JP4587464B2 - Method for producing glyceryl ether - Google Patents

Description

  The present invention relates to a method for producing glyceryl ether.

  Glyceryl ether obtained by hydrolyzing glycidyl ether is a useful compound as, for example, a solvent, an emulsifier, a dispersant, a cleaning agent, a foaming agent and the like.

In general, glyceryl ether is produced using a catalyst. As a method for producing glyceryl ether without using a catalyst, for example, a method of hydrolyzing glycidyl ether with subcritical water is known (Patent Document 1). .
JP 2002-88000 A

  However, in the above method, in order to maintain a high reaction selectivity by using a large amount of water in the hydrolysis reaction while reducing water loss, water is recovered from the reaction mixture after the hydrolysis reaction, and the hydrolysis reaction is performed. When this water is further used in the hydrolysis reaction, the production of by-products other than glyceryl ether increases over time, and the hue of glyceryl ether deteriorates. There was a problem of quality degradation.

  That is, the present invention is an efficient method for producing high-quality glyceryl ether, which can suppress the loss of water to be used and can prevent the deterioration of the hue of glyceryl ether by suppressing the formation of by-products. The purpose is to provide.

  The present inventors have a correlation between the increase of by-products as described above and a decrease in the pH of water used for the hydrolysis reaction, and by adjusting the pH of the water, the production of by-products during the reaction is suppressed. As a result, the present invention was completed.

  That is, the present invention relates to the general formula (I):

(In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms, and OA may be the same or different and has 2 to 4 carbon atoms. Represents an oxyalkylene group, and p represents a number of 0 to 20.)
And a method for producing glyceryl ether, wherein the compound and water are supplied to a reactor and the hydrolysis reaction of the compound is performed under a condition where the water is in a subcritical state, wherein water is removed from the reaction mixture after the hydrolysis reaction. Recovering, adjusting the pH of the water to at least 3.5 and feeding it to the reactor; and a method for producing glyceryl ether; and general formula (I):

(In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms, and OA may be the same or different and has 2 to 4 carbon atoms. Represents an oxyalkylene group, and p represents a number of 0 to 20.)
Step 1 in which a compound represented by the formula (1) and water are supplied to a reactor, and the hydrolysis reaction of the compound is carried out under conditions where water is in a subcritical state, and water is recovered from the reaction mixture after the hydrolysis reaction, A method for preventing coloration of glyceryl ether produced through Step 2 to be supplied to a reactor, wherein the pH of water is adjusted to at least 3.5 and supplied to the reactor in Step 2 above. Regarding the method.

  According to the present invention, it is possible to suppress the loss of water to be used and suppress the formation of by-products to prevent the deterioration of the hue of glyceryl ether and to efficiently produce high-quality glyceryl ether.

  The present invention is a method for producing glyceryl ether using a predetermined glycidyl ether as a raw material, supplying the raw material and water to a reactor, and subjecting the raw material to a hydrolysis reaction under conditions where water becomes a subcritical state. One major characteristic is that it has a step of recovering water from the reaction mixture after the decomposition reaction, adjusting the pH of the water to at least 3.5, and supplying the water to the reactor.

  In the present invention, unreacted water that has not been used for the hydrolysis reaction of the raw material is separated and recovered, and at least a part of the water is supplied (recycled) to the reactor, so that the loss of water used is suppressed. Further, since such water is adjusted to a predetermined pH, the glyceryl ether hue does not progress to the extent that degradation of glyceryl ether or side reaction becomes a problem on the quality of glyceryl ether during the hydrolysis reaction. Deterioration can be prevented. Furthermore, since the hydrolysis reaction is performed under conditions where water is in a subcritical state, the reaction proceeds with high reaction selectivity even in the absence of a catalyst, and the operation for removing the catalyst from the reaction product is omitted. And high-quality glyceryl ether can be produced efficiently.

  In addition, as long as the component demonstrated below does not inhibit the expression of the desired effect of this invention, each can be used individually or in mixture of 2 or more types.

  The glycidyl ether used as a raw material in the present invention is a compound represented by the above general formula (I).

  In the above formula, as the hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms represented by R may be substituted with fluorine atoms, for example, a linear or branched chain having 1 to 20 carbon atoms An alkyl group having 2 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, and the like.

  Specific examples of the hydrocarbon group include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, 2-propyl group, 2-butyl group, 2-methyl-2-propyl group, 2-pentyl group, 3 -Pentyl group, 2-hexyl group, 3-hexyl group, 2-octyl group, 2-ethylhexyl group, phenyl group, benzyl group and the like. Examples of the hydrocarbon group in which the hydrogen atom is substituted with a fluorine atom include a nanofluorohexyl group, a hexafluorohexyl group, a tridecafluorooctyl group, a heptadecafluorooctyl group, and a heptadecafluorodecyl group. The hydrogen atom of the hydrocarbon group exemplified above such as a perfluoroalkyl group is a fluorine atom, the degree of substitution and the substitution position are not particularly limited, and those optionally substituted can be mentioned.

  Specific examples of the oxyalkylene group having 2 to 4 carbon atoms represented by OA include alkylene oxides such as oxyethylene group, oxytrimethylene group, oxypropylene group and oxybutylene group.

  In addition, as carbon number of the hydrocarbon group shown as R, Preferably it is 1-12 from a viewpoint of improving reaction selectivity. Moreover, as p, Preferably it is 0-6, More preferably, it is 0.

  Specific examples of the glycidyl ether suitably used as the raw material include n-butyl glycidyl ether, 2-methyl-propyl glycidyl ether, n-pentyl glycidyl ether, 2-methyl-butyl glycidyl ether, and n-hexyl. Examples include glycidyl ether, 2-methyl-pentyl glycidyl ether, phenyl glycidyl ether, n-octyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, and n-stearyl glycidyl ether.

  In the present invention, the type of water used for the hydrolysis reaction of the raw material is not particularly limited as long as the desired effect of the present invention is not inhibited. Examples of water include ion exchange water, distilled water, reverse osmosis filtration treated water, and the like, and water containing salts such as tap water may be used as long as the essence of the present invention is not impaired. Absent.

  In addition, as water used for the hydrolysis reaction of the raw material in the present invention, at least a part thereof is from a reaction mixture after the hydrolysis reaction (a reaction mixture after all or a part thereof has been subjected to the hydrolysis reaction). Water that has been separated and recovered and whose pH has been adjusted as described below (hereinafter sometimes referred to as recycled water) is used. The pH of the water is 3.5 or higher, and usually the upper limit is about 12. From the viewpoint of further suppressing the production of by-products, the pH is preferably 4 to 9, and more preferably 5 to 8.

  The recycled water may be obtained from the same reaction system or from different reaction systems. As the latter mode, for example, the mode of Example 2 described later can be cited.

  In the present invention, the amount of recycled water used is not particularly limited, but is preferably a molar ratio (recycled water / externally supplied water) to the amount of water (externally supplied water) newly supplied to the reactor from the outside. Is 1 or more, more preferably 10 or more. This ratio can be said to be an indicator of the reduction in water loss, and the higher the value, the less water loss in the manufacturing process. The water used for the hydrolysis reaction of the raw material may be all recycled water.

  In the production method of the present invention, the raw material and water as described above are supplied to a reactor, and the raw material is subjected to a hydrolysis reaction to produce glyceryl ether. In the present invention, the hydrolysis reaction is performed under conditions where water is in a subcritical state from the viewpoint of increasing the reactivity between the raw material and water. The condition that water becomes a subcritical state refers to a condition that can maintain water in a liquid state under a high temperature and high pressure condition. Specifically, the temperature is 100 to 350 ° C., preferably 200 to 300 ° C., And the conditions which can hold | maintain water in a liquid state under the pressure of 0.12-100 Mpa, more preferably 0.5-20 Mpa, still more preferably 1-15 Mpa are more preferable.

  The production method of the present invention is carried out by a batch system in which raw materials are supplied in an amount required per batch and a hydrolysis reaction is performed once, or by a continuous system in which raw materials are continuously supplied and a hydrolysis reaction is performed. can do. In particular, it is preferable to carry out in a continuous manner that has a characteristic that the time required for raising and lowering the temperature is short, the reaction conditions are easily controlled, and the reaction can proceed efficiently.

  The hydrolysis reaction is carried out in a reactor selected according to the embodiment of the production method of the present invention. The reactor is not particularly limited as long as it can perform a hydrolysis reaction under the above-mentioned conditions and can recover the reaction product. For example, in the case of carrying out in a batch system, a tank such as an autoclave A type reactor is preferably used. On the other hand, in the case of carrying out in a continuous mode, a flow-through tubular type such as a tubular reactor, a tower type reactor, a static mixer type reactor, and a semi-batch type such as a continuous stirred tank type reactor Among these, a tubular reactor is particularly preferably used because of its good operability and pressure resistance during high-pressure reaction. Therefore, in the present invention, it is preferable to carry out the hydrolysis reaction continuously using a tubular reactor. All of the above reactors are commercially available. Further, the reactor may or may not have a stirring means, but from the viewpoint of allowing the reaction to proceed uniformly, a reactor having a stirring means is preferable.

  The material of the reactor used in the present invention is not particularly limited, and materials generally used for chemical reactions can be arbitrarily used. Specific examples include steel materials such as pure iron, carbon steel, cast iron, nickel steel, austenitic stainless steels such as SUS304, SUS304L, SUS309, SUS309S, SUS316, and SUS316L, martensitic stainless steels such as SUS403 and SUS420, SUS430, and the like. Ferritic stainless steel, Fe-Cr-Ni alloys such as carpenter 20, copper alloys such as pure copper, aluminum bronze and brass, aluminum alloys such as pure aluminum and duralumin, Ni-Cr-Fe alloys such as Inconel 600 and Inconel 702 Ni-Cu alloys such as Monel, Ni-Mo-Fe-Cr alloys such as Hastelloy B, Hastelloy C, Hastelloy C276, Cobalt alloys such as Stellite 21, Stellite 27, Highness 25, Titanium alloys including pure titanium, tungsten, Jill Metal materials such as zirconium alloys containing molybdenum, molybdenum and chromium; hard glass, quartz glass, porcelain, glass lining, phenolic resin, polytetrafluoroethylene, polyethylene, epoxy resin, polyamide resin and other synthetic resins, alumina, titania, Examples thereof include ceramic materials such as silicon carbide, silicon nitride, and aluminum nitride. Among these, when the reaction is carried out under temperature conditions close to supercritical water conditions where material corrosion is a concern, metallic materials such as austenitic stainless steel, Ni—Cr—Fe alloy, Ni—Mo—Fe—Cr alloy Of Ni—Cr—Fe alloy and Ni—Mo—Fe—Cr alloy are more preferred.

  The amount of water relative to the raw material during the hydrolysis reaction is not particularly limited, but is preferably 10 to 1000 times, more preferably 20 to 500 times the stoichiometric amount in terms of mole. Within such a range, the progress of side reactions such as dimerization between the glycidyl ether as a raw material and the produced glyceryl ether is suppressed, and the reaction selectivity of glyceryl ether is increased. In addition, from the viewpoint of efficient productivity in a continuous reaction operation, a condition range of 40 to 200 times is more preferable from an event peculiar to the present reaction system. Here, the amount of water refers to the total amount of recycled water and externally supplied water. The molar ratio of the amount of recycled water used with respect to the external supply water is preferably set as described above.

  When the method of the present invention is carried out batchwise, it is preferable to charge the raw material and water so that the amount of water relative to the raw material during the hydrolysis reaction is within the above range, while it is carried out continuously. In this case, it is preferable that the amount of water relative to the raw material is within the above range in the steady state of the reaction (that is, the state where the components involved in the reaction are constant).

  When carrying out the hydrolysis reaction, the raw materials and water are supplied individually and / or premixed into the reactor. When supplying it in a reactor without mixing beforehand, it mixes in a reactor. Depending on the chemical structure of the glycidyl ether used as a raw material, the reaction system is not uniform, and therefore mixing is preferably performed using a stirring means having a strong shearing force. As the stirring means, in a batch type, for example, a propeller mixer, an azimuth homomixer, a homomixer, a highly shearable disk turbine type stirring blade, an inclined paddle type stirring blade, a paddle type stirring blade, and the like are preferably used. In the continuous type, for example, a pipeline mixer, a line homomixer, a static mixer, I.V. S. G. Mixers, ultrasonic mixers, high-pressure homogenizers, pumps such as high-shearing centrifugal pumps, and dispersers are preferably used. Further, the hydrolysis reaction is preferably allowed to proceed under the mixing conditions by these stirring means.

  The hydrolysis reaction is performed by controlling the temperature of the internal fluid in the reactor (reaction temperature) and the pressure in the reactor (reaction pressure) under the condition that the water in the reactor is in a subcritical state. The preferable ranges of temperature and / or pressure as conditions for water to be in a subcritical state are as described above. By controlling the temperature and pressure to conditions under which water becomes a subcritical state, the hydrolysis reaction can be carried out efficiently even in the absence of a catalyst. There is an advantage that corrosion can be suppressed.

  In addition, the reaction time varies depending on the reaction temperature and the type of raw material used, and cannot be determined unconditionally. However, in the case of a batch type, from the end of the charging of raw materials, etc., on the other hand, in the case of a continuous type, the reaction reaches a steady state. From about 1 minute to 10 hours. For example, when the reaction is performed at 200 ° C., the reaction time is preferably about 10 minutes. The reaction time in the continuous reactor means the time that the reaction liquid stays in the reactor, and is a value obtained by dividing the volume of the reactor by the raw material flow rate per unit time supplied to the reactor. Indicates.

  In the present invention, since the hydrolysis reaction is carried out under conditions where water is in a subcritical state, the reaction proceeds even in the absence of a catalyst, but it is also possible to add an acid or alkali catalyst. Although it does not specifically limit as a catalyst used in this invention, For example, the acid, base, combined use system of an acid and a base etc. which are generally used in a hydrolysis reaction can be mentioned.

  When the catalyst is used, the amount used is not particularly limited as long as the desired hydrolysis efficiency of the raw material can be obtained, but is preferably 0.01 to 10 weights with respect to 100 parts by weight of the raw material. Parts, more preferably 0.1 to 5 parts by weight.

  As described above, the hydrolysis reaction of the raw material glycidyl ether is carried out. The separation and recovery of water from the reaction mixture after the hydrolysis reaction is preferably performed using, for example, the following separation and recovery means.

  The separation / recovery means used in the present invention means a means capable of recovering components other than water and water from the reaction mixture after the hydrolysis reaction. The recovery of components other than water and the recovery of water may be performed integrally (Aspect 1) or may be performed independently (Aspect 2). From the viewpoint of ease of operation, it is preferable to use a separation and recovery means that can recover components other than water and water according to Embodiment 1.

  In the present invention, the reaction mixture after the hydrolysis reaction has a property of being separated into components other than water (including glyceryl ether as a reaction product) and water depending on the chemical structure of glycidyl ether used as a raw material. Therefore, examples of the separation and recovery means that can recover components other than water and water according to aspect 1 include specific gravity difference separation and membrane separation. Specific gravity difference separation includes static separation such as API type oil separator, CPI oil separator, PPI oil separator, centrifugal separation such as shear press type, Doraval type, wet cyclone and the like. Examples of membrane separation include microfiltration membranes, ultrafiltration membranes, loose RO membranes (loose reverse osmosis membranes), and reverse osmosis membranes. Among these, the stationary separation is performed by supplying the reaction mixture and allowing it to stand, and the reaction mixture is separated into components other than water (upper layer) and water (lower layer). These components are also recovered, and it is preferable because the recovery of components other than water and the recovery of water can be performed integrally.

  On the other hand, examples of the separation / recovery means that can recover components other than water and water according to Aspect 2 include, for example, a means that combines evaporation and Liebig condensation. When the reaction mixture is supplied to the evaporator and then heated above the boiling point of water, the water evaporates, and components other than water remain and are recovered in the evaporator. The evaporated water is cooled by a Liebig condenser and recovered as water. Moreover, you may separate and collect | recover using distillation operations, such as rectification, instead of evaporation operation.

  Note that it is not always necessary to recover all of the water from the reaction mixture. The amount of water to be recovered may be determined as appropriate, and at least a part of the water in the reaction mixture may be recovered.

  Next, the recovered water is pH adjusted to a predetermined value and then supplied to a reactor that performs a hydrolysis reaction. Since the pH of the recycled water decreases with time, the pH of the water is adjusted using, for example, the following pH adjuster.

  Examples of the pH adjusting agent include inorganic ion adsorbents, ion adsorbents such as ion exchange resins, and neutralizing agents such as inorganic bases and organic bases. The production method of the present invention is preferably carried out continuously, but according to the inorganic ion adsorbent or ion exchange resin, it is possible to suppress a decrease in the pH of water by bringing them into contact with water. Therefore, when the production method of the present invention is carried out continuously, it is preferable to use such an adsorbent as the pH adjuster.

  Examples of inorganic ion adsorbents include metal composite oxides such as hydrotalcite, zeolite, and magnesium silicate, metal oxides such as alumina, silica, magnesium oxide, zinc oxide, and calcium oxide, activated carbon, and activated clay. And hydrotalcite is preferred. Examples of the ion exchange resin include a strong basic anion exchange resin, a weak basic anion exchange resin, an anion exchange membrane, and an anion exchange fiber, and a weak basic anion exchange resin is preferable. Especially, since it is excellent in pH adjustment ability, an inorganic ion adsorbent is used suitably. The amount of the ion adsorbent used can be determined by the amount of glycidyl ether used in the reaction, and the amount used is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of glycidyl ether, 0.1 to 10 Part by weight is more preferred.

  Examples of the neutralizing agent include metal carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, water Examples thereof include metal hydroxides such as aluminum oxide, inorganic bases such as metal phosphates such as calcium phosphate and calcium hydrogen phosphate, and organic bases such as ammonia, aniline, ethylamine, diethylamine, triethylamine, butylamine and pyridine.

  Examples of the pH adjustment method include a method in which a column is filled with the inorganic ion adsorbent and ion exchange resin as described above, and the water separated and recovered is passed through the column. As a means for treating the separated and recovered water in the column, there is no problem whether it is performed in a continuous type or a batch type, and in the continuous type, the separated and collected water may be treated in series. You may process cyclically through a storage tank etc. Further, for example, a method of adding a neutralizing agent as described above to the separated and recovered water and adjusting to a desired pH can be mentioned. The pH may be adjusted by any of these methods or a combination of these methods. However, when the production method of the present invention is carried out continuously, the pH of water is easy to adjust. The former method using an adsorbent or the like is more preferable.

  In the present invention, the pH of water indicates a value measured at normal temperature and normal pressure. The method for measuring this pH is not particularly limited, and examples thereof include an indicator method, a metal electrode method such as a hydrogen electrode and an antimony electrode, and a glass electrode method. The technology may be implemented within a numerical range converted to a value at normal temperature and normal pressure in accordance with temperature and pressure changes.

  In addition, when recovering water by the separation / recovery means that can recover components other than water and water according to the aspect 2, the pH of the recovered water may be 3.5 or more. In such a case, it is assumed that the water recovery and the water pH adjustment are performed simultaneously. Further, even if the pH of the recovered water is already 3.5 or more, it is assumed that the pH adjustment is performed in the present invention when the pH adjustment operation as described above is performed.

  In the case where the production method of the present invention is carried out continuously, water is separated and recovered from the reaction mixture discharged from the reactor, as exemplified in Example 1 described later. A mode in which a series of operations are performed in the same apparatus, in which water is passed through a packed column to adjust the pH of the water, and is supplied again to the reactor for use in further hydrolysis reaction through a circulation line. Can be mentioned. On the other hand, when the production method of the present invention is carried out batchwise, as exemplified in Example 2 described later, water is separated and recovered from the reaction mixture, and for example, the neutralizing agent is recovered in the recovered water. A mode in which a series of operations are performed by the same or different apparatuses, such as adding water to adjust the pH of water and supplying water after pH adjustment to the reactor, can be mentioned. The aspect of supplying the recycled water to the reactor is not particularly limited, and may be directly supplied to the reactor, or may be mixed with raw materials and / or externally supplied water and supplied to the reactor. .

  The reaction product glyceryl ether is obtained as a component other than water. Ingredients other than water can usually be used as glyceryl ethers as they are. For example, when a catalyst is used, further, for example, by evaporation, distillation, extraction, microfiltration, adsorption, etc. according to a known method. It is preferable to purify glyceryl ether.

  Thus, glyceryl ether is obtained. If the pH of the water recovered as described above is not adjusted, the pH of the water used for the hydrolysis reaction of the raw material decreases with time, and as a result, decomposition and side reactions of glyceryl ether proceed, Depending on the reactor used, elution of the metal occurs, and the resulting glyceryl ether is deteriorated in hue or accompanied by an irritating odor. According to the production method of the present invention, even when recycled water is used for a hydrolysis reaction for a long time, the occurrence of such various phenomena can be suppressed and high-quality glyceryl ether can be obtained.

  In the present invention, the hue of glyceryl ether is measured by the Gardner method (conforming to JIS K 0071-2). The hue of glyceryl ether obtained by the production method of the present invention is preferably 4 or less.

  Moreover, the pH adjustment of the water recovered from the reaction mixture in the production method of the present invention can be regarded as a means for preventing glyceryl ether coloring when viewed from the glyceryl ether side obtained by such a method. Therefore, as one aspect of the present invention, a step 1 of supplying the compound represented by the general formula (I) and water to a reactor and performing a hydrolysis reaction of the compound under a condition in which the water is in a subcritical state; A method for preventing coloration of glyceryl ether produced through the step 2 of recovering water from the reaction mixture after the hydrolysis reaction and supplying it to the reactor, wherein the pH of the water is set to at least 3.5 in the step 2 There is provided a method for preventing coloration of glyceryl ether, which is adjusted and fed to the reactor. About the operation of each process in the said method, what is necessary is just to follow the said description about the manufacturing method of this invention.

Example 1
The reaction apparatus shown in FIG. 1 was used. The apparatus shown in FIG. 1 includes a tubular reactor 1, a separation / recovery unit 2, a water supply unit 3, and a raw material supply unit 4. The water supply unit 3 and the raw material supply unit 4 are respectively connected to the tubular reactor 1, and the tubular reactor 1 is connected to the separation and recovery unit 2 through a water circulation line 5. A stationary separator is used for the separation and recovery unit 2, and a water treatment unit 6 and a water circulation pump 7 are provided in the water circulation line 5. In the water treatment unit 6, 200 g of KYOWARD 1015 (Kyowa Chemical Industry Co., Ltd. hydrotalcite) as an inorganic ion adsorbent was packed in a SUS column and used.

  When the production of glyceryl ether was started, 13 kg of ion-exchanged water was charged into the separation and recovery unit 2. 2-ethyl-hexyl glycidyl ether as a raw material at 50.1 g / min and ion-exchanged water (initial pH 6.8) at 28.6 g / min from the raw material supply unit 4 and the water supply unit 3, and a separation and recovery unit 2 water was continuously supplied to the tubular reactor 1 (tube diameter: 16 mm, tube length: 11 m, material: SUS316) through the water circulation line 5 at 464.3 g / min, and the reaction mixture was passed through the back pressure valve 8. It was introduced into the separation and recovery unit 2. The tubular reactor 1 was heated with a heater so that the temperature of the internal fluid (reaction temperature) was 275 ° C. On the other hand, the pressure in the tubular reactor 1 (reaction pressure) was set to 8 MPa. In the tubular reactor 1, the hydrolysis reaction of the raw material was performed under such temperature and pressure conditions, that is, under conditions where water was in a subcritical state. In the steady state of the reaction, the amount of water relative to the raw material was 100 times its stoichiometric amount in terms of mole. After the hydrolysis reaction, the reaction mixture was cooled by a cooling part (50 ° C.), and then reached the separation and recovery part 2. In the separation and recovery unit 2, the reaction mixture is separated and water is recovered as a lower layer. After the water is constantly passed through the water treatment unit 6 through the water circulation line 5 to adjust the pH of the water, a tubular reactor is used. 1 was supplied.

  The glyceryl ether was manufactured by the above operation. Glycidyl ether was supplied to start the hydrolysis reaction, and the reaction product was collected every 4 hours until 28 hours later. Reaction selectivity and decomposition rate of glyceryl ether and glyceryl ether calculated from a gas chromatogram of a reaction product obtained while supplying 300 g of 2-ethyl-hexyl glycidyl ether to tube reactor 1 from the start of recovery The hues of are shown in Table 1. Table 1 also shows the pH (measured by the glass electrode method under normal temperature and normal pressure) of the water collected from the reaction mixture after passing through the water treatment unit 6 while collecting the reaction product.

  The reaction selectivity was calculated by the following formula: production rate of produced glyceryl ether / conversion rate of supplied glycidyl ether × 100. Moreover, the decomposition rate was calculated from the generation rate of the glyceryl ether decomposition product. Hue was measured by the Gardner method (based on JIS K 0071-2).

Comparative Example 1
The apparatus similar to that shown in FIG. 1 was used, but here the water treatment unit 6 was not installed, and the water recovered from the separation and recovery unit 2 was directly introduced into the tubular reactor 1 via the water circulation line 5. Set to be.

  When the production of glyceryl ether was started, 13 kg of ion-exchanged water was charged into the separation and recovery unit 2. 2-ethyl-hexyl glycidyl ether as a raw material at 50.1 g / min and ion-exchanged water (initial pH 6.8) at 28.6 g / min from the raw material supply unit 4 and the water supply unit 3, and a separation and recovery unit 2 water was continuously supplied to the tubular reactor 1 through the water circulation line 5 at 464.3 g / min, and the reaction mixture was introduced into the separation and recovery unit 2 through the back pressure valve 8. The tubular reactor 1 was heated with a heater so that the temperature of the internal fluid (reaction temperature) was 275 ° C. On the other hand, the pressure in the tubular reactor 1 (reaction pressure) was set to 8 MPa. In the tubular reactor 1, the hydrolysis reaction of the raw material was performed under such temperature and pressure conditions, that is, under conditions where water was in a subcritical state. After the hydrolysis reaction, the reaction mixture was cooled by a cooling part (50 ° C.), and then reached the separation and recovery part 2. In the separation and recovery unit 2, the reaction mixture was separated into layers, and water was recovered as a lower layer, and was always supplied to the tubular reactor 1 via the circulation line 5.

  The glyceryl ether was manufactured by the above operation. Glycidyl ether was supplied to start the hydrolysis reaction, and the reaction product was collected every 4 hours until 16 hours later. Reaction selectivity and decomposition rate of glyceryl ether and glyceryl ether calculated from a gas chromatogram of a reaction product obtained while supplying 300 g of 2-ethyl-hexyl glycidyl ether to tube reactor 1 from the start of recovery The hues of are shown in Table 1. Table 1 also shows the pH of water recovered from the reaction mixture and in the lower layer of the separation and recovery unit 2.

  The reaction selectivity, decomposition rate, hue, and water pH of glyceryl ether were calculated or measured by the same method as in Example 1.

  In Example 1, an inorganic ion adsorbent was used as a water pH adjuster, and after continuously adjusting the pH of water recovered from the reaction mixture after the hydrolysis reaction, it was circulated through the reactor to cause hydrolysis reaction. Went. As a result, as shown in Table 1, even when the operation was performed for a long time, a high reaction selectivity of glyceryl ether was shown, the decomposition rate was low, and the hue was not deteriorated.

  On the other hand, in Comparative Example 1, the hydrolysis reaction was carried out by directly circulating water recovered from the reaction mixture to the reactor without using a water pH adjuster. As a result, as shown in Table 1, the reaction selectivity tended to decrease with the lapse of operation time, and the decomposition rate was clearly higher than that of Example 1. Moreover, the remarkable deterioration of the hue was recognized.

Example 2
The reaction apparatus shown in FIG. 2 was used. The apparatus shown in FIG. 2 includes a tubular reactor 1, a separation and recovery unit 2, a water supply unit 3, a raw material supply unit 4, and a back pressure valve 8. The water supply unit 3 and the raw material supply unit 4 are connected to the tubular reactor 1, and the tubular reactor 1 is connected to the separation and recovery unit 2. A stationary separator was used for the separation and recovery unit 2.

  In Comparative Example 1, sodium hydroxide was added as a neutralizing agent to water (pH 3.2) separated and recovered 20 hours after the hydrolysis reaction was started by supplying glycidyl ether, and the pH became 6.0. Adjusted as follows. This was continuously supplied from the water supply unit 3 to the tubular reactor 1 at 15.9 mL / min and from the raw material supply unit 4 to 2-ethyl-hexyl glycidyl ether at 1.8 mL / min. The reaction mixture was introduced into the separation and recovery unit 2 through the back pressure valve 8. The temperature of the internal fluid in the tubular reactor 1 was maintained at 280 ° C. with an oil bath. On the other hand, the pressure in the tubular reactor 1 was set to 8 MPa. In the tubular reactor 1, the hydrolysis reaction of the raw material was performed under such temperature and pressure conditions, that is, under conditions where water was in a subcritical state. In the steady state of the reaction, the amount of water relative to the raw material was 100 times its stoichiometric amount in terms of mole. After the hydrolysis reaction, the reaction mixture was cooled by a cooling part (50 ° C.), and then reached the separation and recovery part 2. In the separation and recovery unit 2, the reaction mixture was separated, and the reaction product was obtained as the upper layer. By this operation, the reaction product was recovered 2 hours after the reaction composition became steady. The glyceryl ether selectivity calculated from the gas chromatogram of the reaction product obtained while supplying 20 g of 2-ethyl-hexyl glycidyl ether from the start of the recovery was 98.3%. The decomposition rate of glyceryl ether was 0.7%.

  In Example 2, by adjusting the pH of the water separated and recovered after the hydrolysis reaction of Comparative Example 1, and using this in the hydrolysis reaction, a high reaction selectivity of glyceryl ether can be obtained, and the decomposition of glyceryl ether can be achieved. The rate was also kept low. Further, no deterioration of hue was observed.

  According to the present invention, a high-quality glyceryl ether that can be used for a solvent, an emulsifier, a dispersant, a cleaning agent, a foaming agent and the like can be provided.

It is an apparatus schematic which shows an example of the apparatus used suitably for implementation of the manufacturing method of this invention. It is the apparatus schematic which shows an example of the apparatus used suitably for implementation of the manufacturing method of this invention.

Explanation of symbols

1 Tubular reactor 2 Separation and recovery unit 3 Water supply unit 4 Raw material supply unit 5 Water circulation line 6 Water treatment unit 7 Water circulation pump 8 Back pressure valve

Claims (6)

Formula (I):

(In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms, and OA may be the same or different and has 2 to 4 carbon atoms. Represents an oxyalkylene group, and p represents a number of 0 to 20.)
And a method for producing glyceryl ether, wherein the compound and water are supplied to a reactor and the hydrolysis reaction of the compound is performed under a condition where the water is in a subcritical state, wherein water is removed from the reaction mixture after the hydrolysis reaction. Collect the pH of the water 3 . The manufacturing method of glyceryl ether which has the process of adjusting to 5-9 and supplying to this reactor.   The method according to claim 1, wherein the amount of water relative to the compound represented by the general formula (I) during the hydrolysis reaction is 10 to 1000 times its stoichiometric amount in terms of mole.   The method according to claim 1 or 2, wherein the pH of water is adjusted using an inorganic ion adsorbent.   The method according to any one of claims 1 to 3, wherein the hydrolysis reaction is performed in a temperature range of 100 to 350 ° C.   The method according to any one of claims 1 to 4, wherein the hydrolysis reaction is continuously carried out. Formula (I):

(In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms, and OA may be the same or different and has 2 to 4 carbon atoms. Represents an oxyalkylene group, and p represents a number of 0 to 20.)
Step 1 in which a compound represented by the formula (1) and water are supplied to a reactor, and the hydrolysis reaction of the compound is carried out under conditions where water is in a subcritical state, and water is recovered from the reaction mixture after the hydrolysis reaction, A method for preventing coloration of glyceryl ether produced through Step 2 of supplying to a vessel, wherein the pH of water is 3 . A method for preventing coloration of glyceryl ether, which is adjusted to 5 to 9 and supplied to the reactor.

Images