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1.4 Methanol-Based Synthetic Reactions over Solid-Base Catalysts
1.4 Methanol-Based Synthetic Reactions over Solid-Base Catalysts W. UEDA", H. Ohowaa,K. Iwasaki', T. Kuwabarab,T. Ohshidab, and Y. Morikawab 'Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, Yokohama 227, Japan bResearch Laboratories of Resources Utilization, Tokyo Institute of Technology, Yokohama 227, Japan Abstract Novel methods for catalytically synthesizing a,fkunsaturated compounds and higher alcohols were developed, where methanol was used as a key reagent for C-C bond formation. Reactants were saturated ketones, esters, nitriles, or alcohols besides methanol, and CH,= or CH,- group is introduced into their methyl or methylene carbons by the addition of methanol. For the catalytic synthesis of a#-unsaturated compounds, magnesium oxide activated by manganese ion or chromium ion has been found to give the most effective catalytic performance. The most promising application of this synthetic method is demonstrated by the selective synthesis of acrylonitrile from acetonitrile and methanol over Mn-MgO catalyst. The selectivity to acrylonitrile was more than 95%and no deactivation of the catalyst was observed. The method was also applied to the conversion of acetone to methyl vinyl ketone and methyl propionate to methyl methacrylate. Condensations of various primary alcohols(C2-CJ with methanol were carried out at atmospheric pressure over various metal oxides having a solid-base property. The reactions gave one or two carbon higher alcohol than the reacted primary alcohol. MgO catalyst was most active for the reaction and yielded the alcohol products in high selectivty(>80%). Based on the kinetic measurements, reaction mechanisms for both reactions are discussed. 1. INTRODUCTION Methanol has become one of the major raw chemicals produced presently in chemical industries, ranking third in volume behind ammonia and ethylene. World production of methanol is currently about 20 million tons per year. More production of methanol is now expected since it is assumed that methanol will be utilized more in the future not only as chemical raw material but also as an energy carrier for the various types of engines and for fuel cell[l]. Recently, the utilization of methanol for MTBE is increasing, currently above 23 % of the total production of methanol. Developments of the methods of transforming methanol to industrial chemicals have a long history over several decades[2-41. The development has progressed markedly since methanol was manufactured via the hydrogenation of carbon monoxide over solid catalysts at elevated temperature and pressure. The stimulated industrial and research trend to utilize methanol for chemicals synthesis resulted in many new process developments. Some of methanol-based processes have been industrialized instead of traditional synthetic routs based on olefins. Some of others seem to be technologically ready for commercialization[Sl. The object of this paper is to deal with solid base-catalyzed synthetic reactions of a$-unsaturated compounds[6] and higher alcohols with methanol[7], which are very important and basic among the 35
36
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
various methanol-based synthetic reactions. On the basis of the results of catalytic performance tests and kinetic measurements, both methanol-based synthetic reactions over magnesium oxide catalyst having solid-base are compared in terms of reaction mechanism.
2. EXPERIMENTAL METHODS 2.1 Catalyst Preparation The metal ion-containing catalysts(3 wt%) was prepared by the following impregnation method. Commercial MgO(Soekawa Rika, 99.92%, surface area 11 mZ.g-')is impregnated with an aqueous solution of the corresponding metal nitrate with stirring for 12 hrs at an ambient temperature. Water is then evaporated by heating, followed by drying in air at 110°Cfor 24 hrs. Heat treatment in a nitrogen stream at about 600°C is necessary in order to decompose the impregnated metal nitrate and to desorb water and COr Unless otherwise noted, the prepared MgO was used.
2.2 Catalytic Reaction The reactions to produce a,P-unsaturated compounds were carried out at atmospheric pressure using a continuous flow reaction system with a quartz fixed-bed reactor. The reaction was run at 623 K with 1.3 kPa of substrate in N, carrier. The molar ratio of methanollsubstrate was 10 in all cases and the space velocity (methanol + substrate + N J was 80 ml.min".g-caf'. The reactions of primary alcohols(C,H,,,,OH, n=2-5) with methanol were also carried out at atmospheric pressure using the same continuous flow reaction system with a quartz fixed-bed reactor. The following standard reaction conditions were used; feed gas composition, N, : methanol : C,H,,+,OH = 10 : 3 : 0.15, total flow rate, 66 ml.min-', catalyst weight, 1 g. and reaction temperature range, 573-673 K. 3.
RESULTS AND DISCUSSION
3.1 Synthesis of a, @Unsaturated Compounds a,p-Unsaturated compounds are very important chemicals in the chemical industries, in particular for polymers. The production of these compounds has been accomplished through the catalytic processes based on olefins. For example, acrylonitrile is manufactured by ammoxidation of propene over multicomponent bismuth molybdate catalysts[8]. In recent years, however, other synthetic methods based on the utilization of C, chemicals such as CO, methanol, and methane instead of olefins have been developed markedly. An interesting example is the acrylonitrile synthesis by the oxidative methylenation of acetonitrile with methane over metal oxide catalysts[9]. Since acetonitrile can be synthesized from CO, H,, and NH, catalytically[lO], the process may provide a promising route for acrylonitrile synthesis from C, chemicals only. Many similar approaches have recently been undertaken extensively[111. Other examples are the classical processes where base- or acid-catalyzed condensation reactions with formaldehyde are utilized[ 121. The well-known examples are the condensation of acetaldehyde, where acrolein can be normally obtained because the initially formed aldol condensation product undergoes dehydration simultaneously over the catalysts. In principle, this reaction can be used for the synthesis of other unsaturated compounds. Alternatively, it is possible to carry out this type of reaction with irr situ generation of formaldehyde from methanol by oxidative dehydrogenation[13,141. We have recently developed the reaction for the synthesis of various a,S-unsaturated compounds using methanol as a reagent for C=C bond formation over solid-base catalysts promoted by transition metal ions[5,6,15-20]. General reaction scheme is described in Figure 1. This process is a base-catalyzed reaction, where methyl or methylene group activated by inductive electron withdrawal by the unsaturated substituent such as carbonyl, cyano or phenyl group, is converted into vinyl group by the addition of methanol. The most promising application of this method is demonstrated by the selective formation of acrylonitrile from acetonitrileand methanol[ 161. The conversion of acetonitrile proceeds catalytically at an elevated temperature(>300"C) and yields acrylonitrile(AN)selectively through dehydrogenation,
Methanol-Based Synthetic Reactions over Solid-Base
37
Acryloni trile Acetone Methyl methacrylatee
Acetonitrile
Methyl propionate
+ 4 + HO ,
CH,=CR-Z
Methacrylonitrile
Z = -CN, -COR, -COOR’
-
Figure 1 Catalytic syntheses of a,P-unsaturated compounds with methanol over solid-base. cross-condensation, and dehydration(eq. 1). CYCN
+
CHPH
CH,=CHCN
+ H, +
H,O
,
(eq. 1)
Catalysts are based on metal oxides which are well-known as solid-base materials, such as MgO, CaO, &O,, and so forth. These metal oxides themselves are, however, virtually inactive for this reaction, so that the catalytic properties of these basic oxides must be improved by the addition of small amounts of transition metal cations. Table 1 shows examples for the magnesium-based oxide catalysts. Obviously, a synergism or bifunctional feature of the promoted M-MgO catalysts, depending on the kind of added element, is significant for the catalytic activity and selectivity for the reaction. The addition of manganese, chromium, or iron has a pronounced effect on the course of the reaction; overall catalytic activity based on acetonitrile conversion increased by a factor of 100. The reaction is really selective and by-products are small amounts of propionitrile(PN) and methacrylonitrile(MAN) which are formed by the consecutive reactions of the main product, AN. At the present best conditions, one pass conversion of acetonitrile reaches more than 30% keeping the higher selectivity(>90%) to AN over these catalysts. Stability of these catalysts is extremely good. A prolonged reaction, however, revealed that the activity decreased very slowly but in an appreciable level. Selectivity was almost unchanged during the slow decay of the activity. Slow coke formation Table 1 Synthesis of a$-unsaturated nitriles over metal ion-containing MgO catalysts at 623K Catalyst M”+-MgO
CH,CN Conv.(%)”
MgO Fe3+-MgO C?+-MgO MnZ+-MgO NiZ+-MgO Cu2+-Mg0
0.1 11.2 9.6 9.1
5.5 2.2
AN
Selectivity (%) PN MAN
tr 73.2 94.2 96.4 2.8 91.0
tr 11.6 5.4 2.7 33.5 9.0
1) WIF = 38 g.hr.mol-’, 2) WIF = 145 g.hr.mol-I.
tr tr
0.9
tr
CH,C&CN Conv.(%)”
Selectivity (%) MAN IBN CTN
0.9 5.0 11.0 11.4
65.9 94.6 88.6 97.1
20.9 4.6 6.8 2.2
13.2 0.8 2.3 0.7
2.3
87.5
9.4
3.1
38
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
on the surface, in particular on the surface basic site, seems to be responsible for the slow deactivation because the catalyst was slightly darken. Almost the same activity as of the fresh catalyst can be recovered by calcination of the used catalyst in an air stream at an elevated temperature, followed by the activation process of the catalyst. Looking at the other promoted catalysts, less active catalysts were obtained by the addition of nickel or copper because of remarkable decay of activity in a short reaction time. Characteristically, magnesium oxide containing nickel was extremely inactive for the formation of AN but gave propionitrile in relatively higher yield than the others. Some of the produced AN oligomerized over nickel site to form higher molecular weight compound. It seems that the added nickel ion on the surface of magnesium oxide can catalyze hydrogenation of AN to propionitrile much effectively. The addition of aluminium did not result in appreciable effects on both activity and selectivity. Effect of metal ion content in magnesium oxide on the catalytic property is significant. The formation of AN increases with the Cr content and then decreases after passing through a maximum at 3 wt%. Excess addition causes a decrease in activity and induces the decomposition of methanol and ultimately pure metal oxide used for dopant predominantly catalyzes the decomposition of methanol, so that about 3wt% loading of metal ion is preferable for attaining effective catalytic property for the over-all reaction. The selectivity to AN on the basis of acetonitrile conversion was scarcely affected by the content of metal ion. This activity change is not attributed to surface area change because every catalysts have nearly the same surface area(ca. 100mZ.g-'). Therefore, the drastic increase in activity implies that the reaction needs both functions of added metal ion and surface base site. The activity decreases by the excess addition is thought likely due to the decrease of the surface base site. The above nitrile synthetic process can be applied for the methacrylonitrile synthesis from propionitrile(eq. 2).
CH,CHFN
+
CI-L,OH
-
CH,CCN
EH,
+ H, +
H,O
(eq.2)
Almost the same trend in catalytic performance is observed for MAN synthesis as that for AN synthesis(Tab1e 1). Hence the improved catalytic property of magnesium oxide is obtainable by the specific promotion effect of Mn, Cr, and Fe ions. By using these three catalysts, 95% selectivity to MAN is achieved at about 30% conversion of propionitrile under the optimized conditions. By-products are isobutyronitrile(1BN) and crotononitrile(CTN).
3.2 Condensation of Alcohol to Form Higher Alcohols Numerous attempts have been made in the past to develop synthetic methods for higher alcohols, particularly from C, chemicals such as CO and methanol, and many processes have already been established.[21] One of the important industrial processes is the so-called 0x0 reaction or hydroformylation of alkenes where CO is a key reactant. Other reported methods include homologation of lower alcohols to higher ones using carbon monoxide and hydrogen,[22] and metal- or metal oxide-catalyzed direct synthesis of alcohols from syn gas.[23] In addition, Guerbet reaction, where a primary or secondary alcohol reacts with itself or another alcohol to produce a higher alcohol, is also an important reaction as higher alcohol synthesis. This reaction has been much developed and various types of heterogeneous catalyst have been reported in patents. [24-261 In an extension of our studies on catalysis by solid-base catalysts,[S] we recently developed a new catalytic reaction process for producing higher alcohols using methanol as a main building block(eq. 3). In this reaction, methanol is condensed with other primary or secondary alcohol RCYCHPH
+
[R = H, Alkyl]
CH,OH
-
R HCH,OH
L-4
+
H,O
(eq.3)
Methanol-Based Synthetic Reactions over Solid-Base
39
having a methyl or methylene group at the a-position over metal oxide catalyst having a solid-base property, and then higher alcohols are formed in high selectivities. 3.2.1 Catalytic perfornlance of MgO and metal ion-containing MgO catalysts Table 2 lists the catalytic performance of MgO, CaO, ZnO, and ZrO, in the condensation reaction of ethanol with methanol at 633 K. MgO, a well known solid-base, showed the best catalytic performance in the reactions, yielding higher alcohols selectively in every case. When ethanol was allowed to react with methanol over MgO catalyst, ethanol was readily converted into 1-propanol and 2-methyl propanol Total selectivity to both products was about 80%. Minor products were Cz-, C3-and C4-saturatedcarbonyl compounds and thereby small amount of hydrogen was also formed. Very small amounts of methane and CO were also formed, indicating a few side reactions of methanol took place under the conditions. However, the extents of such reactions were low and thus the excess methanol was most recovered. Other solid-base metal oxide, CaO, was surprisingly inactive. ZnO catalyst was active for the conversion of ethanol but non-selective, mainly catalyzing the dehydrogenation of alcohols to aldehydes. ZrO, catalyst showed acidic character in the present reaction conditions,promoting the formation of various ethers from alcohols. As a result, MgO catalyst was found uniquely active for the condensation of alcohol to produce higher alcohols. The addition effect of metal ions in the MgO catalyst was tested in similar to the catalytic syntheses of a,@-unsaturatedcompounds with methanol and the results are shown in Table 3. Unfortunately, the addition effect was negative in all cases; the MgO catalysts containing metal ion were either less active or less selective. The manganese-containing MgO catalyst, which was most active in the synthesis of a,@-unsaturatedcompounds with methanol, was poorly selective for the Table 2 Condensation of ethanol with methanol over various metal oxide catalysts at 633 K Catalyst Surface Conversion area of ethanol (m2.g-’) (%) MgO
137 65
zro,”
-
CaO ZnO
29.6 0.8 74.5 66.9
1-Propanol 2-Methyl propanol 50.7 34.6 tr 0
Selectivitv(%) 1-Butanol Acet2-Methyl aldehyde propanal
27.6 0 tr 0
0.7
0 0 0
12.4 65.4 84.5 0
1.9 0 0.5 0
1) Main products were dimethyl ether and methyl ethyl ether. Table 3 Condensation of ethanol with methanol over various metal ion-doped MgO catalysts(633 K) Catalyst Surface Conversion M-MgO ama of ethanol (3wt%) (m2.g-’) (%) MgO MJl
Cr
Al
Na cs
137 168 105 106
29.6 32.9 35.1 24.6’’ 0.8 0
1) Various ethers were formed.
Selectivity(%) 1-Propanol 2-Methyl 1-Butanol propanol 50.7 24.3 16.0 4.6 33.3 0
27.6 9.9 7.3 0 0 0
0.7
tr tr 0 0 0
Acetaldehyde
2-Methyl propanal
12.4 31.9 36.4 4.6 66.7
1.9 3.7 5.2 0 0
0
0
40
-
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
\OH
-OH
-OH
Conversion(%) 50
-OH
&OH (40)
(83)
48
&OH
60
(79)
50
-OH
[ ( ): Selectivity/% ]
Figure 2 Condensation of various alcohols with methanol over MgO catalyst at 653 K.
z.-
100
Reactant
at 380°C
c
(pmol/fin)
0
f>
0 0
c 0
0
Reactionrate products
0
,
A
Ethanol l-Propan01 1-Butanol 1-Pentan01
17.9 16.1 18.9 16.8
Cn+,HCnH2,+,CH0
14 11 10 28
2
Figure 3 Comparison of the condensation rates of various alcohols with methanol over MgO. formation of saturated alcohols like 1-propanol and 2-methyl propanol, mainly catalyzing the formation of unsaturated compounds like acrolein, ally1 alcohol, and aldehydes in accordance to its catalytic performance in the reaction of nitriles with methanol, although the catalyst showed a slightly improved activity for the methanol conversion in the reaction of ethanol and methanol. More characteristically, the addition of sodium cation into MgO catalyst resulted in the complete disappearance of the activity, although the sodium ion-containing catalyst would be stronger base than original MgO catalyst. By taking account that the CaO catalyst is also completely inactive for the reaction, it seems that catalysts having much stronger basicity are not suitable for the reaction. Figures 2 and 3 summarize the results of the condensation reaction of various alcohols with methanol over MgO catalyst at the temperature range of 573-673 K. When the other primary alcohol was allowed to react with methanol, the reaction features were almost the same as described above for the ethanol conversion; that is, the reactions readily took place and formed the 2-methyl form of
Methanol-Based Synthetic Reactions over Solid-Base
41
the higher alcohol mainly with small amount of aldehydes produced by the dehydrogenation of the reactant and product alcohols. The only difference between the ethanol reaction and the other reaction is two alcohol products in the ethanol reaction but one higher alcohol product in the other. This is because the propanol produced in the ethanol conversion can subsequently react with methanol to form 2-methyl propanol Two points emerge from the figures. First, the conversions obtained in each reaction under the standard conditions were essentially the same (50-60%)and the temperature dependency of each reaction was also similar as shown in Figure 3. This strongly implies the rate independency of the reactant. Secondly, the product selectivity is little influenced by the reactant; the alcohol selectivity is around 80% in every case and the high molar ratio of alcohol to corresponding aldehyde is also similar in every reaction. 3.2.2 Catalyticperfonncrnce of MgO catalysts containing 0x0 anion As the MgO catalyst was found most active for the condensation reactions of alcohols with methanol, we have tested the catalytic performance of MgO prepared by various methods. The MgO catalyst designated by MgO-(OH) was prepared by the method described in the experimental section. The MgO catalyst designated by MgO-(FD) was prepared by freeze-dry method. In this method a slurry in a boiling water was freeze-dried instead of the evaporation of water and drying at 383 K in the preparation of the MgO-(OH) catalyst. The MgO catalysts designated by MgO-(NO) and MgO-(SO) were prepared by precipitation method from aqueous solution of magnesium nitrate and magnesium sulfate, respectively. Solidification procedure is the same as for the preparation of the MgO-(OH) catalyst. The MgO catalyst designated by MgO-(CO) was from a commercial basic magnesium carbonate which was directly used for the reaction without any treatments except the standard heat-treatment. The MgO catalyst designated by MgO-(ME) was prepared by the use of methanol instead of water as a media. All the other procedures were the same as the MgO-(OH) preparation. The catalytic activities of these prepared catalysts in the condensation of 1-propanol with methanol at 633 K are illustrated in Figure 4. Figure 4 also shows surface area of each catalyst and molar ratio of produced 2-methyl propanol to produced 2-methyl propanal. It can be seen that the catalytic activity of MgO changed significantly by the preparation method. The MgO-(FD) catalyst had the highest surface area among the catalysts prepared here. The crystallinity of MgO-(ME) catalyst particles were very high and thus its surface area was lowest. This catalyst, however, showed the highest specific activity for the formation of 2-methyl propanol in the reaction. Although it is very hard to see any relations among the preparation method, surface area, activity, and selectivity, it appears that such changes are mainly caused by small amount of anion species
I
R a t e 109mol/m2.min Rate 10~pmol/g.min
I MgO-(FD)
I
I
-,
MgO-(NO)
441
18
360
27
MgO-(SO)
295
36
MgO-(CO)
208
16
177
16
13 0
2
4
6
1
2
Figure 4 Catalytic performance of MgO prepared by various methods.
42
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHlDA and Y . MORIKAWA
'
OO
r
IConversion(%) Sel(%) to i-BuOH Yield(%) of i-BuOH
80
60 40
20 0
Figure 5 Addtion effectsof halide anion or 0x0 anions on the catalytic performance of MgO. remained on the MgO surface; these anions may strongly influence the catalytic performance of MgO, since it is very difficult to remove the anions of starting materials completely by repeated washing and since these anion largely change the surface structure of MgO and have electronic effects. We, therefore, conducted experiments to test the addition effect of anions to MgO surface. Various anion-doped MgO catalysts were prepared and tested for the reaction of 1-propanol with methanol. Eight kinds of anion, chloride anion and 0x0 anions, were doped into MgO catalyst as shown in Figure 5. Preparation procedure of these catalysts is the same as for the preparation of metal ion-containing MgO catalyst. Either acidic form of anion or ammonium salt was used in the preparation. Chloride anion-doped MgO catalyst was virtually inactive for the condensation of 1-propanol with methanol, simply because its surface area was low; it was found that chloride anion effectively promoted crystallization of MgO during the heat-treatment. Nitrate anion was ineffective. This might be due to that nitrate anion easily decomposes during the heat-treatment even in the MgO lattice. However, there must be another reason for that the nitrate anion-doped MgO catalyst was Table 4 Condensation of 1-propanol with methanol over various sulfate anion-containing MgO catalysts at 633K Catalyst Added compound (3 wt%)
Conversion/%
Selectivity/%
1-Propanol Methanol ~~
~
~~
none
47.4
8.9
63.5
tr
7.7
(NH4)2 . 0 4 MgSO4 MgSO,.(NHJ,SO, CH, S03H (CH,SOJ,Mg
72.8 78.7 74.1 59.4 58.7
19.7 11.9 15.6 15.5 4.1
70.4 70.0 64.9 62.9 57.8
12.0 2.5 8.5 1.3
4.5 2.0 7.5 3.3 2.7
tr
Methanol-Based Synthetic Reactions over Solid-Base lOOr
I
I
. to i-BuOH
w Conv. of 1-propanol
n
100
$?
1 f z
._5
g
c
43
:F/ Sel. to i-BuOH
80 60
Conv. of 1-propanol
40 20
0
O
wt% Figure 6 Effect of sulfate anion loading on the activity of MgO catalyst in the condensation of 1-propanol with methanol.
O 0
Figure 7 Condensation of 1-propanol with methanol over 1 wt% sulfate anion-doped MgO catalyst at 633 K.
less active than the pure MgO catalyst. The addition of borate anion resulted in no change in the catalytic performance of MgO. Apparent improvement in the yield of 2-methyl propanol was observed by the additions of sulfate and phosphate anions. Particularly, the addition of sulfate anion improved both activity and selectivity. The catalysts modified with silicate, molybdate, and tungstate anions were less selective although the conversion of 1-propanol was higher. Various sulfate anion-doped MgO catalysts were prepared by the use of various sulfate precursor and tested for the reaction of 1-propanol with methanol because the sulfate-doped MgO catalyst showed the highest activity for 2-methyl propanol formation. The results are shown in Table 4. Three kinds of inorganic sulfate precursor and two kinds of organic sulfate precursor were added into MgO catalyst as shown in the table. Apparently every inorganic sulfate dopants were found to be effective to improve the catalytic performance of MgO. The organic sulfate dopants were less effective. It was observed from TPD spectra of CO, and XRD analysis that the surface basicity and the crystallinity of MgO particle did not change by the addition of sulfate anion. Therefore, it seems that the improvement of the catalytic performance by the addition of sulfate anion is attributable to the increase of surface area and the generation of sites which are much highly active for the reaction. Figure 6 shows the effect of loading amount of sulfate anion on the catalytic performance of MgO catalyst in the condensation of 1-propanol with methanol at 633 K. The conversions of 1-propanol and methanol increased with increasing the loading amount of sulfate anion. The selectivity to 2-methyl propanol also increased but further addition caused the decrease in the selectivity after a maximum at about 1 wt %. As a result, the addition of sulfate anion in 1 wt % to MgO catalyst is suitable to achieve the highest catalytic performance in the reaction. By the use of 4 g of lwt% sulfate anion-doped MgO catalyst, 60 % yield of 2-methyl propanol was attained in the condensation of 1-propanol with methanol at 633 K(Figure 7).
3.3 Aspect for Reaction Mechanism Reaction mechanisms for the synthetic reactions of a,P-unsaturated compounds and for the condensation reaction of alcohols with methanol are discussed here on the basis of the following summarized observations. For the synthetic reactions of a,P-unsaturated compounds: 1. MgO catalyst without any additives is virtually inactive.
44
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
2. MgO catalysts containing metal cation, such as Fed*,Cr" ,and Mn2+, which provide Lewis acid site in the MgO lattice, are active and selective. 3. The rate of product formation is not proportional to the total amount of surface base site. 4. A correlation between the rates of reaction and the pKa values of the substrates is observed; the reaction rate is higher for the substrate with a lower pKa value[27]. 5. The kinetic isotope effect on the reaction rate of acetonitrile with methanol was clearly observed only when the methanol deuterated at the methyl group was allowed to react at 603 K, giving k(CH,OH)Ik(CD,OD) = 2.2. No kinetic isotope effects were caused by deuterium substitution at hydroxyl hydrogen of methanol and acetonitrile[181. 6. The exchange reaction between hydroxyl hydrogen of methanol and hydrogen of acetonitrile takes place readily both over Mn-MgO and over Mg0[28]. 7. Methanol is easily decomposed to CO by passing over the metal ion-containing catalyst, while MgO is inactive for methanol decomposition. However, the rate of methanol decomposition is seriously depressed by the existence of substrates[6]. 8. When CO, is co-fed in the reaction acetonitrile with methanol, the reaction readily takes place even over the pure MgO catalyst. For the alcohol condensation with methanol: 1. Pure MgO catalyst is active, while CaO, which is also solid-base catalyst, is inactive. The addition of sodium cation to MgO catalyst completely depresses the catalytic activity of MgO. 2 . The addition of CO, in the feed greatly enhances the rate of alcohol condensation. 3 . Sulfate anion-doped MgO catalyst shows much higher activity than MgO catalyst. 4. Reaction rate is almost independent of primary alcohols used for the reaction as substrates. 5 . No 2-methyl propanal was detected at a very short contact time, indicating that 2-methyl propanol is a primary product and 2-methyl propanal is subsequently formed by the dehydrogenation of produced 2-methyl propanol over MgO catalyst. 6. Both MgO and CaO are active for the reaction of propanal with methanol. However, main product is not 2-methyl propanol but 2-methyl propenal and 2-methyl propenol at a short contact time. 7. Very small kinetic isotope effect on the reaction rate of I-propanol with methanol was observed only when the methanol deuterated at the methyl group was allowed to react at 633 K, giving k(CH,OH)/k(CD,OD) = 1.3. A possible reaction scheme for the catalytic synthesis of a,p-unsaturated compounds is depicted in Figure 8.The following discussion is made for the reaction of acetonitrile with methanol as a representative. Methoxy anion is first formed from adsorbed methanol by 0 - H dissociation on the surface base site. This species may be adsorbed on the added metal ion site because the metal ion is a stronger Lewis acid than magnesium ion. Similarly an intermediate methylene anion formed by a-hydrogen abstraction by the surface base site from adsorbed acetonitrile may also be adsorbed on the added metal ion site. Then, the C-H bond fission of the adsorbed methoxy anion takes place and formed hydride is accepted by the added metal cation. This step seems to be the rate determining one. Once this step occurs on the surface, subsequent attack of the adsorbed methylene anion readily takes place, followed by dehydration and desorption to form products. Methoxy anion is normally a much weaker base than intermediate carbon anion; the intermediate methylene anions may be adsorbed more strongly on the added metal ion site than methoxy anion. The intermediate anion formed from the substrate with higher pKa value can be adsorbed more stably to the metal ion site because of the stronger basic character. Therefore, the hydride accepting ability of metal ions from adsorbed methoxy anions may be affected by the adsorption of intermediate methylene anions, depending strongly on the kind of substrate used. Since the hydride accepting ability of the metal ion is directly related to the rate determining step, the reaction rate must decrease with the increasing pKa value of the substrate. A possible reaction scheme for the catalytic condensation of alcohols with methanol is also depicted in Figure 8. The reaction scheme for the alcohol condensation is essentially the same as that for the synthesis of a,P-unsaturated compounds. However, in order to rationally explain the high ability of MgO catalyst for the alcohol condensation, we tentatively propose a CO, assisted mechanism
Methanol-Based Synthetic Reactions over Solid-Base
45
CH2 'CH2
C'
111
..
.''
H
0-Mg-0-Mg-0-Mg-0 (a) Scheme for the reaction of acetonitrile with methanol to form acrylonitrile
(b) Scheme for the alcohol condensation with methanol Figure 8 Reaction mechanism. as shown in Figure 8, since CO, can be easily formed from higher alcohols and clear enhancement effect of CO, was observed in the condensation reaction. The formed CO, may react with methanol over MgO surface to produce methyl carbonate-like species, -Mg-0-CO-OCH,. This species then reacts with an adsorbed alkoxy anion to form corresponding higher alcohols. The role of sulfate anion doped on the MgO surface is interpreted in a similar manner. The surface sulfate anion reacts with methanol to form methyl ester-like species on the surface and this species then reacts with the adsorbed alkoxy anion. The addition effect of CO, on the reaction of acetonitrile with methanol over pure MgO catalyst is also interpreted similarly. When an adsorbed CO, is present on pure MgO surface, this species may assist the activation of methanol by reacting with methoxy anion and accepting hydride from methyl group as shown in Figure 8, resulting in the higher yield of acrylonitrile. References
[ l ] Tsuneshige, T., PETROTECH, 1993, 16, 208. [2] Kein, W., "Catalysis in C, Chemistry," D. Reidel Publishing Company, Dordrecht, 1983, p.89.
46
W. UEDA, H. OHOWA, K. lWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
Wender, I., Caul. Rev.-Sci. Eng., 1984, 26, 303. Calkins, W.H., Catal. Rev.-Sci. Eng., 1984, 26, 347. W. Ueda, J . Japan Petrol. Inst., 1993, 36, 421. Ueda, W., Yokoyama, T., Kurokawa, H., Moro-oka, Y., and Ikawa, T., J. Japan Petrol. Inst., 1986, 29, 72. Ueda, W., Ohshida, T., Kuwabara, T., and Morikawa, Y., Catal. Lett., 1992, 12, 97. Grasselli, R.K., Burrington, J.D., and Brazdil, J.F., Faraday Discuss.Chem. SOC., 1982, 72, 203. Khcheyan, Kh.E., Revenko, O.M., Shatalova, A.N., Gel'perina, E.G., Klebanova, F.D., and Arunskaya, L.I., Nefiekhimiya, 1979, 17, 586. Monsanto, U.S. Patent 4 179 462, 1979. Firuzi, P.G., Petrol. Chem. U.S.S.R., 24, 80 1984. Vitcha, J.F., and Sims, V.A., Ind. Eng. Chem. Prod. Res. Dev., 1966, 5 , 50. Albanesi, G., and Moggi, P., Appl. Catal., 1984, 6, 293. Ai, M., J. Catal., 1988, 112, 194. Ueda, W., Yokoyama, T., Moro-oka, Y., and Ikawa, T., J. Chem. SOC.,Chem. Commun., 1984, 39. Ueda, W., Yokoyama, T., Moro-oka, Y., and Ikawa, T., Ind. Eng. Chem. Prod. Dev., 1985, 24, 340. Kurokawa, H., Kato, T., Ueda, W., Morikawa, Y., Moro-oka, Y., and Ikawa, T., J . Cafd., 1990, 126, 199. Kurokawa, H., Kato, T., Kuwabara, T., Ueda, W., Morikawa, Y., Moro-oka, Y., and Ikawa, J. Catal., 1990, 126, 208. Ueda, W., Kurokawa, H., Moro-oka, Y., and Ikawa, T., Chem. Lett., 1985, 819. Kurokawa, H., Ueda, W., Morikawa, Y., Moro-oka, Y., and Ikawa, T., MRS It'I. Mtg. on Adv. Mats. 1989, V01.2, p309. Sheldon, R.A., "Chemicals from Synthesis Gas," D. Reidel Publishing Company, Dordrecht, 1983, p. 127. M. Ichikawa,J. Caral., 1979, 56, 127. T. Mizorogi and M. Nakayama, Bull Chem. SOC.Jpn., 1964, 39, 236. M.W. Farrar (Monsanto Chemcal Co.)., US Pat. 2 971 033 1961. G. Pregalia, G. Gregorio and F. Conti (Montecatini Edison S.p.A), French Pat. 1 53 1 2612 1968. R.T. Clark (Celanese Corporation), US Pat. 3 972 952 1976. Ueda, W., Yokoyama, Y., Moro-oka, Y., and Ikawa, T., Chem. Lett., 1985, 1059. Ueda, W., Kuwabara, T., Kurokawa, H., and Morikawa, Y., Chem. Lett., 1990, 265.
36
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
various methanol-based synthetic reactions. On the basis of the results of catalytic performance tests and kinetic measurements, both methanol-based synthetic reactions over magnesium oxide catalyst having solid-base are compared in terms of reaction mechanism.
2. EXPERIMENTAL METHODS 2.1 Catalyst Preparation The metal ion-containing catalysts(3 wt%) was prepared by the following impregnation method. Commercial MgO(Soekawa Rika, 99.92%, surface area 11 mZ.g-')is impregnated with an aqueous solution of the corresponding metal nitrate with stirring for 12 hrs at an ambient temperature. Water is then evaporated by heating, followed by drying in air at 110°Cfor 24 hrs. Heat treatment in a nitrogen stream at about 600°C is necessary in order to decompose the impregnated metal nitrate and to desorb water and COr Unless otherwise noted, the prepared MgO was used.
2.2 Catalytic Reaction The reactions to produce a,P-unsaturated compounds were carried out at atmospheric pressure using a continuous flow reaction system with a quartz fixed-bed reactor. The reaction was run at 623 K with 1.3 kPa of substrate in N, carrier. The molar ratio of methanollsubstrate was 10 in all cases and the space velocity (methanol + substrate + N J was 80 ml.min".g-caf'. The reactions of primary alcohols(C,H,,,,OH, n=2-5) with methanol were also carried out at atmospheric pressure using the same continuous flow reaction system with a quartz fixed-bed reactor. The following standard reaction conditions were used; feed gas composition, N, : methanol : C,H,,+,OH = 10 : 3 : 0.15, total flow rate, 66 ml.min-', catalyst weight, 1 g. and reaction temperature range, 573-673 K. 3.
RESULTS AND DISCUSSION
3.1 Synthesis of a, @Unsaturated Compounds a,p-Unsaturated compounds are very important chemicals in the chemical industries, in particular for polymers. The production of these compounds has been accomplished through the catalytic processes based on olefins. For example, acrylonitrile is manufactured by ammoxidation of propene over multicomponent bismuth molybdate catalysts[8]. In recent years, however, other synthetic methods based on the utilization of C, chemicals such as CO, methanol, and methane instead of olefins have been developed markedly. An interesting example is the acrylonitrile synthesis by the oxidative methylenation of acetonitrile with methane over metal oxide catalysts[9]. Since acetonitrile can be synthesized from CO, H,, and NH, catalytically[lO], the process may provide a promising route for acrylonitrile synthesis from C, chemicals only. Many similar approaches have recently been undertaken extensively[111. Other examples are the classical processes where base- or acid-catalyzed condensation reactions with formaldehyde are utilized[ 121. The well-known examples are the condensation of acetaldehyde, where acrolein can be normally obtained because the initially formed aldol condensation product undergoes dehydration simultaneously over the catalysts. In principle, this reaction can be used for the synthesis of other unsaturated compounds. Alternatively, it is possible to carry out this type of reaction with irr situ generation of formaldehyde from methanol by oxidative dehydrogenation[13,141. We have recently developed the reaction for the synthesis of various a,S-unsaturated compounds using methanol as a reagent for C=C bond formation over solid-base catalysts promoted by transition metal ions[5,6,15-20]. General reaction scheme is described in Figure 1. This process is a base-catalyzed reaction, where methyl or methylene group activated by inductive electron withdrawal by the unsaturated substituent such as carbonyl, cyano or phenyl group, is converted into vinyl group by the addition of methanol. The most promising application of this method is demonstrated by the selective formation of acrylonitrile from acetonitrileand methanol[ 161. The conversion of acetonitrile proceeds catalytically at an elevated temperature(>300"C) and yields acrylonitrile(AN)selectively through dehydrogenation,
Methanol-Based Synthetic Reactions over Solid-Base
37
Acryloni trile Acetone Methyl methacrylatee
Acetonitrile
Methyl propionate
+ 4 + HO ,
CH,=CR-Z
Methacrylonitrile
Z = -CN, -COR, -COOR’
-
Figure 1 Catalytic syntheses of a,P-unsaturated compounds with methanol over solid-base. cross-condensation, and dehydration(eq. 1). CYCN
+
CHPH
CH,=CHCN
+ H, +
H,O
,
(eq. 1)
Catalysts are based on metal oxides which are well-known as solid-base materials, such as MgO, CaO, &O,, and so forth. These metal oxides themselves are, however, virtually inactive for this reaction, so that the catalytic properties of these basic oxides must be improved by the addition of small amounts of transition metal cations. Table 1 shows examples for the magnesium-based oxide catalysts. Obviously, a synergism or bifunctional feature of the promoted M-MgO catalysts, depending on the kind of added element, is significant for the catalytic activity and selectivity for the reaction. The addition of manganese, chromium, or iron has a pronounced effect on the course of the reaction; overall catalytic activity based on acetonitrile conversion increased by a factor of 100. The reaction is really selective and by-products are small amounts of propionitrile(PN) and methacrylonitrile(MAN) which are formed by the consecutive reactions of the main product, AN. At the present best conditions, one pass conversion of acetonitrile reaches more than 30% keeping the higher selectivity(>90%) to AN over these catalysts. Stability of these catalysts is extremely good. A prolonged reaction, however, revealed that the activity decreased very slowly but in an appreciable level. Selectivity was almost unchanged during the slow decay of the activity. Slow coke formation Table 1 Synthesis of a$-unsaturated nitriles over metal ion-containing MgO catalysts at 623K Catalyst M”+-MgO
CH,CN Conv.(%)”
MgO Fe3+-MgO C?+-MgO MnZ+-MgO NiZ+-MgO Cu2+-Mg0
0.1 11.2 9.6 9.1
5.5 2.2
AN
Selectivity (%) PN MAN
tr 73.2 94.2 96.4 2.8 91.0
tr 11.6 5.4 2.7 33.5 9.0
1) WIF = 38 g.hr.mol-’, 2) WIF = 145 g.hr.mol-I.
tr tr
0.9
tr
CH,C&CN Conv.(%)”
Selectivity (%) MAN IBN CTN
0.9 5.0 11.0 11.4
65.9 94.6 88.6 97.1
20.9 4.6 6.8 2.2
13.2 0.8 2.3 0.7
2.3
87.5
9.4
3.1
38
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
on the surface, in particular on the surface basic site, seems to be responsible for the slow deactivation because the catalyst was slightly darken. Almost the same activity as of the fresh catalyst can be recovered by calcination of the used catalyst in an air stream at an elevated temperature, followed by the activation process of the catalyst. Looking at the other promoted catalysts, less active catalysts were obtained by the addition of nickel or copper because of remarkable decay of activity in a short reaction time. Characteristically, magnesium oxide containing nickel was extremely inactive for the formation of AN but gave propionitrile in relatively higher yield than the others. Some of the produced AN oligomerized over nickel site to form higher molecular weight compound. It seems that the added nickel ion on the surface of magnesium oxide can catalyze hydrogenation of AN to propionitrile much effectively. The addition of aluminium did not result in appreciable effects on both activity and selectivity. Effect of metal ion content in magnesium oxide on the catalytic property is significant. The formation of AN increases with the Cr content and then decreases after passing through a maximum at 3 wt%. Excess addition causes a decrease in activity and induces the decomposition of methanol and ultimately pure metal oxide used for dopant predominantly catalyzes the decomposition of methanol, so that about 3wt% loading of metal ion is preferable for attaining effective catalytic property for the over-all reaction. The selectivity to AN on the basis of acetonitrile conversion was scarcely affected by the content of metal ion. This activity change is not attributed to surface area change because every catalysts have nearly the same surface area(ca. 100mZ.g-'). Therefore, the drastic increase in activity implies that the reaction needs both functions of added metal ion and surface base site. The activity decreases by the excess addition is thought likely due to the decrease of the surface base site. The above nitrile synthetic process can be applied for the methacrylonitrile synthesis from propionitrile(eq. 2).
CH,CHFN
+
CI-L,OH
-
CH,CCN
EH,
+ H, +
H,O
(eq.2)
Almost the same trend in catalytic performance is observed for MAN synthesis as that for AN synthesis(Tab1e 1). Hence the improved catalytic property of magnesium oxide is obtainable by the specific promotion effect of Mn, Cr, and Fe ions. By using these three catalysts, 95% selectivity to MAN is achieved at about 30% conversion of propionitrile under the optimized conditions. By-products are isobutyronitrile(1BN) and crotononitrile(CTN).
3.2 Condensation of Alcohol to Form Higher Alcohols Numerous attempts have been made in the past to develop synthetic methods for higher alcohols, particularly from C, chemicals such as CO and methanol, and many processes have already been established.[21] One of the important industrial processes is the so-called 0x0 reaction or hydroformylation of alkenes where CO is a key reactant. Other reported methods include homologation of lower alcohols to higher ones using carbon monoxide and hydrogen,[22] and metal- or metal oxide-catalyzed direct synthesis of alcohols from syn gas.[23] In addition, Guerbet reaction, where a primary or secondary alcohol reacts with itself or another alcohol to produce a higher alcohol, is also an important reaction as higher alcohol synthesis. This reaction has been much developed and various types of heterogeneous catalyst have been reported in patents. [24-261 In an extension of our studies on catalysis by solid-base catalysts,[S] we recently developed a new catalytic reaction process for producing higher alcohols using methanol as a main building block(eq. 3). In this reaction, methanol is condensed with other primary or secondary alcohol RCYCHPH
+
[R = H, Alkyl]
CH,OH
-
R HCH,OH
L-4
+
H,O
(eq.3)
Methanol-Based Synthetic Reactions over Solid-Base
39
having a methyl or methylene group at the a-position over metal oxide catalyst having a solid-base property, and then higher alcohols are formed in high selectivities. 3.2.1 Catalytic perfornlance of MgO and metal ion-containing MgO catalysts Table 2 lists the catalytic performance of MgO, CaO, ZnO, and ZrO, in the condensation reaction of ethanol with methanol at 633 K. MgO, a well known solid-base, showed the best catalytic performance in the reactions, yielding higher alcohols selectively in every case. When ethanol was allowed to react with methanol over MgO catalyst, ethanol was readily converted into 1-propanol and 2-methyl propanol Total selectivity to both products was about 80%. Minor products were Cz-, C3-and C4-saturatedcarbonyl compounds and thereby small amount of hydrogen was also formed. Very small amounts of methane and CO were also formed, indicating a few side reactions of methanol took place under the conditions. However, the extents of such reactions were low and thus the excess methanol was most recovered. Other solid-base metal oxide, CaO, was surprisingly inactive. ZnO catalyst was active for the conversion of ethanol but non-selective, mainly catalyzing the dehydrogenation of alcohols to aldehydes. ZrO, catalyst showed acidic character in the present reaction conditions,promoting the formation of various ethers from alcohols. As a result, MgO catalyst was found uniquely active for the condensation of alcohol to produce higher alcohols. The addition effect of metal ions in the MgO catalyst was tested in similar to the catalytic syntheses of a,@-unsaturatedcompounds with methanol and the results are shown in Table 3. Unfortunately, the addition effect was negative in all cases; the MgO catalysts containing metal ion were either less active or less selective. The manganese-containing MgO catalyst, which was most active in the synthesis of a,@-unsaturatedcompounds with methanol, was poorly selective for the Table 2 Condensation of ethanol with methanol over various metal oxide catalysts at 633 K Catalyst Surface Conversion area of ethanol (m2.g-’) (%) MgO
137 65
zro,”
-
CaO ZnO
29.6 0.8 74.5 66.9
1-Propanol 2-Methyl propanol 50.7 34.6 tr 0
Selectivitv(%) 1-Butanol Acet2-Methyl aldehyde propanal
27.6 0 tr 0
0.7
0 0 0
12.4 65.4 84.5 0
1.9 0 0.5 0
1) Main products were dimethyl ether and methyl ethyl ether. Table 3 Condensation of ethanol with methanol over various metal ion-doped MgO catalysts(633 K) Catalyst Surface Conversion M-MgO ama of ethanol (3wt%) (m2.g-’) (%) MgO MJl
Cr
Al
Na cs
137 168 105 106
29.6 32.9 35.1 24.6’’ 0.8 0
1) Various ethers were formed.
Selectivity(%) 1-Propanol 2-Methyl 1-Butanol propanol 50.7 24.3 16.0 4.6 33.3 0
27.6 9.9 7.3 0 0 0
0.7
tr tr 0 0 0
Acetaldehyde
2-Methyl propanal
12.4 31.9 36.4 4.6 66.7
1.9 3.7 5.2 0 0
0
0
40
-
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
\OH
-OH
-OH
Conversion(%) 50
-OH
&OH (40)
(83)
48
&OH
60
(79)
50
-OH
[ ( ): Selectivity/% ]
Figure 2 Condensation of various alcohols with methanol over MgO catalyst at 653 K.
z.-
100
Reactant
at 380°C
c
(pmol/fin)
0
f>
0 0
c 0
0
Reactionrate products
0
,
A
Ethanol l-Propan01 1-Butanol 1-Pentan01
17.9 16.1 18.9 16.8
Cn+,HCnH2,+,CH0
14 11 10 28
2
Figure 3 Comparison of the condensation rates of various alcohols with methanol over MgO. formation of saturated alcohols like 1-propanol and 2-methyl propanol, mainly catalyzing the formation of unsaturated compounds like acrolein, ally1 alcohol, and aldehydes in accordance to its catalytic performance in the reaction of nitriles with methanol, although the catalyst showed a slightly improved activity for the methanol conversion in the reaction of ethanol and methanol. More characteristically, the addition of sodium cation into MgO catalyst resulted in the complete disappearance of the activity, although the sodium ion-containing catalyst would be stronger base than original MgO catalyst. By taking account that the CaO catalyst is also completely inactive for the reaction, it seems that catalysts having much stronger basicity are not suitable for the reaction. Figures 2 and 3 summarize the results of the condensation reaction of various alcohols with methanol over MgO catalyst at the temperature range of 573-673 K. When the other primary alcohol was allowed to react with methanol, the reaction features were almost the same as described above for the ethanol conversion; that is, the reactions readily took place and formed the 2-methyl form of
Methanol-Based Synthetic Reactions over Solid-Base
41
the higher alcohol mainly with small amount of aldehydes produced by the dehydrogenation of the reactant and product alcohols. The only difference between the ethanol reaction and the other reaction is two alcohol products in the ethanol reaction but one higher alcohol product in the other. This is because the propanol produced in the ethanol conversion can subsequently react with methanol to form 2-methyl propanol Two points emerge from the figures. First, the conversions obtained in each reaction under the standard conditions were essentially the same (50-60%)and the temperature dependency of each reaction was also similar as shown in Figure 3. This strongly implies the rate independency of the reactant. Secondly, the product selectivity is little influenced by the reactant; the alcohol selectivity is around 80% in every case and the high molar ratio of alcohol to corresponding aldehyde is also similar in every reaction. 3.2.2 Catalyticperfonncrnce of MgO catalysts containing 0x0 anion As the MgO catalyst was found most active for the condensation reactions of alcohols with methanol, we have tested the catalytic performance of MgO prepared by various methods. The MgO catalyst designated by MgO-(OH) was prepared by the method described in the experimental section. The MgO catalyst designated by MgO-(FD) was prepared by freeze-dry method. In this method a slurry in a boiling water was freeze-dried instead of the evaporation of water and drying at 383 K in the preparation of the MgO-(OH) catalyst. The MgO catalysts designated by MgO-(NO) and MgO-(SO) were prepared by precipitation method from aqueous solution of magnesium nitrate and magnesium sulfate, respectively. Solidification procedure is the same as for the preparation of the MgO-(OH) catalyst. The MgO catalyst designated by MgO-(CO) was from a commercial basic magnesium carbonate which was directly used for the reaction without any treatments except the standard heat-treatment. The MgO catalyst designated by MgO-(ME) was prepared by the use of methanol instead of water as a media. All the other procedures were the same as the MgO-(OH) preparation. The catalytic activities of these prepared catalysts in the condensation of 1-propanol with methanol at 633 K are illustrated in Figure 4. Figure 4 also shows surface area of each catalyst and molar ratio of produced 2-methyl propanol to produced 2-methyl propanal. It can be seen that the catalytic activity of MgO changed significantly by the preparation method. The MgO-(FD) catalyst had the highest surface area among the catalysts prepared here. The crystallinity of MgO-(ME) catalyst particles were very high and thus its surface area was lowest. This catalyst, however, showed the highest specific activity for the formation of 2-methyl propanol in the reaction. Although it is very hard to see any relations among the preparation method, surface area, activity, and selectivity, it appears that such changes are mainly caused by small amount of anion species
I
R a t e 109mol/m2.min Rate 10~pmol/g.min
I MgO-(FD)
I
I
-,
MgO-(NO)
441
18
360
27
MgO-(SO)
295
36
MgO-(CO)
208
16
177
16
13 0
2
4
6
1
2
Figure 4 Catalytic performance of MgO prepared by various methods.
42
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHlDA and Y . MORIKAWA
'
OO
r
IConversion(%) Sel(%) to i-BuOH Yield(%) of i-BuOH
80
60 40
20 0
Figure 5 Addtion effectsof halide anion or 0x0 anions on the catalytic performance of MgO. remained on the MgO surface; these anions may strongly influence the catalytic performance of MgO, since it is very difficult to remove the anions of starting materials completely by repeated washing and since these anion largely change the surface structure of MgO and have electronic effects. We, therefore, conducted experiments to test the addition effect of anions to MgO surface. Various anion-doped MgO catalysts were prepared and tested for the reaction of 1-propanol with methanol. Eight kinds of anion, chloride anion and 0x0 anions, were doped into MgO catalyst as shown in Figure 5. Preparation procedure of these catalysts is the same as for the preparation of metal ion-containing MgO catalyst. Either acidic form of anion or ammonium salt was used in the preparation. Chloride anion-doped MgO catalyst was virtually inactive for the condensation of 1-propanol with methanol, simply because its surface area was low; it was found that chloride anion effectively promoted crystallization of MgO during the heat-treatment. Nitrate anion was ineffective. This might be due to that nitrate anion easily decomposes during the heat-treatment even in the MgO lattice. However, there must be another reason for that the nitrate anion-doped MgO catalyst was Table 4 Condensation of 1-propanol with methanol over various sulfate anion-containing MgO catalysts at 633K Catalyst Added compound (3 wt%)
Conversion/%
Selectivity/%
1-Propanol Methanol ~~
~
~~
none
47.4
8.9
63.5
tr
7.7
(NH4)2 . 0 4 MgSO4 MgSO,.(NHJ,SO, CH, S03H (CH,SOJ,Mg
72.8 78.7 74.1 59.4 58.7
19.7 11.9 15.6 15.5 4.1
70.4 70.0 64.9 62.9 57.8
12.0 2.5 8.5 1.3
4.5 2.0 7.5 3.3 2.7
tr
Methanol-Based Synthetic Reactions over Solid-Base lOOr
I
I
. to i-BuOH
w Conv. of 1-propanol
n
100
$?
1 f z
._5
g
c
43
:F/ Sel. to i-BuOH
80 60
Conv. of 1-propanol
40 20
0
O
wt% Figure 6 Effect of sulfate anion loading on the activity of MgO catalyst in the condensation of 1-propanol with methanol.
O 0
Figure 7 Condensation of 1-propanol with methanol over 1 wt% sulfate anion-doped MgO catalyst at 633 K.
less active than the pure MgO catalyst. The addition of borate anion resulted in no change in the catalytic performance of MgO. Apparent improvement in the yield of 2-methyl propanol was observed by the additions of sulfate and phosphate anions. Particularly, the addition of sulfate anion improved both activity and selectivity. The catalysts modified with silicate, molybdate, and tungstate anions were less selective although the conversion of 1-propanol was higher. Various sulfate anion-doped MgO catalysts were prepared by the use of various sulfate precursor and tested for the reaction of 1-propanol with methanol because the sulfate-doped MgO catalyst showed the highest activity for 2-methyl propanol formation. The results are shown in Table 4. Three kinds of inorganic sulfate precursor and two kinds of organic sulfate precursor were added into MgO catalyst as shown in the table. Apparently every inorganic sulfate dopants were found to be effective to improve the catalytic performance of MgO. The organic sulfate dopants were less effective. It was observed from TPD spectra of CO, and XRD analysis that the surface basicity and the crystallinity of MgO particle did not change by the addition of sulfate anion. Therefore, it seems that the improvement of the catalytic performance by the addition of sulfate anion is attributable to the increase of surface area and the generation of sites which are much highly active for the reaction. Figure 6 shows the effect of loading amount of sulfate anion on the catalytic performance of MgO catalyst in the condensation of 1-propanol with methanol at 633 K. The conversions of 1-propanol and methanol increased with increasing the loading amount of sulfate anion. The selectivity to 2-methyl propanol also increased but further addition caused the decrease in the selectivity after a maximum at about 1 wt %. As a result, the addition of sulfate anion in 1 wt % to MgO catalyst is suitable to achieve the highest catalytic performance in the reaction. By the use of 4 g of lwt% sulfate anion-doped MgO catalyst, 60 % yield of 2-methyl propanol was attained in the condensation of 1-propanol with methanol at 633 K(Figure 7).
3.3 Aspect for Reaction Mechanism Reaction mechanisms for the synthetic reactions of a,P-unsaturated compounds and for the condensation reaction of alcohols with methanol are discussed here on the basis of the following summarized observations. For the synthetic reactions of a,P-unsaturated compounds: 1. MgO catalyst without any additives is virtually inactive.
44
W. UEDA, H. OHOWA, K. IWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
2. MgO catalysts containing metal cation, such as Fed*,Cr" ,and Mn2+, which provide Lewis acid site in the MgO lattice, are active and selective. 3. The rate of product formation is not proportional to the total amount of surface base site. 4. A correlation between the rates of reaction and the pKa values of the substrates is observed; the reaction rate is higher for the substrate with a lower pKa value[27]. 5. The kinetic isotope effect on the reaction rate of acetonitrile with methanol was clearly observed only when the methanol deuterated at the methyl group was allowed to react at 603 K, giving k(CH,OH)Ik(CD,OD) = 2.2. No kinetic isotope effects were caused by deuterium substitution at hydroxyl hydrogen of methanol and acetonitrile[181. 6. The exchange reaction between hydroxyl hydrogen of methanol and hydrogen of acetonitrile takes place readily both over Mn-MgO and over Mg0[28]. 7. Methanol is easily decomposed to CO by passing over the metal ion-containing catalyst, while MgO is inactive for methanol decomposition. However, the rate of methanol decomposition is seriously depressed by the existence of substrates[6]. 8. When CO, is co-fed in the reaction acetonitrile with methanol, the reaction readily takes place even over the pure MgO catalyst. For the alcohol condensation with methanol: 1. Pure MgO catalyst is active, while CaO, which is also solid-base catalyst, is inactive. The addition of sodium cation to MgO catalyst completely depresses the catalytic activity of MgO. 2 . The addition of CO, in the feed greatly enhances the rate of alcohol condensation. 3 . Sulfate anion-doped MgO catalyst shows much higher activity than MgO catalyst. 4. Reaction rate is almost independent of primary alcohols used for the reaction as substrates. 5 . No 2-methyl propanal was detected at a very short contact time, indicating that 2-methyl propanol is a primary product and 2-methyl propanal is subsequently formed by the dehydrogenation of produced 2-methyl propanol over MgO catalyst. 6. Both MgO and CaO are active for the reaction of propanal with methanol. However, main product is not 2-methyl propanol but 2-methyl propenal and 2-methyl propenol at a short contact time. 7. Very small kinetic isotope effect on the reaction rate of I-propanol with methanol was observed only when the methanol deuterated at the methyl group was allowed to react at 633 K, giving k(CH,OH)/k(CD,OD) = 1.3. A possible reaction scheme for the catalytic synthesis of a,p-unsaturated compounds is depicted in Figure 8.The following discussion is made for the reaction of acetonitrile with methanol as a representative. Methoxy anion is first formed from adsorbed methanol by 0 - H dissociation on the surface base site. This species may be adsorbed on the added metal ion site because the metal ion is a stronger Lewis acid than magnesium ion. Similarly an intermediate methylene anion formed by a-hydrogen abstraction by the surface base site from adsorbed acetonitrile may also be adsorbed on the added metal ion site. Then, the C-H bond fission of the adsorbed methoxy anion takes place and formed hydride is accepted by the added metal cation. This step seems to be the rate determining one. Once this step occurs on the surface, subsequent attack of the adsorbed methylene anion readily takes place, followed by dehydration and desorption to form products. Methoxy anion is normally a much weaker base than intermediate carbon anion; the intermediate methylene anions may be adsorbed more strongly on the added metal ion site than methoxy anion. The intermediate anion formed from the substrate with higher pKa value can be adsorbed more stably to the metal ion site because of the stronger basic character. Therefore, the hydride accepting ability of metal ions from adsorbed methoxy anions may be affected by the adsorption of intermediate methylene anions, depending strongly on the kind of substrate used. Since the hydride accepting ability of the metal ion is directly related to the rate determining step, the reaction rate must decrease with the increasing pKa value of the substrate. A possible reaction scheme for the catalytic condensation of alcohols with methanol is also depicted in Figure 8. The reaction scheme for the alcohol condensation is essentially the same as that for the synthesis of a,P-unsaturated compounds. However, in order to rationally explain the high ability of MgO catalyst for the alcohol condensation, we tentatively propose a CO, assisted mechanism
Methanol-Based Synthetic Reactions over Solid-Base
45
CH2 'CH2
C'
111
..
.''
H
0-Mg-0-Mg-0-Mg-0 (a) Scheme for the reaction of acetonitrile with methanol to form acrylonitrile
(b) Scheme for the alcohol condensation with methanol Figure 8 Reaction mechanism. as shown in Figure 8, since CO, can be easily formed from higher alcohols and clear enhancement effect of CO, was observed in the condensation reaction. The formed CO, may react with methanol over MgO surface to produce methyl carbonate-like species, -Mg-0-CO-OCH,. This species then reacts with an adsorbed alkoxy anion to form corresponding higher alcohols. The role of sulfate anion doped on the MgO surface is interpreted in a similar manner. The surface sulfate anion reacts with methanol to form methyl ester-like species on the surface and this species then reacts with the adsorbed alkoxy anion. The addition effect of CO, on the reaction of acetonitrile with methanol over pure MgO catalyst is also interpreted similarly. When an adsorbed CO, is present on pure MgO surface, this species may assist the activation of methanol by reacting with methoxy anion and accepting hydride from methyl group as shown in Figure 8, resulting in the higher yield of acrylonitrile. References
[ l ] Tsuneshige, T., PETROTECH, 1993, 16, 208. [2] Kein, W., "Catalysis in C, Chemistry," D. Reidel Publishing Company, Dordrecht, 1983, p.89.
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W. UEDA, H. OHOWA, K. lWASAKI, T. KUWABARA, T. OHSHIDA and Y. MORIKAWA
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