JP2000229890A - Production of monovinylacetylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound with a reduced amount of divinylacetylene, being a by-product, formed in producing monovinylacetylene by using cuprous chloride, an aqueous solution of potassium chloride, etc., and a specific component. SOLUTION: In this method for producing (B) monovinylacetylene from (A) acetylene, (C) cuprous chloride, (D) an aqueous solution of ammonium chloride or potassium chloride and (E) an aminocarboxylic acid formula I to formula IV (R1 is H or methyl; R2 is CH2COOH or CH2CH2COOH; R3 is CH2COOH or succinate group of formula V; R4 and R5 are each succinate of formula V or R4 is H and R5 is succinate), an amino acid composed of trans-1,2- diaminocyclohexane-N,N,N',N'-4-acetic acid or its alkali metal salt are used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing monovinyl acetylene by improving the selectivity of a catalyst used for producing monovinyl acetylene by dimerizing acetylene to produce monovinyl acetylene.

[0002]

2. Description of the Related Art Conventionally, a method for producing monovinyl acetylene obtained by dimerizing acetylene uses a so-called Newland catalyst which is carried out by passing acetylene through an aqueous solution of cuprous chloride and ammonium chloride or potassium chloride. I have. At this time, 1,5-hexadiene-3-yne (divinyl acetylene) and 1,3-hexadiene-5-yne (acetylene vinyl), which are by-products of the sequential reaction, are produced. To reduce this, increase the potassium chloride / cuprous chloride ratio in the catalyst composition or
Alternatively, there is a method of increasing the space velocity of acetylene gas, but in that case, the yield of the main product, monovinyl acetylene, decreases.

Divinylacetylene, a by-product, is a substance that is easily oxidized, and when oxidized, a peroxide is generated. Since this peroxide is a very dangerous substance that is ignited by an impact, it is produced. Higher amounts are very undesirable.

[0004] On the other hand, various studies have been made on methods for reducing divinylacetylene.
For example, JP-A-49-54307 discloses that the yield of monovinyl acetylene is improved by adding an alkali metal salt of aminocarboxylic acid and a specific organic solvent to a catalyst solution of cuprous chloride and alkali chloride or ammonium chloride. Japanese Patent Application Laid-Open No. 50-93903 discloses a method of increasing the molar ratio of cuprous chloride to alkali chloride or ammonium chloride and further adding an alkali metal salt of aminocarboxylic acid or an alkali metal salt of aminosulfonic acid. For example, methods for improving activity and selectivity have been proposed. However, no effect was observed for typical aminocarboxylic acids, ethylenediamine-N, N, N ', N'-4-acetic acid and trinitro-N, N, N-3-acetic acid. When the molar ratio of ammonium chloride or potassium chloride to cuprous chloride is increased, the selectivity is improved, but the activity is significantly reduced. Further, these documents only describe an alkali metal salt of aminocarboxylic acid, and there was no example in which aminocarboxylic acid itself was examined.

Further, at present, no effective catalyst system other than copper is known. For this reason, in the production of monovinyl acetylene, there has been a demand for the development of a new copper-based catalyst that reduces the production ratio of divinyl acetylene as a by-product.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the drawbacks of these conventional techniques, namely, to reduce the amount of divinylacetylene by-product without reducing the production ratio of monovinylacetylene as a main product. It is to provide a new copper-based catalyst to reduce the amount.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have studied various structures of aminocarboxylic acids or alkali metal salts thereof with the current catalyst system. The following equations (a), (b),
When the reaction is carried out by adding an aminocarboxylic acid having the structure of (c) or (d) or an alkali metal salt thereof as a catalyst activator, the reaction proceeds extremely quickly and is a by-product. The present inventors have found that the amount of divinylacetylene produced is significantly reduced, and have reached the present invention. As the aminocarboxylic acid, an alkali metal salt thereof is described in JP-A-50-93903, but ethylenediamine-N, N, N ', N'- which is a representative aminocarboxylic acid is used.
No effect was observed with 4-acetic acid and trinitro-N, N, N-3-acetic acid. On the other hand, surprisingly, it was surprisingly found that only the aminocarboxylic acids represented by the following general formulas (a) to (d) and the aminocarboxylic acid of (e), or an alkali metal salt thereof, were used. Was done.

[0008]

Embedded image

(Here, R1 represents hydrogen or a methyl group.)

[0010]

Embedded image

(Here, R2 represents CH ₂ COOH or CH ₂ CH ₂ COOH group.)

[0012]

Embedded image

(Here, R3 is a CH ₂ COOH group or a succinic acid group represented by the following formula (1).)

[0014]

Embedded image

[0015]

Embedded image

(Here, R4 and R5 are succinic groups represented by the following formula (1), or R4 is hydrogen and R5 is a succinic group.)

[0017]

Embedded image

(E) trans-1,2 diaminocyclohexane-N, N, N ', N'-4-acetic acid

The present invention relates to a method for producing monovinyl acetylene from acetylene using an aqueous solution of cuprous chloride and ammonium chloride or potassium chloride, wherein the aminocarboxylic acid represented by the general formulas (a) to (d) is used. A method for producing monovinylacetylene, characterized by coexisting an acid or an aminocarboxylic acid (e) or an alkali metal salt thereof. In the present invention, the aminocarboxylic acid may be imino-N, N-2-acetic acid, N, N-di (2-hydroxyethyl) glycine, N, N- (2-hydroxyethyl).
Glycine succinate, ethylenediamine 2-succinic acid or trans-1,2-diaminocyclohexane-N,
The method for producing monovinylacetylene as described above, which is N, N ', N'-4-acetic acid.

When an alkali metal salt of aminocarboxylic acid is used as the catalyst activator, a sodium salt is preferred. Further, as the catalyst activator, the above-mentioned general formula (a)
It is preferable to use the aminocarboxylic acids of (d) and (e) in order to better exhibit the effects of the present invention.

That is, according to the present invention, monovinyl acetylene (also referred to as 1-butyn-3-ene, hereinafter sometimes referred to as MVA) is produced from acetylene with an aqueous catalyst of cuprous chloride and ammonium chloride or potassium chloride. In doing so, it is to improve the yield of monovinyl acetylene by adding a specific aminocarboxylic acid or an alkali metal salt thereof as a catalyst component to form a highly active catalyst.

The procedure of the method for producing monovinylacetylene in the present invention is not different from the ordinary production method except that the catalyst having the above specific composition is used. That is, in addition to cuprous chloride and ammonium chloride or potassium chloride as a catalyst, aminocarboxylic acids represented by formulas (a) to (d) or aminocarboxylic acids of (e), or alkali metal salts thereof are added. A ternary catalyst is used.

In the catalyst composition of the present invention, the molar ratio of ammonium chloride or potassium chloride to cuprous chloride is not particularly limited. Is preferable, and the molar ratio is more preferably 0.95 to 1.2. When the molar ratio is less than 0.85, the selectivity of monovinylacetylene decreases, and when the molar ratio is more than 1.5, the conversion of monovinylacetylene decreases.

In the production method of the present invention, it is preferable to add a solvent of monovinylacetylene in addition to cuprous chloride, ammonium chloride or potassium chloride and aminocarboxylic acid or an alkali metal salt thereof. As the solvent for monovinylacetylene, petroleum solvents such as amylbenzene, isopropylbenzene, diethylbenzene, tetramethylhexane, n-paraffin, isoparaffin, and polyhydric alcohols or ether compounds are used. Examples of the polyhydric alcohol include ethylene glycol and propylene glycol, and examples of the ether include propylene glycol monobutyl ether and triethylene glycol monobutyl ether. Particularly, triethylene glycol monobutyl ether is preferable. The amount of the solvent used is preferably 5 to 250% by volume based on the aqueous catalyst solution.

In the method of the present invention, the above general formula (a)
Specifically, the aminocarboxylic acid represented by the formula (I) is imino-N, N-2-acetic acid; the compound represented by the formula (b) is N, N-di (2-hydroxyethyl) glycine;
N, N- (2-hydroxyethyl) .glycine succinate; (d) ethylenediamine-2-succinic acid; and (e) trans 1,2-diaminocyclohexane-N, N, N ', N'-4. -Acetic acid.
In the present invention, two or more of the above-mentioned aminocarboxylic acids or alkali metal salts thereof may be used in combination.

Next, the amount of the aminocarboxylic acid or the alkali metal salt thereof according to the present invention is as follows.
It is preferably used at a ratio of 1.0 to 10 mol per mol, more preferably at a ratio of 2 to 5 mol per 100 mol of cuprous chloride. The use of less than 1.0 mole of aminocarboxylic acid or its alkali metal salt per 100 moles of cuprous chloride has little effect, and adding more than 10 moles improves the selectivity but lowers the conversion.

The reaction temperature is not particularly different from the conventional catalyst system. That is, it is preferable to carry out in the range of 55 to 90 ° C. If the temperature is lower than 55 ° C., the conversion is not sufficient, and if it exceeds 90 ° C., acetaldehyde increases, and the effect of improving the conversion is not large.

[0028]

EXAMPLES Next, the usefulness of the present invention will be described more specifically by showing examples of the present invention. Example 1 Internal diameter 2.5 cm, length 10 m, internal diameter 20 at the top of reactor
2.8 kg of cuprous chloride, 2.0 kg of potassium chloride, 2.6 k of water
g, 1.5 ml of concentrated hydrochloric acid, 3.0 liters of triethylene glycol monobutyl ether as a solvent and imino-N which is an aminocarboxylic acid of the general formula (a) as a catalyst performance improver. , N-2
-Charge 216 g of acetic acid and dissolve by heating to 80 ° C. Thereafter, 100 parts of acetylene was added from under the reactor.
It was introduced at 0 liter / Hr. The reaction conditions are as follows. Reaction temperature 80 ° C. Gas pressure 1.2 kg / cm ² Gas load Acetylene 240 L / catalyst solution The gas coming out of this reactor is analyzed by gas chromatography, and the acetylene conversion and the monovinylacetylene yield (hereinafter, selectivity) ) Was calculated. The specific analysis method is as follows.

Gas analysis method: Gas chromatograph 8A manufactured by Shimadzu Corporation, Column:
Diethylene glycol succinate (DEGS) 15%, Chromosolve W 60/80 mesh, glass 3mmφ ×
3 m, carrier gas: helium 30 ml / min, detector: TCD (thermal conduction type) Gas analysis values and reaction results Gas analysis values were expressed in mol%. The conversion was shown by the fraction (%) of the reaction acetylene to the feed acetylene.
The selectivity of monovinyl acetylene was determined by a conversion based on acetylene based on all acetylene reacted. These values are shown in Table 1.

Example 2 The same as Example 1 except that the catalyst additive was N, N-di (2-hydroxyethyl) glycine.

Example 3 The same as Example 1 except that the catalyst additive was glycine succinate, N, N- (2-hydroxyethyl).

Example 4 The same as Example 1 except that the catalyst additive was ethylenediamine 2-succinic acid.

Example 5 Example 1 was repeated except that the catalyst additive was trans-1,2-diaminocyclohexane-N, N, N ', N'-4-acetic acid.
Is the same as

Comparative Example 1 This is the result of performing the reaction in Example 1 without adding a catalyst activator, that is, with the catalyst composition according to the prior art. (Potassium chloride / cuprous chloride = 0.95)

Comparative Example 2 A representative aminocarboxylic acid, ethylenediamine-
This is a system in which N, N, N ', N'-4-acetic acid (EDTA) is added to carry out a reaction.

Table 1 shows the results of the reaction results of monovinyl acetylene by taking the examples in which the type of the catalyst additive was changed, the system in which the catalyst additive was not added, and the system in which EDTA was added as a comparative example.

[0037]

[Table 1]

In Examples 1 to 5 and Comparative Example 2, the amount of aminocarboxylic acid added was 5 moles per 100 moles of cuprous chloride. In Table 1, MVA represents monovinyl acetylene, DVA represents divinyl acetylene, and ADV represents acetylene divinyl.

Example 6 The same as Example 1 except that the ratio of the aminocarboxylic acid (a) was 1 mole (43 g) per 100 moles of cuprous chloride.

Example 7 Example 1 was repeated except that the ratio of the aminocarboxylic acid (a) was 10 mol (430 g) per 100 mol of cuprous chloride.
Is the same as

Example 8 Example 8 is the same as Example 1 except that the molar ratio of potassium chloride to cuprous chloride was changed to 0.85.

Example 9 Example 9 is the same as Example 1 except that the molar ratio of potassium chloride to cuprous chloride was changed to 1.5.

When the amount of the additive was changed, the amount of KCl /
Table 2 shows the results of the reaction results in which the molar ratio of CuCl was changed.

[0044]

[Table 2]

[0045]

When the catalyst additive of the present invention is used in the production of monovinyl acetylene by dimerizing acetylene to produce monovinyl acetylene, the amount of by-product divinyl acetylene by-product can be reduced without reducing the production ratio of monovinyl acetylene. And monovinyl acetylene can be efficiently produced.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AA02 AC21 BA02 BA05 BA28 BA34 BA37 BA51 BB11 BB14 BB15 BB31 BC14 BC32 4H039 CA21 CF20 CL11

Claims (8)

[Claims] When producing monovinylacetylene from acetylene using an aqueous solution of cuprous chloride and ammonium chloride or potassium chloride, the following general formula (a):
A method for producing monovinylacetylene, comprising coexisting the aminocarboxylic acid represented by (d) or the aminocarboxylic acid of (e), or an alkali metal salt thereof. Embedded image (Here, R1 represents hydrogen or a methyl group.) (Where R2 is CH ₂ COOH or CH ₂ CH ₂ CO
Represents an OH group. ) (Where R3 is a CH ₂ COOH group or the following formula (1)
A succinic acid group represented by ) Embedded image (Here, R4 and R5 are succinic acid groups represented by the following formula (1), or R4 is hydrogen and R5 is a succinic acid group.) (E) trans-1,2 diaminocyclohexane-N,
N, N ', N'-4-acetic acid 2. The addition amount of the aminocarboxylic acid or the alkali metal salt thereof is 1.0 to 100 mol per cuprous chloride.
2. The method for producing monovinyl acetylene according to claim 1, wherein the ratio is 10 mol. 3. The method according to claim 1, wherein the aminocarboxylic acid is imino-N, N-2.
Acetic acid, N, N-di (2-hydroxyethyl) glycine, glycine N, N- (2-hydroxyethyl) succinate, ethylenediamine2-succinic acid or trans-
1,2-diaminocyclohexane-N, N, N ', N'
The method for producing monovinyl acetylene according to claim 1 or 2, wherein -4-acetic acid is used. 4. The method for producing monovinyl acetylene according to claim 1, wherein ammonium chloride or potassium chloride is used in a molar ratio of 0.85 to 1.5 with respect to 1 cuprous chloride. 5. The method for producing monovinyl acetylene according to claim 1, wherein a solvent of monovinyl acetylene is used. 6. The method for producing monovinyl acetylene according to claim 5, wherein the solvent of monovinyl acetylene is at least one selected from petroleum solvents, polyhydric alcohols and ether compounds. 7. The solvent for monovinylacetylene is amylbenzene, isopropylbenzene, diethylbenzene,
The method for producing monovinyl acetylene according to claim 5, wherein the method is at least one selected from tetramethylhexane, n-paraffin, isoparaffin, ethylene glycol, propylene glycol, propylene glycol monobutyl ether, and triethylene glycol monobutyl ether. . 8. The method for producing monovinyl acetylene according to claim 5, wherein the solvent of monovinyl acetylene is triethylene glycol monobutyl ether.