CA1055677A - Basic carbonate for manufacture of copper-containing catalyst - Google Patents
Basic carbonate for manufacture of copper-containing catalystInfo
- Publication number
- CA1055677A CA1055677A CA235,123A CA235123A CA1055677A CA 1055677 A CA1055677 A CA 1055677A CA 235123 A CA235123 A CA 235123A CA 1055677 A CA1055677 A CA 1055677A
- Authority
- CA
- Canada
- Prior art keywords
- copper
- aluminum
- solution
- carbonate
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to a basic mixed carbonate of copper and aluminum of the empirical general composition CumAl6(CO3)0.5mO3(OH)m+12 where m is a number between 2 and 6, as obtained by precipitating, at pH 8 to 9.5 and a temperature of from 60° to 90°C, (a) an aqueous dilute solution of copper and aluminum salts capable of being precipitated by carbonate, the copper and aluminum being present in said solution in an atomic ration of from 2:6 to 6:6, with (b) an aqueous alkali metal carbonate or bicarbonate solution, the atomic concentration of alkali being about twice the concentration of copper and aluminum in said solution. This copper-containing material dried and annealed for 1 to 8 hours at 350° to 600°C, is suitable as catalyst precursor for the manufacture of butynediol-1,4.
The present invention relates to a basic mixed carbonate of copper and aluminum of the empirical general composition CumAl6(CO3)0.5mO3(OH)m+12 where m is a number between 2 and 6, as obtained by precipitating, at pH 8 to 9.5 and a temperature of from 60° to 90°C, (a) an aqueous dilute solution of copper and aluminum salts capable of being precipitated by carbonate, the copper and aluminum being present in said solution in an atomic ration of from 2:6 to 6:6, with (b) an aqueous alkali metal carbonate or bicarbonate solution, the atomic concentration of alkali being about twice the concentration of copper and aluminum in said solution. This copper-containing material dried and annealed for 1 to 8 hours at 350° to 600°C, is suitable as catalyst precursor for the manufacture of butynediol-1,4.
Description
~ O ~ Z . ;~50 D 8 ~!5 ~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
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. ` ~
~ '; ' --1 , .~ ~ ' ,.
; ' ' ' .~. ' . , . : , ' ' . : ' , , , ~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.
.,.1 ,.
':, .,~:,. .
:, . .
,~:
",`: : . .~ ...... .
~L~S5{~77 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 3080 go 3~80 80 2.72 50 -2052 70 2~58 80 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 , , ` ~55~77 oOz. ~09825 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~
,~ . , .
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 .
. . . . ... ... . .. . ..
., .,. :.... . .,.. :. ; . :: ' : ~'; ' :
- 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 ; -5~
, ~ . , ;, . ..
., . .. : .
~:: . . . ..
~ 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.
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 ' ' .:
O.Z0 ~0~825 5 5~7 ~
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 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
',:
";
.. ~................ .
~055~77 ozo 309825 ~
.: ~
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.
, ' .
. . .
1 ':
.
.' , .
. ~ .
..
; ' '~ ' , . . . . . , . . -.~
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. ` ~
~ '; ' --1 , .~ ~ ' ,.
; ' ' ' .~. ' . , . : , ' ' . : ' , , , ~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.
.,.1 ,.
':, .,~:,. .
:, . .
,~:
",`: : . .~ ...... .
~L~S5{~77 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 3080 go 3~80 80 2.72 50 -2052 70 2~58 80 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 , , ` ~55~77 oOz. ~09825 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~
,~ . , .
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 .
. . . . ... ... . .. . ..
., .,. :.... . .,.. :. ; . :: ' : ~'; ' :
- 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 ; -5~
, ~ . , ;, . ..
., . .. : .
~:: . . . ..
~ 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.
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 ' ' .:
O.Z0 ~0~825 5 5~7 ~
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 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
',:
";
.. ~................ .
~055~77 ozo 309825 ~
.: ~
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.
, ' .
. . .
1 ':
.
.' , .
. ~ .
..
; ' '~ ' , . . . . . , . . -.~
Claims (4)
1. Basic mixed carbonate of copper and aluminum of the empirical general composition CumAl6(CO3)0.5mO3(OH)m+12 where m is a number between 2 and 6, as obtained by precipitating, at pH 8 to 9.5 and a temperature of from 60° to 90°C, (a) an aqueous dilute solution of copper and aluminum salts capable of being precipitated by carbonate, the copper and aluminum being present in said solution in an atomic ratio of from 2:6 to 6:6, with (b) An aqueous alkali metal carbonate or bicarbonate solution, the atomic concentration of alkali being about twice the concentra-tion of copper and aluminum in said solution.
2. Basic carbonate as claimed in claim 1, wherein a layer lattice of aluminum oxide hydrate is present, between the layers of which a basic copper carbonate is present.
3. A process for the manufacture of butynediol by reacting acetylene and aqueous formaldehyde solution in the presence of a copper-containing catalyst forming copper (I) acetylide in the presence of acetylene, at a temperature in the range from 60° to 85°C, wherein the copper-containing catalyst is a basic mixed carbonate of copper and aluminum as claimed in claim 1, and which has been dried and annealed for 1 to 8 hours at 350° to 600°C prior to use in the manufacture of butynediol.
4. A process as claimed in claim 3, wherein the catalyst is suspended in the aqueous acetylene-containing formal-dehyde solution.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2445303A DE2445303C3 (en) | 1974-09-21 | 1974-09-21 | Basic carbonate suitable for the production of a copper-containing catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1055677A true CA1055677A (en) | 1979-06-05 |
Family
ID=5926475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA235,123A Expired CA1055677A (en) | 1974-09-21 | 1975-09-04 | Basic carbonate for manufacture of copper-containing catalyst |
Country Status (8)
| Country | Link |
|---|---|
| JP (2) | JPS5156800A (en) |
| BE (1) | BE833597A (en) |
| CA (1) | CA1055677A (en) |
| CH (1) | CH616638A5 (en) |
| DE (1) | DE2445303C3 (en) |
| FR (1) | FR2285342A1 (en) |
| GB (1) | GB1512797A (en) |
| NL (1) | NL7510838A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8637668B2 (en) | 2010-06-15 | 2014-01-28 | Basf Se | Process for preparing a cyclic tertiary methylamine |
| US8884015B2 (en) | 2012-06-01 | 2014-11-11 | Basf Se | Process for the preparation of a mono-N-alkypiperazine |
| US8927712B2 (en) | 2012-06-01 | 2015-01-06 | Basf Se | Process for the preparation of a mono-N-alkylpiperazine |
| US8933223B2 (en) | 2010-10-14 | 2015-01-13 | Basf Se | Process for preparing a cyclic tertiary amine |
| US8981093B2 (en) | 2012-06-06 | 2015-03-17 | Basf Se | Process for preparing piperazine |
Families Citing this family (52)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2838184A1 (en) * | 1978-09-01 | 1980-03-13 | Basf Ag | METHOD FOR PRODUCING TERTIA AMINES |
| DE3410069A1 (en) * | 1984-03-20 | 1985-10-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING POLYMERS CONTAINING HYDROXYL GROUPS |
| JPH0336453Y2 (en) * | 1985-05-07 | 1991-08-01 | ||
| DE3539266A1 (en) * | 1985-11-06 | 1987-05-07 | Basf Ag | METHOD FOR PRODUCING TRIALKYLAMINE |
| DE3605005A1 (en) * | 1986-02-18 | 1987-08-20 | Basf Ag | METHOD FOR PRODUCING N-METHYLPIPERAZINE |
| DE3724239A1 (en) * | 1987-07-22 | 1989-02-02 | Basf Ag | METHOD FOR PRODUCING ALIPHATIC N, N-DIALKYL SUBSTITUTED AMINO ALCOHOLS |
| DE3803581A1 (en) * | 1988-02-06 | 1989-08-17 | Basf Ag | METHOD FOR PRODUCING 1,2,4-BUTANTRIOL |
| US4910304A (en) * | 1988-04-20 | 1990-03-20 | Basf Aktiengesellschaft | Preparation of N-substituted cyclic amines |
| DE19624283A1 (en) * | 1996-06-18 | 1998-01-02 | Basf Ag | Process for the preparation of N-substituted cyclic amines |
| DE19709488A1 (en) * | 1997-03-07 | 1998-09-10 | Basf Ag | Process for the N-alkylation of amines |
| BRPI0815978A2 (en) | 2007-08-29 | 2015-02-18 | Basf Se | PROCESS FOR PREPARING AMINES AND USING A REACTION EFFLUENT AND A MONOAMINE |
| CN102159311B (en) * | 2008-09-19 | 2013-07-10 | 巴斯夫欧洲公司 | Method for continuous production of amine using aluminium-copper catalyst |
| ES2590457T3 (en) | 2008-11-05 | 2016-11-22 | Basf Se | Procedure for the production of N, N-substituted 3-aminopropane-1-oles |
| US20110313188A1 (en) | 2009-02-09 | 2011-12-22 | Basf Se | Method for improving the catalytic activity of monolithic catalysts |
| WO2010089265A2 (en) | 2009-02-09 | 2010-08-12 | Basf Se | Hydrogenation catalysts, the production and the use thereof |
| US20110313187A1 (en) | 2009-02-09 | 2011-12-22 | Christof Wilhelm Wigbers | Method for improving the catalytic activity of monolithic catalysts |
| US8455693B2 (en) | 2010-05-21 | 2013-06-04 | Basf Se | Process for preparing 2-(2-tert-butylaminoethoxy)ethanol (tert-butylaminodiglycol, TBADG) |
| CA2798971C (en) | 2010-05-21 | 2018-07-24 | Basf Se | Process for preparing 2-(2-tert-butylaminoethoxy)ethanol (tert-butylaminodiglycol, tbadg) |
| WO2011157710A1 (en) | 2010-06-15 | 2011-12-22 | Basf Se | Process for preparing a cyclic tertiary methylamine |
| WO2012049101A1 (en) | 2010-10-14 | 2012-04-19 | Basf Se | Method for producing a cyclic tertiary amine |
| WO2012055893A1 (en) | 2010-10-29 | 2012-05-03 | Basf Se | Process for preparing 1,4-bishydroxyethylpiperazine |
| US8436169B2 (en) | 2010-10-29 | 2013-05-07 | Basf Se | Process for preparing 1,4-bishydroxyethylpiperazine |
| WO2012084914A1 (en) | 2010-12-23 | 2012-06-28 | Basf Se | Thermoplastic elastomer composition and method for the production thereof |
| EP2822921B1 (en) | 2012-03-07 | 2018-06-20 | Basf Se | Method for thermal integration in the hydrogenation and destillation of c3-c20 aldehydes |
| US9035110B2 (en) | 2012-03-07 | 2015-05-19 | Basf Se | Process for heat integration in the hydrogenation and distillation of C3—C20-aldehydes |
| TWI654177B (en) | 2013-10-31 | 2019-03-21 | 德商巴斯夫歐洲公司 | Process for preparing carboxylic acid esters and use thereof as plasticizer |
| EP3077453B1 (en) | 2013-12-06 | 2018-03-28 | Basf Se | Softener composition which contains tetrahydrofuran derivatives and 1,2-cyclohexane dicarboxylic acid esters |
| PL3092266T3 (en) | 2014-01-09 | 2018-12-31 | Basf Se | Plasticizer composition containing furan derivatives and 1,2-cyclohexanedicarboxylic ester |
| BR112016024512A2 (en) | 2014-04-22 | 2017-08-15 | Basf Se | ? process for producing carboxylic esters? |
| DE102015207291A1 (en) | 2014-04-24 | 2016-03-10 | Basf Se | Plasticizer composition containing furan derivatives and 1,2-cyclohexanedicarboxylic acid ester |
| TW201605945A (en) | 2014-07-08 | 2016-02-16 | 巴斯夫歐洲公司 | Molding compounds containing esters of dicarboxylic acids and esters of 1,2-cyclohexanedicarboxylic acid |
| TW201609628A (en) | 2014-07-08 | 2016-03-16 | 巴斯夫歐洲公司 | Plasticizer composition which comprises diesters of aliphatic dicarboxylic acids and dialkylesters of terephthalic acid |
| TWI706979B (en) | 2014-08-19 | 2020-10-11 | 德商巴斯夫歐洲公司 | Plasticizer composition comprising polymeric dicarboxylic esters |
| TWI686444B (en) | 2014-09-04 | 2020-03-01 | 德商巴斯夫歐洲公司 | Plasticizer composition comprising polymeric dicarboxylic esters |
| TW201619119A (en) | 2014-10-09 | 2016-06-01 | 巴斯夫歐洲公司 | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and 1,2-cyclohexane dicarboxylic esters |
| TW201619120A (en) | 2014-10-09 | 2016-06-01 | 巴斯夫歐洲公司 | Plasticizer composition which comprises cycloalkyl esters of saturated dicarboxylic acids and terephthalic esters |
| ES2707345T3 (en) | 2015-01-30 | 2019-04-03 | Basf Se | Plasticizing composition containing polymeric esters of dicarboxylic acids and dialkyl esters of terephthalic acid |
| US20180282511A1 (en) | 2015-09-30 | 2018-10-04 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and terephthalic acid dialkyl esters |
| US20180291180A1 (en) | 2015-09-30 | 2018-10-11 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and dicarboxylic acid diesters |
| PL3356459T3 (en) | 2015-09-30 | 2020-05-18 | Basf Se | Plasticizer composition containing polymeric dicarboxylic acid esters and dicarboxylic acid diesters |
| US10550242B2 (en) | 2016-01-20 | 2020-02-04 | Basf Se | Plasticiser composition containing aliphatic dicarboxylic acid esters and diesters selected from 1,2-cyclohexane dicarboxylic acid esters and terephthalic acid esters |
| PL3433309T3 (en) | 2016-03-23 | 2020-11-16 | Basf Se | Polymer composition containing a cycloalkyl alkyl dicarboxylic acid diester as a plasticizer |
| US20190161597A1 (en) | 2016-08-01 | 2019-05-30 | Basf Se | Plasticizer composition |
| WO2018024591A1 (en) | 2016-08-01 | 2018-02-08 | Basf Se | Plasticizer composition |
| WO2018024597A1 (en) | 2016-08-01 | 2018-02-08 | Basf Se | Plasticizer composition |
| WO2018210720A1 (en) | 2017-05-16 | 2018-11-22 | Basf Se | Hydroformylation method for the large-scale production of aldehydes and/or alcohols |
| WO2019185409A1 (en) | 2018-03-29 | 2019-10-03 | Basf Se | Pvc composition containing at least one plasticizer having at least one carboxylic acid ester group, and containing at least one carbodiimide compound |
| EP3747860B1 (en) | 2019-06-04 | 2023-07-26 | Basf Se | Novel cyclohexanone based plasticisers |
| KR20230170939A (en) | 2021-04-14 | 2023-12-19 | 바스프 에스이 | Process for continuous production of amines in gas phase using recirculating gas mode |
| CN114804227B (en) * | 2022-04-24 | 2023-07-07 | 南通金通储能动力新材料有限公司 | Layered structure sodium ion battery positive electrode material precursor and preparation method thereof |
| WO2024133358A1 (en) | 2022-12-21 | 2024-06-27 | Basf Se | Plasticizer compound |
| WO2024153687A1 (en) | 2023-01-19 | 2024-07-25 | Basf Se | Method for producing 1,2-cyclohexane dicarboxylic acid dialkyl esters |
-
1974
- 1974-09-21 DE DE2445303A patent/DE2445303C3/en not_active Expired
-
1975
- 1975-09-04 CA CA235,123A patent/CA1055677A/en not_active Expired
- 1975-09-15 NL NL7510838A patent/NL7510838A/en not_active Application Discontinuation
- 1975-09-17 CH CH1204575A patent/CH616638A5/en not_active IP Right Cessation
- 1975-09-19 GB GB38507/75A patent/GB1512797A/en not_active Expired
- 1975-09-19 FR FR7528760A patent/FR2285342A1/en active Granted
- 1975-09-19 BE BE160182A patent/BE833597A/en not_active IP Right Cessation
- 1975-09-22 JP JP50113808A patent/JPS5156800A/en active Granted
-
1981
- 1981-06-24 JP JP56096801A patent/JPS5778947A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8637668B2 (en) | 2010-06-15 | 2014-01-28 | Basf Se | Process for preparing a cyclic tertiary methylamine |
| US8933223B2 (en) | 2010-10-14 | 2015-01-13 | Basf Se | Process for preparing a cyclic tertiary amine |
| US8884015B2 (en) | 2012-06-01 | 2014-11-11 | Basf Se | Process for the preparation of a mono-N-alkypiperazine |
| US8927712B2 (en) | 2012-06-01 | 2015-01-06 | Basf Se | Process for the preparation of a mono-N-alkylpiperazine |
| US8981093B2 (en) | 2012-06-06 | 2015-03-17 | Basf Se | Process for preparing piperazine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5717850B2 (en) | 1982-04-13 |
| JPS5156800A (en) | 1976-05-18 |
| DE2445303A1 (en) | 1976-04-08 |
| DE2445303B2 (en) | 1978-08-03 |
| DE2445303C3 (en) | 1979-04-05 |
| NL7510838A (en) | 1976-03-23 |
| CH616638A5 (en) | 1980-04-15 |
| BE833597A (en) | 1976-03-19 |
| GB1512797A (en) | 1978-06-01 |
| JPS5778947A (en) | 1982-05-17 |
| FR2285342B1 (en) | 1979-06-22 |
| FR2285342A1 (en) | 1976-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1055677A (en) | Basic carbonate for manufacture of copper-containing catalyst | |
| US4009124A (en) | Basic mixed carbonate of copper and aluminum and process for manufacturing a copper-containing catalyst | |
| JP3232326B2 (en) | Copper-based catalyst and method for producing the same | |
| JP4062647B2 (en) | Catalyst for steam reforming of methanol | |
| US5580536A (en) | Composite oxide having oxygen absorbing and desorbing capability and method for preparing same | |
| US5571492A (en) | Composite oxide having oxygen absorbing and desorbing capability | |
| EP0042471B1 (en) | Catalyst and method for producing the catalyst | |
| US3787332A (en) | Carbon monoxide conversion catalysts | |
| US4305842A (en) | Preparation of improved catalyst composition | |
| US3971735A (en) | Methanol production catalyst and process for preparing the same | |
| US3899577A (en) | Carbon monoxide conversion catalysts | |
| EP0057796B1 (en) | Catalyst, catalyst support and oxychlorination process | |
| JP2002537204A (en) | Settling process | |
| EP0541329B1 (en) | Composite metal hydroxide and process for the production thereof | |
| US4935393A (en) | Process for catalytic reduction of nitrogen oxides | |
| JP2553143B2 (en) | Synthesis of zeolite L | |
| US4107089A (en) | Catalyst for the synthesis of methanol and method for preparing same | |
| JP2000290452A (en) | Mg-al-based hydrotalcite type particle powder, stabilizer for chlorine-containing resin and production of the same powder | |
| JP2002079101A (en) | Catalyst precursor for methanol steam reforming, catalyst for methanol steam reforming and its manufacturing method | |
| US4062899A (en) | Butynediol manufacture | |
| JP2000290451A (en) | Mg-al-based hydrotalcite type particle powder, stabilizer for chlorine-containing resin and production of the same powder | |
| US4092372A (en) | Catalyst for the production of isoprene | |
| US5108973A (en) | Crystalline copper chromium aluminum borate | |
| GB2065628A (en) | Process for the recovery of molybdenum | |
| US4118227A (en) | Process for producing dicalcium silicate power |