JP2979399B2 - Method for producing alkylene oxide adduct - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an alkylene oxide adduct of an organic compound containing active hydrogen.

[0002]

2. Description of the Related Art Alkylene oxide adducts have recently been gaining importance as they are used as surfactants, raw materials for toner binders, defoamers, and the like, and are expected to be developed for applications and improved performance. Therefore, there is a demand for a method of manufacturing at lower cost. The most important of the alkylene oxide adducts are those obtained by adding an alkylene oxide to an alcohol, a fatty acid, an aliphatic amine, an aliphatic amide, or an aliphatic ester. They form a very important nonionic activator group.

[0003] The alkylene oxide adduct as described above can be prepared, for example, by spraying the alkylene oxide into the active hydrogen-containing organic compound or by spraying the active hydrogen-containing organic compound into a reaction vessel filled with the alkylene oxide. It can be obtained by bringing an alkylene oxide into contact with an active hydrogen-containing organic compound to carry out an addition reaction. 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.

Japanese Patent Application Laid-Open No. 55-49332 describes a process for producing alkylene glycol monoether by a fixed bed using a clay containing a montmorillonite structure exchanged with a certain type of quatin as a solid catalyst. I have.

In this method, 1) an alkylene glycol monoether can be produced in good yield from an alcohol and an alkylene oxide. 2) Since a solid catalyst is used, steps such as catalyst separation and post-treatment are required. Can be omitted,
There are advantages.

However, since this method is a liquid-liquid fixed bed reaction in which the active hydrogen-containing organic compound and the alkylene oxide are both reacted in a liquid state, the addition reaction proceeds rapidly at the inlet of the reactor. Therefore, 1) a sharp rise in temperature occurs due to the heat generated by the addition of the alkylene oxide, resulting in an increase in pressure. 2) As the ratio of alkylene oxide to alcohol increases, the calorific value further increases, and the quality increases. In some cases, there is a problem that the surface is deteriorated.

Japanese Patent Publication No. Hei 7-2662 also discloses an embodiment of a liquid-liquid fixed-bed reactor using a similar solid catalyst. It is necessary to suppress the heat generation and the pressure rise during the reaction by keeping the addition amount low. In other words, in order to suppress heat generation and pressure rise, it is necessary to relatively reduce the amount of added alkylene oxide, and as a result, a product having a high added mole number cannot be obtained. In order to obtain a product having a high addition mole number, the obtained reaction product can be circulated for reaction, but in this case, production efficiency is consequently reduced.

[0008] In the alkylene oxide addition reaction using a fixed bed, there is no example in which the number of moles added can be made higher than in these examples. This is because it is difficult to cope with the above-mentioned exothermic reaction at the initial stage of the reaction and the accompanying sharp increase in pressure.

Japanese Patent Application Laid-Open No. 52-151108 discloses an addition reaction of ethylene oxide using a conventional homogeneous base catalyst by a tubular reactor having a similar reaction form to the liquid-liquid fixed bed reaction. This is not a fixed bed reaction but a liquid-liquid homogeneous reaction, but the reaction mode is similar to the liquid-liquid fixed bed reaction, and according to this comparative example, it is difficult to increase the number of moles added. Is shown.

[0010] As Comparative Example 1 shown here, the inner diameter is 9.
Using a 4 mm, 25 m long reaction tube, 3.75 k of a higher alcohol having an average molecular weight of 208 adjusted to 170 ° C.
An example is described in which g / Hr is supplied to a reaction tube, and ethylene oxide is injected at a rate of 2.4 kg / Hr at a time from the reaction tube inlet. Under these conditions, the maximum temperature is at least 400 ° C. and the pressure is at least 100 kg / cm ² · G at 1.8 m at the inlet of the reaction tube, and it is difficult to continue the reaction further. Says that it is brownish and syrupy and does not stand practical use.

From this result, even when the same alkylene oxide addition mole number (3 mole addition) as that of this comparative example is obtained by the liquid-liquid fixed bed reaction, the heat generation at the reactor inlet is also reduced. It can easily be presumed that the pressure increase accompanying the above is very large.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing an alkylene oxide adduct which does not require a high pressure resistance facility and has good production efficiency.
It is a further object of the present invention to provide a method for producing an alkylene oxide adduct in which the reaction can be easily controlled and, as a result, safe and stable operation can be performed with simple equipment.

[0013]

Means for Solving the Problems The present inventors performed an addition reaction by a gas-liquid fixed bed reaction in a reaction tube filled with a solid catalyst, and it was confirmed that the production efficiency was improved by a high-concentration catalyst reaction, and the alkylene oxide was reduced. By conducting the reaction in the gaseous state, it has been found that the alkylene oxide concentration in the liquid can be made relatively uniform throughout the reaction tube, and there is no sudden heat generation and the accompanying pressure rise, thus enabling safe and stable operation. The present invention has been completed. Furthermore, in the case of the prior art, if the alkylene oxide addition amount is high, the quality deteriorates due to the reaction temperature rise due to the reaction heat, but according to the method of the present invention, the quality of the alkylene oxide adduct obtained surprisingly decreases. I confirmed that I could not see it.

That is, the gist of the present invention is that [1] an active hydrogen-containing organic compound and an alkylene oxide are allowed to flow through a reaction tube filled with a solid catalyst, and an addition reaction between the active hydrogen-containing organic compound and the alkylene oxide is performed. A method for producing an alkylene oxide adduct, characterized in that the alkylene oxide is in a gaseous state and the active hydrogen-containing organic compound is in a gas-liquid fixed bed reaction in a liquid state,
[2] The method according to the above [1], further comprising an aging step.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The active hydrogen-containing organic compound used in the present invention is not particularly restricted but includes, for example, alcohols, fatty acids, amines, amides, esters and the like, and mixtures thereof.

Examples of the alcohol include, for example, those having 6 to 2 carbon atoms.
Aliphatic alcohols having 2 to 2 carbon atoms, linear or branched synthetic alcohols having 1 to 20 carbon atoms, phenols such as nonylphenol, tribenzylphenol, styrenated phenol, and paraoctylphenol; monoglycerides, diglycerides, glycerin, and ethylene glycol. Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 22 carbon atoms, and examples of the amine include coconutamine, octylamine, laurylamine, myristylamine, stearylamine, oleylamine, tallowamine, and other primary amines, and distearyl. Tertiary amines such as secondary amines such as amines, dimethylcoconutamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dilaurylmonomethylamine, and trioctylamine However, as amides, alkyl alkanolamides, etc., and as esters, fatty acids of monohydric alcohols such as lower alcohols, aliphatic alcohols and phenols or polyhydric alcohols such as ethylene glycol and glycerin Ester, and the like.

Examples of the alkylene oxide include lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide.
These may be used alone or as a mixture.

These alkylene oxides may be used in combination with an inert gas. The inert gas is not particularly limited as long as it does not hinder the addition reaction of the alkylene oxide. Specifically, a nitrogen gas, a helium gas, a neon gas, an argon gas and the like can be mentioned. These may be used alone or as a mixture.

As the solid catalyst used in the present invention, for example, a compound of an alkaline earth metal element such as barium, strontium and calcium (for example, barium phosphate compound B
a ₃ (PO ₄ ) ₂ ); a complex of an antimony pentahalide such as antimony pentabromide or antimony pentachloride with a Lewis base; a general formula (1) such as dialkylaluminum fluoride or alkylaluminum difluoride;

[0020]

Embedded image

(X represents a fluorine atom;¹ And R^Two Is
Each of a hydrogen atom and an alkyl having 1 to 20 carbon atoms
Represents a group or a halogen atom. R¹ And R^Two Few of
At least one is an alkyl group. Alumini indicated by)
Oxide compound supported on a gel carrier, etc .;
Alium³⁺, Ga³⁺, In³⁺, Tl³⁺, Co³⁺,
Se³⁺, La³⁺, Mn²⁺, Ba²⁺, Si⁴⁺, Cs⁺, B
³⁺, Fe³⁺, Y³⁺And Ce ³⁺One selected from the group consisting of
More than one metal ion is added by impregnation or coprecipitation.
Activated aluminum / magnesium hydroxide
Formula (2) nMgO · Al_Two O_Three ・ MH_Two O · (2) (where n and m are positive numbers)
g composite oxide; hydrotalcite, calcined high
Dortalsite, zirconium oxysulfate, mosquito
Lucium salt / aluminum trialkoxide / inorganic acid
Combined; calcined hydrotalcites (eg,
A commercially available catalyst is Kyowa Chemical Industry Co., Ltd.
Manufactured by Kyoward 2000), JP-A-8-32
No. 3200, formed from a catalyst or Mg
Molded catalysts such as O, CaO, BaO, and ZnO;
You.

The reaction tube used in the present invention is filled with a solid catalyst and serves as a fixed bed reaction site. The size of the reaction tube may be appropriately selected so that it can be cooled to such an extent that the quality of the alkylene oxide adduct arising from the heat generated by the reaction does not deteriorate, and is not particularly limited, but the inner diameter is preferably 9 mm to 2 m. , More preferably 15 mm to 1 m, still more preferably 20 mm to 500
mm. The thickness is preferably 9 mm or more from the viewpoint of uniform liquid wettability of the catalyst, and is preferably 2 m or less from the viewpoint of heat removal and equipment cost. The length is preferably 0.5 to 12
m, more preferably 1 to 10 m, still more preferably 1 to
8m. It is preferably 0.5 m or more from the viewpoint of productivity, and preferably 12 m or less from the viewpoint of operating conditions such as pressure loss.

In the production method of the present invention, since the rise in pressure during the reaction is suppressed, the strength of the reaction tube is designed to withstand a pressure of about 30 atm, preferably about 20 atm, and more preferably about 15 atm. It is not necessary to have a thick structure as in a conventional reaction tube for performing a liquid-liquid reaction.

An object made of inert particles or the like which does not affect the addition reaction may be provided below the solid catalyst to fix the solid catalyst in the reaction tube. The provision may prevent the liquid phase and the gas phase introduced into the solid catalyst from becoming uneven. Such inert particles include porcelain such as lahiscilling, McMahon, and spheres, iron, and stainless steel packing.
In the present invention, a multi-tube reactor in which a plurality of reaction tubes are provided may be used.

The form of the gas-liquid fixed bed reaction of the present invention includes:
For example, there are gas-liquid downward cocurrent fixed beds, gas-liquid countercurrent fixed beds, and gas-liquid upward cocurrent fixed beds. The active hydrogen-containing organic compound, alkylene oxide and inert gas are supplied to the reaction tube, for example, as follows. Here, when no inert gas is used, the gas phase is formed of alkylene oxide. In this case, the alkylene oxide does not need to be supplied as a gas to the reaction tube, and the alkylene oxide may be supplied as a liquid as long as a part or all of the alkylene oxide becomes gas in the reaction tube.

When a gas-liquid fixed-bed reaction is carried out in a continuous gas phase (hereinafter referred to as “Embodiment-1”), for example, an inert gas is allowed to flow through a reaction tube in advance to change the continuous gas phase. There is a mode in which a liquid active hydrogen-containing organic compound and a liquid or gaseous alkylene oxide are then supplied to a reaction tube. In the case where the liquid phase performs the gas-liquid fixed bed reaction in the continuous phase (hereinafter, referred to as “aspect-2”), for example, the liquid active hydrogen-containing organic compound is supplied upward into the reaction tube in advance, and the liquid There is a mode in which a continuous phase is formed, and then an inert gas and a liquid or gaseous alkylene oxide are supplied upward to the reaction tube.

The flow of the liquid phase and the gas phase in the reaction tube is as follows:
It is preferable that the gas flow is in the continuous phase and the operable range is widened in the downward cocurrent.

The flow rate of the active hydrogen-containing organic compound to the reaction tube is not particularly limited, and varies depending on how many moles of the alkylene oxide is added to the active hydrogen-containing organic compound, the catalytic activity and the like. However, usually, the Reynolds number based on the particle of the liquid in the reaction tube is 100.
It is preferably 0 or less, more preferably 500 or less, and particularly preferably 200 or less. The Reynolds number of the liquid, in addition to the active hydrogen-containing organic compound, should be determined in consideration of the liquid state alkylene oxide,
Actually, most of the alkylene oxide is gasified, so that the Reynolds number of the active hydrogen-containing organic compound may be practically used as the Reynolds number of the liquid.

The flow rate of the alkylene oxide to the reaction tube is not particularly limited. When efficiently obtaining an alkylene oxide adduct having a high addition mole number, which is one of the features of the present invention, [alkylene oxide] /
The molar ratio of the [active hydrogen-containing organic compound] is preferably 1.1 times or more, more preferably 1.3 times or more, and particularly preferably 1.5 times or more the desired number of moles.

When an inert gas is used in the present invention,
The supply amount to the reaction tube is not particularly limited, but specifically, the Reynolds number based on the particle of the gas in the reaction tube is preferably 300,000 or less, more preferably 100,000 or less, and particularly preferably. Is 50,000 or less. When ethylene oxide is used as the alkylene oxide, it is preferable to supply an inert gas such that the concentration of ethylene oxide in the gas phase is outside the explosion limit.

[0031] The pressure in the reaction tube is not particularly limited, and may be a known level which is usually carried out. Specifically,
30 atm is preferable, and 2 to 20 atm is more preferable. Further, 2 to 15 atm is more preferable. 1 atm or more is preferable from a viewpoint of productivity, and 30 atm or less is preferable from a viewpoint of equipment cost.

The reaction temperature depends on the catalytic activity and the like, but may be appropriately selected within a range in which the addition reaction proceeds smoothly and does not cause deterioration in the quality of the alkylene oxide adduct to be produced. I just need. For example, 2
The temperature is preferably from 0 to 300 ° C, more preferably from 30 to 250 ° C. Furthermore, 40 to 230 ° C. is particularly preferred. The temperature is preferably 20 ° C. or higher from the viewpoint of reactivity, and is preferably 300 ° C. or lower from the viewpoint of preventing quality deterioration.

The resulting alkylene oxide adduct is contained in the liquid component and reaches the outlet of the reaction tube. At the liquid outlet of the reaction tube, a gas-liquid separator may be provided for efficiently separating the gas component and the liquid component. In the gas-liquid separation section, the gas component is separated into a liquid component containing an alkylene oxide adduct and an unreacted raw material. From such a liquid component, an alkylene oxide adduct and an unreacted raw material can be easily separated by ordinary purification means. When the liquid phase flows upward, the top of the reaction tube serves as a reaction tube liquid outlet, and the bottom of the reaction tube serves as a reaction tube liquid inlet. When the liquid phase flows downward, the top of the reaction tube serves as a reaction tube liquid inlet, and the bottom of the reaction tube serves as a reaction tube liquid outlet.

In the present invention, the production of the alkylene oxide adduct may be performed in a closed system in which the supplied gas component is not discharged to the outside of the reaction system, and the supplied gas component is discharged to the outside of the reaction system. It may be performed in an open system. When the production method of the present invention is performed in the above-described closed system, the gas components, that is, the unreacted alkylene oxide gas or the mixed gas of the alkylene oxide gas and the inert gas is recycled without being discharged to the outside of the system. There are aspects. By circulating and recycling, the utilization efficiency of the inert gas and the alkylene oxide can be improved, and the amount of the alkylene oxide discharged to the atmosphere can be reduced. Specifically, this is achieved by connecting a gas outlet portion of the reaction tube where gas components accumulate (for example, the upper part of the gas-liquid separation unit) and a gas inlet portion of the reaction tube with a pipe. For more effective circulation, a pump, a blower, an ejector using a raw material liquid, or the like may be used. When the gas phase flows upward, the top of the reaction tube serves as a gas outlet of the reaction tube, and the bottom of the reaction tube serves as a gas inlet of the reaction tube. When the gas phase flows downward, the top of the reaction tube serves as a gas inlet for the reaction tube, and the bottom of the reaction tube serves as a gas outlet for the reaction tube.

When circulating, the alkylene oxide may be supplied in an amount consumed by the addition reaction and in an amount dissolved in the liquid component and discharged from the reaction tube. Since it is sufficient to supply only the amount dissolved and discharged, the use efficiency of raw materials and the like is improved, and the pressure and reactivity in the reaction tube can be kept constant, and safe operation can be performed.

When the present invention is carried out in the above-mentioned open system, gas components are discharged from the gas outlet of the reaction tube.

In the present invention, the number of moles of the alkylene oxide added to the alkylene oxide adduct is determined from the design aspect of the reaction apparatus (for example, the catalyst volume in the reaction tube, the number of the reaction tubes when a multi-tube reactor is used). Or, in view of individual reaction conditions (for example, adjustment of the supply rate of the supplied active hydrogen-containing organic compound, adjustment of the amount of dissolved alkylene oxide by controlling the supply amount and control pressure of the alkylene oxide), it is adjusted to a desired degree. Can be done easily.

The type of reaction in the addition reaction of the present invention is not particularly limited as long as it is a gas-liquid fixed bed reaction in which the alkylene oxide is in a gas state and the active hydrogen-containing organic compound is in a liquid state in the reaction tube. However, the above-mentioned embodiment-1 and embodiment-2 are exemplified.

First, embodiment-1 will be described. Aspect-1
In the reaction tube, the active hydrogen-containing organic compound flowing down or ascending on the filled catalyst surface and the alkylene oxide present in the gas phase are brought into contact with each other,
An addition reaction between the active hydrogen-containing organic compound and the alkylene oxide occurs. Examples of the form of the aspect-1 include a gas-liquid downward cocurrent fixed bed, a gas-liquid countercurrent (liquid phase is downward, gas phase is upward) fixed bed, and a gas-liquid upward cocurrent fixed bed.

By performing the addition reaction under the condition that the gas phase is a continuous phase, 1) the alkylene oxide concentration in the liquid can be made substantially uniform throughout the reaction tube, and the reaction proceeds uniformly throughout the reaction tube. The reaction is gentler than the liquid-liquid reaction, and there is no need to use a high-pressure equipment for the reaction tube. 2) The degree of temperature rise is suppressed, and the quality (hue, etc.) of the resulting alkylene oxide adduct is good. There is an advantage that it becomes.

Here, "the gas phase is a continuous phase" means a state in which the gas phase exists continuously from the gas inlet of the reaction tube to the gas outlet. In the present invention, specific examples of the gas phase include two modes of 1) a gas phase composed of an alkylene oxide gas and 2) a gas phase composed of an inert gas and an alkylene oxide gas.

The alkylene oxide may be supplied as a liquid, a gas, or together with an inert gas. The alkylene oxide may be gasified in the reaction tube as it is in proportion to the vapor pressure, and the remaining alkylene oxide may be liquefied. When the ratio of the amount of alkylene oxide gasified in the reaction tube to the total amount of alkylene oxide supplied to the reaction tube is defined as the gasification rate, the degree of gasification of the alkylene oxide, that is, the gasification rate is particularly limited. is not. Furthermore, the gasification rate cannot be determined unconditionally because it differs depending on the catalyst activity and the heat removal properties of the reactor. However, under conditions where the gas phase becomes a continuous phase in the reaction tube, for example, 0.4 or more is preferable, .
6 or more is more preferable, and 0.7 or more is particularly preferable. The gasification rate is preferably 0.4 or more in order to gasify the alkylene oxide to perform a gas-liquid reaction and perform a uniform reaction in the entire reaction tube. Such a gasification rate can be adjusted to a desired level by appropriately adjusting the pressure in the reaction tube, the amount of the alkylene oxide to be supplied, the temperature in the reaction tube, and the like. The gasification rate can be estimated by performing a vapor-liquid equilibrium calculation using, for example, the vapor pressures of the alkylene oxide and the organic compound containing active hydrogen.

When the reaction is carried out under the condition that the gas phase becomes a continuous phase, a gas component comprising an alkylene oxide gas and / or an inert gas, and an active hydrogen-containing organic compound, and optionally further containing an alkylene oxide The resulting liquid component is JOURNAL OF CHEMICAL ENGINEER
ING OF JAPAN VOL.10 NO.6 461-467 FUKUSIMA, S. et.a
In the wavy region (the region where the liquid forms a thin film on the solid catalyst surface and the thin film surface undulates and flows down), indicated by l, the trickle flow (tr)
It is preferable that the liquid is supplied to the reaction tube so that the liquid flows down in an area where the liquid forms a thin film on the surface of the solid catalyst and the surface of the thin film flows down smoothly. In order to flow down in such a region, according to the following conditions,
Preferably, a gas phase and a liquid phase are provided.

That is, the Wavy region or the trickle flow region is defined as a Reynolds number (Re _l ) based on a liquid particle.
And in the graph showing the relationship between the Reynolds number of the particle reference gas (Re _g) (FIGS. 1 and 2), in Figure 1,
A region surrounded by the straight line (I), the straight line (II), the straight line (III) and the vertical and horizontal axes of the graph (that is, the region (a), the region (b), the region (c)), or the straight line in FIG. (I), the straight line (II), the straight line (III), and the area enclosed by the vertical and horizontal axes of the graph (that is, the area (d), the area (e), and the area (f)). Re of gas component to be supplied
It is more preferable in the present invention to supply the gas component and the liquid component so that the value of _{g and} the value of Re _l of the liquid component satisfy the condition existing in such a region.

In FIG. 1 and FIG. 2, the straight line (I)
= Re_l ^0.45・ Re_g ^0.13A straight line that satisfies (Formula (I))
And the straight line (II) is 0.34 = φ^-0.1・ Re_l ^0.52・
Re _g ^-0.47 Indicates a straight line satisfying (Expression (II)),
(III) is 18 = φ^-0.2・ Re_l ^0.27・ Re_g ^0.2 ・
(D_p/ T)^-0.5Shows a straight line that satisfies (Equation (III))
You.

From the equations (I), (II) and (III), the intersection P between the straight line (II) and the straight line (III) and the intersection Q between the straight line (I) and the straight line (II) are determined.

The graph of FIG. 1 is a graph Re _g at Point P indicates a case Re _g is smaller than at the point Q.
When Re _g of the gas components supplied is greater than the value of Re _g at Point Q, Re _l of the liquid component supply is linear (I)
Region of the left boundary line shown in (area (a)) to be present in, i.e., Re _l is the formula of the liquid component is supplied (A)

[0048]

(Equation 1)

The liquid component may be supplied so as to satisfy the above conditions.

[0050] less than the value of Re _g Re _g of the gas components supplied is at the point Q, and is greater than the value of Re _g at Point P, the liquid components supplied Re _l linear (I
The liquid component to be supplied exists in the region (region (b)) on the left side of the boundary line shown by I), that is, the Re _{1 of the} liquid component to be supplied is represented by the formula (B).

[0051]

(Equation 2)

The liquid component may be supplied so as to satisfy the above conditions.

[0053] When Re _g of the gas components supplied is less than the value of Re _g at Point P, the liquid components supplied Re _l
Is present in a region (region (c)) below the boundary line shown by the straight line (III), that is, Re _{1 of the} liquid component to be supplied is represented by the formula (C).

[0054]

(Equation 3)

The liquid component may be supplied so as to satisfy the above conditions.

The graph of FIG. 2 is a graph showing the case Re _g at Point P is Re _g greater than or equal at the point Q. Re _{l of the} liquid component supplied is R at point P
If the value is greater than the e _l, Re _g of the gas components supplied by such present in a lower region of the boundary line shown by a straight line (III) (region (d)), i.e., the gas components supplied Re _g has the formula (D)

[0057]

(Equation 4)

A gas component may be supplied so as to satisfy the above conditions.

[0059] less than the value of Re _l Re _l of the liquid component supply is at the point When the P, greater than Re _l at Point Q, the lower border of Re _g of the gas components supplied is represented by a straight line (II) region (area (e)) to be present in, i.e., Re _g is the formula of a gas component is supplied (E)

[0060]

(Equation 5)

A gas component may be supplied so as to satisfy the above conditions.

[0062] When Re _l of the liquid components supplied is less than the value of Re _l at the point Q, the gas components supplied Re _g
There straight left area of (I) (region (f)) to be present in, i.e., Re _g is the formula of a gas component is supplied (F)

[0063]

(Equation 6)

A gas component may be supplied so as to satisfy the above conditions.

Reynolds number Re based on liquid particles_lIs
Re_l= D_sG_l/ Μ_lThis is a value determined by [-]. gas
Particle-based Reynolds number Re_gIs Re_g= D_sG_g
/ Μ _gThis is a value determined by [-]. Where d_sIs the catalyst
Sphere equivalent diameter [cm], G_lIs the mass flow rate of the liquid [g / cm^Two 
.Sec], μ_lIs the viscosity of the liquid [g / cm · sec],
G_gIs the mass flow rate of the gas [g / cm^Two .Sec], μ_gIs
It is the viscosity of the gas [g / cm · sec]. Catalyst surface
The form factor φ is φ = s / d_p ^Two The value obtained by [-]
You. Here, s is the total surface area per one catalyst [cm^Two ]
And d_pIs the diameter [cm] of the catalyst. Reaction tube inner diameter
Is T [cm].

Next, embodiment-2 will be described. Aspect-2
In the method, the active hydrogen-containing organic compound and the alkylene oxide are added to each other by contacting the active hydrogen-containing organic compound rising in the reaction tube filled with the catalyst with the gaseous alkylene oxide dispersed in the liquid phase. A reaction occurs.

By performing the addition reaction under the condition that the liquid phase is a continuous phase, 1) the alkylene oxide concentration in the liquid can be made substantially uniform throughout the reaction tube, and the reaction proceeds uniformly throughout the reaction tube. Therefore, the reaction becomes milder than the liquid-liquid reaction, and there is no need to use a high-pressure-resistant reaction tube.
The degree of temperature rise is suppressed, and the quality (hue, etc.) of the resulting alkylene oxide adduct is improved.
There is an advantage.

Here, “the liquid phase is a continuous phase” means that the liquid phase is
It refers to a state that exists continuously from the reaction tube liquid inlet to the liquid outlet. Specific embodiments of the liquid phase in the present invention include: 1) a liquid phase composed of an active hydrogen-containing organic compound and a partially liquefied (dissolved) alkylene oxide; 2) an active hydrogen-containing organic compound; Two embodiments of a liquid phase comprising an oxide adduct and a partially liquefied alkylene oxide are exemplified.

The alkylene oxide may be supplied as a liquid, a gas, or together with an inert gas. The alkylene oxide may be gasified in the reaction tube as it is in proportion to the vapor pressure, and the remaining alkylene oxide may be liquefied.

Further, the gasification rate of the alkylene oxide in the embodiment-2 is not particularly limited, and cannot be unconditionally determined because it varies depending on the catalytic activity and the heat removal property of the reactor. 0.4 or more is preferable, 0.6 or more is more preferable, and 0.7 or more is especially preferable from the viewpoint of performing a uniform reaction as a whole. As described above, the addition reaction can be carried out by a gas-liquid fixed bed reaction by carrying out as in Embodiment-1, Embodiment-2, etc., but from the viewpoint of operability and simplification of reactor design, Embodiment-1 is used. preferable. Also, among the aspects-1, it is more preferable that the gas flow be a downward cocurrent (both liquid phase and gas phase are downward) from the viewpoint of making the gas phase a continuous phase and increasing the operable range.

It is more preferable that the obtained liquid component containing an alkylene oxide adduct is further aged. By aging, the alkylene oxide dissolved in the liquid component can be further added to an alkylene oxide adduct or an unreacted organic compound containing active hydrogen. The aging is further performed by providing an aging step, specifically, the aging reaction in which the liquid component separated at the reaction tube liquid outlet is filled with a solid catalyst similar to the solid catalyst that can be used in the above reaction tube. This is achieved by introducing the mixture into an aging reaction tube and performing an addition reaction between a dissolved unreacted alkylene oxide, an alkylene oxide adduct, and an unreacted active hydrogen-containing organic compound in the aging reaction tube.

According to such an aging method, an addition reaction occurs in the liquid component, and therefore, unlike the conventional aging method after the reaction by the semi-batch method, the residual reaction is efficiently carried out without being affected by the vapor-liquid equilibrium of the alkylene oxide. Can be removed by reaction.

The shape of the aging reaction tube is not particularly limited.
From the viewpoint of the back mixing of the liquid and the plug flowability, a tube type is preferable, and the size varies depending on the aging conditions such as the activity of the catalyst and the aging temperature, but the inner diameter is preferably 9 to 1500 mm, more preferably. 15-1200m
m, more preferably 20 to 800 mm. 9 mm or more is preferable from the viewpoint of pressure loss,
From the viewpoint of plug flow, 1500 mm or less is preferable. The length is preferably 10 to 1000 cm, more preferably 40 to 900 cm, and still more preferably 50 to 800 cm.
cm, particularly preferably 100 to 700 cm. It is preferably at least 10 cm from the viewpoint of the back mixing of the liquid and the plug flowability, and preferably at most 1,000 cm from the viewpoint of the pressure loss.

The rate at which the liquid component containing the alkylene oxide adduct is passed through the ripening reaction tube is not particularly limited, and varies depending on the activity of the catalyst to be charged.
HSV is preferably 0.1 to 100, more preferably 0.2 to 70. Further, it is more preferable to pass the solution through 1 to 50. It is preferably 0.1 or more from the viewpoint of reducing equipment costs, and is preferably 100 or less from the viewpoint of sufficiently aging the unreacted alkylene oxide.

The aging temperature and pressure are set to be equal to or lower than the temperature and pressure of the gas-liquid separation section at the bottom of the reaction tube, and / or to equal or higher than the dissolved alkylene oxide. Is sufficient to prevent gasification. Such conditions can be achieved by controlling the temperature of the jacketed pipe or controlling the pressure with a pump or the like. Further, a flash distillation facility such as a flash tank for further removing low-boiling by-products may be provided at the outlet of the aging reaction tube.
By flash-distilling a reaction product in which unreacted dissolved alkylene oxide has been further reduced by aging, low-boiling by-products such as dioxane can be removed without discharging alkylene oxide.

The liquid component containing the alkylene oxide adduct obtained after the reaction may be recycled from the liquid outlet of the fixed bed reaction tube to the liquid inlet. This makes it possible to further increase the number of moles of alkylene oxide added to the alkylene oxide adduct.

Next, a reactor which can be suitably used in the present invention will be described. Examples of the reactor used in the present invention include a fixed-bed reactor having a reaction tube filled with a solid catalyst. The fixed bed reactor used in the present invention includes a reaction tube filled with a solid catalyst, an alkylene oxide feed line for supplying an alkylene oxide to the reaction tube, and an activity for supplying an active hydrogen-containing organic compound to the reaction tube. A fixed-bed reactor provided with a hydrogen-containing organic compound feed line, in which an alkylene oxide feed line and an active hydrogen-containing organic compound feed line are connected to the top of the reaction tube. In addition,
The alkylene oxide feed line may be connected to the bottom of the reaction tube. Further, in such a fixed-bed reactor, an inert gas feed line for supplying an inert gas to a reaction tube is connected to the top or bottom of the reaction tube, or the reaction at the bottom or top of the reaction tube. It is more preferable that the tube liquid outlet is provided with a gas-liquid separator for efficiently separating the gas component and the liquid component.

Further, as the fixed bed reactor used in the present invention, when used in the production method of the present invention, from the viewpoint of reducing alkylene oxide dissolved in the obtained liquid component, the reaction tube bottom or the reaction tube may be used. It is more preferable that an aging reaction tube is connected to a reaction tube liquid outlet portion or a gas-liquid separation portion at the top. As such a fixed bed reactor, for example, FIG.
An apparatus as shown in FIG. The apparatus shown in FIG. 3 is exclusively used under the condition that the gas phase in the reaction tube becomes a continuous phase.

Next, the present invention will be described with reference to FIG. The active hydrogen-containing organic compound is supplied from the active hydrogen-containing organic compound feed line 6 to the top of the reaction tube, which is the reaction tube liquid inlet. The alkylene oxide is supplied from the alkylene oxide feed line 3 to the top of the reaction tube. Inert gas is inert gas feed line 4
It is supplied to the top of the reaction tube.

The liquid component supplied to the top of the reaction tube 1 is distributed to each reaction tube by a liquid distributor provided at the top of the reaction tube. The liquid component supplied to the reaction tube 1 flows down on the solid catalyst 7 via the inert particles 5.

The addition reaction between the active hydrogen-containing organic compound and the alkylene oxide takes place in the reaction tube 1. The alkylene oxide adduct generated here is taken in the liquid component and flows down.

At the bottom of the reaction tube, which is the liquid outlet of the reaction tube, a liquid component containing an alkylene oxide adduct of an active hydrogen-containing organic compound, an unreacted gas alkylene oxide or a mixture of the alkylene oxide and an inert gas is added. The contained gas component is obtained. In the gas-liquid separation section 10, the desired alkylene oxide adduct can be obtained by separating the liquid component and the gas component and discharging the liquid component out of the reactor. Further, the gas component may be discharged from the gas discharge line 9.

In the fixed bed reactor shown in FIG. 3, a jacket 2 through which a fluid can flow may be provided around the reaction tube 1. Providing the jacket 2 is preferable because the temperature of the fluid flowing through the jacket 2 can be adjusted to adjust the reaction tube 1 to a desired temperature.

Further, from the viewpoint of effectively reacting and removing a trace amount of alkylene oxide dissolved in the liquid component containing an alkylene oxide adduct, the fixed bed reactor may be further provided with an aging reaction tube 8. good.

[0085]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 Kyowa Chemical Industry Co., Ltd. was used as a catalyst in a fixed bed reactor shown in FIG. 3 (however, no aging reaction tube was provided).
Kyoward 2000 molded catalyst (Kyoward 203
2) per reaction tube (inner diameter 28 mm, length 4 m)
Filled. As the inert particles, stainless steel lahissiling was used. Active hydrogen-containing organic compound feed line 6
More lauryl alcohol was supplied. Lauryl alcohol as a liquid component was distributed by a liquid distributor at the top of the fixed bed reactor, and was allowed to flow down the reaction tube at a flow rate of 2.4 kg / hr per reaction tube. Further, liquid ethylene oxide is supplied from the alkylene oxide feed line 3 to the reaction tube 1.
At a flow rate of 7.8 kg / hr per reactor, nitrogen gas was supplied from the inert gas feed line 4 at a rate of 5.2 kg / hr per reactor tube.
r.

The temperature inside the reaction tube was kept at 135 ° C., and the pressure was kept at about 6.4 atm. The generated liquid component containing polyoxyethylene lauryl ether and the gas component containing unreacted ethylene oxide and nitrogen gas were continuously separated in the gas-liquid separation unit 10. The gas component was discharged from the gas discharge line 9. At this time, the particle-based Reynolds number of the liquid component at the inlet of the reaction tube is 2.1, the particle-based Reynolds number of the gas component is 1181, and the particle-based Reynolds number of the liquid component at the outlet of the reaction tube is 2.4. The Reynolds number of the gas component on a particle basis was 742. From this, it was confirmed that the flows of the liquid phase and the gas phase were in the wavy region, and ethylene oxide was a continuous phase. The gasification rate of ethylene oxide was determined from the flow rates of ethylene oxide, nitrogen gas, and lauryl alcohol, and the respective vapor pressures at the temperature and pressure during the reaction. Table 1 shows the gasification rates of the examples thus determined.

The Reynolds number of each component is as follows:
I asked. The equivalent spherical diameter of the catalyst (d_s) Is 0.38cm
And the mass flow rate of the liquid at the inlet (G_l) Is 0.1
147 g / cm^Two ・ Sec, viscosity of liquid (μ_l) Is 0.
02122 g / cm · sec.
Reynolds number (Re _l) Is Re_l= D_sG_l
/ Μ_lTo 2.1. Gas mass flow rate at inlet
Liquid flow rate (G_g) Is 0.6215 g / cm^Two ・ Sec, mo
Viscosity (μ_g) Is 0.0002 g / cm · sec.
Therefore, the Reynolds number (Re_g)
Is Re_g= D_sG_g/ Μ_gFrom 1181.

Mass flow rate of liquid at outlet Portion of liquid flow ( _Gl )
The 0.3457g / cm ² · sec, since the viscosity of the liquid (mu _l) is a 0.05508g / cm · sec, Reynolds number of the particle reference liquid component (Re _l) was 2.4. Mass flow rate of gas at outlet
_g ) is 0.3906 _g / cm ² · sec and the gas viscosity (μg) is 0.0002 _g / cm · sec.
The Reynolds number of the particle reference gas component (Re _g) 742
Met.

The number of moles of ethylene oxide added to the ethylene oxide adduct of lauryl alcohol was determined by stirring the liquid component withdrawn from the fixed bed at 80 ° C. and 30 torr for 30 minutes to degas unreacted ethylene oxide. Calculated from the hydroxyl value of the degassed liquid component. Table 1 shows the results. The color of the ethylene oxide adduct of lauryl alcohol produced was APHA = 5 or less, and it was found that no rapid temperature rise occurred in the reaction tube.

[0091]

[Table 1]

Example 2 Lauryl alcohol was caused to flow through the reaction tube at a flow rate of 2.4 kg / hr per reaction tube through an active hydrogen-containing organic compound feed line. In addition, the preheated and gasified ethylene oxide and nitrogen gas were mixed and supplied from the gas feed line 4. Each feed rate is 7.8 kg of ethylene oxide gas per reaction tube
/ Hr, nitrogen gas is 5.2 kg / h per reaction tube
r. Other conditions were the same as in Example 1 to obtain an ethylene oxide adduct of lauryl alcohol. Table 1 shows the results. In this case, the flow of the liquid phase and the gas phase in the reaction tube was in the wavy region, and it was confirmed that ethylene oxide was a continuous phase. Further, the hue of the produced ethylene oxide adduct of lauryl alcohol was APHA = 5 or less, and it was found that no rapid temperature increase occurred in the reaction tube.

Example 3 The same procedure as in Example 1 was repeated except that lauryl alcohol was allowed to flow down from the active hydrogen-containing organic compound feed line at a flow rate of 8.1 kg / hr per reaction tube. An oxide adduct was obtained. Table 1 shows the results. In this case, the flow of the liquid phase and the gas phase in the reaction tube was in the wavy region, and it was confirmed that ethylene oxide was a continuous phase. Further, the hue of the produced ethylene oxide adduct of lauryl alcohol was APHA = 5 or less, and it was found that no rapid temperature increase occurred in the reaction tube.

Example 4 The same procedure as in Example 1 was repeated except that lauryl alcohol was allowed to flow down from the active hydrogen-containing organic compound feed line at a flow rate of 6.8 kg / hr per reaction tube. An oxide adduct was obtained.
Table 1 shows the results. In this case, the flow of the liquid phase and the gas phase in the reaction tube was in the wavy region, and it was confirmed that ethylene oxide was a continuous phase. Further, the hue of the produced ethylene oxide adduct of lauryl alcohol was APHA = 5 or less, and it was found that no rapid temperature increase occurred in the reaction tube.

Example 5 A fatty acid methyl ester having a molecular weight of 217 was added to an active hydrogen-containing organic compound feed line at a rate of 4.9 per reaction tube.
It was caused to flow down in the reaction tube at a flow rate of kg / hr. In addition, the preheated and gasified ethylene oxide and nitrogen gas were mixed and supplied from the gas feed line 4. The respective feed rates are as follows.
The rate was 5.4 kg / hr per reactor, and the nitrogen gas was 3.6 kg / hr per reactor tube. Other conditions were the same as in Example 1 to obtain an ethylene oxide adduct of methyl ester. Table 1 shows the results. In this case, the flow of the liquid phase and the gas phase in the reaction tube was in the wavy region, and it was confirmed that ethylene oxide was a continuous phase. Further, the hue of the ethylene oxide adduct of the generated methyl ester was APHA = 10, and it was found that no sharp temperature rise occurred in the reaction tube.

The Reynolds number of each component was determined as follows. Sphere equivalent diameter of the catalyst (d _s) is a 0.38 cm, mass flow rate fluid flow rate of the liquid at the inlet (G _l) 0.2
34g / cm ² · sec, the viscosity of the liquid (mu _l) 0.0
Because it is 10g / cm · sec, Reynolds number of the particle reference liquid component (Re _{l) is, Re l = d s G l} / μ l
To 8.9. The mass flow rate of the gas at the inlet portion The liquid flow rate (G _g ) is 0.430 _g / cm ² · sec and the viscosity (μ _g ) of the gas is 0.0002 _g / cm · sec.
The Reynolds number of the particle reference gas component (Re _g) is, Re
_g = was d _{s G g} / μ _g from 817.

Mass flow rate of liquid at outlet Portion of liquid flow ( _Gl )
Is 0.339g / cm ² · sec, the viscosity of the liquid (mu _l)
Was 0.050 g / cm · sec, and the Reynolds number (Re _l ) of the liquid component on a particle basis was 2.6.
The mass flow rate of the gas at the outlet part The liquid flow rate (G _g ) is 0.325
g / cm ² · sec, gas viscosity (μ _g ) is 0.000
Since it was 2 g / cm · sec, the Reynolds number (Re _g ) of the gas component on a particle basis was 618.

The hue in the above embodiment was measured using an APHA tube based on JIS K-0071-5 Hazen unit color number test method. The production efficiency was determined as the amount of product produced per unit volume of the reaction tube.
That is, the product flow rate [kg / Hr] was determined from the flow rate [kg / Hr] of the raw material active hydrogen-containing organic substance and the number of moles added, and the product flow rate was calculated by dividing this by the catalyst volume [L].

Table 1 shows that the ethylene oxide adduct having a high ethylene oxide addition mole number can be efficiently obtained by the production method of the present invention. In addition, all of the obtained ethylene oxide adducts had good hue, indicating that the quality was good.

Table 2 shows the Reynolds numbers of the components at the inlet and outlet of the reaction tube in the above example.

[0101]

[Table 2]

[0102]

According to the production method of the present invention, an alkylene oxide adduct having a good hue can be safely and stably obtained at a good production efficiency without using a high pressure resistance facility. The effect is achieved.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a Reynolds number (Re) based on a particle of a liquid.
It is a graph showing the relationship between _l) and Reynolds number of the particle reference gas and (Re _g).

FIG. 2 is a diagram illustrating a Reynolds number (Re) based on a particle of a liquid.
It is a graph showing the relationship between _l) and Reynolds number of the particle reference gas and (Re _g).

FIG. 3 is a schematic configuration diagram showing one embodiment of a fixed bed reactor used in the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 reaction tube 2 jacket 3 alkylene oxide feed line 4 inert gas feed line 5 inert particles 6 active hydrogen-containing organic compound feed line 7 solid catalyst 8 aging reaction tube 9 gas discharge line 10 gas-liquid separation unit

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G65 / 26 C08G65 / 26 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Osamu Tabata 1334 Minato, Wakayama-shi (56) References JP-A-3-148234 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 41/03 C07B 41/04 C07C 43/11 C07C 67/26 C07C 69/28 C08G 65/26

Claims (6)

(57) [Claims] An active hydrogen-containing organic compound and an alkylene oxide are allowed to flow through a reaction tube filled with a solid catalyst, and an addition reaction between the active hydrogen-containing organic compound and the alkylene oxide is performed. A method for producing an alkylene oxide adduct, which is carried out by a gas-liquid fixed bed reaction in which the active hydrogen-containing organic compound is in a liquid state. 2. The method according to claim 1, wherein the active hydrogen-containing organic compound and the alkylene oxide are allowed to flow under the condition that the gas phase in the reaction tube becomes a continuous phase. 3. The gas phase in the reaction tube is a gas phase composed of an inert gas and an alkylene oxide gas or a gas phase composed of an alkylene oxide gas.
The manufacturing method as described. 4. The production method according to claim 1, wherein both the liquid phase and the gas phase in the reaction tube are downward cocurrent. 5. The production method according to claim 1, wherein the liquid phase and the gas phase are circulated so as to flow in a wavy region or a trickle flow region. 6. The production method according to claim 1, further comprising an aging step.