CA1205449A - Process for synthesizing a multicomponent acidic catalyst composition containing zirconium by an organic solution method - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for preparing a catalyst composition wherein a Metal Hydrocarboxide I, such as aluminum sec-butoxide, a Metal Hydrocarboxide II, such as zirconium butoxide, an acidic phosphorus-oxygen composition, such as phosphoric acid, and water, are reacted in the presence of a liquid organic medium, such as acetone, to form a catalyst precursor composition, which is then calcined to form the catalyst, is disclosed. The catalyst is useful for condensing carboxylic acids or their ester with aldehydes or acetals to synthesize .alpha.,.beta.-ethylenically unsaturated acids or esters, such as methylmethacrylate.

Description

:
1 BACXG~OUND OF T~E INVENTION
.... ~

2 The present invention relates to acidic catalyst

3 compositions, their preparation, and use to synthesize, for

4 example ~,3-unsaturated carboxylic acids, their functional derivatives, or olefinic oxygen-containing or-6 ganic compounds.
7 It is ~nown that olefinic compounds can b~ syn-8 thesizad by reacting aldehydes or acetals with organic com-g pound~ containing carbonyl groups such as carboxylic acids, e~ters, aldehydes, and ketones. Such reac~ions can be 11 illu~trated by the following equations:
12 ca3cH2-co2~ca3 + H~O --bC~3-~c-cO2ca3 + ~2 (Eq. 1) 13 ~o~oaldehyte C~2 14 C~3-Ca2-C02-C~3 ~ C~2-(octl3)2 ~' CH3-l~-C02-S~3 ~ 2G~130~ tEq. 2) ~lethylal C~12 16 It will be noted that equations 1 and 2 use formaldehyde or 17 methylal, re~pec~ively, as alternative reactants. These 18 are conventional rezctants which are each associated with 19 certain disadvanta5es depending on the choice of catalyst.
Catalysts employed for the re ctions of e~ua~ions 1 or 2 21 can broadly be classified as basic or acidic. It is well 22 kncwn, that ba5ic catalysts, when employed in co~junction ' 23 with ~he reaction of equaticn l, wi]l cause disproportionation j 24 of formaldehyde to H2, CO2, and methanol, in accordance with ~he Cannizzaro reaction thereby reducing the selec-26 tivity of the reaction to desired products such as methyl-27 methacrylate ~MM~) and/or methacrylic acid (L~A). In addition, 2~ the use o~ a basic catalyst also causes decarboxylation of 29 the co-reactant carboxylic acid or ester thereof whether formaldehyde is smpLoyed as a reactant or not, thereby 31 ~urther reducing the selectivity to desired products. ~ur-2 thermore w~en formaldehyde is manufactured in the vapor phase, it is adsorbed and dissolved in water to reduce its 34 potential to polymerize. Methanol is also employed ~s a 35 polymerization inhibitor. Consequently, formaldehyde is 6 generally sold economically as a 35~45 wt.~ mixture of the 37 same with the remainder ~eing water and methanol. The .. . . __. . . . . . . . .... ...
38 presence of 3uch large am~unts of ~water and methanol makes 39 it diicult to economically achieve a concentrated reac-~54'-~9 1 tant feed ~tream. I~ view of the disadvantages of the 2 base-catalyzed ~ormaldehyde based synthesis route, attempts 3 have been made to replace formaldehyde with a less trouble-4 some reactant such as dimethoxy methane, also known as methylal. However, when methylal is employed in conjunction 6 with a base catalyst, co~ersion of met~yLal is very low.
7 Such low conversions are believed to be attributable to the 8 inability of the basic catalyst to efficie~tly hydrolyze 9 the methylal to formaldehyde which in turn reacts with the car~oxylic acid or ester co-reactant. This problem has 11 been alleviated to some extent by the use of acid catalysts.
12 ~owe~er, e~en with conven~ional acid catalysts, tne conver-13 sion of methylal is still well under 100~. Furthermore, it 14 ha~ been reported (see Albanesi et al discussed herein-after) that certain acid catalysts also lead to decarboxy-16 lation of, for e~ample, methylpropionate producing CO2 and 17 dimethyl ether.
18 Ob~iously, the most efficient use of methylal 19 w~uld be to conver~ 100% thereof to MMA and/or MA while keeping co-reacta~t decarboxylation to a minimum. Such 21 high e~ficiency reactions are difficult, however, to 22 achieve in practice. A suitable and relatively economic 23 alternative would be to produce reusable by-products which 24 could be recycled in as efficient manner as po~ible. One reusable by-product from methylal is formaldehyde. ~owever, j 26 when less than 100~ conversion of methylal occurs, optimum 27 use of process credits would necessitate recove~y and 28 recycle not only of formaldehyde, but also of unconverted 29 methylal. This complicates the recycle procedure relative to the recycle of formaldehyde alone. Furthermore, i~ one 31 gee~s to ra~ycle formaldehyde, the decompositi~n thereof to 32 COi and ~2 must also be minimized. Similar considerations 33 apply to the undesired decarboxylation reactions which also 34 produce unusable products that cannot be recycled.
Acc~rdingly, and in view of the above it ~ould be 36 o~ ~xtreme economic ~ignificance if a catalyst could be 37 devel~p~d which is capable of employing either methylal or 38 formaldehyde a~ a reactant for the production of ,~-39 ethylenically un~aturated product~ for carb~xylic acids or

5~

1 their deri~ative.~ without, or with at lea~t reduced, 2 attendant u~desirable side reactions which occur when 3 employing conventional acidic or basic catalysts.
4 Various processes and catalysts have been proposed for the aforedescribed reactions.

6 For example, U.S. Patent No. 3,100,795 describes

7 the u~e of basic catalysts such as natural or syn~hetic

8 (e.g. zeolitesi, alkali and alkaline earth metal aluminosili-g catesi a~ well as alkala and alkaline eaxth metal hydro-xide~ supported on natural or syn~hetic aluminosilicates or 11 silica gels, to catalyze the reac~ion betwee~ methanol, 12 propionic acid, an~ formaldehyde to orm methylmethacrylate.
13 ~he co~version to methylmethacrylate based on formaldehyde 4 i3 reported in Example 5 as 66% and the yield is reported a~ 39%, although such terms as conversion and yield are 16 left undefined in this patent. Neither ~he catalyst.c o~
17 the preRent i~ention nor the method of its preparatioR are 18 diqclosed in this patent.
19 U.S. Patent No. 3,840,588, assigned to ~onsanto, describes the use o alkali metal hydroxides or oxides dis-21 per~d on a support having a surface area o~ 350 to 1000 22 ~2/gm~ Suita~le supp~rt ~aterials include aluminas, thorias, 23 magnesias, silica-aluminac, and silicates. In addition to 24 hydroxides or oxides, o~her alkali metal compounds may be depo-~ited on the support such as c~rboQatec, nitrates, sul-26 phateg, phosphate~, inorganic salts, acetates, propionates 27 or cther car~oxylates. All of such supported catalysts are 28 ~asic catalysts and no reaction between the catalysts and 29 their supQorts is even alleged, iimpla impregnation procedures being employed for deposition. These catalysts are employed 1 in thq rea~t on of formaldehyde and saturated alkyl carb-2 oxylates to form ~ ethylenically unsaturated ecters at 33 temperatures o~ at least 400 to 600C. A methylmethacrylate 34 selecti~ity of 82 ~ole ~ at formaldehyde conversions o~ 9a%
are reported in thi~ patent at a reaction temperature of 36 40~C and a space time yield of 490 L/hr ~Table IX, Run 7).
37 ~owever, at 430C and higher space time yield~ o~ 960 L/hr 38 ~Ex~mple 1) the selectivity to methylmethacrylate of 92 39 mole ~ is obtained at a formaldehyde conversion oP only ps~
.

1 67~. At reaction temperature~ ~elow 400~C, it i alle~ed 2 that selectivities drop significantly, e.g., to below 40%
3 (see FIG. 2) due to the CanAizzaro reaction (Col. 3, Lines 4 29 et seq~. Moreover, water must be employed in the feed s stream in strictly controlled amounts to obtain good 6 selectivity. In the absence o~ water, formaldehyde 7 con~ersion is negli~ible, and in the pre-~ence of too much 8 water ~electivity drops dras~ically. The sequired use of g water nece~sitates the use of alcohols in the feed stream to 5uppress hydrolysi5 of the ester reactant and reduce the 11 amou~t of ester in the reaction zo~e by acting as a diluent 12 (qee Col. 3, Lines 55 et se~) as well ~s complicating the 13 o~erall process to implement strict control of the water 14 conte~t of the feed stream. This control of water content ca~ be ~urther complicated by the in-situ production of 16 water i~ the ~eactor. Thus, selectivities and yields 17 ach~eved in this pate~t are obtained at the sacrifice o~
18 gimplicity o~ process design and overall process economics.
19 U.S. Patent Mo. 3,933,888, assigned to Rohm and ~aa~ Co., discloses the reaction of ~ormaldehyde ~ith an 21 alk~noic acid o~ its eYter i~ the presence of basic catalysts ~ .
22 ~ontaining basic pyro~enic silica (e.g. SA of 150 ~o 300 23 m2~g) alona or impregnated wit~ acti~ating agents which 24 p~o~ide additional basic sites to the pyrogenic silica when 25 calcined. Such activating agents include alkali and alka- .
Z6 line earth m~tal hydroxides, oxides, amides, and salts such ~7 ~5 ~ar~cQates, oxalates ph~sphAtes, e.g., Na3PO4, Na2~PO~, 28 gU~3, Na4SiO4- The identit~, impregnation, and calcination 29 procedures, of the activating agant is always selected to 30 pro~id~ a b~sic catalyst. A molar ratio of alkanoic acid:for-31 maldehydé:water:methanol of from 1-1:0. oi o tG ~ 6: O . 03 iS
32 di~closed. With a molar ratio of prop~onic acid:formalde-33 hyde:water:m~thanol of 20:20:50.1 and a maximum o~ 34%
34 co~ver~ion o~ formaldehyde and propionic acid to methacrylic 35 acid and methylmethacrylate, selecti~ities (referred to in l .
36 this patent as yields) to ~A + .~M~ no greater than 69%, 37 baced on formaldehyde conv0rted, or 80~, based on propionic 3~ acid converted, are achieved. When reacting methyl propionate F

.

~2~

i ratio, the .electivity to MA + MMA based on a formaldehyde 2 conversion of 25% is 63% (see Ex. 24). Furt.hermore, from 3 the data of Table III in this pa~ent, it can be calculated 4 that for every lOO moles of formaldehyde in the .eed, 34 5 moles thereof are converted to MA + MMA, and 45 moles 6 thereof remain unreacted. About 21 moles of formaldehyde 7 are unaccounted for.
8 ~.S. Patent No. 4,118,58~, assigned to BASF, is g directed to a process for synthesizing ~ ethylenically lQ unsaturated acids or esters such as methacrylic acid and ll methylmethacrylate from the reaction of propionic acid 12 and/or methylpropionate with dimethoxym~thane (methylal) in 13 the presence of catalysts (most of which are acidic) based 14 on one or more salts selected from phosphates and silicates 15 of: ~agnesium, calcium, aluminum, zirconium, thorium and 16 titanium. 5uch salts can be used alone or together with 17 oxide of the same aforedescribed magne~ium et al metals, 18 and additionally boric acid and/or urea. ~hus, a typical 19 acidic catalyst consists of aluminum phosphate, titanium 20 dioxide, boric acid, and urea. Included within the list of 21 62 possible combinations of various materials are aluminum 22 .phosphate and aluminum siLicate, or aluminum phosphate, 23 aluminum silicate, and boric acid. Such ca~alys~s can be 2~ modified with alkali and/or alkaline earth metal: carboxyLates, 25 oxides, silicates and hydroxides. The method of catalyst 26 prepa~ation includes mixing and heating the constituent 27 components of the ca~alyst in water, evaporating the water 28 and drying. Other methods are disclosed, such as forming a paste, or precLpLtation from aA aqueous solution, but each 30 of the~e alternate methods employs water as the liquid 31 medium. The components of the catalyst are de~cribed at 32 Col. 6, Line~ 44 et seq, as ~eing present in the catalyst 33 as a mere mix~ure, as membexs of a crystal lattice, or in 34 the form of mixed crystals. This patent therefore does not 35 disclose a catalyst composition of the present invention 36 wherein the components thereof have been reacted in a 37 li~uid organic medium to form an amorphous or substantially 38 amorphous material, nor does it disclose the method of 39 preparing such a catalyst. The highest conversion of 1 meth~lal reported in this patent is 92~ at a sel~ctivity 2 ~rererred to in the patent as yield) to ~MA of 95~ when 3 employing cataly~t of Tio2, AlPO4, H2BO4, and urea, and a 4 reaction time of 30 min. As described hereinafter at Comparative Example 1, such selectivlties drop drastically when the reaction 6 t~me is extended to 2.5 hours ~fter dis~arding the first 15 m mutes 7 of product.
8 U.S. Patent No. 4,147,718, assigned to Rohm Gmb~,

9 is directed to a metAod ~or making ~ unsaturated carboxylic acids and their unctional derivatives, such as 11 methacrylic acid aQd methyl~ethacrylate, from the reaction 12 of methylal (dimethGxymethane) with propionic acid or its 13 corr~sponding e~ter or ni~rile, in the presence of a 14 catalyst, which catalyst is a combination of silicon dioxide provided with basic sites (as described in U.S.
16 Patent No. 3,933,888) and aluminum oxide, ~hich optionally 17 may al30 be provided with basic sites in a Qimilar manner.
18 Aqueous impregnation procedures are ~mplo~cl or incorporation 19 of the basic sites, and the resulting basic silioon dioxide and aluminum oxid~ oomponents are merely then optionally mdxed or ar-21 ranged in separate layers. Thus, the acid catalys~s of the present 22 invention are not disclosed in this patent. The highest selectivity 23 bo MM~ is 87.1~ bu~ at a conversion of propionic acid or methylprop-24 îonate o~ only 13.3~. me highest conversion reported is 42% at a MMk selectivity of 78%.
26 U.S. Patent No. 4,324,908, assigned to SO~IO, is 27 directed to a promoted phosphate catalyst for use in syn~
28 thesizing a~-unsaturated products, which catalyst 29 requi~es the presence of at least one or more of Fe, Ni, Co, ~n, Cu, or Ag, as promoters in conjunction with phos-31 phorus and oxygen. $he catalysts of the present invention 32 do not require the presence of such promoter metals in any 33 form. The highest per pass conversion of methylal to MMA +
34 MA is 52.9~ at a methylal conversion of 97.6~.
Alba~esi, G., and Moggi, P., Chem. Ind. (Milan) 36 Vol. 63, p. 572~4 (l98l~ disclose the use of Groups 3, 4, 37 and 5 metal oxid~s in unsupported, or SiO2 supported form, 38 for the condensation reaction between the methyl hemiacetal -1 of formaldehyde (C~30C~20~) and methylpropionate to form 2 methylmethacrylates. Ten percen~ W03 supported on SiO2 is 3 reported as the best catalyst relative to other disclosed 4 catalysts because the decomposition of formaldehyde to C0 5 and C02 and the decarboxyiatio~ of methylpropionate, occur 6 least over this ca~alyst. However, the highes~ reported 7 formaldehyde conversion when employing the tun~sten catalyst 8 is only 37.5~. Furthermore, it is disclosed that gamma-g alumina, silica-alumina and molec~ r sieves tend to conver~

10 the hemlacetal of formaldehyde bo dime~hylether and formaldehyde

11 which in tuxn tend to immediately decompose to C0 and H2

12 above 40QC while in contact witn these materials.

13 U.S. Patent No. 4,275,052, by the inventor herein,

14 i~ directed to a process for synthesizing a high surface area alumina support (e.g., 300 to 700 m2/g) from organic 16 solutions o~ aluminum alkoxides ~y the hydrolysis of these 17 alkoxi~es with water. In accordance with this process, a 18 first solution of ~n aluminum alkoxide dissolved in an 19 organic solvent selected from ethers, ketones, and aldehydes, is mixed with a second solution comprising water and a 21 similar organic solvent. The resulting material is dried 22 and calcined, pre~erably in a water frae environment, i.e., 23 a dry gas, since the presence of water at these steps ar 24 the preparation will adver~ely a~fect the surface area or the alumina. ~he resulting alumina i9 u~ed as a 4upport or 26 oarrier mat~rial ~or catalytic components capable of pro-27 moting variou5 hydrocarbon con~ersion reactio~s such as 28 dehydrogenation, hydrocrackin~, a~d hydrocarbon oxidations.
29 Conventional promoter~ are employed for such reactions 30 including platinumf rhenium, germanium, cobalt, palladium, 31 rhodium, ruthenium, osmium and iridium. Thus, the use of 32 these aluminas to catalyze the synthesis of a ~ ~ -un 33 saturated products is not disclosed. Furtherm~re, the 34 reaction between aluminum alkoxide with other hydrocarboxides, 35 such as a zirconium alkoxide, and an acidic phosphorus 36 compound is also not disclosed.
37 U.S. Patent No. 4,233,1a4 is direct~d to an aluminum 38 phosphate alumina composition prepared by mixing and reac~

1 ^ting in the pre3ence of moist air, an aluminum aLkoxide and 2 an organic phosphate of the formula ~RO)3PO wherein R is, 3 ~or example, alkyl or aryl. The phosphor~s of the resulting 4 composition is alleged to be in the ~orm of AlPO~ based on x-ray analysis, but in some preparations the amorphous 6 nature of the product is said to make identification of the 7 phosphorus species diff icult. The amorphous nature of 8 these samples is b~lieved to be attributable to low calcina-g tio~ temperatures, e.g., below 600C. ~he mole ratio of alumin~ to alu~inum p~o5phate will depend upon the mole 11 ratio of aluminum alXoxide to organic phosphate employed in 12 the cy~thesis and the amount of aluminum phosphate in the 3 fi~al product can rangP from 10 ~o 30% by weight. Mixed 4 alumi~a-me~al oxide~aluminum phosphates are also disclosed wh~rein a mixture o~ metal al~oxides can ~e employed.
16 Thus, a SiO2-A12O3-AlPO4 can be prepared from a mixture of 17 silicon alkoxide and aluminum alkoxide with an organic 18 phosphate. Uowever, ~rom the description provided in this 19 patent, it does not appear that the optional metal oxides (~-g. SlO2) added initially a-~ metal alkoxides (e.g. silicon 21 alXoxide) react with the organic phosphate.. For example, 22 silicon alkoxide is merely converted to the corresponding 23 oxide, i.e., SiO2. This is confirmed at Col. 3, Lines 3, 24 18, and 22, and Exampies 4 to 9 wherein the optional additional metal3 are reported as being present as WO3 26 (Example-q 4 and 5) ~oO3 ~Example 6), SiO2 (Example 7 an~
27 8~, Zro2 (Example 9) (see also the characterization of 28 Cat~lyst G, Table VI). The or~anic phosphat~ employed in 29 preparing the cataly~ts of this patent do not possess an acidic hydrogen nor is an ether, aldehyde, or ketone or 31 mixtures thereof employed as a solvent medium (note Example 32 5 of thi patent employs an isopropyl alcohol organic 33 phosphate mixture during the preparation procedure, alcohol 34 alone being impermissible in the present invention) as required by the present invention. The resulting composi-36 ~ion is employed as a catalyst or catalyst support for 37 processes such as cracking, hydrocracking, is~merization, 38 polymerization, disproportionation, demetallization, hydro-39 sulfurization, and desul~urization. Use of ~he composition l as a catalyst for the synthesis of ~,B -unsaturated pro-2 ducts is not disclosed.
3 Alumil~a-aluminum phosphate-silica zeolite ca~ lysts 4 are disclosed in U.S. Patent Nos. 4,158,621 and 4,228,036.
In view of the commercial importance of ~,3-6 unsaturated products, such as methylmethacryla.e, there has 7 been a continu~ng search for catalysts which can produce 8 such products at improved co~versions, selectivities, : g and/or yields. The present invention is a result of this search.
11 S~A~ o~ sy~
12 In one aspect of the present invention there is 13 provided a proceSs for preparing a catalyst composition 14 which comprises: ~1) reacting in admixture at least one Metal ~ydrocarboxide I, at lea~t one Metal Hydrocarboxide 16 II, at least one acidic phosphorus-oxygen containing com-l~ pound, and water in the presence of at least one liquid 18 organ$c medium comprising at least 50~ by weight, based on 19 the weight of said medium, of at least one member selected ~rom ~he group consisting of organic aldehyde, organic 21 ketone, and organic ether, said reaction being conducted in 22 a man~er sufficient to ~a) avoid contact of ~etal ~ydro-23 carboxides I and II with water prior to contact of ~etal 24 ~ydrocarboxides I and II with the acidic phosphorus-oxygen containing compound and (b) form a catalyst precursor 26 compoqition; ~2) eparating said ~atalyst prec~rsor 27 composition from said reaction admixture; ~3) calcining 28 3a~d catalyst precursor composition to form said catalyst 29 composition; wherein said process: (i) the metal Ml of said ~etal Hydrocarb~xide I comprises aluminum; and (ii) 31 the m~tal, ~2, of said Metal ~ydrocarboxide II compris2s 3~ zirccnium.
33 In another aspect of the present invention there 34 is provided a catalyst composition prepared by the above process.
36 In a further aspect of the present invention 37 there is provided a process for using said cataLyst composi-38 tion to prepare ~,~-ethylenically unsaturated acids or 39 their acid derivatives.

~S~4~

_ 2 The catalyst composition of the present invention 3 is prepared by reacting at least one Metal (Ml) Hydrocar-4 boxide (referred to herein as Hydrocarboxide I), at least one Metal (M2) Hydrocarboxide ~re~erred to herein as 6 Hydrocarboxide II), at least one acidic phosphorus-oxygen 7 containing compound, and water in the presence of at least 8 one liquid organic medium under conditions and in a manner g sufficient to form a catalyst precursor composition which is then calcined to form an acidic catalyst composition.
~ The resulting catalyst composition comprises an inorganic 12 amorphous or substantially amorphous oxide material com-13 prising the following components xeacted therein:

14 Ml/M2/P/O (I) wherein Ml comprises aluminum and can further include at 16 lea~t one additional Group 3b element ~of the Periodic 17 Chart) selected from Ga, In, and Tl, 18 M2 compris~s zirconium, and can rurther include at least one additional Group 4b eleme~t selected from Si, Sn, and Ge, preferably Si. For ease of d.~scussion and description 21 the aforede~cribed Group 3b and 4b elements ~hich can 22 constitute Ml and M2 are referred to generically as metals, 23 although it is recogniæed that the texm "metal" as applied 24 to Si is an unco~ventional use of this term.
It i~ to be understood that the precise structure 26 of the metal-phosphorus oxide catalysts of the present 27 invention has not yet been determined although the components 28 of the catalyst composition are believed to be reacted with ~ each other during the preparative procedure and the re-30 sulting catalyst is therefore not believed to be a mere 31 mixture of oxides.
32 Hydrocarboxides I and ~I are selected to be capable 33 of undergoing hydxolysis o the organic portion thereof in 34 the presence of water~ and capa~le of being solubilized or 3S at le st partially solubilized in the organic medium and P54~

1 other components of the reaction mixture.
2 Suitable Hydrocarboxides I which can be employed 3 as the starting material can be represented by the structural 4 formula.

(M~ OR)3 (II) 6 wherein ~1 is as described above (Al), and R is a 7 substituted or unsubstituted hydrocarbyl radical indepen-~ dently selected from the group consisting of alkyi, typically 9 alkyl having from about 1 to about 8 carbons, preferably from about 2 to about 6 carbons, and most preferably from 11 about 3 to about 4 carbons, aryl, typically aryl having 12 from 6 to about 14 carbons, preferably from about 6 to 13 about 10 carbons, and most preferably 6 carbons, aralkyl, 14 and alkaryl, typically aralkyl and alkaryl wherein the alkyl and aryl por~ions thereof are as d~fined immediately 16 abov~ respectively; cycloalkyL, typically cycloalkyl having 17 from about 4 to about 12 carbons, preferably from about S
18 to about 10 carbons, and most preferably from about 6 to 19 about 8 carbons, all of the above described hydrocarbyl carbon numbexs being exclusive o substituents; said R
21 ~ubstituents being selected from ether groups, typically 22 ether groups represented by the structural formulae: -O-23 Rl, -Rl-o-R2~ wherein Rl and R2 are independently selected 24 rom the group consisting of alkyl, typically about Cl to 25 about Clo alkyl, preferably about Cl to about Cs alkyl, and 26 most preerably about Cl to about C3 alkyl; and ester 27 groups, typically ester groups represented by the structural 28 formulae:
29 0 o o o 30 ~ il ~ \\ /l 31 -C-O-Rl, -0-C-Rl, -R2~0-C~ and R2 o 32 wherein Rl and R2 are as defined above.
33 Preferred Hydrocarboxide I compounds include the 34 alkoxides.

~?544g 1 Representative examples of suitable ~ydrocarboxides 2 I of formula II include: aluminum ~ri: n-butoxide, sec-3 butoxide, isobutoxide, isopropoxide, n propoxide, ethoxide, 4 methoxide, phenoxide, benzoxide, napthoxide, methoxyethoxide, 5 3-~methoxy carbonyl) propoxide, 3-(ethyl carbonyl oxy) 6 butoxide, cyclohexoxide, 1,3-(dimethyl)-2-phenoxide, l,2 7 (methoxy)-4- benzoxide, and mixtures thereof.
8 Similar representative hydrocarboxides can be 9 formed replacing part, or all of the aluminum present 10 therein with any one or more of the other aforedescribed 11 Group 3b elements.
12 The preferred Hydrocarboxides I include aluminum tri:
13 ~ec-butoxide, n-butoxide, n-propoxide, isopropoxide, meth-14 oxide, ethoxide, and mixtures thereof.
Hydrocarboxide II which is employed as a s~arting 16 material in the precursor forming reaction can be represented 17 by the structural formula 18 (M2~ OR)4 ~III) 19 wherein M2 and R are as described above in connection with 20 structural formulae I and II above, respectively. The 21 cpecific hydrocarboxide ~ groups can be the same as illus-22 trated above in connection with the aluminum hydrocarboxides 23 and can be employed with any of the aforedescribed Group 4b 24 elements.
Preferred ~ydrocarboxides II include zirconium:
2~ tetraethoxide, tetra-n~propoxide, tetraisopropoxide, tetra-27 methoxide, tetra-n-butoxide~ tetraisobutoxide, and mixtures 28 thereof~
2g Th~ ~cidic phosphorus-oxygen containing com~ound 30 which can be employed as a starting material must possess 31 at least one acidic hydrogen and be capable of reacting 32 with the Hydrocarboxides I and II or the hydrolyzed- inor-33 ganic product thereof, and the use of the term "acidic 34 phosphorus oxygen compound" is indicative of this require 3~ ment. Representative examples of suitable acidic phos-36 phorus-oxygen containing compounds include phosphorus acid 1'5~45~

l (P~OH)3), phosphonous acid (~P~OH)2), phosphinous acid 2 (H2POH), phosphenous acid (o=PO~), phosphoric acid 3 ~P(O)(OH)3), phosphonic acid (HP(0)(0~)2), phosphinic acid 4 (~2P(O)(O~)), phosphenic acid (O=P(O)OH), phosphine oxide (~3PO), phosphoranoic acid (H4POH), phosphorane dioic acid 6 (H3P(OH)2), phosphorane trioic acid (H2P(OH)3), phosphorane-, 7 tetroic acid (HP(0~)4~, phosphorane pentoic acid t~P)~OH)s), as well as any of the aforenoted acids having one or more ~ but not all o~ the acidic hydrogens replaced with an alkyl group, typically Cl to C~o~ preferably Cl to Cs and most 11 preferably Cl to C3 alkyl.
l~ In addition, polyphosphoric acid, an acid commer-13 clally available as a mixture of orthophosphoric acid with 14 pryophosphoric~ triphosphoric and higher acids, sold on the basis of it5 calculated H3P04 content (e.g. 115%), and 16 super phosphoric acid sold at 105% H3P04 content, can also 17 be employ~d as starting materials.
l~ ' The preferred acidic phosphorus-oxygen compound l9 is phosphoric acid.
Upon hydrolysis of ~ydrocarboxides I and II and 21 reaction with the acidic phosphorus oxygen compound, 22 organic alcohols are formed. Since it is desired that 23 residual organic material in the catalyst composition be 24 minimized~ it is preferred as a mat~er of convenience to select the identity of the organic moiety of the Hydrocar-26 boxides such that the alcohols derived therefrom can be 27 easily vaporized, e.g., alkoxides having ~ewer than about 28 10 carbons are most preferred.
29 The organic medium used.in the preparation of the 30 cat~lyst precursor should be a liquid at reaction temperature 31 and is selected from: aldehydes, ketones, ethers, and mix-32 tures thereof typically containing from about l to about 33 20,.pref~rably from about l to abou~ 10, and most preferably 34 ~rom about 1 to about 5 carbon atoms.
More specifically, the organic moiety to which 36 the aldehyde, ketone, and ether functional groups can be 37 attached includes alkyl, typically about Cl to C2o7 1 preferably about Cl to Clo, most preferably about Cl to Cs 2 alkyl, aryl, typically about C6 to C14, preferably about C6 3 t~ Clo~ ~ost preferably C6 aryl, cycloalkyl, typlcally 4 about C~ to C~o, preferably abou~ C6 to C12, most preferably about C6 to Clo cycloalkyl, aralkyl and alkaryl wherein the 6 alkyl and aryl groups thereof are described above.
7 Each class of liquid organic medium can contain 8 one or more, typically 1 to 3, functional groups as well as g mixtures of functional groups. Furthermore, the preferred organic moiety of liquid organic medium is a sa~urated ali-11 phatic compound.
12 Representative aldehydes include benzaldehyde, 13 acetaldehyde, propionaldehyde, m tolualdehyd~, trioxane, 14 valeraldehyde, butyraldehyde, oæalaldehyde, malonaldehyde, adipaldehyde.
16 Representative ketones include ace~one, 3-pentanone, 17 methylethylketone, cyclohexanone, dimethyl ketone, diethyl 18 ketone, dibutyl ketone, methyl isopropyl ketone, methyl 19 sec-butyl~etone, benzophenon2, and mixtures thereof.
Representative ethers include dimethyl ether, 21 diethyl ether, dibutyl ether, tetrahydrofuran, anisole, 1 22 dioctyl ether, 1,2-dimethoxyethane, 1,4-dimethoxybutane, ! 23 diethylene ether, 1,1,3,3-tetramethoxypropane, and mixtures thereof.
Preferred organic media comprise acetone, 26 diethylether, acetaldehyde~ methylethyl ketone, 3-penta-27 none, 1,2-dimethoxyethane and mixtures thereof.
28 The most preferred organic medium is acetone or a 29 mixture of acetone and diethylether.
The organic medium is believed to undergo electro-31 static field interactions with the metals of Hydrocarboxides 32 I and II and the reaction intermediates which for~ upon 33 ccntact of the Hydrocarboxides I and II, the acidic phosphorus 34 compound and water in the reaction mixture. This interaction 35 is believed to occur through complexation of the organic 36 medium with ~he various species present in the reaction -

- 15 -1 mixture. Thus, 4he organic medium is not inert and only 2 certain organic media have been found suitable for this 3 purpose as described herein. The organic medium also 4 functions as a solvent and/or suspending agent for the 5 Hydr~car~oxides I and Il and phosphorus containin~ compound, 6 and any oomplexes and reaction intermediates thereof, as a 7 solvent and/or suspending agent of the resulting ~atalyst 8 precurso.r, as a liquid for providing uniform heating and/or g mixing of the catalyst forming reactants, and as a medium 10 capable of bringing Hydrocarb~xides I and II, the phosphorus-ll oxygen compound, and water into intimate contact for 12 reaction. To perform the latter function it is desirable l~ to select the organic medium such that it is at lea~t 14 mi~cible, preferable soluble, with or in, water, the 15 catalyst forming reactants, and the Hydrocarboxide derived

16 alcohol. It is also preferred to select the organic medium

17 so that it will be completely or substantially removed from

18 the catalyst precurs~r during drying and/or calcination.

19 Thus, organic media with low molecular weight, and high

20 vapor pres~ure are preferred. Minor amounts of alcohol,

21 ~uch as the hydrocarboxide derived alcohol can be tolexated

22 within t~e organic medium initially or as it forms. Minor

23 amounts of esters can also be included although this is not

24 preferred. By minor amount as used herein is meant less

25 than 50%, preferably less than 25%, and most preferably

26 less than 10~, by weight of the organic medium. Minor

27 amounts of inert diluents can be employed to reduce the

28 c08t of organic medium, such as paraffins, aromatic

29 compounds, and mixtur~s thereof, although this is not p~eferred.
Thus, the organic medium is selected so tha~ it 31is a liquid at reaction temperature, preferably dissolves, 32or at least partially dissolve5 the precursor formi~g reactants 33and comprises at least 50~, preferably at least 75~, and 34most preferably at least 90% (e.g. 100~), by weiqht thereof, 350f any onè or more of said aldehyde ketone, and ether. It 36is preferred to exclude the presence of any organic 37alcohol, ester, or acid from the initial starting composition D5~4S~

1 o~ the liquid organic medium.
2 The catalyst precursor forming reaction i5 conducted 3 by providing a reaction admixture comprising at least one 4 Hydrocarboxide I, at least one Hy~rocarboxide II, water, 5 and liquid organic medium. H~wever, the order of addition 6 of the components is critical to the extent that it must be 7 conducted in a manner sufficient to avoid contact of either 8 of the Hydrocarboxides I and II with water prior to contact g of said Hydrocarboxides I and II with the acidic phosphorus-oxygen containing compound, to avoid premature reaction of 11 the water and the Hydrocarboxides I and II. Thus, a wide 12 variety of admixture se~uencec are possible subject to the 13 above constraints.
14 The preferred method of admixture is to initially 15 prepare two separate solutions typically at ambient tem-16 perature and pressure. The ~irs~ solution contains Hydro-17 carboxides I and II dissolved in a suitable organic liquid 18 medium. The second solution contains the acidic phosphorus-19 oxygen compound, water, and organic liquid medium, preferably 20 the ~ame medium used in, or at least miscible with, the 21 fir~t solution. The two solutions are then mixed preferably 22 ~y the addition of Solution 2 to Solution 1. While very 23 ~mall amounts o~ water may be tolerated in the first solution, 24 it is preferred that it be anhydrous. An alternative preferred 25 variation is to withhold a portion of the needed amount of 26 Hydrocarboxides I and~or II from the first solution (e.g.
2~withhold about 30~ by weight of the total ~ydrocaxboxide I
2~and/or II, combine the solutions and then add the remainder of ~ydrocar~oxide I and/or II. Stepwise addition of the 30Hydrocarboxides can also be accompanied with stepwise addition 310f organic medium. An alternative addition procedure is to 32prepare 3 separate solutions containing respectively, Hydro-33carboxide I and liquid organic medium (Solution 1), Hydro-34carboxide II and liquid organic medium (Solution 2), and 35 the acidic phosphorus-oxygen compound, water, and liquid 360rganic medium (Solution 3~. The solutions are then combined 3~simultaneously, or individually by separately adding Solution 1 3 to Solutions 1 and/or 2, and admixiny the resulting solutions 2 The rela~ive amounts of Hydrocarboxides I and II
3 and acidic phosphorus-oxygen containing compound employed 4 to form the ca~alyst precursor orming admixture determines the gram atom ratios of the componen~s in the catalyst.
6 Thus, while any effective amount of said materials may be 7 initially present in said admixture, it is contemplated 8 that such effective amounts constitute a mole ratio of g Hydrocarboxide I:Hydrocarboxide II of typically from about 1:3.5 to about 1:0.5, preferably from about 1:2 to about 11 1:0.7, and most pre~erably from about l:l.5 to about 1:0.8.
12 The mole ratio of Hydrocarboxide I-acidic phosphorus-oxygen 13 compound in the reaction mix~urP is typically controlled to 14 be from about l:l.5 to about 1:0.5, preferably from about l:l.25 ~o about 1:0.7, and most preferably from about 1:1.1 16 to about l:o.gs.
17 Water i~ also critical to the catalyst preparative 18 process of the present invention. The water hydroxyzes 1~ Hydrocarboxides I and II to form alcohols and corresponding 20 metal oxides and/or hydxoxides. Consequently, the amount 21 o water employed is related to the amount of ~ydrocarboxides 22 I and II present in the reaction admixture and preferably 23 is effective to obtain complete hydrolysis thereof. Exact 24 ~toichiometric ratios, however, are no~ required. Thus, 25 while any efective amount of water can be employed to form 26 the reaction admixture, it is contemplated that such effective ~7 amount~ constitut2 a mole ratio of the sum of the moles of 28 Hydrocarboxide~ I and II:H20 of typically from about 3:1 to 29 about 1:300, preferably from about 2:L to about 1:10, and

30 mogt preferably from about 1:1 to about 1:6.

31 The precursor forming reaction must be conducted

32 in the presence of at least some li~uid oxganic medium (the

33 composition of which is defined above). As the amount of

34 suitable ether, aldehyde, and/or ketone liquid or~anic

35 medium employed in the reaction mixture is decreased, the

36 concentration of the Hydrocarboxide derived alcohol produced

37 in-situ increases to the extent that the aforedescribed

38 complexation is decreased and the undesirable effects associated 1 with employing alcohol as the predominant organic medium 2 during the precursor formation become increasingly more 3 pronounced, namely, the yield of the ~ unsaturated 4 products described herein suffers drastically. The amount of organic medium present during the precursor forming 6 re~ction is therefore selec~ed to effect a stirrable solution 7 or partial solution of reactants, and improve the yield of 8 ~ unsaturate~ product derived from the use of the g resulting catalyst relative to the yield of said product obtainable from a ~atalyst prepared in the absence of said :la organic medium. Thus, while any effective amoun~ of 12 organic medium may be employed, it is contemplated that 13 such effective amount constitute typically at least about 14 25~, preferably at least about 40~, and most pref2rably at least about 50%, and _dn range typically from abou'; 25 to 16 about 95~, preferably from about ~0 to about 90~, and most 17 preferably from about 60 to about 85%, by weight, of the 18 reaction admixture, ba ed on the combined weight of Hydro-1~ carboxide I and II, the phosphorus-oxy~ n compound, organic 20 medium and water.
21 Furthermore, it is contemplated that the amount 22 of watèr in the reaction mixture is controlled to be typi-23 cally not greater than about 25%, preferably not greater 24 than about 20%, and most preferably not greater than about 15%, and can vary typically from about 5 to about 25%, 26 preferably from about 8 to about 20~, and most preferably 27 from about 10 to about 15~, by weight, based on the 28 combined weight of liquid organic medium and water in the ~ precursor Eorming admixture.
The resulting admixture is preferably mixed vigo-31 rously and continuously during its formation and during the 32 ~eaction to effect intimate contact and reac~ion between 33 the component reactants of the admix~ure. This can be _ _. . __ ., . , ~. .
34 achieved with conventional stirring means, by refluxing or both. Thus, in a batch operation an especially convenient 36 means of conducting the admixing is to mechanically stir 37 one solution while admixing into it the other solution. In 1 a continuous mixing operation, a convenient means of 2 conduc~ing the admixing is to simultaneously pump the two 3 solutions through a single means such as an in-line mixer.
4 If reluxing is employed during the catalyst precursor forming reaction, the liquid organic medium is preferably 6 selected so that it will boil at the selected reaction 7 temperatures described hereinbelow. Removal of the 8 Hydrocarboxides I and II derived alcohol by-product by 9 diqtillation can also be employed and is preferred when large amounts of said alcohol by-product are produced in-11 ~itu.
12 Th~ pxecursor forming reaction temperature is 13 effective to achieve complete reaction and is controlled in 14 conjunction with the prescure and in a manner sufficient to avoid vaporization and loss of ~he essential liquid 16 componènts o~ the reaction of the reaction admi~ture (e.g., 17 excluding by~product alcohol).
18 Thus, while any effective temper~ture may be 19 employed, it is contemplated tha~ such effective temperature~
20 typically will be at least 5C, preferably at least 10C, and most preferably at least 15C, and can vary typically 22 from about 5 to about 200C, preferably from abou~ 10 to 23 about 150C, and most pre~erably from about 15 to about 24 100C.
The precursor forming reaction time is selected 26 in conjunction with the reaction temperature and the amounts ~7 o~ Hydrocarboxides I and II to permit substantially complete ~8 reaction at the above reaction temperatures. Such reaction 29 time~ typically will vary from about 0.15 to about 40 30 hours, prefexably from about 0.2 to about 30 hours, and 31 most preferably from about 0.5 to about 20 hours, as measured 32 rom the initiation of contact of all of the reactive componen~
33 o~ the admixtureO It is desired to conduct admixture of 34 Hydrocarboxides I and/or II with the acidic phosphorus 35 oxygen compound to permit a slow reaction therebetween 36 Thi~ is typically achieved by controlling the addition 37 times thereof to be between about 0.5 and about 15 hours.

~2~P5~

1 The reaction genexally will be substantially complete after 2 typically from about 0.3 to about 10, preferably from about 3 0.5 to about 8, and most preferably from about 0.5 to about 4 5 hours, measured from completion of the formation of the reaction admixture at ambient temperature. Higher reaction 6 temperatures will cause completion of the reac~ion in shorter 7 times.
8 The reac~ion pressure is not critical provided 9 undue loss of the liquid contents of the reaction ad~ixture is avoided, and can be atmospheric, subatmospheric or 11 superatmospheric.
12 While not critical, upon passage of the aforedes-13 cribed reaction times and apparent completion of the 4 reaction, it is preferred to allow the con~ents of the admixture to age for periods of typically from about 1 to 16 about 30 hour~, and preferably from about 2 to about 22 7 hours, ~.g., at rea tion temperatures of typically from 18 about 10 to about lOOQc to assure that complete reaction 19 has occurred.
Upon completion of the reaction and optional 21 agin~ the catalyst precursor is separated from the organic 22 medium. Generally, the organic medium is selected so that 3 the catalyst precursor is insoluble therein at room te~ature.
24 Thus, precursor separation can be accomplished in a variety 25 of ways. Typically, it takes place in two stages, namely, 26 by bulk separation and then final purification, e.g., by 27 drying~
28 3ulk separation can be accomplished by filtering 29 the reac~ion ~dmixture to recover the catalyst precursor as 30 a~ilter cake, by centrifuging the reaction admixture, and 31 separating, e.g., by decanting, the supernatant liquid or-32 ganic medium from the solid precursor, or by evaporating 33 the liquid organic medium to form a cake or paste of the 34 catalyst precur~or.
The precursor solids, after bulk separation, are 36 then typically subjected to conditions sufficient to remove 37 any residual liquid organic medium or any organic contami-~Z~5~

1 nants. This can be achieved by dryin~, preferably continuous 2 drying, to evaporate residual oxganic liquid ~edium, by 3 washing the precursor solids with water or wi~h an organic 4 medium, preferably an organic medium, having a higher vapor pressure than the organic medium employed to form ~he ad-6 mixture to facilitate drying, or by employing both procedures.
7 Thus, before final purification is conducted, the separated 8 catalyst precursor solids can be washed in a liquid organic 9 Imedium one or more times to remove any residual unreacted materials and/or any other organic soluble species followed 11 ~y a repetition of bulk separation procedures and then 12 dryiny, although this is not required.
13 Drying can be achieved by heating the precursor, 14 e.g. by exposing the precursor to air at a temperature of from about 20 to about 160~C for a period of from about 0.5 16 to about 30 hours or by placing it in a forced circulation 17 oven maintained at a temperature typically between about 40 18 and about 250C for about 0.5 to about 30 hours. Alter-. ~ , .. . _ _ __ . .
19 natively, the precursor can be air dried at room tempera-ture for between about 1 to about 40 hours and then placed 21 in the forced circulation oven until constant weight is 22 attained. Drying under reduced pressure at room or elevated 23 temperatuxe, such as by using a vacuum oven is preferred.
24 The isolated precursor composition is then calcined to form the final composition capable of catalyzing the 26 formation of ~ unsaturated products described 27 herein. Calcination can be conducted in a separate step or 28 in-situ in the reactor and involves heating the precursor 29 composition to a sqlected temperature or temperatures within a de~ined temperature range. Preferably the calci~ation 31 procedure is conducted in stages by heating the precursor 32 in a stepwi~e ~ashion at increasingly higher temperature 33 plateaus until a temperature of at least about 60aC is 34 attained.
Accordingly, and in view of the above, calcination 36 is conducted at temperatures of typically from about 600 to 37 about 1300C, prefexably from about 700 to about 1000C

~2~

1 (e.g. 750 to 850C), and most preferably rom about 750 to 2 about 1000C (e.g. 750 ~o 950C) for a period of typically 3 fxom about 1 to about 48 hours, preferably from about 2 to a about 30 hours, and most preferably from about 2.5 to about 20 hours. Most preferably, the final t~mperature plateau 6 during calcination will be at least 720 to about 950C for 7 a period of about 0.5 to about 30 (e.g. 2 to 20) hours.
8 However, it is preferred to subject the precursor 9 to a precalcination procedure by heating it at temperatures of typically from about 400 to about 599 and most preferably 11 from about 450 to about 599C, for periods of typically 12 from about 0.1 to about lQ, and preferably from about 0.5 13 to about 8 hours. Calcination and precalcination can be ~ conducted as two different steps as by heating first at a selected precalcination temperature and then at a selec~ed 16 calcination temperature or by gradually increasing the 7 temperature from a precalcination range to a calcination 18 range.
19 The atmosphere undex which calcination is conducted 20 includes oxygen or an oxygen containing gas such as air~
21 nitrogen, helium, or other inert gas. At the higher cal-22 ci~ation temperatures it is preferred to include oxygen in 23 the calcination atmosphere.
24 While not essential, it is preferred that the 25 calcination atmosphere be passed as a moving gaseous stream 26 o~er the precursor composition.
27 Calcination can b~ conducted before, after, or 28 during intermediate stages of shaping of the catalyst pr~sor 29 a~ described h~reinafter.
30~ The catalyst precursor or catalyst itself i5 31 adaptable to use in the various physical forms in which 32 catalysts are commonly used as particulate or powdered 33 material in a contact bed, as a coating material on monolithic 34 structures generally being used in a form to provide high 35 ~urface area, as spheres, extrudates, pellets and like 36 configurations. The precursor or catalyst, can if desired, 37 be composited with various catalyst binder or supportmaberials, ?5;44~

1 or physical property modifier~ such as attrition resistance 2 modifiers, which do not adversely affect the catalyst or 3 the reactions in which the catalyst is to be employed.
4 Thus, various siz~d powders can be produced by 5 grinding the catalyst to the desired size by any conventional 6 or convenient means. Extrudates and pellets of various 7 sizes and shapes can be prepared by using any conventional 8 or convenient means. Utilizing a conventional screw ~ype 9 extruder, the dough or paste is processed through a die 10 plate generally comprising orifice openings in the 1/32-1~2 11 inch diameter range to form generally cylindrical particles.
12 The freshly extruded material may be collec~ed in the form 13 of ~trands of indefinite or random lengthq to be dried and 14 sub3~quently broken into extrudate par~icles; or the fre~hly extruded material may be cut into random or 16 predetermined lengths of from about 1/4 inch to about 1/2 17 inch and subseque~tly dried; or the freshly ex~ruded 18 material may be formed into spheres, for example, by the process whereby the extrudate strands are collec~d in a spinning drum, the strands becomin~ seg~nted and sFheroidized 21 under the spinning influence of the drum.
22 While the above description of the method of pre-23 paring the catalyst of the present invention is provided 24 with respect to the minimum components which must be 25 employed therein, it is contemplated that such catalysts 26 m~y have other additives (e.g. which modify the catalyst 27 properties) or promoters incorporated therein which typically 28 enhance the rate and/or selec~ivit~ of the intended reaction 29 for which the catalyst will eventually be employed to catalyze.
30 A pre~erred promoter for this purpos~ is boron. Catalysts 31 o the psesent i~vention which contain boron exhibit slightly 32 better activity at lower reaction temperatuses when employed 33 to cataiyze the synthesis of the ~ ethylenically 34 unsaturated produc~s described herein. Boron can be in-corporated into the catalyst composition during preparation 36 of the catalyst precursor or by impregnation of the catalyst 37 precursor or catalyst with a suitable boron compound prior S~4~t 1 or subsequen~ to calcination procedures. Preferably, the 2 boron compound is incorporated during preparation of the 3 catalyst precursor. This can be achieved by selecting a 4 suitable boron compound which preferably is soluble in the liquid organic medium. Representative examples of such 6 boron compounds include boron acetate, boron hydrocarboxides, 7 prefera~ly boron alkoxides, wherein the hydrocarboxide 8 portion is as described in connection with ~ydrocarboxides 9 I and II, big (di-acetoboron) oxide, boric acid, and mixtures thereof~ The boron compound can be adde~ to the precursor U forming admixture directly or to any of the solutions which 12 are combined to form the precur~or forming admixture.
13 Alternatively, a boron compound can be impregnated 14 into the cataly~t ~omposition by Gonventional means, such as by con~act of the catalyst composition wi~h an impreg-16 nating solution having the boron compound dissolved therein~
17 Compounds of ti~anium, such as, ~iO2 or titanium hydrocar-18 boxide similar to the hydrocarboxides disclosed herein, can also be included in the catalyst in a similar manner~
Furthermorè minor amounts (up to abo~t 49%) of 21 silicon hydrocarboxides, e.g. alkoxides, can also be included 22 in the ca~alyst precursQr preparative procedure. Typically 23 such amounts can vary from abou~0.1 to about 45 , preferably 24 from about 0.2 to about 35 , and most preferably from about 0.4 to about 30 mole ~ of ~ydrocarboxide II can be 26 a silicon hydrocarboxide.
27 The catalysts of the present invention have a 23 surace area of typically from about 10 to about 300, and 29 pre~erably from about 15 to about 170 m2/g, as determined by the fiET method, the general procedures and theoxy for 31 which are disclosed in H. 8runaur, P. Emmett and E. Teller, 32 J. Of Am. Chem. Soc. Vol. 60, p. 309 (1938).
. . .
33 In most instances, the Al/Zr/P/O catalystj of the 34 present invention are believed to be characterized by the a~sence of any distinct crystalline phases, i.e., they are 36 substantially amorphous within the limits of detection of 37 the x ray diffrac~ion technique.

6P5~4~

1 ~he catalyst~ of ~he present invention can be em-2 ployed to improve any one or more of the rate, conversion 3 and selectivity of the following well known reac~ion types:
4 (1) Th~ condensatio~, e.g~, vapor phase rondensa tion, of at least one aldehyde, or aldehyde forming com-6 pound, i.e.~ aldehyde precursor ~e.g. methylal), with at 7 least one carboxylic acid or derivative thereof, such as an 8 e~ter, to for~ ,~-unsaturat~d acids or ~ters. Such g reac ion ca~ ~e represented by the folio~ing equation R -CH2-CO2R + R CHO R3-C-Co2R ~ H20 (Eq. 3) 11 (i) (ii) CHR
12 wherein R3~ R4, and R5 which may be the ~ame or differe~t 3 repre~ent hydrogen, or a hydrocar~yl radical as descr$bed 14 in conjunction with the un~ubstituted R group ~f formula II
described hereinabove. Since these r~actions are conducted 16 in the vapor phass, the identity o~ hydrocarbyl groups R3, 17 R4, and RS is qelected so that the respective reactants are 18 vaporizable without substantial decomposition under reaction 19 condition~. Reactant tii) of eq. 3 can altern~tively be replaced with acetals (e.g., methylal), or hemiac~tals 21 repre~ented by the structural formula R5-C~(oR4)~ and R5-22 C~(o~)oR4.
Z3 ~2) The condensation, e.g., vapor phasa c~n~ation, 24 o at least one carbonyl containing compound with at least one aldehyde, acetal, and/or hemiacetal to ~orm at least 26 one ~,~-unsaturat~d product aR represented by the 27 following reactions:
( i) ( ii) 28 R3-~2-C~o ~ CH30CH20H ~ R3-C-~o ~ CH30H + H20 (Eq.. 4 ( i) ( ii) 31 R3-CH2-C~10 + C~20 ~. R3-C-CH~ + ~2 ~Eq. 5) 32 ~2 33 (i) (ii) 34 R3-CH2-CHo I CH30CH20CH3 ~ R3C-CHo + 2CH30H (Eq. 6) ~ ~, ..~ `' .

- ~-z~s~

l wherein R3 is as described above~
2 (3) The esterification or hydrolysis of an est2r 3 as represented by the following reversible reac~ion:
4 R3-Co2H + R4-oH ~-- R3CooR4 ~ H2O (Eq. 7) wherein R3 and R4 are as described above.
6 (4) The conversion of an alcohol to an ether or 7 hyrolysis of the ether ~o an alcohol as represented by the -8 rev~rsible reaction:
9 2 R3-oH = R3-o-R3 ~ H20 (Eq. 8) wherein R3 is as described aboYe.
ll (51 The reaction of an ether with a carboxylic 12 acid to form an ester and alcohol as represented by the 13 r~action:

14 R3 COOH ~ ~4-o-~4 = R3 cooR4 ~ R40~ (Eq. 9) ~6) Other organic reactions which can ~e catalyzed 16 by acidic catalysts, such as dehydration, isomerization, 17 alkylation, cracking and the like.
18 Representative examples of suitable esters which can be employed i~ the reaction of equation 3 include methyl acetate, ethylacetate, methyl propionate, ethyl propionate, 21 methyl n-butyrate and the methyl ester of phenyl acetic 22 acid. Representative acids which can be employed in the 23 reaction of the above equations include the corresponding 24 free acids of the above identified esters.
If formaldehyde is employed as a reacta~t in any 26 of the a~oredescribed reactions, particularly equations 3 27 and 4, it can be used in any convenient form. For example, 28 it can be anhydrous paraformaldehyde, trioxane or in the 29 form of an aqueous of alcoholic solution as are available commercially. If desired, the process may be coupled 31 directly with a process for the manufacture of formaldehyde 32 or its polymers.

l Processes for the production of ~,3-unsaturated 2 products in acc~rdance with the reaction of equations 3 to 3 6 are well known as described hereinafter. ~hus, starting 4 materials (i) and (ii) of equa~ions 3 ~o 6 are employed in stoichiometric amounts, or in excess of either one over the 6 other. Accordingly, the mole ratio of starting materials 7 (i) and ~ii) of equations 3 to 6 typically can vary from 8 about 100:1 to 1:1.5, preferably from about 50-1 to about 9 1:1, and most preferably from about 10:1 to abou~ 201.
The above reactions are preferably conducted in 11 the vapor phase in the presence of the catalyst of the 12 present invention, continuously or batchwiqe, in a fixed or 13 fluidized bed~ The catalyst may b~ charged to a tube or on 14 trays or in a fluid bed, etc. through which the reactant mixture is passed. The reactor system may consist of a 16 series of catalyst beds with optional interstage heating or 17 cooling betwean the beds if desired. ~t is als~ an e~lx~n~nt 18 of the invention to use either upflo~ or downflow of the l9 reactants through the reactor, with periodic reversal of gas flow al~o being contemplated to maintain a clean catalyst 21 bed. If desired the gaseous feed may be charged together 22 with an in~rt carrier gas, e.g.l nitrogen, ~*x~ o~ides, low 23 mDleculæ weigh~ ~y~c~xns or Cfi to Clo aromatic hydrocarbons.
24 The reaction temperature of the abo~e reactions (E~. 3 to 6) will typically vary from about 170 to about 26 450, preferably rom about 200 to about 400, an~ most preferably 27 from about 250 to about 380C, under atmospheric or super-28 atmo9pheric pressure (e.g. 1 to 150 psig).
29 Suitable feed rates of reactants to the reaction ;

zone typically can vary from about 0.2 to akout 20, preferably 31 from about 0.4 to abo~t 10, and most preferably from about 32 0.5 to about 5 hr.~l LHSV.
33 The following examples are given as specific 34 illustrations of the claimed invention. It should be un~ers~d however, that the invention is not limited to the specific 36 details set forth in the examples. All parts and percentages 37 in the examples as well as in the remainder of the specifi-38 cation are by weight unless otherwise specif ied .

PS~4~3 -1 In the following examples, unless otherwise speci 2 fied, each catalyst is tested in the following manner: A
3 glass tube reactor 20 inches in length, 1 inch O.D. and 4 about 0.8 inch I.D., is stoppered at the bottom with glass wool, loaded with 20cc of catalyst sample, on top of which 6 is placed lOcc of glass wool, followed by the addition of a 7 sufficient number of 4mm diameter glass balls to fill the 8 remaining reactor tube volume. The glass balls serve as a g preheating zone about 7 inches in length within the tube.
The reactor is then mounted in a vertical furnace having a 11 heating chamber 2,5cm in diameter and 30.5cm in length~ A
12 liquid reac~ant feed stream i3 then ~assed downward through 13 the reactor tube at a se~ected~urnace temperature as described 14 herein. The feed stream is vaporized in the preheating zone and contacts ~he catalyst as a vapor. A11 rezctions 16 are carried out under ambient atmospheric pressure. The 17 reactant feed stream is passed through the reactor at a 18 liquid hourly Sp2Ce velocity (L~5V) of 1 hr-l, i.e., the liquid feed is pumped through the reactor at a rate sufficient to displace 1 empty reactor volume of liquid every hour.
21 The r~actor ef1uent for the first 15 minutes after each 22 start-up is discarded, but is collected thereafter for a 23 period of 2.5 hours in an ice trap. The total liquid 24 effluent collected during this time is analyzed by gas chromatography, mass spectrophotometry, and NMR. Analysis 26 for formaldehyde, other aldehydes, and ketones is condu-27 cted by reacting the respective reaction products with 28 o-benzylhydroxylamine hydrochloride and sodium acetate, 29 said reaction being conducted in the presence of at least 55~, by weight methanol based on the weight of the mix-3~ ture. Unless otherwide specified, the liquid reactant 32 feed stream comprises 10%, by weight, methylal and 90%, 33 by weight, methyl propionate, based on the total weight 34 of the feed stream, and total conversion of methylal, ~5 selectivity, and yield are calculated as follows:

5~¢4~

~echylal Conver~ion (%) = A-B x lOO
3 Selectivity to MMA + _ C
4 MA % ( Sl ~ A-B-D x lOQ
Selecti~ ity to 6 formaldehyde (%) = D x lOO
7 ( S2) A-B

8 Yield of M~ + MA
9 (Z) A x 100 10 Yield of MMA + MA ~ F = +D
11 (%) CA x 100 12 wherein in the above equa~ions:
13 A = moles of methylal in feed 14 B = moles of methylal in reaction product 15 C = moles of MM~ + MA in reaction product 16 D - moles of formaldehyde in reaction product 17 F = formaldehyd~
2 m~thyl methacrylate MA - m~thacrylic acid 20 EXAM~LE 1 21 ~wo solutions were prepared. In the first solution 22 131.6g of zirconium tetra n~butoxide butanol couplex 23 [Zr(OC4~-n)-C4HgO~] and 128.1g of aluminum tri-sec-butoxide 24 ~Al~OC4~g)3) ana 4g.68g ~f tetra ethyl or~ilicate were dissolved 25 .in 908g of diethylether. A~ter stirring this solution for 26 7 minutes, 500cc of acetone were added thereto and this 27 ~olution designated Solution 1. The second 5olution was 28 prepared by di~solving 50.2g of an 85% aqueous solution of 29 H3PO4 and 26.69g of water in 250cc of acetone. Afte.r stirring 30 Solution 1 for an additional 3 minutes, the second solution 31 was slowly added at 25C to Solution 1 over a period o~
32 8.5 hours with continuous vigorous mechanical stirring.
33 After completion of the addition, the reaction mixture was 34 allowed to age at room temperature overnight (i.e. 1~ hours) 35 with mechanical stirring and then refluxed for 2.5 hours.
36 A white precipitate was separated from the reaction mi~ture 5~4~

1 by cooling to room temperature, followed by filtration and 2 the precipitate dried in air at 117C for 2 days in a vacuum 3 oven. The dried solid was then calcined in aix at 460C
4 for 1 hour, 520C for 4.5 hours, in air. The calcined 5 product was ground to a powder -16 mesh (Tyler sieve series).
6 The powder, 104.75g was mixed with 2.09g of water soluble 7 starch and pelletized to 0.5 inch diameter pellets. The 8 pellets were then calcined in air at 600C for 17 hours, 9 750C for 5.5 hours. The calcined pellets were ground to 0-6 ~16 mesh granules and designated Sample Ao 11 Only part of these Sample A granules were further 12 calcined at 820C for 6 hours and designated Sample B. A
3 portion of the 5ample B granules wexe then calcined at 14 880C for 6 hours and designated Saraple C. From each of 15 the alternatively calcined cataiyst samples were removed 16 20cc, i.e., 10.38g of Sample A calcined to a maximum of 17 750C, 10.73g of Sample B calcined to a maximum of 820C, 18 and 12.04g of Sample C. Each sample was placed in a reactor 13 and tes~ed a~ descrihed above. ~he results are summarized 20 at Table 1, Run 1 (Sample A), and RUQ 2 (Sample B) and Run 21 3 (Sample C).
22 It is to be noted that the butanol couplex employed 23 in this and the ollowing examples is the commercially 24 available form of the zirconium alkoxide due to its pre-25 paration in butanol. The butanol is believed to be replaced 26 by the acetone ~olvent and the butanol is so minimal that 27 it is not believed to affect the results.

29 Two ~olutions were prepared in general accordance 30 with Example 1, using 153.12g of aluminum tri-sec-butoxide, 31 250g zirconium tet~a-n-butoxide, butanol comple~, ~nd 800cc 32 acetone for Solution 1, an~ 68-16g of ~5% aqueou~ H3~O4 solution, 33 28.36g water, and 200cc of acetone or Solution 2. Only 65 34 volume % of Solution 2 was slowly added to Solution 1 to 35 form the reaction mixture under continuous vigorous mixing.
36 At this point, 450cc of acetone and 20.41g of boric acid 37powder were added to the continuously stirred reaction ~2~

1 mixture followed by addition of the remaining 35 volume ~
2 of Solu~ion 2. Abou~ 5 hours were required for completion 3 of the addition of Solution 2 to Solution 1. The rea~tion 4 mixture was then aged overnight wi~h mechanical stirring.
5 A white precipitate was separated from the reac~ion mixture 6 by filtration and dried at 65-140C overnight in a vacuum 7 oven. The dried solid was then calcined in air at 300C
8 for 2.5 hours. The calcined product was ground to a powder g ~+16 mesh) and 154.4g of this powder mixed with 12.52g water soluble starch and 138.9g water. The resulting mixture 11 wa~ extruded through a 1/8" nozzle and the extrudate dried 12 at room temperature for 1 hour. The dried extrudate was 13 then calcined in air at 310C for 0.5 hour, 400C for 1 14 hour, 570C for 3 hours, and 750C for 5 hours in air. A
20cc (15.24g) sample was tested as described above and the 16 results summarized at Table lr Run 4.

18 This comparative example i9 intended to illustrate tb~ performance of a typical acidic catalyst disclosed in U.S. Patent No. 4,118,588. Thus, 75g TiO2 (anatase) powder, ~1 57.5g AlP04 powder, and L8.7g H3BO3 powder were mixed and 22 the mixture mixed with 48.2g aqueous urea solution, which 23 had been prepared by dissol~ing 37.5g urea in lOOg dionized 24 water, to form a thick p ste. The paste was dried at 120C
for 3 hours and then ealcined at 600C for 3 hours. ~he 26 calcin~d paste was ground to -6 +16 mesh granules.
27 A 20cc (15.89g) catalyst sample was loaded into a 28 gla~ reactor and after placing the reactor in a verticle 29 furnace, a feed stream containing 10 wt.~ methylal ~olution in methyl propionate was passed through the reactQr at a 31 flow rate of 1 hr.~1 LHSV at ~urnace tempera~ures of 350;
32 370; and 390C. Protuct samples were removed at each 33 reaction temperature, and analyzed as described hereinabove.
34 The results are summarized at Table 2, Runs 6 to 8.

35 COM*ARATIVE EXAMPLE 2 36 This example is intended to illustrate the performance 37 of a conventional basic catalyst such as also disclosed in S~4~

1 U.S. Patent ~,118,588. Thus, 60g of AlPO4 powder were mixed 2 with 4.35g LioH powder. The resulting mixture was mixed 3 with 85.91g water at about 90C to evaporate water and form 4 a solid mass. The solid mass was further dried at 210C
for 1.5 hours, and then calcined at 520C for 3 hours. The 6 calcined mass was ground to -6 +16 mesh granules. A 20cc 7 tll.82g) sample thereof was then loaded into the glass 8 reactor and tested in accordance with Comparative Example 1 9 using the ~ame feed stream recited therein and a furnace temperature of 350C (Run 9) and 370C (Run 10).

11 COMPAR~TIVE EXAMPLE 3 12 This example is intended to illustrate the performance ~3 of a basic catalyst on the silica gel supp~t such as 14 illustrated in U.S. Paten~ ~o. 3,100,795 but using methylal instead vf formaldehyde. Thus, 0.65g of ROH was dissolved 16 in ~25g water and 53.80g of ~ilica gel (-8 ~12 mesh, 300 17 m2/g surface area and lcc/g pore volume) was impregnated 18 with this KOH solution.
19 A 20cc sample of the impregnated product was loaded i~ a glass rea~tor and subjected following thermal 21 treatment in N~ flow ~800cc/min) prior to the catalyst 22 test:
23 200C i hour 24 350C 30 minutes 435C 5 hours 26 Catalyst testi~g was carried out at 370C ~Run 27 11) and 420C (Run 12) furnace t~mperatures, in accordance 28 with Comparative Example 1 and the results summarized at 29 Table 2, Runs 11 and 12.

CO~PARATIVE EX~MPLE 4 31 This example is intended t~ illustrabe the performance 32 of an acidic catalyst such as described in the Albanesi et 33 al article described above. Thus, 36.87g of the silica gel 34 used in Comparative Example 3 was impregnated with tungstic acid solution prepar2d by mixing 5.04g tungstic acid powder 36 with 400ml water. The impreynated product was calcinad at 1 410C for 13.5 hours, 600C for 5 hours, and then 880C for 2 6O5 hours. A 20cc sample thereof was tested in accordance 3 with Comparative Example 1 at a furnace temperature of 4 350C and product sample removed and analyzed as described herein and the results summarized at Table 2, Run 13.
6 COMPA~A5~V~ ~X MPL~ 5 7 This example is intended to illustrate the 8 criticality of Hydrocarboxide II to catalyst composition of ~ the present invention, by omitting zirconium tetrabutoxide therefrom. Accordingly, two solutions were prepared in 11 general ccsrdance with Example 1 using 250g of aluminum 12 tri-sec-butoxide dissolved in 1150cc acetone for Solution 13 1, and 102.07g of 87.8% aqueous ~3PO4 solution in 250cc 14 acetone for Solution 2. Solution 2 was slowly added to Solution 1 to form a reaction mixture as per Example 1.
16 After 12 hours from completion of the Solution 2 addition, 17 a white precipitate was separated by filteration and dried 18 at 98C overnight in a vacuum oven. The dried product was 19 calcined a~ 400C for 2 hours, and 580C for 3 hours in air. The calcined product was ground to a powder (+16 21 mesh) and 26.0g thereof was ~ixed with 4g water. The 22 mixture was pelletized (0~5 inch diameter) and the pellets 23 calcined at 120C for 1 hour, 200C for 2.5 hourq, and 24 600C for 3 hours. The calcined pellets were ground to -5 +16 mesh granules. A 20cc t9.54g) cataly~t sample was 26 teYted as in Comparative Example 1 using a ~w~ce tempera~ure 27 of 350C and ~he results summarized at Tabl 2, Run 14.

28 OMPA~A~IVE EX~MPLE 6 29 This example illustrates the effect on catalys~ -performance of substituting a Group 4b metal alkoxide such 31 as Ti for zirconium. Accordingly, two solutions were 3~ prepared in general accordance with Example 1 u~ïng 320g 33 titanium tetrabutoxide, 160g aluminum tri-sec-butoxide, and 34 1300cc acetone for Solution 1, and 71.20g of 85% aqueous ~3PO4 solution, 51.32g water and 300cc acetone for Solution 1 2. After adding 80 volume % of Solution 2 to Solution 1 bo 2 form a reaction mixture as per Example 1, 3.675g of boric 3 acid was added to the reaction mixture under continuous 4 agitation at 25C, followed by the addition of the remaining 20 volume ~ of Solution 2 to the same. Aîter completion of 6 ~he addition (total addition time being about 5 hours~, the 7 reaction mixture was aged for 18 hours at 25C with 8 mechanical stirring. A white precipitate was separated g from the r~action mixture by filtration and the filt2r cake dried at 65-135C for 18 hours in a vacuum oven. The dried ~1 filter cake was calcined at 200C for 1 hour and then 530C
12 for 4 hours in air. The calcined product was ground ~o a 13 powder (+16 mesh) and 146.77g thereof mixed with 12.48g of 14 water soluble stareh and then 8g water. The mixture was ~xtruded through a 1/16 inch nozzle. The extrudate was 16 dried a~d then calcined at 570C for 3 hours in air and 17 designated Sample A. A portion of Sample A was further 18 calc~ned at 750C or 6 hours and designated Sample B.
19 20cc portion of Samples A and B were tested in accordance with Comparative Example 1 at a furnace temperature of 21 350C and the result~ summarized at Table 2, Runs 15 and 22 1~. A portion of Sample ~ was further calcin~d at 750C
23 for 6 hours.

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-x ': '' 1 DISCUSSION OF RESUL~S
2 Referring to Table 1, it can be seen that all 3 of the methylal conversions of Runs 1 to 4 employing methyl propionate as a co-reactant in addition to methylal are 100% at yields of MA + MMA of from about 6 43 ~o 51~. Such yields are achieved with the formation 7 of foxmaldehyde as the predominant and re-usable by-8 product such that the yield of MA + MMA + Formaldehyde g ranges typicaily from 54 to 93% . The total con~ersion of methylal simplifies the re-cycle of by-products since 11 only one ~y-product, formaldehyde, need be recycled. The 12 high combined s~lectivities to M~ + MMA + F illustrate 13 that ~he Cannizzaro reaction, which decomposes formalde-14 hyde to H2 and CO2 is increasingly avoided as the catalyst calcination temperature increases. Similarly, this data 16 show that formaldehyde decomposition which occurs over 17 many metal oxide catalysts as described by Albanesi et al 18 also is substantially avoided.
19 Referring to Table 2, Comparative Example 1, 20 ~uns 6 to 8,illustrate5 the p~rformance of a TiO2, AlPO4, 21 H3BO3, urea deriv~d acidic catalyst prepared in general 22 accordance with Example 4 of U.S. Patent No. ~,118,588.
23 However, contrary to the testing procedure of '588 Example 2~ 4 ~r~action time 30 min. ), in Comparative Example 1, the initial 15 minutes of product are discarded and the product 26 collected thereafter for 2.5 hours w~s tested. The total 27 methylal conversion was onl~ 91.3% at 350 C furnace b~rature 28 and the yield of MA + MMA was only 16.7~. This c4ntrasts 29 with a xeported 95% yield in Exampl@ 4 o~ the '588 patent a~ter imme~iate analysis of product from start-up. While 31 conversions are improved in Runs 7 and 8 of Comparative 32 Example 1 at higher furnace temperatures of 370 and 390C, 33 MA + MMA yields still remain drastically below those of 34 the present invention at about 20%.
Comparativa Example 2, Runs 9 and 10, illustrates 3~ the performance ~f another catalyst disclosed in the '588 37 patent, namely, LiO~ impregnated AlPO4, i.e., methylal ~.2~

1 conversions of 80 to 85% at MMA ~ MA yields of about 40%.
2 Such conversions and yields are substantially inferior to 3 those of the present invention.
4 Comparative Example 3, Runs 11 and 12, illustrates 5 an almost non-existent methylal conversion (3.4%) from a 6 conventional basic ca~alyst, iOe., a KOH silica impregnated 7 gel.
8 The tungstic acid impregnated silica gel of g Comparative Example 4 also per~orms poorly, producing a methylal conversion of only $1.7~ and a MA + MMA yield of 11 4.2%.
12 The omission of zirconium alkoxide from the 13 catalyst of Comparative Example 5, Run 14, is believed to 14 be responsible for the substantial drop in MA + MMA yield ~ to 11.1~. It is ~herefore concluded that the zirconium 16 Hydrooarboxide II is critical to the psrformance of the 17 catalyst of the present invention.
18 Comparative Example 6 further confirms the 19 criticality of ~ydrocarboxide II by substituting titanium tetrabutoxid2 for zirconium t~trabutoxide and using a 21 boron containing additive. While methylal conversion is 22 100~ in Run 15, M~ + MMA yield is only 35.8%
23 While the yield of MMA + MA + F in Run 16 is 94%, 24 the yield of MM~ ~ MA is only about half or less of that shown for Runs 1 to 4.
26 The principles, preferred embodiments and modes 27 of op~ration of the present invention have been described 28 in the foregoing specification. The invention which is 29 i~tended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, 31 since these are to be regarded as illustrative rather 32 than restrictive. Variatlons and changes may be made by 33 those skilled in the art without departing from the spirit 34 of the invention.

Claims (37)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OF PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a catalyst composition which comprises:
(1) reacting in admixture at least one Metal Hydrocarboxide I, at least one Metal Hydrocarboxide II, at least one acidic phosphorus-oxygen containing compound, and water in the presence of at least one liquid organic medium comprising at least 50% by weight, based on the weight of said medium, of at least one member selected from the group consisting of organic aldehyde, organic ketone, and organic ether, said reaction being conducted in a manner sufficient to (a) avoid contact of Metal Hydrocarboxides I and II with water prior to contact of Metal Hydrocarboxide I and II with the acidic phosphorus-oxygen containing compound, and (b) form a catalyst precursor composition;
(2) separating said catalyst precursor composi-tion from said reaction admixture;
(3) calcining said catalyst precursor composi-tion to form said catalyst composition;
wherein said process:
(i) the metal M1, of said Metal Hydrocarboxide I comprises aluminum; and (ii) metal, M2, of said Metal Hydrocarboxide II comprises zirconium.

2. The process of Claim 1 wherein Metal Hydro-carboxide I is represented by the structural formula:

(I) wherein M1 is as described in Claim 1, and R is at least one substituted or unsubstituted hydrocarbyl radical independently selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and cycloalkyl, said substituents when present on R being selected from the group consisting of ether groups, ester groups, and mixtures thereof; and Metal Hydrocarboxide II represented by the structural formula:

(II) wherein M2 is as described in Claim 1 and R is as described in conjunction with structural formula I of Claim 2.

3. The process of Claim 1 wherein the liquid organic medium comprises at least 75%, by weight, based on the weight of said organic medium of at least one aldehyde.

4. The process of Claim 1 wherein the liquid organic medium comprises at least 75%, by weight, based on the weight of said organic medium of at least one ketone.

5. The process of Claim 1 wherein the liquid organic medium comprises at least 75%, by weight, based on the weight of said organic medium of at least one ether.

6. The process of Claim 1 wherein the liquid organic medium is selected from the group consisting of acetone, diethylether, acetaldehyde, methylethyl ketone, 3-pentanone, 1,2-dimethoxyethane and mixtures thereof.

7. The process of Claim 1 wherein said Metal Hydrocarboxide I is at least one aluminum alkoxide, and said Metal Hydrocarboxide II is at least one zirconium alkoxide.

8. The process of Claim 1 wherein said acidic phosphorus-oxygen compound is selected from the group consisting of phosphorus acid, phosphonus acid, phosphinous acid, phosphenous acid, phosphoric acid, phosphonic acid, phosphinic acid, phosphenic acid, phosphine oxide, phos-phoranoic acid, phosphorane dioic acid, phosphorane trioic acid, phosphoranetetroic acid, phosphorane pentoic acid, polyphosphoric acid, and mixtures thereof.

9. The process of Claim 8 wherein at least one but not all of the acidic hydrogens of said acidic phosphorus-oxygen compounds are replaced with a C1 to C10 alkoxide group.

10. The process of Claim 8 wherein the acidic phosphorus-oxygen compound is phosphoric acid.

11. The process of Claim 1 wherein said catalyst precursor composition is calcined within a temperature range of from about 600 to about 1300°C.

12. The process of Claim 11 wherein the calcination temperature is from about 700 to about 1000°C.

13. The process of Claim 11 wherein the calcination temperature is from about 750 to about 950°C.

14. The process of Claim 11 wherein said catalyst precursor composition is precalcined at a temperature of from about 400 to about 599°C prior to calcination.

15. The process of Claim 1 wherein boron, is incorporated into said catalyst composition.

16. The process of Claim 15 wherein boron is incorporated into said catalyst composition by admixing a boron containing compound with said reaction admixture.

17. The process of Claim 16 wherein said boron compound is boric acid.

18. The process of Claim 1 wherein not greater than 25%, by weight, water based on the combined weight of water and liquid organic medium is present in said reaction admixture.

19. The process of Claim 7 which comprises:
(1) providing a liquid reaction admixture comprising:
(a) Metal Hydrocarboxide I, Metal Hydrocarboxide II, and the acidic phosphorus-oxygen containing compound at respective mole ratios of from about 1:3.5:1.5 to about 1:0.5:0.5;
(b) water in an amount (i) sufficient to achieve a mole ratio of the sum of the moles of Metal Hydrocarboxides I and II:H2O of from about 3:1 to about 1:300, and (ii) not greater than about 20%, by weight, based on the weight of liquid organic medium and water in the reaction admixture; and (c) liquid organic medium in an amount of at least about 25%, by weight, based on the weight of said liquid admixture, said liquid organic medium being selected to dissolve therein Hydrocarboxides I and II, and the acidic phosphorus-oxygen compound;
(2) providing said liquid admixture at a temperature of from about 5 to about 200°C, for a period of from about 0.15 to about 40 hours in a manner sufficient to achieve intimate contact and reaction between the Metal Hydrocarboxides I and II, water, and the acidic phosphorus-oxygen composition to form a catalyst precursor composition;
(3) separating said catalyst precursor composition from the liquid reaction admixture thereby removing residual organic medium from the catalyst precursor composition and recovering the catalyst precursor as a dry solid material; and (4) calcining said catalyst precursor composition solid in air within the temperature range of from about 650 to about 1000°C for a period of from about 1 to about 48 hours to form said catalyst composition.

20. The process of Claim 19 wherein:
(a) Metal Hydrocarboxide I, Metal Hydrocarboxide II, and the acidic phosphorus-oxygen composition are present in said admixture at respective mole ratios of from about 1:2:1.25 to about 1:0.7:0.7;
(b) water is present in said reaction admixture in an amount (i) sufficient to achieve a mole ratio of the sum of the moles of Metal Hydrocarboxides I and II:H2O of from about 2:1 to about 1:10 and (ii) not greater than about 15%, by weight, based on the weight of the liquid organic medium and water;
(c) the liquid organic medium present in said reaction admixture comprises at least 75%, by weight, thereof of any of said aldehyde, ketone, and ether, and said liquid organic medium comprises at least 40%, by weight of said reaction admixture based on the weight of Hydrocarboxides I and II, the acidic phosphorus oxygen composition, liquid organic medium and water;
(d) the catalyst precursor is calcined within a temperature range of from about 700 to about 950°C.

21. The process of Claim 19 wherein the liquid organic medium as initially added to said admixture consists essentially of said aldehyde, ketone, ether or mixtures thereof.

22. The process of Claim 19 wherein said catalyst precursor composition, prior to separation from the liquid reaction admixture, is aged at a temperature of from about 10 to about 100°C, for a period of from about 1 to about 30 hours.

23. The process of Claim 19 wherein the catalyst precursor solids are precalcined at a temperature of from about 400 to about 599°C
for a period of from about 0.1 to about 10 hours prior to calcination thereof.

24. The process of Claim 19 wherein said liquid reaction ad-mixture is provided by mixing an anhydrous solution comprising Metal Hydro-carboxides I and II, and liquid organic medium, with a solution comprising the acidic phosphorus-oxygen composition, water, and liquid organic medium.

25. The process of Claim 19 wherein the Metal Hydrocarboxide I is selected from the group consisting of aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-isobutoxide, aluminum tri-isopropoxide, aluminum tri-n-propoxide, aluminum tri-ethoxide, aluminum tri-methoxide and mixtures thereof; Metal Hydrocarboxide II is selected from the group consisting of zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetramethoxide, zirconium tetrapropoxide and mixtures thereof; the acidic phosphorus-oxygen compound is phosphoric acid; and the liquid organic medium is selected from the group consisting of acetone, diethylether and mixtures thereof.

26. The process of Claim 25 wherein the Metal Hydrocarboxide I is aluminum sec-butoxide and Metal Hydrocarboxide II is zirconium tetra-butoxide.

27. In a process for the vapor phase condensation of at least one member selected from the group consisting of aldehyde and aldehyde pre-cursor with at least one member selected from the group consisting of carboxylic acid and carboxylic acid derivative, to form the corresponding .alpha.,.beta.-unsaturated acid or acid derivative, in the presence of a catalyst composition, the improvement comprising employing as the catalyst composition a catalyst composition prepared in accordance with Claim 1.

28. In a process for the vapor phase condensation of at least one carbonyl containing compound with at least one member selected from the group consisting of aldehyde, acetal, hemiacetal and mixtures thereof, to form the corresponding .alpha.,.beta.-unsaturated product, in the presence of a catalyst composition, the improvement comprising employing as the catalyst composition a catalyst composition prepared in accordance with Claim 1.

29. The catalyst composition when prepared by the process of any of claims 1 to 3.

30. The catalyst composition when prepared by the process of any of claims 4 to 6.

31. The catalyst composition when prepared by the process of any of claims 7 to 9.

32. The catalyst composition when prepared by the process of any of claims 10 to 12.

33. The catalyst composition when prepared by the process of any of claims 13 to 15.

34. The catalyst composition when prepared by the process of any of claims 16 to 18.

35. The catalyst composition when prepared by the process of any of claims 19 to 21.

36. The catalyst composition when prepared by the process of any of claims 22 to 24.

37. The catalyst composition when prepared by the process of any of claims 25 or 26.