Note: Descriptions are shown in the official language in which they were submitted.
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~o55677 ~,
BASIC CARBONATE FOR MANUFACTURE 0~ COPPER-CONTAINING CA~ALYST
Thls lnvention relates to copper oontaining materials suitable
as catalyst precursors ror the manufacture o~ butynediol l~4.
It is known to produ¢e basio carbonates of the general ~ormula
Me(II)6Me(III)2(0~)l6o 4 H2
where the metal Me(II) is a divalent lon-~ormillg metal and Me(III) -~
is a trivalent ion-forming metal. Accordlng to German patent
2~024,282, these compounds have the structure of natural manasseite.
Examples of metal atoms which may be inoluded ln thls crystal struc-
ture are as ~ollowsO ~
Niokel9 ¢obalt, ma~nesium9 manganese~ zinc9 copper as Me(II)~ and ; ~-
10 aluminum, iron and chromium as Me(III~O ;
Compounds of these metals having tha orystal structure Or
manas~eite are reoommended as ¢atalysts or oatalyst preoursorsO The
aatalyst~ obtained are desoribed as partioularly aotive.
However, their drawbaok is that they are ~requently insu~
c~ently stable to thermal and even ohemioal in Muenoe. For example,
i~ a compound of the metal composltlon Cu4Mg2A12 is held at 350C
~or 6 hours, the copper is then mainly present ln oxide ~orm, as
may be demonstrated by X-ray analy~is. Furthermore, the magnesium
1 i8 no longer resistant to the attaok o~ weakly aoid media.
i 20 We have now round a ba~io oarbonate whioh oontRins oopper and
I alumlnum and whioh is partioularly suitable ror the manurQoture o~
j copp~r-oontaining catalysts. It ha~ the general oompositlon
~I CumAl6(c03)o~sm(oH)m+l2 9 ; .
where m may be an integer or non-integer between 2 and 6, and has ~ i
a number o~ advantages over ¢arbonates o~ manasseite ~tructure. ` ~
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~556~7 -Z 309825
A basic Garbonate o~ the composltion o~ the invention may be
obtalned by mlxlng a preferably 1 M aqueous solutlon of salts o~
copper and aluminum whlch can be precipitated by carbonates~ which
solution contains copper and alumlnum ln ~n atoml¢ ratio o~ copper
to aluminum o~ m:6~ with a preferably approximately 2 M solution
containing an alkali metal carbonate and/or bicarbonateD such that
the resulting mixture has a pH of from 8 to 9.5 and pre~erably ~rom ~`~
.. . .
80 1 to 8.5~ the temperature of the mixture being malntalned at from
60 to 90CO The resulting precipitate may be washed and then be ;~
dried9 if desired9 at a temperature below 100Co However; the inven- ~ ;tion is not restricted to the carbonates obtained by the above
recipe. For exampler other suitable solukionc o~ aluminum and copper
salts are those in which the total molar concentration is from about
0.05 to about ~O The amount and con¢entration o~ the al~ali metal
oarbonate ~olution should ¢ontain an equivalent amount o~ carbonate
and it~ molar conc~ntration is pre~erably twice as great.
By determining the carbon dioxide~ the water tltratable ac¢ord-
ing to Fisoher and the total loss on ignition and by determining
the copper and aluminum in appropriate samples in ¢onventlonal
`! ~
, 20 manner, it has been possible to arrive at the arorementioned prob-
:
able oompositlon given in ~ormula formO ,~
The X-ray diagrams Or the compounds (~lg.l~ ln which the
compound ha~ the compositlon
CU5Al6(co3)2.5oHl7o3)
indicate a layer latticeO It has a remote simllarity to the X-ray
1 dlagram of manasseite (Flg~ 2)~ although it has characteristic
<~ properties whlch have not hitherto been described.
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Table~ d values of Guinler photographs (CuKa)
New compound Cu~Mg~A12 manasseite
Cu5A16 carbonate (F~go 2 )
(Fig. 1)
drelative intensity d re:lative intensity
7065 100 7065 100
3080 go 3~80 80
2.72 50 -
2052 70 2~58 80
2041 40
203g 10
2,24 50 2.28 60
2.0~ 20 .
1.89 50 1~94 1~0
1.72 30 1-73 10
1.59 10 106~ 10
1.56 30 .
1.54 10
.
1~52 30 1.5~ ~0 :
7 3o 1.50 30
1.44 30
Remjarks
The d-values may show slight devlations from those given abovP
at various water contentsO Slight impurities (Al(OH)3) are usually ~.
~oundO Lines o~ low relatlve inkenslty were not measured, i.e~ the
I abo~e lists contaln only the maJor l~nes.
.l It is seen that the ¢ompound Or the invention is a novel com-
pound of copper and aluminum~ Presumably, the constant elements of -;
.l~ the layer lattice in the novel materlal are ~ormed by an alumlnum
oxide hydrate, whllst basic copper carbonate will be present in
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various amounts in the interstitlal spaces. However, the layer ` -~
lattice whould seem to require, for lts ~orrnationD that a certain ~ ~-
minimum number of said lnterstitial spaces be filledO
When used industrially as catalyst9 the novel compound has the
partloular advantage or being thermoresistant as regard~ the
distribution o~ the copperO On heat~ng to above 80 to 100C9 it
liberates water and carbon dioxide and finally becomes amorphous9
as determlned by X-ray analysisA Howeverg the flne dlstributlon of
copper and aluminum in the original compound seems to remain~
10 surprlsingly even when held ~or relatively long perlods at tempera- -
tures at which the said dlstribution is lost in similar prior art
compounds.
If a sample of the novel compound oontainlngJ for example,
copper and aluminum in the ratio Cu5A16 is held at ~50C ~or 6 hours,
no lines of any kind are then ~ound in the ~-ra~ diagram. The sample
remains amorphous even when tempered ~or 6 hours at 50C, i.e. no
recrystalllzation takes place, ~rom which a uniform distributlon o~ `
the oopper in the heated sample may be concluded~ ;
The range o~ existence Or our novel compound is limited by two
di~erent ~actor~, ~s already indicatedO Ir the ooncentration o~
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opper is too high, there is the increasing tendency o~ the oopper
no longer to precipitate as a mixed crystal in the ~orm o~ the
novel compound but as a pure copper aompound in the ~orm Or malachite.
It is not pos~lble to manu~acture the pure compound when the atomlc
ratio o~ copper to aluminum is as low as 11:10. In this case portions
, Or both the novel compound and malaohite are always ~oundO At larger
-1 copper ooncentratlons, the new compound is no longer ~ound~ From
thls it may be concluded that the number of lnterstit~al spaces
available ~or the copper ls limited or that at a large excess of ;;
~ 30 oopper the mixture prererentially forms the mala¢hite structure ~or
; thermodynamic reasonsO
I~ the concentration Or copper is too low, lt will not be
su~ioient to ~orm exclusively or stabllize the new lattlc~ and there
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- OOZo 30~25
~055677
ls always obtained the h~drarglllite lattlceO This is inevltably
the case at atoml¢ ratlos o~ copper to aluminum o~ less than 2-60
.. . ..
Compounds of the type claimed in the present invention may be
prepared by preoipltation ~rom aqueous salt solutions wlth a basic
carbonate-containlng precipitant ln aqueous solutionO It is import-
l . .. .
ant to maintaln a relatively narrow pH and temperature range 0 It
has been ~ound parti¢ularly suitable to use a basic pH range9
parti¢ularly one from 800 to 8~59 and a temperature range of ~rom
60 to 90C and in particular one ~rom 75 to 85C~ Suitable salts
are9 ~or example~ nitrates, sulrates~ a¢etates9 formates and otherwater-soluble salts.
Sultable pre¢lpitants are alkali metal carbonates and bi-
carbonates9 particularly sodium bi¢arbonate and mi~tures o~ sodium
carbonate and sodium bicarbonate having a pH o~ rrom 8 to 905. In
some cases use may be made o~, say, sodlum hydroxide, lr the copper
and aluminum salts used show an aoid reaotion. A parti¢ularly suit-
able pre¢lpitant is a solution whloh has been obtained by heatin~
water wlth (sparingly soluble) sodium bioarbonate in an amount of
~rom 100 to 200 g/l, heatlng being contlnued untll the bicarbonate
2Q ls completely dlssolvedO As is well known, oarbon dioxide is given
i
~¦ o~ and a portion o~ the bicarbonate ls converted to oarbonate.
~I Metal salt and preclpitant are preferably used in approximately 1 M
and 2 M solution respeotivelyO Preoipitatlon may be carried out
oontinuously or batahwise.
¦ The ~reshly preolpitated substance may be amor~hous, but it
crystallizes on drying~ Followlng elutriation o~ the mother li~uor
wlth cold water and drylng Or the preclp~tate at from 70 to 80C9
the latter always has the composition and struoture olaimed in the
present invention.
~ 30 To ~onvert the above substanoe to a oatalyst teO~0 a oopper
;l oatalyst ror the synthesis o~ butynedlol from ~ormaldehyde and
a¢etylene or ~or oarbon monoxide oonversion)~ the oompound is
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~ 0 S 56 ~ ZO 309825
generally held ("annealed") for ~rom 1 to 8 hours at ~50~ to 600C
and pre~erably ~rom 500 to 550Co Following milling and sifting
to give a suitable particle slze distributionJ e~gO diameters of
~rom 60 to 200/ug there is obtained a particularly actlve ~orm
whloh is preferably usQd ~or suspenslon catalysls. Alternativel~,
the annealed compound may be prepared in a disorete ~orm suitable
for use as a ~ixed~bed catalyst~ eOgO ropes9 pellets, spheres and
rings.
The compounds c>~ the invention are used industrially ~or the
manufacture o~ catalystsO They are particularlg suitable ~or ethy-
nylation (e.g, the a~orementioned preparation o~ butynediol), C0-
conver~ion (particularly at low temperature) and methanol synthesis.
The manufacture Or the compounds o~ the lnvention is clescribed
below in an Example. Compounds havlng a oomposition dlf~erent ~rom
that given in the Example are prepared in a simllar manner using
various proportions o~ oopper and aluminum salts. The use o~ the
oompounds ls desoribed in oomparison with oatalysts o~ the prior
art.
EXAMPLE 1
Uslng commercially available nitrates o~ copper (Cu(N0~)2.~H20)
and aluminum (Al(NO~)3~9H20) a mlxed solution is prepared which
contains one ~ram atom of Cu + Al per liter. The atomio ratio o~
oopper to aluminum ls set at 1:1~2 by using appropriately weighed
amounts o~ the said salts. The precipitant solution is initially
a 2 M solution o~ sodlum bl¢arbonateO In order to dissolve the
sparin~ly soluble sodlum bicarbonate, the mixture ls held at 80C ~-~
~or one hour with occaslonal stirringO The precipitant is used in
exoess so that the molar ratio of sodium ions to nitrate lons
is 1055gl. The stlrred container (oapacity 10 liters) used ~or
the precipltation is ~illed wlth water at 80C in an amount
~0 sufficlent for the s~irrer balde to dip beneath the surface
thereof~ The two solutions are also held at 80 C. After startlng
:,
the stirrer, the precipitant is flrst ~ed to the
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stirred oontalner until the pH therein is ~0~ At this stage, the
feed of nitrate solution at a rate of 5 l/hour is commen¢edO The
feed rate of the precipitant solution is regula~ed so as to malntain
a pH ln the stirred ¢ontainer of from 800 to 8~5 throughout the
precipitating periodO Followlng preoipltation~ water is added so as
to give a temperature o~ 70Co Stirring ls ¢ontinued for one hour,
a~ter whlch the temperature has fallen to about 60C~ The major
portion of the preclpitated solid is washed wlth cold water a number ~ ;
of times until no more nltrate can be detected in the ~iltered wash-
lngs by the Bru¢in method.
The pre¢ipitate ls meohanically ~reed ~rom washing water as
~ar as possible and is then dried in a dryin~ oablnet at from 70
to 80Co A~ter this treatment~ the pre¢ipitate has an outwardly dry
, appearan¢e and a turquolse-blue oolor and lts X-ray dla~ram shows
the llnes typi¢al Or the novel ¢ompound. Arter annea}ing ~or 6 hours
at ~50C, the ¢olor is olive green and after annealing for 6 hours
at 550C lt is dark olive~ Neither of the X-ray diagrams o~ these
2 annealed samples shows any lines.
Comparlson o~ ¢ompounds produoed ln the manner o~ the in~entlon
with oatalysts o~ the prior art:
A compound havlng the same atomio ooncentration Or Cu as ln
; Example 1 was prepared in the manner desoribed in Example 1 ~rom~'~ the serles Or Cu-M~-Al man~sseites by known methodsO The metals
, present in the compound had an atomic ratio of Cu:Mg:Al of
.6:2.4:2Ø Thls ¢ompound having the typical X-rag diagram o~
~ manasseite (Figo 2) was annealed for 4 hours at ~50 C. The result-
`~ ing substan¢e had an X-ray diagram showing di~use but distinot
lines o~ CuO (Fig~ ~)0
EXAMPLES 2 T0 5
Bg varying the proportionsD ¢ompounds may be obtained by the
~ ~0 method des¢ribed ln Example 1 to giva the ~ollowlng metal ratiosO
.. CU6A16Y CU4A165 CU~A16; CU2A
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~055~77 ozo 309825 ~
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The remalning components (CO~ OH~radicals~ O) correspond to the - .
emplrlcal ~ormula o~ Example lo ~-
Application
The ¢ompound prepared in the manner des¢ribed in Example 1 was `~
annealed ~or 2 hours at ~50Co A sample of the resulting catalyst '
praoursor was found to be amorphous when examined by X-rays and its
:~ oolor was dark oliveO The partlele size was between 60 and 200/Uo
A suf~iclent quantity Or this catalyst precursor was slurried
in a 30% aqueous ~ormaldehyde solution to glve a suspension~oon~
taining 308% w/w o~ catalyst precursor~ The suspension was trans- ~ -
10 ~erred to a heated reaction vessel and aoetylene was inkroduced :
through the base of the vessel under atmospherlc pressure9 a neutral
reaction being maintained by the addltion o~ aqueous oaustic soda
solution, ,
;, The conversion o~ the divalent Qopper present in the oatalyst . ~.
, preour~or to the acetylide 0~ monovalent copper begins above about
1 60C and was ¢arried to oompletion at 70Co
A~ter raising the temperature to 85C~ the de~radatlon of the `-
~ormaldehyde by reaction with the acetylene to form butynediol
was ~ollowed analytically. It was found that arter a rea¢tion time
' 20 o~ 3 hours 75% o~ the rormaldehyde originally present had been
.~ converted to butyne diol.
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