JPH11152242A - Production of alkylene oxide adduct - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an alkylene oxide adduct of an oil and fat derivative, capable of reducing a production cost, readily controlling a reaction and using a raw material more efficiently. SOLUTION: In this method for producing an alkylene oxide adduct of an oil and fat adduct using a falling film reactor, the method is characterized by supplying a specific amount of an alkylene oxide and not discharging an alkylene oxide as an unreacted gas after the reaction to the outside of the reactor. The falling film reactor is equipped with a vapor-liquid separating part at the bottom of a reaction tube and has a closed structure not discharging a supplied gas component to the outside.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an alkylene oxide adduct of a fat or oil derivative. Furthermore, the present invention relates to a falling film reactor suitably used for producing an alkylene oxide adduct of a fat or oil derivative.

[0002]

2. Description of the Related Art Alkylene oxide adducts of fats and oils derivatives have recently been gaining importance, such as being used for surfactants, toner binder raw materials, defoamers, etc., and are expected to develop applications and improve performance. Therefore, there is a demand for a method of manufacturing at lower cost. Among the alkylene oxide adducts of the oil and fat derivatives, the most important ones are alkylene oxides added to aliphatic alcohols, fatty acids, aliphatic amines, aliphatic amides, alkyl phenols, esters and the like. They form a very important nonionic activator group.

[0003] The alkylene oxide adducts of the above-mentioned fats and oils derivatives can be prepared, for example, by spraying the fats and oils derivatives into a reaction vessel filled with the alkylene oxides by spraying the alkylene oxides into the fats and oils derivatives. And an oil-and-fat derivative to cause an addition reaction to be obtained. In both cases, the alkylene oxide is added later as the reaction progresses (semi-batch operation) and the liquid reaction mixture is stirred until the desired amount of alkylene oxide has reacted.

[0004] In addition, DE-4128827 A1 describes a method for producing an alkylene oxide adduct of a fat derivative using a falling film reactor (FFR).

This method can 1) continuously produce an alkylene oxide adduct of a fat or oil derivative,
2) Since the adduct having undergone the addition reaction comes into contact with a lower concentration of alkylene oxide, the distribution of the number of added alkylene oxide in the obtained adduct is narrower.
Since the reaction temperature can be easily adjusted by controlling the temperature of the reaction tube, it is easy to optimize the reaction time and the amount of by-products generated. 4) In the lower part of the FFR, alkylene oxide in the gas phase There is an advantage that the concentration decreases along the direction of the falling liquid film with the progress of the addition reaction, and the unreacted alkylene oxide remains only slightly in the inert gas at the outlet of the reaction tube.

However, since this method is an open system, the gaseous component containing alkylene oxide after gas-liquid separation is discharged out of the reaction system without being recovered and reused. Therefore, it is necessary to provide a facility for removing the alkylene oxide, and the unreacted alkylene oxide cannot be reused. Further, in order to remove low boiling components such as alkylene oxide dissolved in the product after the reaction, a step of subjecting the product after the reaction to a reduced pressure treatment is required.

[0007] As described above, in the conventional method using FFR, there are factors that hinder cost reduction in terms of equipment, raw material utilization efficiency, and additional steps.

In the reaction, since the alkylene oxide concentration in the lower part of the reactor decreases, it is necessary to raise the reaction temperature in order to maintain the reaction efficiency, and it is necessary to consider the control of the reaction temperature.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing an alkylene oxide adduct of a fat or oil derivative which can further reduce the production cost. Furthermore, an object of the present invention is to easily control the reaction,
It is an object of the present invention to provide a method for producing an alkylene oxide adduct of a fat or oil derivative that can use raw materials more efficiently. A further object of the present invention is to provide a manufacturing apparatus suitably used for the manufacturing method of the present invention.

[0010]

Means for Solving the Problems The present inventors have found that in FFR, the gaseous component is not discharged out of the reactor, but the gaseous alkylene oxide is used in excess of the desired addition amount, and the alkylene oxide of the oil or fat derivative is used. The production of the oxide adduct was performed, and it was found that not only the utilization efficiency of the alkylene oxide was improved but also the quality of the obtained alkylene oxide adduct was not unexpectedly reduced, and the present invention was completed.

That is, the gist of the present invention is that [1] a fat or oil derivative or a mixture of a fat or oil derivative and a catalyst is brought into contact with a gaseous alkylene oxide in a reaction tube of a falling film reactor to add the fat or oil derivative and the alkylene oxide. Performing the reaction, in the method for producing an alkylene oxide adduct of an oil or fat derivative, supplying an alkylene oxide in an amount such that the mole fraction of the alkylene oxide in the gas component in the reaction tube is 0.2 or more, and Discharging the liquid component containing the obtained alkylene oxide adduct to the outside of the falling film reactor without discharging the unreacted gaseous alkylene oxide to the outside of the falling film reactor; Production method, [2] Gas-liquid separator is provided at the bottom of the 応管, falling film reactors, wherein a gaseous component supplied has a sealed structure which is not discharged to the outside, it relates.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Regarding the production method of the present invention The method for producing an alkylene oxide adduct of an oil / fat derivative of the present invention comprises a falling film reactor (FFR).
In the reaction tube of the above, the addition reaction of the oil or fat derivative and the alkylene oxide by contacting the oil or fat derivative or a mixture of the oil or fat derivative and the catalyst with the gaseous alkylene oxide, the method for producing an alkylene oxide adduct of the oil or fat derivative, While supplying the amount of alkylene oxide in which the mole fraction of alkylene oxide in the gas component in the tube is 0.2 or more, without discharging the unreacted gaseous alkylene oxide after the reaction to the outside of the falling film reactor. And discharging the obtained liquid component containing the alkylene oxide adduct to the outside of the falling film reactor.

The oil / fat derivative used in the present invention is not particularly limited, and examples thereof include alcohols, fatty acids, amines, amides, alkylphenols, esters and the like. Furthermore, alcoholates having higher reactivity are also included in the fats and oils derivatives. Examples of the catalyst used in the present invention include, for example, alkali catalysts such as NaOH and KOH, and acid catalysts such as BF ₃ O (C ₂ H ₅ ) ₂ complex, antimony pentahalide, and tin pentachloride. . The amount of the catalyst to be used is not particularly limited, and may be a conventionally used known amount. Preferably it is 0.001-0.05 mol with respect to 1 mol of fat derivatives, More preferably, it is 0.005-0.5 mol with respect to 1 mol of fat derivatives.
02 mol.

The fat derivative or a mixture of the fat derivative and the catalyst is supplied to the FFR, for example, as follows. When no catalyst is used, the fat or oil derivative is directly supplied to the FFR. In the case where an alkali catalyst is used and an alcohol is used as the oil / fat derivative, it is more preferable that a part of the alcohol is changed to an alcoholate by performing a dehydration treatment before supplying to the FFR. In this case, an alkaline catalyst is used for the production of the alcoholate. The water generated at this time is preferably removed, and the water content is, for example,
0.1% by weight or less of the obtained alcoholate-containing alcohol is preferred. The alcoholate-containing alcohol thus obtained is supplied to the FFR as a liquid component.

When an alkali catalyst is used and a fat or oil derivative other than alcohol is used, for example, when an alkylphenol is used as a fat or oil derivative, it is preferable to perform a dehydration treatment to partially convert the phenolate to a phenolate. . Similarly, when using an amine or an amide,
It is preferable to perform a dehydration treatment before supplying to the FFR.
When a fatty acid is used, soap is generated by a dehydration treatment using an alkali catalyst. This soap can be treated like alcoholate. When an acid catalyst is used, the oil derivative or the acid catalyst may be simply mixed and supplied.

The amount of the fat or oil derivative or the mixture of the oil or fat derivative and the catalyst to be supplied to the FFR is not particularly limited.
When the inner diameter of the reaction tube is 10 to 500 mm, the liquid flow rate per unit surface area per FFR reaction tube is 0.005.
-20 g / Hr / cm ² , preferably 0.01-10 g
/ Hr / cm ² is more preferred. From the viewpoint of uniformly forming a liquid film in the reactor, 0.005 g / Hr / cm
² / number or more is preferred, and from the viewpoint of obtaining a product having a high alkylene oxide addition mole number, 20 g / Hr / cm ² /
The following is preferred.

As the alkylene oxide, for example,
Examples include ethylene oxide and propylene oxide. These may be used alone or as a mixture. Such an alkylene oxide is supplied as a gas. The alkylene oxide may be supplied as it is to the FFR, or may be supplied together with an inert gas such as nitrogen gas.

Further, the alkylene oxide is supplied by a parallel flow operation or a countercurrent flow operation of supplying the alkylene oxide to the fat or oil derivative or the mixture of the oil and fat derivative and the catalyst flowing down in the reaction tube in parallel. Is also good. In addition, even when the supply direction of the alkylene oxide is not actively operated, the alkylene oxide falls along with the fat or oil derivative flowing down, and the unreacted alkylene oxide at the bottom of the reaction tube passes through the central portion of the reaction tube. Then, the mixture is circulated to the top of the reaction tube, and convection which is a substantially co-current operation is generated, and the reaction proceeds.

The point that the reaction rate is maintained without raising the reaction temperature even in the last reaction in one pass from the top of the reaction tube to the bottom of the reaction tube by the co-current operation or from the bottom of the reaction tube to the top of the reaction tube by the counter-current operation. , The alkylene oxide is supplied to the FFR in an amount necessary for obtaining a desired number of moles of the alkylene oxide addition product. Specifically, inside the reaction tube of the FFR,
At least in the case of the above-mentioned reaction final part, that is, in the case of the co-current operation, the amount at which the molar fraction of the alkylene oxide in the gas component at the bottom of the reaction tube is 0.2 or more may be supplied. In the case of countercurrent operation, it is sufficient to supply an amount such that the mole fraction of alkylene oxide in the gas component at the top of the reaction tube is 0.2 or more.

Further, in the case of the co-current operation, the mole fraction of alkylene oxide in the gas component at the top of the reaction tube is 0.1.
25 to 1.0, more preferably 0.25 to 0.7
It is. The molar fraction of alkylene oxide in the gas component at the bottom of the reaction tube is preferably 0.2 or more. From the viewpoint of avoiding the explosion range of the alkylene oxide, the mole fraction of the alkylene oxide in the gas component at the top of the reaction tube is preferably 1.0 or less. From the viewpoint of maintaining the reaction rate without increasing the reaction temperature even at the bottom of the reaction tube, the mole fraction of alkylene oxide in the gas component at the bottom of the reaction tube is preferably 0.2 or more. The molar fraction of each gas component at the bottom of the reaction tube can be determined, for example, from the difference between the amount of alkylene oxide present in the FFR and the amount of alkylene oxide added to the product.

In the case of countercurrent operation, the mole fraction of alkylene oxide in the gas component at the bottom of the reaction tube is 0.1.
25 to 1.0, more preferably 0.25 to 0.7
It is. The mole fraction of alkylene oxide in the gas component at the top of the reaction tube is preferably 0.2 or more. In the case of the countercurrent operation, the above-mentioned final reaction portion means the top of the reaction tube, and it goes without saying that the portion corresponding to the top of the reaction tube during the cocurrent operation is the bottom of the reaction tube.

The pressure in the FFR is not particularly limited, and may be a known degree which is usually carried out. In particular,
For example, 1 to 20 atm is preferable, and 2 to 15 atm is more preferable. The supply amount of the inert gas such as nitrogen is not particularly limited, and it is more preferable that the amount satisfies the above-mentioned pressure range in the FFR and the range of the mole fraction of the alkylene oxide.

In the present invention, the alkylene oxide adduct of the fat or oil derivative is produced by a known addition reaction using FFR. In the reaction tube, an oil or fat derivative or a mixture of the oil and fat derivative flowing down while forming a thin film on the inner wall surface of the reaction tube and the alkylene oxide as a gas component of the reaction tube come into contact with each other, and the addition of the oil and fat derivative and the alkylene oxide A reaction occurs.

The resulting alkylene oxide adduct is contained in the liquid component and reaches the gas-liquid separation section at the bottom of the reaction tube of the FFR. In the gas-liquid separation section, a gas component containing unreacted alkylene oxide and a liquid component containing alkylene oxide adduct are separated. Then, only the separated liquid component is discharged out of the FFR.
In this way, an alkylene oxide adduct of a fat or oil derivative is produced without discharging unreacted gaseous alkylene oxide after the reaction to the outside of the FFR. Thus, the unreacted gaseous alkylene oxide after the reaction is converted to F
By manufacturing an alkylene oxide adduct without discharging it out of the FR, it is possible to improve the use efficiency of the alkylene oxide without deteriorating the quality of the obtained alkylene oxide adduct and to eliminate the need to remove the alkylene oxide from the product. Is achieved.

The size of the FFR reaction tube used in the present invention is not particularly limited.
m is preferred. The length is preferably 1 to 12 m. The temperature in the reaction tube is not particularly limited, and may be a known temperature range that is usually adopted. For example, 20-300 ° C
Is preferable, and 30 to 250 ° C is more preferable.

According to the above-mentioned production method of the present invention, 1) only the liquid component is taken out of the FFR by gas-liquid separation. As for the oxide, it is only necessary to supply the dissolved component and the consumed component to the liquid component side, so the use efficiency of the raw material is good. 2) The reaction efficiency is also high because the alkylene oxide concentration in the liquid component is high even in the lower part of the reactor. Good, there is an advantage that there is no need to raise the reaction temperature.

From the viewpoint of more effectively transferring the alkylene oxide in the reaction tube of the FFR, unreacted gaseous alkylene oxide is circulated from the bottom to the top or from the top to the bottom of the FFR reaction tube. More preferred. The unreacted gaseous alkylene oxide transferred to the top or the bottom comes into contact with the fat or oil derivative or the mixture of the oil or fat derivative and the catalyst again, so that the utilization efficiency of the alkylene oxide as a raw material is improved, which is preferable.
Such circulation of the unreacted gaseous alkylene oxide can be achieved, for example, by providing a pipe connecting a portion of the bottom of the reaction tube of the FFR where the gas component is accumulated and a top of the reaction tube of the FFR. Further, a device such as a pump may be provided in the middle of the pipe from the viewpoint of more efficiently circulating the alkylene oxide.

When a device such as a pump is not used, gaseous alkylene oxide is transferred from the top to the bottom in the reaction tube, and is transferred again to the top through the piping. When a device such as a pump is used, similarly to the above, it may be operated to transfer the gaseous alkylene oxide in the reaction tube from the top to the bottom, or to transfer the inside of the reaction tube from the bottom to the top. Is also good.

It is more preferable that the obtained liquid component containing an alkylene oxide adduct is further aged. By aging, the slightly dissolved alkylene oxide in the liquid component can be further added to the alkylene oxide adduct. The aging is specifically performed by introducing a liquid component containing the obtained alkylene oxide adduct into a tube-type aging reaction tube, and in the aging reaction tube, performing an addition reaction between the dissolved alkylene oxide and the alkylene oxide adduct. Is achieved. In such an aging method, an addition reaction occurs in the liquid component, so that the remaining alkylene oxide can be removed more efficiently than in the batch aging method without being affected by the vapor-liquid equilibrium of the alkylene oxide.

The shape of the aging reaction tube is not particularly limited as long as it is of a tube type.
Those having a length of 00 mm and a length of 30 to 500 cm are preferable.
The residence time in the aging reaction tube may be a time sufficient to cause the alkylene oxide dissolved in the liquid phase to disappear by the addition reaction, for example, 0.5 to 30.
Minutes, preferably 1 to 15 minutes. Also,
The pressure may be controlled as long as the dissolved alkylene oxide is not gasified.

The obtained liquid component containing the alkylene oxide adduct may be circulated from the bottom to the top of the reaction tube of the FFR. This makes it possible to increase the number of moles of alkylene oxide added to the alkylene oxide adduct. The liquid component transferred to the top again comes into contact with the gaseous alkylene oxide. Such circulation of the liquid component is achieved by connecting the portion of the reaction tube at the bottom of the FFR where the liquid component is accumulated and the top of the reaction tube of the FFR. Further, in the present invention, the number of moles of alkylene oxide added to the alkylene oxide adduct is adjusted by adjusting the length of the reaction tube or by appropriately adjusting the residence time or the like by adjusting the supply rate of the fat or oil derivative to be supplied. The desired degree can be adjusted by appropriately adjusting the partial pressure of the alkylene oxide.

In addition, the method of flowing down the thin film of the FFR is such that a generally used packing such as Raschig ring, bell saddle, ball, McMahon, and Dickson packing is filled in addition to a general single pipe, and a thin film is formed on the packing. You may let it flow down. As the FFR used in the present invention, for example, the FFR of the present invention is preferably used.

2. About the Falling Film Reactor of the Present Invention The falling film reactor of the present invention is characterized in that a gas-liquid separation section is provided at the bottom of the reaction tube and has a sealed structure in which supplied gas components are not discharged to the outside.

Further, as the falling film reactor (FFR) of the present invention, when FFR is used in the production method of the present invention, from the viewpoint of reducing alkylene oxide dissolved in the obtained liquid component, the gas-liquid separation section The one to which the aging reaction tube is connected is more preferable.

The FFR of the present invention is a sealed one.
The term “sealing” as used herein refers to the supply of a substance to the FFR, the FFR
Means that the emission from the plant can be controlled. This means that, for example, a gas-liquid separation unit that can provide a valve in the supply line for raw materials, etc., or separate gas and liquid components at the bottom of the reaction tube and discharge only the liquid component out of the falling film reactor Can be achieved. By making the FFR a closed structure in this way, an alkylene oxide adduct can be obtained without discharging the supplied gas component to the outside. For gas-liquid separation, it is more preferable to attach a liquid level indicating controller (LIC) in order to keep the liquid level of the liquid component discharged out of the FFR constant. The volume of the gas-liquid separation unit may be arbitrarily set, and is preferably designed according to LIC control accuracy.

As the FFR, for example, an apparatus as shown in FIG. 1 or 2 is used. Next, the present invention will be described with reference to FIG. The fat / oil derivative or a mixture of the fat / oil derivative and the catalyst is supplied as a liquid component from the liquid feed line 6 to the top of the reaction tube of the FFR. Also,
Gaseous alkylene oxide is supplied from the alkylene oxide feed line 3 to the top of the FFR reaction tube.
An inert gas such as nitrogen is supplied from a conduit 4 to the top of the reaction tube of the FFR.

The liquid component supplied to the top of the reaction tube of the FFR is distributed to each reaction tube by a liquid distributor provided at the top of the reaction tube, and flows down to form a thin film on the inner wall surface of the reaction tube 1. The gas component is transferred from the top to the bottom of the FFR through the reaction tube 1 as the liquid component flows down the reaction tube 1. Therefore, there is no need to discharge the gas component out of the FFR to create a flow of the gas component.

The addition reaction between the oil derivative and the alkylene oxide occurs in the reaction tube 1. The alkylene oxide adduct of the oil or fat derivative generated here flows down while being contained in the liquid component.

At the bottom of the reaction tube of the FFR, a liquid component containing an alkylene oxide adduct of a fat or oil derivative,
A gas component containing unreacted gaseous alkylene oxide is obtained. In the gas-liquid separation unit 10 at the bottom of the reaction tube of the FFR, a liquid component and a gas component are separated, and the liquid component is separated from the FF.
By discharging the oil outside R, a desired alkylene oxide adduct of a fat or oil derivative can be obtained.

In the FFR shown in FIG. 1, a jacket 2 through which a fluid can flow may be provided around the reaction tube 1. Providing such a jacket 2 is equivalent to the jacket 2
It is preferable that the temperature of the reaction tube 1 can be adjusted to a desired temperature by adjusting the temperature of the fluid flowing therethrough.

From the viewpoint of effectively removing trace amounts of alkylene oxide dissolved in the liquid component containing the alkylene oxide adduct, the FFR may be further provided with an aging reaction tube 8.

The alkylene oxide is spontaneously transferred to the bottom of the FFR reaction tube by the flowing liquid. From the viewpoint of performing this transfer more effectively, the gas circulation line 5 is used.
May be provided. The gas circulation line 5 connects a portion of the bottom of the reaction tube of the FFR where gas components are accumulated and a top of the reaction tube of the FFR. By providing such a gas circulation line 5, gas components circulate in the FFR, and the transfer of alkylene oxide from the top to the bottom of the reaction tube 1 is performed more effectively.

Further, a device such as a pump 9 may be provided in the gas circulation line 5 from the viewpoint of more efficiently circulating gas components. At this time, the circulation method includes blowers,
In addition to an ejector, any other commonly used method such as a reboiler utilizing a density difference due to heating may be used. When the gas component is circulated using the pump 9 or the like, the reaction tube 1
The gas component therein may be co-current or counter-current to the liquid component.

Further, a liquid circulation line 7 may be provided for bringing the obtained liquid component containing the alkylene oxide adduct into contact with the gaseous alkylene oxide again. The liquid circulation line 7 connects a portion of the bottom of the reaction tube of the FFR where the liquid component is accumulated and a top of the reaction tube of the FFR. By providing such a liquid circulation line 7, the product can be recirculated, so that a product with a high added mole number, which is difficult to obtain by a one-through reaction, can be obtained.

Next, the present invention will be described with reference to FIG. FIG. 2 is a schematic explanatory view showing one embodiment of the FFR that can be used in the production method of the present invention, in which the flow of the gas component in the reaction tube 1 is countercurrent to the flow of the liquid component. It is. Specifically, a gas component flow is provided by providing a pump 9 or the like in the gas circulation line 5 and circulating the gas component from the top of the reaction tube of the FFR to the portion where the gas component is accumulated at the bottom of the reaction tube of the FFR. Can be countercurrent to the flow of the liquid component. At this time, the alkylene oxide feed line 3 and the conduit 4 may be connected to the gas circulation line 5.

When the flow of the gas component is countercurrent to the flow of the liquid component, upward energy is added to the flow of the fluid component, so that the residence time of the liquid component is increased and the reaction rate is increased. There is an advantage that it is advantageous for the production of a high addition mole number of AO adduct as compared with the flow operation.

[0047]

Example 1 20 kg of lauryl alcohol was charged into a raw material tank, and 0.02 mol of KOH was added to 1 mol of lauryl alcohol. Next, an alcoholate was produced while removing water produced at 110 ° C. and 10 Torr. The water content of the alcoholate-containing lauryl alcohol thus obtained was 0.03% by weight.
This was used as a raw material liquid component.

Next, the raw material liquid component was supplied from the liquid feed line 6 to the falling film reactor (FFR) shown in FIG. The raw material liquid component is distributed by a liquid distributor at the top of the reaction tube of the FFR, and inside the reaction tube 1 having an inner diameter of 28 mm and a length of 9 m at a flow rate of 1.2 kg / hr per reaction tube, the inner wall surface of the reaction tube 1 Was allowed to flow so that a thin film was formed. In addition, ethylene oxide gas and nitrogen gas were supplied from the alkylene oxide feed line 3 and the conduit 4. The temperature in the reaction tube was maintained at 185 ° C., the partial pressure of ethylene oxide was 4.3 atm, and the partial pressure of nitrogen was 8.0 at.
m (the ethylene oxide mole fraction was 0.35).
Under these conditions, a liquid component containing an ethylene oxide adduct of lauryl alcohol was obtained at the bottom of the FFR reaction tube. The aging reaction tube 8 was not provided.

From the gas-liquid separation unit 10 at the bottom of the FFR reaction tube,
Only the obtained liquid component was extracted out of the FFR. Also,
Through the gas circulation line 5, the pump 9 provided in the gas circulation line 5 is operated, and the gas component after the gas-liquid separation is changed to F
The FR was transferred to the top of the reaction tube and reused. The liquid circulation line 7 was closed. In order to prevent the partial pressure of ethylene oxide in the FFR from dropping with the ethylene oxide addition reaction, ethylene oxide was continuously supplied from the alkylene oxide feed line 3 to maintain the partial pressure of ethylene oxide. The ethylene oxide partial pressure at the bottom of the FFR reaction tube was 4.2 atm, and the nitrogen partial pressure was 8.0 atm.
atm (ie the ethylene oxide mole fraction is 0.34). The partial pressure of each gas component at the bottom of the reaction tube is
It was determined from the difference between the amount of ethylene oxide present in the column and the amount of ethylene oxide added to the product.

Regarding the number of moles of ethylene oxide added to the ethylene oxide adduct of lauryl alcohol, F
Hydroxyl value (KOHmg) of liquid component extracted outside FR
/ G). The amount of ethylene oxide dissolved in the obtained liquid component was evaluated based on the amount of dioxane in the liquid component to be treated. That is, the obtained liquid component was subjected to a sulfation treatment, the remaining ethylene oxide was changed to dioxane, and quantified by gas chromatography analysis. Table 1 shows the evaluation results.

Example 2 20 kg of lauryl alcohol was charged into a raw material tank, and 0.02 mol of KOH was added to 1 mol of lauryl alcohol. Next, an alcoholate was produced while removing water produced at 110 ° C. and 10 Torr. The water content of the alcoholate-containing lauryl alcohol thus obtained was 0.03% by weight.
This was used as a raw material liquid component.

The raw material liquid component was allowed to flow down to an FFR having one reaction tube having an inner diameter of 28 mm and a length of 1 m at a flow rate of 1.4 kg / Hr / tube such that a thin film was formed on the inner wall surface of the reaction tube. Ethylene oxide gas and nitrogen gas were supplied from an alkylene oxide feed line and a conduit. The temperature inside the reaction tube was kept at 150 ° C., the partial pressure of ethylene oxide gas was set at 2 atm, and the partial pressure of nitrogen was set at 3 atm.
Further, both the gas circulation line and the liquid circulation line were closed. The ethylene oxide partial pressure at the bottom of the reaction tube was 1.1 atm, and the nitrogen partial pressure was 3 atm. Under these conditions, a liquid component containing an ethylene oxide adduct of lauryl alcohol was obtained at the bottom of the FFR reaction tube. Note that no aging reaction tube was provided.

FFR together with ethylene oxide addition reaction
In order to prevent the partial pressure of ethylene oxide from dropping inside, ethylene oxide was continuously supplied from an alkylene oxide line to maintain the partial pressure of ethylene oxide.
The number of moles of ethylene oxide added to the ethylene oxide adduct of lauryl alcohol was calculated from the hydroxyl value of the liquid component extracted outside the FFR. Table 1 shows the evaluation results.

Example 3 A raw material tank was charged with 20 kg of lauryl alcohol, and 0.05 mol of KOH was added to 1 mol of lauryl alcohol. Next, an alcoholate was produced while removing water produced at 110 ° C. and 10 Torr. The water content of the alcoholate-containing lauryl alcohol thus obtained was 0.03% by weight.
This was used as a raw material liquid component.

The temperature of the reaction tube 1 was set to 160 ° C., and SUS 3 having a height and a diameter of 5 mm and a thickness of 0.3 mm was placed in the reaction tube 1.
Example 1 except that a Raschig ring made of 04 was filled.
In the same manner as in the above, an ethylene oxide adduct of lauryl alcohol was obtained. The flow rate of the raw material liquid component was 1.9.
kg / hr / tube, the FFR reaction tube has an inner diameter of 28 mm,
The one having a length of 4 m was used. The ethylene oxide partial pressure at the top of the reaction tube was 4.2 atm, the nitrogen partial pressure was 8 atm,
The ethylene oxide mole fraction was 0.34. The ethylene oxide partial pressure at the bottom of the reaction tube was 3.6 atm, and the nitrogen partial pressure was 8 atm. Table 1 shows the evaluation results.

Example 4 20 kg of lauryl alcohol was mixed with 0.005 mol of BF ₃ O (C ₂ H ₅ ) ₂ per mol of the alcohol, and this was used as a raw material liquid component. The flow rate of the raw material liquid component was 2.2 kg / hr / tube, and the temperature in the reaction tube was 8
Except that the temperature was changed to 0 ° C., an ethylene oxide adduct of lauryl alcohol was obtained in the same manner as in Example 1. The ethylene oxide partial pressure at the top of the reaction tube was 1.4 at.
m, the nitrogen partial pressure was 3.7 atm, the ethylene oxide mole fraction was 0.27, the ethylene oxide partial pressure at the bottom of the reaction tube was 1.2 atm, and the nitrogen partial pressure was 3.7 atm. Table 1 shows the evaluation results.

Example 5 Example 1 was repeated except that the aging reaction tube 8 was connected to the FFR.
An ethylene oxide adduct of lauryl alcohol was obtained in the same manner as described above. The liquid component extracted from the gas-liquid separation unit 10 of the FFR was continuously supplied to an aging reaction tube 8 having an inner diameter of 28 mm and a length of 60 cm. In the aging reaction tube 8,
Under the conditions of 12.2 atm, 180 ° C., and a residence time of about 8 minutes, ethylene oxide dissolved in the liquid component was further added to an ethylene oxide adduct of lauryl alcohol. The ethylene oxide partial pressure at the bottom of the reaction tube of the FFR was 4.2 atm, and the nitrogen partial pressure was 8 atm. Table 1 shows the evaluation results.

Embodiment 6 A method of circulating ethylene oxide gas is shown in FIG. 2. The gas circulating line 5 shown in FIG. 2 is used to operate a pump 9 provided in the gas circulating line 5 to separate gas and liquid from the top of the reaction tube of the FFR. An ethylene oxide adduct of lauryl alcohol was obtained in the same manner as in Example 3, except that it was transferred to the later gas component side and reused. The ethylene oxide partial pressure at the top of the reaction tube was 3.6 atm, and the nitrogen partial pressure was 8 atm.
m, the ethylene oxide partial pressure at the bottom of the reaction tube is 4.2a
tm and a nitrogen partial pressure of 8 atm. Table 1 shows the evaluation results.

[0059]

[Table 1]

From the above results, according to the production method of the present invention, even if the gaseous ethylene oxide is not positively discharged to the outside of the FFR, the supply amount of the ethylene oxide is excessively increased with respect to a desired addition mole number. It was found that even when supplied, an ethylene oxide adduct of a fat or oil derivative having a quality comparable to that of a conventional product could be obtained. Therefore, it can be said that the manufacturing method of the present invention aims to reduce the production cost.

[0061]

According to the production method of the present invention, the gas component of the raw material can be used efficiently, so that the production cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing one embodiment of an FFR that can be used in the manufacturing method of the present invention.

FIG. 2 is a schematic explanatory view showing one embodiment of an FFR that can be used in the manufacturing method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 reaction tube 2 jacket 3 alkylene oxide feed line 4 conduit 5 gas circulation line 6 liquid feed line 7 liquid circulation line 8 aging reaction tube 9 pump 10 gas-liquid separation unit

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300

Claims (7)

[Claims] 1. An alkylene oxide of an oil or fat derivative, wherein an oil or fat derivative or a mixture of an oil or fat derivative and a catalyst is brought into contact with a gaseous alkylene oxide in a reaction tube of a falling film reactor to perform an addition reaction between the oil or fat derivative and the alkylene oxide. In the method for producing an adduct, alkylene oxide is supplied in such an amount that the mole fraction of alkylene oxide in the gaseous component in the reaction tube becomes 0.2 or more, and the unreacted gaseous alkylene oxide after the reaction is formed. A method for producing an alkylene oxide adduct of a fat or oil derivative, wherein the liquid component containing the obtained alkylene oxide adduct is discharged to the outside of the falling film reactor without discharging it to the outside of the ring film reactor. 2. An unreacted gaseous alkylene oxide is circulated from the bottom to the top or from the top to the bottom of the reaction tube of the falling film reactor to be brought into contact with the fat or oil derivative or the mixture of the oil or fat derivative and the catalyst again. The manufacturing method as described. 3. The method according to claim 1, wherein the obtained liquid component containing the alkylene oxide adduct is further aged. 4. The process according to claim 1, wherein the obtained liquid component containing the alkylene oxide adduct is circulated from the bottom to the top of the reaction tube of the falling film reactor and brought into contact with the gaseous alkylene oxide again. Method. 5. A gas-liquid separator is provided at the bottom of the reaction tube,
A falling film reactor having a sealed structure in which supplied gas components are not discharged to the outside. 6. The falling film reactor according to claim 5, wherein an aging reaction tube is connected to the gas-liquid separation section. 7. The production method according to claim 1, wherein the falling film reactor is the falling film reactor according to claim 5 or 6.