JPS59161326A - Preparation of acetaldehyde - Google Patents

Abstract

PURPOSE:In reacting methanol with carbon monoxide and hydrogen in a gaseous phase, to obtain acetaldehyde in a heterogeneous system advantageously, by using both a catalyst obtained by supporting cobalt and/or palladium on a carrier and a methyl halide as a promotor. CONSTITUTION:In preparing acetaldehyde useful as an intermediate for various kinds of organic chemicals by reacting methanol with carbon monoxide and hydrogen in a gaseous phase, a catalyst obtained by supporting cobalt and/or palladium, preferably cobalt and palladium on a carrier preferably active carbon is used, and a methyl halide such as methyl iodide is used as a promotor, to give the desired compound advantageously. Since this method is carried out in a heterogeneous system, handling such as recovery of solvent is easy. Since the methyl halide can be used in a gaseous phase instead of a liquid phase, a common stainless steel can be used as a material for device without anxiety of corrosion, and use of poison such as arsenic is not required.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing -Cace1 aldehyde by reacting methanol, -carbon oxide, J2 and hydrogen.

Ace1-Aldehyde is an important industrial eutectic as an intermediate for 3 types of octene (9M U?3), and is currently being used for oxidation of ethylene, hydration of acetylene, It is produced by oxidation or dehydrogenation of ethanol, conversion of paraffinic hydrocarbons, etc.

However, since there is a limit to the availability of petroleum, methods are being considered to synthesize various industrial chemicals, including acetic acid aldehydes, starting from coal other than petroleum.

In particular, a method in which -Nidized carbon and hydrogen are first obtained from these starting materials, methanol is produced from these, and this methanol is utilized is expected to be a useful production method.

Presence of a compound containing cobalt as the main catalyst and phosphine, halogen, antimony, arsenic, bismuth, etc. as the co-catalyst, methanol, fi
It is known from U.S. Pat. In the presence of a catalyst, ace1-aldehyde is produced from methanol, -carbon oxide and hydrogen!
A method for performing B is known from Japanese Patent Application Laid-Open No. 5G-25128.

(However, such a reaction requires a non-7G% high pressure, and it is difficult to recover the catalyst because it is a homogeneous oil phase reaction.)
Mari"r% ic+ 'IA%'l noro+!!!,
There were many problems such as the handling of arsenic, bismuth, and antimony-based Di products.

Those who are enlightened should add Kohar 1~ and/or Palladium to each (
Using a catalyst supported on a Φ carrier, aretoalde di 1 ~ ζ・',! We succeeded in creating a new system and solved the above problems. 1 coi/l (invention (1 yo methanol, -j'jj carbon dioxide Jj yohi water 2
ζ and react these in the gas phase to produce acetaldehyde.
1j6J, at least one of cobalt and palladium is supported on a carrier (a catalyst supported on this, a promoter and one
．． -C ha[' methyl chloride is used. This test of strength (ha,
Because it is a heterogeneous system, handling such as recovery of the catalyst is easy, and the methyl halide is
1"-(Use (I)
U tjhi ni na lζ. Also, there is no need to use the above-mentioned "Una 745".

In this Komei, there is no limitation on the method of holding the catalyst on the carrier, but
Typically, an aqueous solution of Kobal 1~ salt or/or O palladium salt, acidic water? It is obtained by soaking various carriers with 8 liquid or organic solvent solution to support iM, and after drying, reducing treatment in a hydrogen stream.

All palladium salts can be used in water, 0; dihydric water, i1 (dissolved in J soot, etc.). Kohar 1-1 Kobal chloride!, Negative monoacid Kobal 1~, Palladium salt is palladium chloride or each representative and industrially used -19
water.

To Kobal 1, when using only one side of palladium, j
[Supported on 84 E. However, the weight ratio as metal is 0.2-30
%, preferably 1.0 to 20%, or when both are used (J1 each 0.1 to 30%, lxT each 0.
．． 5 to 20% of
A range of 1 to 100, preferably 05 to 20, is suitable.

In general, it is preferable to use both in combination in terms of mechnol conversion rate, etc. Furthermore, two or more types of supported catalysts supported under different conditions may be used in combination so as to fall within the above range, if necessary. Na;J3
Below these ranges, the reaction yield is poor, and above these ranges, the corresponding effect is low.

In addition, in any case, it is a relatively harmonious coal.
'51.

Methyl halide (methyl iodide)] ζ (Yes, 1' molar ratio to methanol (1,01~10%
, Ql-1 or 0, 0! -to i・5% range C'
Attachment 1j [1 is recommended for jl-station 11'I.

:Ij and potassium may be added to the above catalyst as necessary.
Monkey. 0.01~8C for each car
However, there is a 719jHζ' increase in the amount of filtration added to 11t/t of aldehyde, but below this range there is no noticeable effect, and it often lowers the rate by 1μmC(,1 -C11!) .

With this invention, 1,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000,000, 130,000,000, 100,000, 1,000, 100, 100, 100, 100, 100, 10, 10, 1, 1, 1, 1, 1, 1, 1, 2, 2, 2, 2 and 2, 2, 2 and 22 Asssssssssssssssssssssssssssssssssssssssssssssssbuts->
! The anti-1-core strip ('! Or, on the other hand, 1j30~220''C is preferable because the opposite is true.

The pressure is hydrogen partial pressure, - rIbs 1 bromide, bromine partial pressure, ahi 1 - aldehy 1 - the speed of formation (J, j * becomes 1
f171 pump, reactor, etc. 10-2 in terms of equipment materials
oo1(g, / c+t? Q, good J, or 10-
, εi at 100kCI/CTfG; Elm is excessive.

The partial pressure ratio of G O/H2 is preferably in the range of 1 to 6 because although the yield of X-culm acetaldehyde is large, the by-product of methyl acetate also increases.

The partial pressure ratio of synthesis gas (mixture of carbon oxide and hydrogen)/methanol is 2 or more, preferably 4 or more, since the yield of culm acetate is large and the yield of aldehyde is 2. Also, from an industrial practical standpoint, 5
0 or less, preferably 1;'t. 20 or less. Catalyst amount (carrier load) W (U!') and raw material waste supply i'JL f'l F (nlol / tll) (
7) Comparatively, ＼＼l/F) is the conversion 'S -, selection ', and catalyst loss 1~, etc.! A culm of from 1 to 100, preferably from 2 to 50, is suitable. In addition, unreacted substances and by-products can be recycled after separation and purification as necessary.

Note that the invention can be carried out using various types of catalyst beds, such as fixed beds, fluidized beds, spouted beds, or combinations thereof.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Actual fMI series 1 ``Hull 1 ~ includes 11091゛'' Warming =] Pal [
Aqueous solution of ~? 1. A hydrochloric acid-resistant water bath solution of palladium chloride containing 40 gr of palladium, J, or both salts in a hydrochloric acid aqueous solution containing 20 gr of each metal, was mixed with commercially available activated carbon (
Wu LU common article ding 呆着面I 箭white:i:'2C), 5iQ2
('Hatakude' Ison Chemical Co., Ltd. product I l))
, and t, IA & 203 (East) Corner High Heat Soil 1 Product K S -99651γ - Aluminum) All of them were mixed well with lkq, - left to stand day and night, then evaporated to dryness, and further dried at 110°C for a day and night. So, the water line is 450' in the air current.
C3 Use any of the treated, cooled, and smelt as a catalyst C
Pressure fixation: AE 3j! J:iI: Fill the reactor with water.

Co/T12/CH301-1/CI-
1,, 1 mole j, Hika < 4,! ] / 4
, 5/1/0, 00! i) Kongo dregs were supplied. Methanol and waxed methane (preliminarily vaporized in an evaporator and then combined with carbon monoxide prefecture J3 hydrogen and 1
The mixture was combined and sent to the reactor. The pressure inside the reactor is 40k
CI/cI11', Excerpt 1' The gas temperature is 21 (1'C
was maintained. Touch! AI: Ratio of weight W (c+r) to raw material gas supply point F (mol/l+r) ('#/
F) is 4. It was set as Ogr-cat l+r/n101. The results are shown in iMo 1.

Example 1 Column 2 A catalyst containing 1 to 10 cobal and palladium on activated carbon as used in Example 1 [■] or catalysis (1 kg of "■" and 10 gr potassium) including j
A solution of l'1 negative potassium in water was mixed overnight, immersed for a day and night, then evaporated with 2N, dried at 110°C for a day and night, treated in a hydrogen stream at 450°C for 3 hours, and left to cool. [
II]! i=! I: Medium C pressurized [4 constant flow JM type reactor was filled.

In this reactor, the cell ratio of C○/H2/Cl-130H/CH31 is 8. A mixed gas of /2/I/O-,005 was supplied in the same manner as in run M1. The pressure inside the reactor is 55
kg,,i'CTTI', output locus) crystal 1 quality is 18
It was maintained at 0°C. \・■、' F < gr-ca
t</mOl> was determined as shown in Table 2.

Table 2 (shown here)

p:fj)'j (\+□t Co 4.OPd
4. OCO2, OCo 2. OCO2,096/'rod) Pd2. OPd2. OPa 2.
0] Kawako i Saisei Charcoal Activated Carbon Activated Carbon S, 02
to ρ203 Meknorjj+7. 'ization: $ (111t
i! %) 7.4 12. G7. G1.
1 24.41 Reaction product yield:! , ;k <1110
19i+)! Aldehyde to that 1 1.87 0.10 2.8! i 0.11
0.62 methane 1. GOA, 13 2.05 0
．． 2'l 2,75 dimedil" 2~del 1.27 2.76 LJ, 5G O, 18
10,77 Methyl acetate 0.5'+ 1.134 0,890,29
1.32 Ethanol 000 00 -j'tl~F7ruU" Hi1Hei1Shaku2 and (111
01%) 35.08 2.1f3 /li, G7
13,02 4. Oi~\j,' JT 3, G4 5. /IG 10. ．． 92 3. G4
5.46 10.92 Methanol conversion plant purchase 1110
1%) 14.311 ”17.34 5!1.53 17.
87 30,45 72,9Fi (reacted cow product yield 1.;
(mO (%) on core 1~Arahit 7.04 11.08 3/1.62 ji, A6
1!1.0・, San 1. H(+)methane 1.0OL38 6,82 1.03 2.72
10', 38 Dimedyl Ether L050.54 0. G4 0.75 0.72
0,73 Intoxicated Methyl 2.2G 2,10 4.84 Jj, 30
6.2! + 13.45 echnol 0 0.38 2,72 0 (11,
971) 7se1~Aldehy1-Selectivity (11101%)
]G6.60 73. GΩ G5.19 G5. Of
j58. G8! ! 7. G5 agent Akimine Ozu

Claims (1)

[Claims] 1. Methanol, - made! To react carbon and hydrogen in the gas phase to produce zetalde, add at least one part of 1 cum of balan to the carrier. Tight tactile motion (and accelerator doji (
The use of [-I methyl silane] is particularly important. 2. Claims in which the JEI body is talkative carbon -I
i, i method. 3. Take care of Kobal 1-d3 and Palladium 4-
Claim 11i using a catalyst having J, I+
lri]-1 [b) method of j.