Result: catalysis using calcined product from Example 7:
38 mol percent, cat~lysis using c~lcined product ~rom Example 8:
10 53 mol percent.
Catalytic dehydLuy~l~ation of alcohols
The al~ ed reactor i~ charged with the calcined product
15 from Example 2 milled to ~ particle aize of ~r 1 to 2 mm. While
flushing with nitrogen, the reactor is heated to 450 C and after
reaching this temperature is flushed with nitrogen ~or a ~urther
30 minutes. S~hs~qu~r~tly, methanol vapor is passed tnrough the
reactOr ~t this t _ _r~-l uLt:. The reaction mixture leaving the
20 reactor is passed through a cold trap ~o as to condense out water
~ormed. The gas~ous fraction i~ analyzed by gas llr t~Ldpl~y.
According to this, the reaction ~ixture contain~ as main
ts ethene, propene and various butenes, as well as
unreacted methanol. The aYr~ri~ t is repeated using the
25 lln~A~ain^cl product ~rom Example 7 which had previously been
pelletized in the rollowing manner: 400 g o~ the product were
moistened with 320 g of water and pa~sed through an extruder. The
extruder was set such that eA IAL uddte~ hAving a diameter of 3 mm
and a length of about 4 mm were ~ormed. These were rounded in a
30 pelletizing drum and the pellets were dried at 130 C for 3 hour~.
The dehydrogenation of metnanol over these pellets likewise gave
as sisnifi~-nt products ethene, propene and various butenes.
Catalytic cleavage/reaLLahg t of hydrocarbons
The .~ ina~l products from ~3xample 7 and Exaople 8 were uased as
catalyasts for the catalytic cleavage and reaLLar.y. t of
hydrocarbons. In this way, the ~uitability ~or use in
P~ LV. 1.. r ir~l cracking and reforming pL~cesses is determined. The
40 model hydrocarbon used waas n--hexane.
The ab~ rlt~ h~d reaction mbe was in each case charged with
10 g of the substance to be tested. At a ~urnace t _ -ral UL~ of
400 C, the auLaLdnce3 were each ~lushed for 1 hour with helium.
45 5uL3~ 1.1y~ the reaction tubes were cooled in a stream o~
helium to 250-C. The heliurl ~tream was then pa~sed through liquid
n--hexane at room t ~ ~i atuLe and thus saturated with gaâeous
0050~45700 21 8~58S
.
17
n--hexane prior to being in-Lc,du~ed into the reaction tube. The
flow rate was adiusted such that the residence time in the
catalyst wa6 about 10 seconds. After leaving the reaction tube,
the ga~ stream was fractionated ~y g~i chromatography. Th~
S proportion~; of the cracking products ~ Cl to CS ), the
rearrangement products ( iso-C6 ) and the unreacted n--hexane were
thus det~rm;n~ The sum of all the ~ropo~tions was set to 100~.
Result:
Product from Example 7: Cl to CS: 87S
iso-C6: SS
unreacted: 8
15 Product from ~xample 8: Cl to CS 95
i~o-C6 29
unreacted: S S
20 Use as ethoxylation catalyst
Reaction of clo~ with ethylene oxide: 6 g of the calcined
product from Example 6 were r u,,~ d~d in 407.3 g (2.19 mol) of
n~l (Lorol~ C12, hydroxyl number 298, Eienkel) and trans-
25 ferred to an autoclave. The autoolave was flushed with nitrogenand evacuated for 30 minutes at O-C. subsegu_~.tly, 192. 7 g
(4.38 mol) of ethylene oxide were injected a little at a time
over a period of 75 minutes at 180 C and a pres~ure of at mo5t
S bar. After the ethylene oxide addition was complete, the
30 mixture was allowed to react for 30 minutes. The cataly~t was
filtered off vi~ a suction filter. Th~2 yield wa~ 600 g and the
product had a hydroxyl number of 206.5 (calculated hydroxyl
number: 204 7 ) .
3s
