JPS6034930A - Manufacture of unsaturated carboxylic acid and/or ester of same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing unsaturated carboxylic acids and/or esters by reacting formaldehyde or acetaldehyde with a saturated carboxylic acid in the gas phase at elevated temperatures in the presence of a catalyst.

U.S. Pat. No. 3,701,798 discloses that formaldehyde and the general formula RC112X or ' is a carbon-carbon bond or a divalent saturated aliphatic hydrocarbon having 1 to 20 carbon atoms, and (It's full)
one or more inorganic oxides of rare earth metals of the ranknid series impregnated onto a silica gel, alumina or diatomaceous earth support in a mixture with a compound having a functional group having Describes a process for the preparation of an α,β-unsaturated compound having the general formula: % formula %: where R, R′ and X are as defined above, comprising passing over a catalyst consisting essentially of .

U.S. Pat. No. 4,324,908 discloses a vapor mixture of a saturated monocarboxylic acid or its ester and formaldehyde or a formaldehyde derivative using the empirical formula, aPOX (wherein A is Fe, Ni, Co, Mn, Cu, or at a temperature of about 200-450 °C in the presence of a medium with a of 0.2-3.0 and X determined by the nature and oxidation state of the other elements. A method for making unsaturated carboxylic acids and esters is described that includes passing into a reaction zone.

U.S. Pat. No. 4,324,908 further teaches that the catalyst can be used unsupported, but with suitable supports, such as silica, alumina, silica and alumina? The preferred use of metals, amorphous silica-alumina, crystalline aluminosilicates, titania, natural clays, etc. is disclosed. In the background of the invention, other catalysts found to be useful for this reaction include type X or type Y zeolites containing cesium, rubidium or potassium cations as found in U.S. Pat. No. 4,115,424. It is disclosed that this is an example. However, in reality, U.S. Patent No. 4.115,4
．． No. 24 has 5iOz/A fi in the range of about 2 to 8,
0. Catalysts comprising crystalline aluminosilicates of bojazite structure containing potassium, rubidium or cesium cations or combinations thereof and containing boron or phosphorus or combinations thereof, and alkyl toluene to styrene and ethylbenzene with molar ratios. For use in synthesis, it is not relevant for the production of unsaturated carboxylic acids and esters.

It has now been discovered that high-silica synthetic crystalline aluminosilicates catalyze the reaction of formaldehyde or acetaldehyde with saturated carboxylic esters or anhydrides to form unsaturated carboxylic acids and/or esters. High Silica Crystalline Aluminosilicates, Zunawara Crystalline aluminosilicates with a silica to alumina molar ratio greater than 10:1 not only have a higher silica to alumina molar ratio, but they are also more acidic and have a higher Types X and Y used in the method of U.S. Pat. No. 4,115,424 in terms of their mechanical and thermal stability.
It is distinguished from type zeolite.

Therefore, the present invention is a method for producing an unsaturated carboxylic acid and/or its ester by reacting an aldehyde including formaldehyde or acetaldehyde with a saturated carboxylic acid derivative in the presence of a catalyst at high temperature in the gas phase, comprising: The saturated carboxylic acid derivative is an ester or anhydride, and the catalyst is 0.9±0.2M2/+10: A 1 zo3:YS
iOz:zllzO [wherein M is H'' and/or a transition metal and/or rare earth metal cation having a valence n, Y is an integer greater than 10, and 2 is an integer ranging from 0 to 40. an integer molar ratio of oxides.

7) The Ltdehyde reactant is formaldehyde acetaldehyde, preferably formaldehyde.

Formaldehyde can be derived from any commercially available source of formaldehyde, such as aqueous, alcoholic or polymeric formaldehyde. Suitable formaldehyde sources include formalin, methylal and trioxane. Similarly, acetaldehyde can be derived from any suitable commercially available source of acetaldehyde.

Saturated carboxylic acid esters suitably have the formula: % formula % [where R is hydrogen, phenyl or a 4J aliphatic hydrocarbon group, R2 is a carbon/carbon bond or a divalent aliphatic hydrocarbon group, X is a functional group having the formula: % where R3 is a hydrocarbon group or a substituted hydrocarbon group. Suitable carboxylic acid esters include methyl acetate,
Includes ethyl acetate, propyl acetate, methyl propionate, ethyl butyrate, ethyl heptanoate, ethyl heptanoate and dimethyl adipate.

Particularly preferred reactants are formaldehyde and methyl acetate formed by methyl acrylate and/or acrylic acid, and acetaldehyde and methyl acetate formed by methyl methacrylate and/or methacrylic acid.

The saturated carboxylic acid anhydride may suitably have the formula: R'CII□C0,0,Cl12RS@, where ll' and R5 are independently hydrogen or an alkyl group. Suitable alkyl groups are 01-c
6 alkyl group. Examples of suitable carboxylic anhydrides include acetic anhydride, propionic anhydride, and mixed anhydrides thereof. The reaction of formaldehyde with acetic anhydride produces products containing acrylic acid.

Although the molar ratio of acid derivative to aldehyde is not critical,
However, a range of 1:1 to 25:l is suitable. However, the optimum ratio can be easily determined by one skilled in the art depending on the reaction conditions and the nature of the reactants.

Regarding the crystalline aluminosilicate having the above composition, Y
is preferably in the range of 15 to 100. Various synthetic crystalline aluminosilicates conforming to the above formula may be suitably used. Examples of preferred types of crystalline aluminosilicates are those listed by the Straft Commission of the International Zeolite Association (T.
heStructure Comm1ssion of
the International Zeolite
WlMoMeier and 11.I published in 1978 by WlMoMeier
The Atlas of Zeolite Structural Tyves (the At1as
of ZeoliteStructure Types
) is shown as MFI zeolite. These generally include (i) a silica (SiO□) source, (11) an alumina source (8i 203), and (iii) a mineralizing agent selected from alkali and alkaline earth metal oxides and salts (Xzzb O, where b is the valence of X), (1■
) An organic base (B) as described below, and (V) water and/or alcohol (11011) in the following molar ratio, S
iO2:8A203.12: greater than 1, preferably 15:1 to 100:l 5i02:Xzzb O=1000: 1 to 50:
l5iO7:B = 50:1 to 1:20, and Si
O□: 11□0 or ROI: 80-220"C1 preferably 120-175°C from a gel containing less than 10
It is produced by crystallization at a temperature in the range of 0.5 hours or more.

The term organic base used is the reaction: B+11□0 +BIl" + 1'O to OH-
g+oK(here = ([111”) (O1+-
:1/CB)) is less than 7.

Suitable organic bases include:

(i) Formula: I? 'R2R'rl'N'' is an inorganic anion).

Preferably) 1+, R2, R3, and R4 are 1 to 5
is an alkyl group containing 5 carbon atoms.

Preferably X- is a halide or hydroxide ion. Suitable tetraalkylammonium salts include tetraethylammonium hydroxide and tetrapropylammonium hydroxide. Alternatively, precursors of tetraalkylammonium compounds can be used.

(11) Formula: %Formula% (In the formula, X is an integer in the range of 1 to 20) or R'R"N(C1lzh N(CHz)z NR3R'
(wherein y and 2 are integers ranging from 1 to 20).

Suitable amines include 01-C9 primary monoalkylamines;
Examples include n-ethylamine, n-propylamine, and n-butylamine.

(iii) Mono-, di- and tri-alkanolamines, such as monoethanolamine, jetanolamine and triethanolamine, or their precursors in the form of alkylene oxides and ammonia.

Suitable silica sources include, for example, sodium silicate, silica hydrogel, silica gel, silica sol, and silicic acid. A preferred silica source is an aqueous colloidal dispersion of silica particles. A suitable commercially available silica source is LUDOX manufactured by DuPont.
) Colloidal silica (*registered trademark).

Suitable alumina sources include, for example, thorium aluminate,
Contains aluminum sulfate and alumina. A preferred alumina source is thorium aluminate prepared by dissolving finely divided alumina in excess sodium hydroxide solution.

Preferred mineralizing agents are alkali and alkaline earth metal hydroxides and halides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium bromide and calcium bromide. A preferred mineralizing agent is sodium hydroxide.

silica, alumina, alkali or alkaline earth metals are supplied by one or more initial reactants;
They can then be mixed in any suitable order. For example, lithium silicate is a source of both sodium and silica, and aluminosilicate is a source of both alumina and silica.

Thus, the alumina source and silica source can be supplied in whole or in part by aluminosilicates, which can be crystalline or amorphous.

Certain MFI-type zeolites and their preparation using organic bases are described, for example, in U.S. Pat. No. 3,702. ．． No. 886, No. 3.709.979, No. 4,205,053,
Nos. 4,166.099, 4,139,600 and 4.15LL89; British Patent No. 1.365.31
No. 8 and No. 1.567.948, and European Patent Application Nos. 2899 and 2900.

Alternatively, organic bases are described in the Applicant's European Patent Application No. 30811, US Pat. No. 4.199.556 and British Application No. 2.018,232A.

or ferrierite as described in British Patent No. 1,436,524, European Patent Application Publication No. 57049
Theta-1 described in U.S. Pat. No. 4,209', FU-1 described in U.S. Pat. ZSM-5 described in No. 4.229.424
Other crystalline aluminosilicates such as ZSM-35, ZSM-23 and zeolite beta described in US Pat. No. 4,146.584 can be used.

In addition, dealuminated faujasite can also be used.

The crystalline aluminosilicate produced almost certainly contains ions other than hydrogen and transition metal ions, such as alkali metal and/or alkaline earth metal ions, organic nitrogen ions and ammonium ions, and/or in its pores. and an organic base precipitated on the surface.

In order to obtain a force insect medium with the desired composition, it is necessary to replace the exchangeable cations with hydrogen ions or transition metal ions. This can be accomplished using conventional ion exchange techniques. Additionally, calcination of the crystalline aluminosilicate after exchange is desirable, and in fact necessary, prior to exchange of crystalline aluminosilicate derived from some organic bases. Roasting can be carried out by heating at a temperature in the range of 400 DEG to 600 DEG C. for at least 0.5 hours, preferably in a stream of air.

Suitable transition metal ions include the metals of group I of the periodic table according to Mendeleev, such as iron, cobalt and manganese;
as well as ions of metals of the lanthanide series, such as praseodymium.

The temperature at which the acid derivative is reacted with the aldehyde is suitably 30
It can range from 0 to 525°C, preferably from 350 to 500°C, although higher and lower temperatures can be used if desired. Although the pressure is not critical, it is appropriate that the pressure be consistent with maintaining the reactants at 17°C.

The process can be operated batchwise or continuously, preferably continuously. The residence time for continuous operation is preferably short, for example less than 20 seconds.

Instead of using formaldehyde in certain variants of the invention, the formaldehyde precursor can be supplied in the form of methanol and oxygen-containing gas if the catalyst also contains an oxidizing component or an oxidizing/dehydrogenating component. The methanol used can be any suitable commercially available methanol, although purer or impure grades can be used if desired. The oxygen-containing gas may suitably be air, but if desired an oxygen-enriched gas, such as molecular oxygen or a molecular oxygen/air mixture, or an oxygen-poor, such as air/inert gas mixture, may be used. . The oxidizing or oxidizing/dehydrogenating component of the catalyst suitably includes one or more of the elements copper, silver, molybdenum, tungsten, vanadium, chromium and antimony alone, or the elements iron, cobalt, nickel, Included in combination with one or more of bismuth, alumina-11, phosphorus, titanium, selenium and tellurium. The element can be exchanged using exchangeable cations associated with the synthetic crystalline aluminosilicate using conventional methods, or alternatively can be impregnated into the synthetic crystalline aluminosilicate using known methods, or Can be replaced and impregnated. Examples of suitable catalysts are crystalline aluminosilicates in which at least some of the H, transition metal or rare earth metal cations have been exchanged with copper or silver cations. Alternatively, the catalyst may comprise a mixture of the synthetic crystalline aluminosilicate and an oxidation or oxidation/dehydrogenation catalyst comprising the element unsupported or supported on an inert support.

Suitable such oxidation or oxidation/dehydrogenation catalysts are available from Earnest Benn Limited.
Lim1ted) Hankosoku (E, G, 1lancock) published by London and Tonbridge
) kH+ "Propylene and its collective derivatives (P
ropylene and Its Industry
l Derivatives) J l 973・(
(page 391) in Chapter 10 entitled "Catalyst Types Associated with the Oxidation of Propylene to Acrylic Acid". Furthermore, as an alternative, synthetic crystalline aluminosilicates in which the cations are H'' and/or transition metal and/or rare earth metal cations may be used, in whole or in part, for example with copper and/or silver cations. Can be mixed with exchanged synthetic crystalline aluminosilicate.

In this modification, the high temperature used is appropriately 250-450℃,
Preferably, the temperature can be in the range of 300 to 40°C.

The invention will now be illustrated with reference to the following examples. In the example
MF I (NH3) on zeolite X-Mo1? Mention zeolites. X-MF 1 (Nll,) zeolite is a MFI type heptaolide crystallized from a gel containing ammonium ions as described in EP-A-30811, where X is a cation, e.g. H.

X-MOR zeolite is a mordenite type zeolite with X cations. X-MF I (Nll:l)
Both type and X-MOR zeolites have a silica to alumina molar ratio greater than 10=1.

Example 1 A sample of the hydrogen form of X-M F ,+ (N113) zeolite was loaded into a quartz U-tube reaction in the form of pellets. Zeolite 10~20mj! was used. 39 U tube reactor
Placed in a molten tin bath kept at a temperature of 0° C., a feed consisting of a 3:1 molar ratio of methyl acetate and formaldehyde was passed over the zeolite with a contact time of 4 seconds (NTP).

The feed flow across the zeolite was supported by a slow flow of nitrogen. The products of the reaction were removed from the gas phase using a methanol stripper, and the product yield was determined by GC analysis of the effluent from the stripper.

Example 2 The X-MFI (N)I:+) zeolite was replaced with Pr-M+N1 (NH3) zeolite and the temperature was set at 350'c.
The procedure of Example 1 was repeated except that the contact time was increased to 8 seconds (NTP).

Example 3 The procedure of Example 2 was repeated except that the temperature was increased to 400° C. and the contact time was decreased to 4 seconds (NTP).

Example 4 The procedure of Example 2 was repeated except that the temperature was increased to 425°C.

Example 5 Example 3 except the contact time was increased to 8 seconds (NTP)
The procedure was repeated.

Example 6 HMF I (Nll:+) zeolite was mixed with
The procedure of Example 1 was repeated except that a thin zeolite was substituted.

Example 7 H-MFI (Nlh) zeolite was converted into Cr MFI (Nlh) zeolite.
The procedure of Example 1 was repeated except that Il+) zeolite was substituted.

Example 8 HMF I (Nll:+) zeolite with La-MOR
The procedure of Example 1 was repeated except that the zeolite was replaced and the temperature was increased to 425'C.

Example 9 HMF I (Ntl+) zeolite was converted into H-MF I
(Nll:l) The procedure of Example 1 was repeated, except that a water-smoked sample of zeolite was substituted.

After one hour of operation for Examples 1-9, the results in terms of percent yield (moles) relative to formaldehyde fed are shown in the table.

Example 10 Hydrogen type zeolite MF I (NIl+) 12.
5B was placed in a quartz U-tube reactor and heated to 390°C in a bath of molten JLF tin. A mixture of acetic anhydride and formaldehyde (3:2 mol) was passed over the catalyst at a rate of 23 mβ/hour. After 1 hour of operation, the reaction product was analyzed by capillary G, C, and was shown to have a 6.5 mole percent yield of acrylic acid based on the formaldehyde feed.

Example 11 Molybdenum-loaded hydrogen MFI zeolite 1-12.5mβ was mixed with 5% fiJ15mβ loaded on Davison 57 silica. The catalyst was then activated at 500° C. in a stream of air for 18 hours.

At the end of this time, a 2:1 molar mixture of methyl acetate and methanol was passed in the gas phase over the catalyst at 390° C. with a stream of dry air. A sample of the raw acid stream was analyzed after 1 hour and was shown to contain methyl acrylate. The molar yield of methyl acrylate based on the methanol supplied is 7.25.
%Met.

Example 12 This time, silver-exchanged MFI type zeolite was used as a catalyst (12.5m7
The test conditions were exactly the same as described in Example 11, except that it was used as a sample. Both methyl acrylate and acrylic acid were detected as products. After 1 hour of driving,
The molar yield of methyl acrylate based on the methanol supplied was 4.5%.

Example I2 Example 12 was repeated except that a reaction temperature of 420°C was used in this example. After 1 hour of operation, the molar yield of methyl acrylate in item 1 was 57%.

Example 14 The procedure of Example 11 was followed, but in this example chromium crosslinking was used. AMFI zeolite 1~ was used. After 1 hour of operation, the molar yield of methyl acrylate was 0.9%.

Continuation of page 1 Priority claim [Phase] May 18, 2019 [Phase] United Kingdom (GB) [Share] @ 19B3 * May 25 @ Igi+) Su (GB).

0 Inventor David Bode British
Steward 87 B313713 B314475 Sally Ipson Christchurch Maw Procedure Amendment l
F (method) % formula % 1, Incident display Patent Application No. 73837 of 1982 3,
Relationship with the person making the amendment in 111 cases: Applicant 4, agent

Claims (1)

[Claims] fi+ formaldehyde or ace! - A method for producing an unsaturated carboxylic acid and/or its ester by reacting an aldehyde containing an aldehyde with a saturated carboxylic acid iF4 in the presence of a catalyst at high temperature in the gas phase, the method comprising: a saturated carboxylic acid derivative; 5 ester or anhydride and the catalyst is 0.9 ± 0.2 NZ/llO:
8It203:YSiO□:ZII20 [wherein M is H'' and/or a transition metal and/or rare earth metal cation having an original valence n, Y is an integer greater than 10, and 2 is a synthetic crystalline aluminosilicate having a full composition with respect to oxides with a molar ratio of 0 to 40, an integer in the range from 0 to 40. (2) The method according to claim i11, wherein the aldehyde is formaldehyde. (3) The acid derivative has the formula: %Formula% [However, the formula R1 is hydrogen, phenyl or an aliphatic hydrocarbon group, R2 is a carbon/carbon bond or a divalent aliphatic hydrocarbon group, and X is a formula , -COOR" (wherein R3 is a hydrocarbon group or a substituted hydrocarbon group)) is a saturated carboxylic acid of
The method described in item 1) or item (2). (4) The method according to any one of claims (1) to (3), characterized in that formaldehyde and methyl acetate are reacted to produce methyl acrylate and/or acrylic acid. (5) Any one of claims 11 to 3, characterized in that methyl methacrylate and/or methacrylic acid is produced by reacting acetaldehyde and methyl acetate.
The method described in section. (6) Claim No. 1, wherein the acid derivative is a saturated carboxylic acid anhydride of the formula:
) or the method described in paragraph (2). (7) Claim No. 1, which is characterized by a product containing acrylic acid produced by reacting formaldehyde and Nishi-san's acid anhydride.
6) The method described in section 6). (8) The method according to any one of claims (1) to (7), wherein the synthetic crystalline aluminosilicate is an MFI type zeolite. (9) Claims (1) to (4), (6) to (8) The modified method described in any one of paragraphs. 00) The oxidizing component or oxidizing/dehydrogenating component of the catalyst contains one or more elements of copper, silver, molybdenum, tungsten, vanadium, chromium and antimony alone or iron, cohal, nickel, bismuth, aluminum , in combination with one or more of the following elements: phosphorus, titanium, selenium and tellurium.
9) The method described in section 9).