JPH08169856A - Production of polyhydric alcohol - Google Patents

Abstract

PURPOSE: To easily obtain a polyhydric alcohol in a high yield and in a high quality by reacting an aliphatic aldehyde with formaldehyde in the presence of a specific base catalyst. CONSTITUTION: An aliphatic aldehyde (e.g. n-butylaldehyde) is reacted with formaldehyde in the presence of a basic catalyst consisting mainly of a bicarbonate salt and a carbonate salt produced by oxidizing or hydrolyzing a formate salt at -5 to 110 deg.C under a pressure of 1-2.3kg/cm<2> to obtain the objective polyhydric alcohol. The formate salt by-produced by the reaction of the aliphatic aldehyde with the formaldehyde is oxidized or hydrolyzed in the presence of a noble metal catalyst or a reduced nickel catalyst to produce a basic compound containing the bicarbonate salt as a main component. The basic compound is recycled and reutilized for the reaction. The polyhydric alcohol is useful as a raw material for polyester resins, alkyd resins, polyurethanes, polycarbonate resins, plasticizers, surfactants, lubricants, cosmetic base agents, reactive monomers, etc.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyhydric alcohol useful as a raw material for polyester resins, alkyd resins, polyurethane resins, polycarbonate resins, plasticizers, surfactants, lubricating oils, cosmetic bases, reactive monomers and the like. Manufacturing method.

[0002]

2. Description of the Related Art As a method for producing a polyhydric alcohol,
There is known a method of performing an aldol condensation reaction of an aliphatic aldehyde represented by the formula (i) with formaldehyde in the presence of a base catalyst, and then carrying out a two-step reaction of a crossed Cannizaro reaction.

Embedded image (At least one of R ^{1 to} R ³ is a hydrogen group, and the other is a linear or branched aliphatic group having 1 to 22 carbon atoms).

This method is disclosed in Japanese Patent Laid-Open No. 63-139141.
JP-A-58-162538 and the like, all of which are processes based on the co-production of polyhydric alcohol and formate. The base catalyst in this method is
Alkali and alkaline earth metal hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide,
Calcium hydroxide, lithium hydroxide, sodium carbonate,
Potassium carbonate, calcium carbonate, lithium carbonate and the like are used, and as the amine compound, particularly tertiary amines such as trimethylamine, triethylamine, diethylmethylamine, dimethylethylamine, diisopropylamine, tributylamine and the like are used.

As a method for producing neopentyl glycol (hereinafter referred to as NPG) which is one of polyhydric alcohols, hydroxypivalaldehyde (hereinafter referred to as HPA) is first synthesized by an aldol condensation reaction in the first step of the reaction. Then
Then, a method for producing NPG by hydrogenation is disclosed in Japanese Examined Patent Publication No.
-53421, JP-A-1-299239, JP-A-4
No. 182442 and the like. Further, in the trimethylolpropane (hereinafter referred to as TMP) production method,
Similarly, the method of hydrogenating after the aldol condensation reaction,
JP-A-53-92705, JP-A-63-287738
No. etc.

[0005]

In the method for producing a polyhydric alcohol in the presence of a base catalyst, an equimolar amount of formic acid salt is by-produced in addition to the main objective polyhydric alcohol. This formate is used in the production of hydrosulfite, for example,
The demand is limited. For this reason, most of the formate that is unavoidably produced as a by-product is disposed of, but this is accompanied by environmental pollution, and the disposal is expensive.

Further, in the method for producing NPG by hydrogenating after the aldol condensation reaction, the hydrogenation reaction requires 50
A high pressure of about 150 kg / cm ² is required, and the equipment is complicated. Further, when TMP is produced by the same method, the yield is low and the production amount per unit time is small. Further, there is no case where TMP is industrially proved by this method.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to a method for producing a polyhydric alcohol having the above-mentioned problems. As a result, the formate produced as a by-product by the crossed Cannizuaro reaction is converted into a noble metal catalyst or a reduced state in an aqueous solution. In the presence of a nickel catalyst, an oxidation or hydrolysis reaction is carried out to give a basic compound whose main component is a hydrogen carbonate, which is or is heated or concentrated by heating to convert most of it into a carbonate. The present invention has been accomplished by finding that the basic compound serves as a catalyst to efficiently produce a polyhydric alcohol by circulating the polyhydric alcohol into the reaction system.

That is, according to the present invention, an aliphatic aldehyde represented by the formula (i) is reacted with formaldehyde in the presence of a base catalyst mainly composed of a hydrogen carbonate and a carbonate produced by oxidation or hydrolysis of a formate. A method for producing a polyhydric alcohol,

Embedded image (At least one of R ^{1 to} R ³ is a hydrogen group and the other is a linear or branched aliphatic group having 1 to 22 carbon atoms), and a formate salt by-produced by the reaction of an aliphatic aldehyde and formaldehyde. In the method for producing a polyhydric alcohol, which is oxidized or hydrolyzed in the presence of a noble metal catalyst or a nickel catalyst in a reduced state, and the resulting hydrogen carbonate and a basic compound containing a carbonate as a main component are circulated in the reaction and reused. is there.

The reaction of an aliphatic aldehyde with formaldehyde to produce a polyhydric alcohol in the present invention is
It is a two-step reaction consisting of an aldol condensation reaction and a cross-Cannizaro reaction. It is represented by the following reaction formula, including a reaction to obtain a hydrogen carbonate from a formate produced as a by-product of the cross-Cannizaro reaction and a reaction in which the hydrogen carbonate becomes a carbonate. . The following reaction formula is a typical reaction example of the present invention in the case of producing TMP from normal butyraldehyde (hereinafter referred to as NBAL). (1) Aldol condensation reaction CH ₃ CH ₂ CH ₂ CHO + 2HCHO → CH ₃ CH ₂ C (CH ₂ OH) ₂ CHO (2) Crossover Cannituaro reaction CH ₃ CH ₂ C (CH ₂ OH) ₂ CHO + HCHO + Na ₂ CO ₃ + H ₂ O → CH ₃ CH ₂ C (CH ₂ OH) ₃ + HCOONa + NaHCO ₃ (3) Reaction to obtain hydrogen carbonate from formate (3-1) In case of oxidation HCOONa + 1/2 O ₂ → NaHCO ₃ (3-2 ) In the case of hydrolysis HCOONa + H ₂ O → NaHCO ₃ + H ₂ (4) Reaction in which hydrogen carbonate becomes a carbonate ₂ NaHCO ₃ → Na ₂ CO ₃ + H ₂ O + CO _{2 In} addition, carbonate is a catalyst for cross-Cannizaro reaction And is a reactant, and is recycled to the reaction system.

In the present invention, the aliphatic aldehyde represented by the formula (i) may be a synthetic product or a natural product, for example, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, pentanal, hexanal, heptanal, octanal, decanal and dodecanal. , Tetradecanal, hexadecanal, eicosanal, docosanaal, octadecanal, isopalmityl aldehyde, isostearyl aldehyde, isodocosanaal and the like. These can be used alone or as a mixture of two or more kinds.

The formaldehyde used in the present invention may be an aqueous formaldehyde solution or solid paraformaldehyde, and an appropriate form is used depending on the intended polyhydric alcohol. The amount of formaldehyde used also differs in theoretical molar amount depending on the intended polyhydric alcohol. For example, ^one of R ^{1 to} R ^{3 in} the formula (i) is H and the other two are CH ₃ (hereinafter referred to as “I”).
In the case of BAL), the molar ratio is 2.0 to 2.5 times that of IBAL. When n-butyraldehyde (hereinafter referred to as NBAL) in which two of R ^{1 to} R ^{3 in} the formula (i) are H and the rest is C ₂ H ₅ , the molar ratio is 3.0 to 6. It is a 0-fold molar amount. Further
In formula (i), two of R ^{1 to} R ³ are H, and the rest are C 6 to 2
When the aliphatic aldehyde is 2, the molar ratio is 3.
It is a molar amount of 0 to 8.0 times.

In the present invention, the basic compound in the aldol condensation reaction and the crossed Cannizaro reaction is a hydrogen carbonate produced by the oxidation or hydrolysis of a formate salt, which is at a temperature of 50 ° C. or higher. Since a part becomes a carbonate while releasing CO ₂ , it is substantially a mixture of both. This salt may be any of sodium, potassium, lithium, calcium and ammonium salts, but the sodium salt is generally used for industrial implementation. The amount of the base compound used is 1 to 5 times the molar ratio of the aliphatic aldehyde, and in order to suppress the by-products and obtain the target polyhydric alcohol in a high yield, the amount of the basic compound should be adjusted according to the type of aliphatic aldehyde. Need to be adjusted. For example, if the aliphatic aldehyde is IBAL, 2.01-2.
It is a 10-fold molar amount and, in the case of an aliphatic aldehyde having 6 to 22 carbon atoms, a 3- to 4-fold molar amount.

As described above, in the crossed Cannizaro reaction, a formate is formed by the reaction of formic acid and a basic compound formed by alkanal and formaldehyde. In the present invention, hydrogen carbonate obtained by oxidizing or hydrolyzing the formate is obtained. A mixture of a salt and a carbonate formed from the hydrogen carbonate (the above reaction for obtaining the hydrogen carbonate and the carbonate is referred to as a basic conversion reaction) is used as a catalyst for the aldol condensation reaction and the crossed Cannizaro reaction. This basic conversion reaction is carried out in an aqueous solution by using Ru, Rh, Pd, Pt, Os,
A noble metal catalyst such as Ir or a nickel catalyst in a reduced state is used.

In the present invention, the first-stage aldol condensation reaction and the second-stage crossover Cannizuaro reaction may be carried out under different reaction conditions, or may be carried out successively in the same reactor without distinction. . The aldol condensation reaction and the crossed Cannizaro reaction are carried out by using one or two of R ^{1 to} R ^{3 in} the formula (i).
When one is a lower aliphatic aldehyde having 1 to 4 carbon atoms, it is usually carried out without a solvent. In the aliphatic aldehyde having 5 to 22 carbon atoms, a tertiary alcohol such as tertiary butyl alcohol or tertiary heptyl alcohol is used as a reaction solvent,
The solvent is added to the aliphatic aldehyde of the formula (i) in an amount of 0.5 to 1
It is preferable to use 0 times the amount.

The reaction temperature of the aliphatic aldehyde and formaldehyde is -5 to 110 ° C, preferably 25 to 60 ° C, and the optimum temperature varies slightly depending on the type of the aliphatic aldehyde. For example, when trimethylolethane (hereinafter referred to as TME) is produced from propionaldehyde in which two of R ^{1 to} R ^{3 in} formula (i) are H and one is —CH ₃ , the reaction temperature is 30 to 80. ℃. When trimethylolnonane (hereinafter referred to as TMN) is produced from decanal, the temperature is 25 to 60 ° C, and further 1 ° C after the temperature reaches 60 ° C.
It is preferable to age for about a time.

Since the basic compound used in the present invention is a mixed salt of hydrogencarbonate and carbonate, carbon dioxide gas is generated during the cross-Cannizaro reaction in the second step of the reaction. Therefore, in order to prevent the harmful effect of carbon dioxide gas foaming, that is, to prevent blowing out of the reactor in a gas-liquid mixed state, the reaction is carried out under reduced pressure, normal pressure or increased pressure, preferably under a pressure of 1 to 2.3 kg / cm ^2.
It is preferable to perform O _{2 out} of the system under discontinuous or continuous mild conditions. Therefore, for example, NBAL
In the case of producing TMP by the reaction of aldehyde with formaldehyde, first, a basic liquid consisting of hydrogencarbonate and a mixed salt of carbonate and NBAL are dropped into a formaldehyde aqueous solution separately from a nozzle at a constant rate. Used.

There are several methods for obtaining the target polyhydric alcohol from the reaction product solution thus obtained.
This method differs depending on the conditions under which the reaction was carried out, and the treatment method varies depending on the physical properties of the polyhydric alcohol of interest, especially the difference in solubility in water.

For example, in the case of producing TMP, after the reaction, the concentration of formate in the reaction product solution is 25 to 30% by weight.
Until the target TMP
And formate are separated. As the solvent used here, NBAL which is also a reaction raw material is selected, or ketones such as methyl ethyl ketone and isobutyl ketone, alcohols such as isobutyl alcohol and isopropyl alcohol, and esters such as acetic acid butyl ester are effective.

Further, in the formula (i), all ^three R ^{1 to} R ³ are H, from acetaldehyde to pentaerythritol (hereinafter,
In the case of producing PE), the reaction product solution is concentrated and then cooled, and the crystallized PE and the formate salt in the aqueous solution are solid-liquid separated. The PE separated as a cake was washed with water,
Dry to a product.

In the formula (i), two of R ^{1 to} R ³ are H and 1
One is an aliphatic aldehyde having 5 to 22 carbon atoms, for example, octanal having 8 carbon atoms to trimethylol heptane (hereinafter,
In the case of producing (TMH)), TMH and formate can be separated by adding water after the reaction and separating into an organic phase and an aqueous phase. The TMH in the organic phase is further purified after distilling off the solvent to obtain highly pure TMH.

On the other hand, the formate salt separated in the aqueous phase, as it is or after being treated with activated carbon, causes deterioration of the catalyst such as organic acid salts other than sodium formate and a concentrated substance of formaldehyde, and further formose produced from formaldehyde. After removing the substances, adjust the sodium formate concentration with water, send it to the formate conversion column, and use a noble metal catalyst or a nickel catalyst in a reduced state in the presence of molecular oxygen (generally in the presence of air), or In the presence, a basic compound whose main component is hydrogen carbonate is used. The type of activated carbon used here may be a coconut grain type or a coal type, and the shape may be any of granular activated carbon, activated carbon fiber, honeycomb activated carbon, sheet activated carbon, and activated carbon molded body. As described above, the noble metal catalyst for the basic conversion reaction for obtaining hydrogen carbonate and carbonate from formate is Ru, Rh, Pd, Pt, Os, Ir,
Au, Ag, etc. are used, and the multi-way catalyst which mixed these 2 or more types may be sufficient. Among these, especially Pd, Ru
Is valid. The reduced nickel catalyst is a general reduced nickel catalyst used for hydrogenation reaction and the like, and examples thereof include expanded Raney nickel, commercially available reduced nickel, stabilized nickel, nickel formate and the like. These catalysts may be any of catalysts supported on carbon or oxides such as Al, Zr and Ti, and may be in the form of flakes, spheres, cylinders, or powder. The method of using the catalyst may be either a fixed bed method or a suspension method.

The basic conversion reaction of hydrogencarbonate by the oxidation or hydrolysis of the formate salt and further conversion of the hydrogencarbonate to carbonate is carried out by a conventional method at a temperature of 50 to 200 ° C., preferably 60 to 160 ° C., and a pressure of It is carried out under normal pressure to a pressure of up to 100 kg / cm ² . The obtained hydrogen carbonate and the basic compound containing the carbonate are, as they are or after being heated and concentrated to give most of the carbonate, are circulated to a reactor for aldol condensation and crossed Cannizuaro reaction.

The present invention will now be described with reference to the drawings. FIG.
FIG. 4 is a flow chart showing an example of a polyhydric alcohol production apparatus according to the method of the present invention, and specifically, the case of producing TMP from NBAL will be described. In FIG. 1, first, formaldehyde is fed from route 2, NBAL is routed from route 3, and mixed solution of sodium hydrogencarbonate and sodium carbonate recovered from route 4 from route 4 is fed to the aldol condensation reactor 1 to carry out aldol condensation.

The obtained aldol condensation reaction solution is
It is sent to the crossed Cannizaro reactor 6 from 5 and sodium hydroxide is supplied from the line 7 to carry out the crossed Cannizaro reaction. Here, the amount of sodium hydroxide supplied via the route 7 is determined by the amount of sodium hydrogen formate converted and recovered into sodium hydrogen carbonate and sodium carbonate in the subsequent step. That is, if the recovery rate is 98%, 2% of alkali will be deficient, so it is necessary to replenish it in proportion to the amount. Further, in the method of the present invention, the main compounds of the basic compound in the cross canneararo reaction are sodium hydrogen carbonate and sodium carbonate, so that carbon dioxide (C
O ₂ ) is generated, so that the reaction is carried out while purging CO ₂ through the route 8.

[0025] The cross-over Cannizaro reaction solution is neutralized from route 9 through a neutralization tank.
The solution is sent to 10 and the pH is adjusted to 7.0 with formic acid from route 11. Next, the solution is sent from the path 12 to the condensing can 13, where the path 14 is used until the concentration of sodium formate becomes 25 to 30% by weight.
It is concentrated while distilling off more water. In the extraction tower 17, the reaction concentrate from the route 15 in the middle stage, and the routes 36 and 38 in the lower middle stage.
The extractant is supplied, and the cleaning water is supplied from the route 16 to the middle and upper stages,
Phase transfer extraction is continuously performed, and the extract is extracted from the upper path 32.
The raffinate residue is withdrawn from each of the lower paths 18. This raffinate is sent to a raffinate treatment distillation column 19, where a small amount of a low boiling fraction such as a raffinant remaining therein is cut from a route 20, while the bottom distillate is routed from a route 21. The solution is sent to the activated carbon treatment tower 22, where the substance causing the catalyst deterioration is removed, and then the solution is sent from the path 23 to the dilution tank 24, and the water from the path 25 is added to adjust the sodium formate concentration to 12-18. It is prepared so as to be wt%.

This prepared liquid is sent to a formate conversion column 28 through a route 26, and sodium formate is converted into sodium hydrogen carbonate. In this formate conversion tower 28, a noble metal catalyst or a nickel catalyst in a reduced state is used, and air from the path 25 is used as necessary. When converted at a temperature of 50 ° C. or higher, a part of sodium hydrogen carbonate is converted into sodium carbonate, which can be supplied to the aldol condensation reactor 1. However, in order to further increase the basicity, a formate salt is used. Conversion tower 28
The reaction liquid from is sent to the heating tank 30 through the route 29, and 90 to 100
Most of the sodium hydrogen carbonate is converted to sodium carbonate by heating to ° C. The carbon dioxide gas generated at this time is purged from the path 31. The liquid thus converted from sodium formate into sodium hydrogen carbonate and sodium carbonate is supplied to the aldol condensation reactor 1 via the route 4 and used for the next reaction.

On the other hand, the path 32 extracted from the upper stage of the extraction tower 17
The extract is sent to the de-extraction tower 33, the extractant and the dissolved water are distilled out from the top of the tower through the path 34, and separated into an aqueous phase and an organic phase in the separation tank 35, and the aqueous phase is passed through the path 37. It is taken out of the system. The organic phase is withdrawn from the path 36 and used again as an extractant. Further, the residual liquid at the bottom of the de-extraction tower 33 is sent to the first distillation tower 40 through the path 39, the low boiling point having a lower boiling point than TMP is distilled off at the top of the tower, and the crude TMP is extracted from the bottom of the tower. Be done. Coarse TMP is the route
The liquid is sent to the purification tower 43 from 42, and purified TMP is obtained from the route 44 at the top of the tower. The residual liquid in the kettle is extracted from the path 45 at the bottom of the tower.

[0028]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Example 1 [Manufacturing trimethylolpropane (TMP) from n-butyraldehyde (NBAL) and formaldehyde and using a noble metal catalyst for basic conversion reaction] (First reaction) First, a 12% by weight aqueous formaldehyde solution 3
Sodium hydrogencarbonate 316.7 g (3.77 mol) and sodium carbonate in 200 g (12.78 mol) 2
A basic aqueous solution containing 0.1 g (0.19 mol) and N
BAL289g (4.0mol) 0.5 from a separate nozzle
Added over time. During this time, the reaction temperature is 30 to 75 ° C.
The reaction was continued for 30 minutes while maintaining Immediately after the reaction, formic acid was added to neutralize to pH 7. Next, the reaction product solution was concentrated under reduced pressure until the sodium formate concentration reached 20% by weight, and 1500 g of NBAL was used as a solvent and extraction was performed in three portions. The three extracts were mixed and NBAL was recovered by distillation under reduced pressure, followed by distillation under a reduced pressure of 1 mmHg using an Oldershaw distillation column with 5 distillation stages, and the initial fraction 43
After removing g, 479.7 g of TMP as a main fraction
I got This corresponds to a yield of 89.5 mol% based on the NBAL of the raw material.

On the other hand, the extraction residue in the NBAL extraction is 772.5.
g in a glass tube with an inner diameter of 13 mm filled with 150 ml of activated carbon (trade name: Kuraray Coal GCL, manufactured by Kuraray Chemical),
LSV [charged material liquid amount (ml / hr) / activated carbon (ml)] = 0.
It was passed at 2 hr ⁻¹ and a temperature of 50 ° C. Then water 2049.
5 g was added to adjust the sodium formate concentration to 10% by weight. This sodium formate aqueous solution was introduced into a packed bed type reaction tube having an inner diameter of 15 mm and a tower length of 300 mm equipped with a raw material supply conduit, an oxygen supply supply conduit, an external heat source heater and a cooling jacket to carry out a basic conversion reaction. The reaction tube was uniformly filled with 100 ml of 0.5 wt% Pd / C-supported catalyst, and LSV [charged material liquid amount (ml / hr)] was charged therein.
/ Catalyst filling amount (ml)] = 3.0 hr ⁻¹ The raw material solution prepared above was supplied from the upper part of the reaction tube. Oxygen was automatically prepared with the air supplied so that the partial pressure in the system was always 3.5 kg / cm ² . The reaction temperature was 130 ° C., and the temperature was controlled automatically by an external heat source heater and cooling water. Table 3 shows the results of composition analysis of the obtained basic conversion liquid. From this analysis result, the basification yield shown by the ratio of the total amount of sodium hydrogen carbonate and sodium carbonate to the charged amount of sodium formate is 99 mol%.

(Second reaction) 852.9 g (12.78 mol) of 45% by weight aqueous formaldehyde solution was added with 2720.5 g of the total amount of the basic conversion liquid obtained in the first reaction and 289 g of NBAL (4.0 mol). Added over 0.9 hours. Thereafter, the same reaction as the first reaction was performed. After the reaction, the yield of TMP obtained by distillation was 91.0 mol% based on NBAL. The TMP quality is shown in Table 1 along with the initial quality. On the other hand, the raffinate for the NBAL extraction was an aqueous solution of sodium formate that had been treated with activated carbon in the same manner as in the first reaction to obtain a hydrogen carbonate and a basic conversion liquid containing carbonate as a main component. The basification yield was 99.5 mol%.

(3rd to 10th Reactions) The same operation as in the 2nd reaction was repeated. The basification yield was 99.6 mol% on average from 3 to 10 times. Table 1 shows the measurement results of the TMP quality at each time in Example 1.

[Table 1] (First time) (Second time) (Third time) (Fourth time) (Fifth time) Melting point (℃) 58.6 58.8 58.5 58.6 58.6 Acid content (%) 0.001 or less 0.001 or less 0.001 0.001 or less 0.001 or less Water (%) 0.02 0.02 0.03 0.02 0.03 Ash content (%) 0.001 or less 0.001 or less 0.001 or less 0.001 or less 0.001 or less 0.001 or less Melt color (APHA) 20 15 20 10 10 (6th) (7th) (8th) (9th) (10th) Melting point (℃) 58.7 58.9 58.8 58.7 58.7 Acid content (%) 0.001 0.001 0.001 0.001 or less 0.001 or less Moisture (%) 0.03 0.03 0.02 0.01 0.03 Ash content (%) 0.001 or less 0.001 or less 0.001 or less 0.001 or less 0.001 or less Melted color (APHA) 15 10 10 15 10

Example 2 [Production of pentaerythritol (PE) from acetaldehyde and formaldehyde and use of precious metal catalyst in basic conversion reaction] (First reaction) 20% by weight formaldehyde aqueous solution 450
Sodium hydrogen carbonate (powder) 269.09 g (3.2 mol) and sodium carbonate 3 in 0 g (29.97 mol)
Acetaldehyde containing 2 g (0.15 mol) 137.
5 g (3.12 mol) was added from a separate nozzle over 0.8 hours. During this time, the reaction temperature was raised to 65 ° C. while controlling, and the reaction was continued for 40 minutes while maintaining the temperature at 65 ° C. Immediately after the reaction, formic acid was added to neutralize to pH 7.
Next, the residual formaldehyde remaining in the reaction product solution was 1.
After recovering under pressure distillation of 5 kg / cm ^2, the distillate was further concentrated under reduced pressure until the sodium formate concentration reached 15% by weight. This concentrated liquid was cooled to 25 ° C. to crystallize PE, and the crystallized PE was separated and collected by a centrifugal separator. This was dried to obtain 356.4 g of a product PE. This corresponds to a yield of 84.0 mol% based on acetaldehyde. On the other hand, 954 g of water was added to 1208 g of the filtrate for temporary separation by centrifugation and 1208 g of the filtrate for washing with water, and treated with activated carbon as in Example 1,
A basic conversion reaction was performed. The basification yield was 99.2 mol%. Table 3 shows the composition analysis results of the basic conversion liquid.

(Second reaction) A total of 2620 g of the basic conversion solution obtained in the above-mentioned initial reaction and 137.5 g of acetaldehyde (3.12 mol) in 455.3% by weight aqueous solution of formaldehyde (1995.3 g, 29.97 mol). ) Was added separately from a nozzle over 0.8 hours. Thereafter, the same reaction as the first reaction was performed. After the reaction, the yield of PE obtained by crystallization was 84.5 mol% based on acetaldehyde. The PE quality is shown in Table 2 along with the initial quality. On the other hand, the basic filtrate was subjected to a basic conversion reaction in the same manner as in the initial reaction of the separated filtrate obtained by centrifugation. The basification yield was 99.9 mol%.

[0035]

[Table 2] PE quality (Example 2) (First reaction) (Second reaction) Melting point (° C) 183.1 183.0 Monopentaerythritol (%) 96.5 96.6 Moisture (%) 0.06 0.07 Ash (%) 0.06 0.06

[0036]

[Table 3] Composition analysis of basic conversion liquid (wt%) (Example 1) (Example 2) Sodium formate 0.83 0.80 Sodium hydrogen carbonate 10.74 6.53 Sodium carbonate 1.39 1.33 Formaldehyde 0.31 1.10 Trimethylolpropane 0.04 ─ Normal butyraldehyde 0.01 ─ Monopentaerythritol ─ 0.31 Water 85.96 88.98 Other 0.72 0.95

Example 3 [Manufacturing trimethylolnonane (TMN) from decanal and paraformaldehyde, using a noble metal catalyst for basic conversion reaction] (First reaction) 97% by weight of pararumaldehyde 77.4
g (2.5 mol) and tertiary heptyl alcohol 260 g
And sodium bicarbonate 71.5 g (0.85 mol)
And 8.0 g (0.07 mol) of sodium carbonate were charged and kept at 40 ° C. with stirring. This is decanal 80.0
g (0.51 mol) was added over 4.0 hours, and the reaction was continued for another 1.0 hour. Final reaction temperature is 87 ℃
Rose to. Immediately after the reaction, formic acid was added to neutralize to pH 7. 120 g of water was added to this reaction product solution, and the mixture was stirred for 0.5 hour and then left to stand. Since this liquid was separated into two phases, the phases were separated, and the organic phase was further repeatedly washed with water, and then the solvent was distilled off to obtain 89.5 g of a reaction product TMN. This is a yield of 80.5 mol% based on the raw material decanal. on the other hand,
72 g of water was added to 495 g of the aqueous phase obtained in the above two-phase separation,
The basic conversion reaction was carried out in the same manner as in Example 1, and the obtained reaction product solution was concentrated to dryness under reduced pressure at a temperature of 90 ° C or lower. The basification yield was 95 mol%.

(Second reaction) The same reaction as the first reaction was carried out using a basic salt containing sodium carbonate as a main component, which was recovered by concentration to dryness. After the reaction, the yield of TMN obtained by two-phase separation was 81 mol% based on decanal. On the other hand, the basification yield was 96 mol%.

Example 4 [Manufacturing neopentyl glycol (NPG) from isobutyraldehyde (IBAL) and using a noble metal catalyst for the basic conversion reaction] (First reaction) 40% by weight aqueous formaldehyde solution 112
6.1 g (15.0 mol) was charged and the temperature was kept at 30 ° C. Add IBAL 514.9 g (7.14 mol) and 4
667 g (8.0 mol) of 8 wt% sodium hydroxide
Was added with stirring over 0.75 hours. The temperature was raised to 60 ° C. while controlling the reaction temperature, and the reaction was continued for 10 minutes while maintaining the temperature at 65 ° C. Immediately after the reaction, add formic acid and add p
The H7 was neutralized. The reaction product solution was extracted with methyl isobutyl ketone (hereinafter referred to as MIBK) as a solvent. MIBK is first extracted from the extract by vacuum distillation,
Subsequently, it was distilled under a reduced pressure of 70 mmHg to obtain 720.3 g of NP.
Got G. This is a yield based on IBAL of 96.8 mol%
Equivalent to.

On the other hand, as for the raffinate, first, a low boiling fraction such as methanol was distilled off. In addition, the formaldehyde remaining in about 1% in the extraction residual liquid was recovered by using IBA with sodium hydroxide as a catalyst.
It was recovered as hydroxypivalaldehyde (referred to as HPA) which is a precursor of NPG in an aldol condensation reaction with L. That is, after this aldol condensation reaction, the mixture was allowed to stand and separated into two phases. The IBAL phase containing HPA in the upper layer is used as it is as the second IBAL raw material. Further, the raffinate in the lower layer was diluted by adding water to a sodium formate concentration of 11% by weight, and then subjected to a basic conversion reaction in the same manner as in Example 1. The basification yield was 100 mol%.

(Second reaction) In 790.3 g (15.0 mol) of 57% by weight aqueous formaldehyde solution, the total amount of the basic conversion liquid obtained in the above-mentioned initial reaction and the above-mentioned HPA were added.
514.9 g (7.14 mol) of IBAL containing
It was added over 0.75 hours and the reaction was carried out in the same manner as the first time. After the reaction, the yield of NPG obtained by extraction and distillation was IBA.
It was 96.0 mol% based on L. On the other hand, the basification yield was 99.9 mol%.

Example 5 [Manufacturing trimethylolpropane (TMP) from n-butyraldehyde (NBAL) and formaldehyde and using reduced nickel catalyst for basic conversion reaction] (First reaction) First, a 15% by weight formaldehyde aqueous solution 4
Sodium carbonate 95.4 in 85 g (2.42 mol)
Basic aqueous solution containing g (0.90 mol) and NBAL
54.6 g (0.75 mol) was added through a separate nozzle over 0 and 5 hours. During this time, the reaction temperature is 30 to 90 ° C.
The temperature was raised for 30 minutes, and the reaction was continued for 30 minutes while maintaining 90 ° C. Immediately after the reaction, formic acid was added to neutralize to pH 7. Next, the reaction product solution was adjusted to a sodium formate concentration of 25
Concentrate under reduced pressure to wt% and then add N 2 to the solvent.
Extraction was performed using BAL 600 g in three portions. This 3
The extracts were mixed twice, and NBAL and dissolved water were recovered by atmospheric distillation, and then distilled under a reduced pressure of 1 mmHg using an Oldershaw distillation column having 5 distillation stages, and an initial fraction of 3.8 was obtained.
After removing g, 75.2 g of TMP was obtained as a main fraction. This corresponds to a yield of 75.0 mol% based on NBAL. On the other hand, 151.0 g of raffinate from NBAL extraction
L in a glass tube with an inner diameter of 13 mm filled with 150 ml of activated carbon (trade name: Kuraray Coal GCL, manufactured by Kuraray Chemical).
SV [charged raw material liquid amount (ml / hr) / activated carbon (ml)] = 0.2
It was passed at hr ⁻¹ and a temperature of 50 ° C. Next, 320.0 g of water
Was added to prepare a sodium formate concentration of 13% by weight.

Raney nickel used in the decomposition reaction of formate was prepared by the following procedure. To a 1000 ml beaker to which 400 g of a 20% aqueous sodium hydroxide solution was added, 75 g of Raney alloy (containing 50% by weight of nickel and 50% by weight of aluminum) was gradually added. During this time, the temperature in the system is set to 3
The temperature was kept below 0 ° C. 11 after adding all Raney alloy
The mixture was heated to 0 ° C., 4 hours later, 100 ml of 20% sodium hydroxide aqueous solution was added, and the mixture was further heated for 3 hours. After the generation of hydrogen was completed, the mixture was allowed to cool to room temperature and repeatedly washed with water until the pH of the washing liquid reached about 8 to carry out a developing operation. In a 500 ml SUS autoclave equipped with a stirrer,
470 g of 13 wt% sodium formate aqueous solution prepared by MP synthesis reaction and 30 g of expanded Raney-Nickel prepared by the above procedure are added, and the system pressure is adjusted to 15 kg / cm ² by air while adjusting at 180 ° C for 5 hours. It was stirred. After 5 hours, the mixture was allowed to cool to room temperature and the catalyst was filtered to obtain a basic conversion liquid. From the composition analysis result of the obtained decomposition liquid, the basification yield was 81.9 mol% of the theoretical value.

(Second reaction) Into 181.7 g (2.42 mol) of a 40% by weight aqueous formaldehyde solution, 470.0 g of the basic conversion liquid obtained in the first reaction and NBA were obtained.
L44.3g (0.61mol) from another nozzle to 0.9
Added over time. Thereafter, the same reaction as the first reaction was performed.
After the reaction, the yield of TMP obtained by distillation was 75.5 mol% based on NBAL. The TMP quality is shown in Table 4 along with the initial quality. On the other hand, the raffinate for the NBAL extraction was an aqueous solution of sodium formate that had been treated with activated carbon in the same manner as in the first reaction to obtain a basic conversion solution containing hydrogen carbonate and carbonate as the main components. The basification yield was 80.8 mol%.

[0045]

[Table 4] TMP quality (Example 5) (First reaction) (Second reaction) Melting point (° C) 59.5 58.9 Acid content (%) 0.001 or less 0.001 or less Water content (%) 0.02 0.02 Ash content (%) 0.001 Below 0.001 Melt color (APHA) 20 10

Example 6 [Production of pentaerythritol (PE) from acetaldehyde and formaldehyde and use of reduced nickel catalyst for basic conversion reaction] (First reaction) 20% by weight formaldehyde aqueous solution 168
Sodium hydrogencarbonate 14 in 0 g (11.19 mol)
2.8 g (1.7 mol) and sodium carbonate 32 g (0.
A basic aqueous solution containing 30 mol) and 89.3 g (2.03 mol) of acetaldehyde were separately added from a nozzle over 0.8 hours. During this time, while adjusting the reaction temperature,
The temperature was raised to 85 ° C, and the reaction was continued for 40 minutes while maintaining the temperature at 85 ° C. Immediately after the reaction, formic acid was added to neutralize to PH7. Next, the formaldehyde remaining in this reaction product solution was recovered under pressure distillation of 1.5 kg / cm ² , and this distillation residue solution was further concentrated under reduced pressure until the sodium formate concentration reached 25% by weight. This concentrated liquid was cooled to 25 ° C. to crystallize PE. Next, this crystallized PE was separated and collected by a centrifuge, and the wet PE was dried to obtain 231.9 g of a product PE. This corresponds to a yield of 84.0 mol% based on acetaldehyde. On the other hand, water 420g was added to the primary separation filtrate and washing filtrate 760g of centrifugation, after activated carbon treatment in the same manner as in Example 5 was subjected to basic conversion reaction. The basification yield was 90.6 mol%.

(Second reaction) The total amount of the basic conversion reaction product liquid obtained in the above initial reaction was 1180 g in 840.4 g (11.19 mol) of a 40% by weight aqueous formaldehyde solution.
And 189.3 g (2.03 mol) of acetaldehyde were added separately from a nozzle over 0.8 hours. Thereafter, the same reaction as the first reaction was performed. After the reaction, the yield of PE obtained by crystallization was 84.5 mol% based on acetaldehyde. PE
The quality is shown in Table 5 along with the initial quality. On the other hand, the separation filtrate obtained by centrifugation was subjected to a basic conversion reaction in the same manner as in the initial reaction. The basification yield was 99.7 mol%.

[0048]

Table 5 PE quality (Example 6) (First reaction) (Second reaction) Melting point (° C) 183.2 183.1 Monopentaerythritol (%) 96.4 96.6 Moisture (%) 0.05 0.07 Ash (%) 0.02 0.05

Example 7 [Production of neopentyl glycol (NPG) from isobutyraldehyde (IBAL) and formaldehyde and use of reduced nickel catalyst for basic conversion reaction] (First reaction) 40% by weight formaldehyde aqueous solution 112
6.1 g (15.0 mol) was charged and the temperature was kept at 30 ° C. Add IBAL 514.9 g (7.14 mol) and 4
667 g (8.0 mol) of 8% by weight sodium hydroxide were added with stirring over 0.75 hours. While adjusting the reaction temperature, raise the temperature to 60 ° C, and while maintaining it at 65 ° C, 1
The reaction was continued for 0 minutes. Immediately after the reaction, add formic acid and add p
Neutralized to H7. The reaction product solution was extracted with methyl isobutyl ketone (MIBK) as a solvent. MIBK was recovered from the extract by vacuum distillation and then 70 mmHg
Distillation under reduced pressure gave 720.3 g of NPG. This corresponds to a yield of 96.8 mol% based on IBAL.

On the other hand, the raffinate residue was prepared by first distilling off a low boiling fraction such as methanol. About 1% of formaldehyde remaining in the raffinate was recovered as hydroxypivalaldehyde (HPA) which is a precursor of NPG by an aldol condensation reaction with IBAL using sodium hydroxide as a catalyst. That is, after the aldol condensation reaction, the mixture was left standing and separated into two phases. The IBAL phase containing HPA in the upper layer is used as it is as the second IBAL raw material. The lower layer raffinate was diluted by adding water so that the sodium formate concentration was 11% by weight. This sodium formate aqueous solution was subjected to a basic conversion reaction using a raw material supply conduit and a packed bed type reaction tube equipped with an external heat source heater and a cooling jacket and having an inner diameter of 40 mm and a tower length of 1000 mm. 1000 ml of stabilized nickel in the reaction tube
Of LSV [charged raw material liquid amount (ml
/ Hr) / catalyst filling amount (ml)] = 1.0 hr ⁻¹ , the raw material of the preparation liquid was supplied from the upper part of the reaction tube. The reaction temperature was 160 ° C., and the temperature control was automatically performed by an external heat source heater and cooling water. The pressure in the system is 15 kg.
It was adjusted with air to be / cm ² . By repeating the above basic conversion reaction 5 times, the basic conversion yield became 99.0 mol% or more of the theoretical value.

(Second reaction) In 790.3 g (15.0 mol) of 57% by weight aqueous formaldehyde solution, the total amount of the basic conversion liquid obtained in the above-mentioned initial reaction and the above-mentioned HPA were added.
514.9 g (7.14 mol) containing IBAL was added over 0.75 hours, and the reaction was carried out in the same manner as the first time. After the reaction, the yield of NPG obtained by extraction and distillation was IBA.
It was 94.5 mol% based on L. On the other hand, by repeating the basic conversion reaction 5 times, the basic conversion yield was 9% of the theoretical value.
It was 9.0 mol% or more.

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, a polyhydric alcohol can be efficiently produced without substantially forming a low value-added formate by-product.
It can be easily manufactured. That is, according to the method of the present invention, it is not necessary to discharge the formate out of the system except the amount required for the product, and the imbalance between the demands of the polyhydric alcohol and the formate can be solved. Further, the method of the present invention is industrially extremely advantageous because a polyhydric alcohol can be easily obtained from an aliphatic aldehyde and formaldehyde in a high yield and a high quality.

[Brief description of drawings]

FIG. 1 is a flow chart showing an example of a polyhydric alcohol production apparatus according to the method of the present invention.

[Explanation of symbols]

 1: Aldol condensation reactor 6: Crossed Canniaro reactor 10: Neutralization tank 13: Condenser 17: Extraction tower 19: Extraction liquid treatment distillation tower 22: Activated carbon treatment tower 24: Dilution tank 28: Formate conversion tower 30: Heating tank 33: Extraction tower 35: Separation tank 40: First distillation tower 43: Purification tower

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[Procedure amendment]

[Submission date] January 31, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

In the present invention, the basic compound in the aldol condensation reaction and the crossed Cannizaro reaction is a hydrogen carbonate produced by the oxidation or hydrolysis of a formate salt, which is at a temperature of 50 ° C. or higher. Since a part becomes a carbonate while releasing CO ₂ , it is substantially a mixture of both. This salt may be any of sodium, potassium, lithium, calcium and ammonium salts, but the sodium salt is generally used for industrial implementation. The amount of the basic compound used is 0.8 to 2.0 times the molar amount relative to the aliphatic aldehyde, and in order to suppress the by-product and obtain the target polyhydric alcohol in a high yield,
Adjustment is required according to the type of aliphatic aldehyde.
For example, if the aliphatic aldehyde is IBAL, 1.01
In the case of an aliphatic aldehyde having 6 to 22 carbon atoms, it is 1.0 to 2.0 times mol.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Example 5 [Manufacturing trimethylolpropane (TMP) from n-butyraldehyde (NBAL) and formaldehyde and using reduced nickel catalyst for basic conversion reaction] (First reaction) First, a 15% by weight formaldehyde aqueous solution 4
Sodium bicarbonate in 85 g (2.42 mol) 7
Basic aqueous solution containing 5.6 g (0.90 mol) and N
54.6 g (0.75 mol) of BAL was added through a separate nozzle over 0 and 5 hours. During this period, the reaction temperature was raised from 30 to 90 ° C. in 30 minutes, and the reaction was continued for 30 minutes while maintaining 90 ° C. Immediately after the reaction, formic acid was added to neutralize to pH 7. Next, the reaction product solution is concentrated under reduced pressure until the sodium formate concentration reaches 25% by weight, and thereafter,
600 g of NBAL was used as the solvent, and extraction was performed in three portions. These three extracts were mixed and subjected to atmospheric distillation to produce NB
AL and dissolved water were recovered and then distilled under reduced pressure of 1 mmHg using an Oldershaw distillation column with a distillation stage number of 5 to remove 3.8 g of the initial fraction and then 75.2 g as a main fraction.
Was obtained. This is a yield based on NBAL, 75.
This corresponds to 0 mol%. On the other hand, the extraction residual liquid 1 in NBAL extraction
51.0 g of 150 ml of activated carbon (trade name Kuraray Coal G
CL, made by Kuraray Chemical Co., Ltd., in a glass tube with an inner diameter of 13 mm, LSV [charged raw material liquid amount (ml / hr) / activated carbon (m
l)] = 0.2 hr ⁻¹ and the temperature was 50 ° C. Next, 320.0 g of water was added to adjust the sodium formate concentration to 13% by weight.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C07C 29/38 31/18 Z 9155-4H 31/22 9155-4H 31/24 9155-4H // C07B 61 / 00 300 (72) Atsushi Iwamoto, 3-10 Mizushima Kaigan Dori, Kurashiki City, Okayama Sanritsu Gas Chemical Co., Ltd. Mizushima Plant (72) Akira Mori, 3-10 Mizushima Kaigan Dori, Kurashiki City, Okayama Prefecture Chemical Company Mizushima Factory

Claims (3)

[Claims] 1. A hydrogen carbonate formed by oxidation or hydrolysis of a formate and a base catalyst containing carbonate as a main component in the presence of
a method for producing a polyhydric alcohol, which comprises reacting an aliphatic aldehyde represented by the formula (i) with formaldehyde; (At least one of R ^{1 to} R ³ is a hydrogen group, and the other is a linear or branched aliphatic group having 1 to 22 carbon atoms). 2. A formate formed as a by-product of the reaction of an aliphatic aldehyde and formaldehyde is oxidized or hydrolyzed in the presence of a noble metal catalyst or a nickel catalyst in a reduced state, and the obtained hydrogen carbonate and carbonate are contained as main components. The method for producing a polyhydric alcohol according to claim 1, wherein the basic compound is recycled to the reaction and reused. 3. A formate is obtained by oxidizing or hydrolyzing a formate produced as a by-product by the reaction of an aliphatic aldehyde and formaldehyde in the presence of a noble metal catalyst or a nickel catalyst in a reduced state to obtain a hydrogen carbonate and a carbonate. The method for producing a polyhydric alcohol according to claim 2, wherein the aqueous solution is treated with activated carbon.