WO2011002023A1 - アクロレインの合成方法及び装置 - Google Patents
アクロレインの合成方法及び装置 Download PDFInfo
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- WO2011002023A1 WO2011002023A1 PCT/JP2010/061145 JP2010061145W WO2011002023A1 WO 2011002023 A1 WO2011002023 A1 WO 2011002023A1 JP 2010061145 W JP2010061145 W JP 2010061145W WO 2011002023 A1 WO2011002023 A1 WO 2011002023A1
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- glycerin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to a method and an apparatus for synthesizing acrolein from glycerin by-produced when producing fatty acid methyl ester (biodiesel fuel) from fat and oil waste.
- Biodiesel fuel which is carbon neutral, has attracted attention as a fuel for diesel engines.
- Biodiesel is known to be obtained by transesterifying triglyceride and monohydric alcohol contained in raw materials such as vegetable oil, animal oil, or waste oil thereof, and then removing by-product glycerin (Formula 1).
- monohydric alcohol and fatty acid ester having a low viscosity By using the monohydric alcohol and fatty acid ester having a low viscosity by the reaction of Formula 1, it can be used as a fuel.
- glycerin raw materials such as nitroglycerin, pharmaceuticals, cosmetics, and sweeteners are generally used, but all of them require high purity and there is no mass demand. For this reason, the present condition is that the glycerin obtained by refine
- Patent Document 1 The method relating to biodiesel production described in Patent Document 1 refers to purification of glycerin, which is a by-product, by distillation or the like.
- glycerin which is a by-product, by distillation or the like.
- it is difficult to establish economic efficiency because extra cost is required by performing a process for purifying glycerin.
- the purity of glycerin cannot always be high with the described method, it is highly possible that it is not suitable for commercial use.
- Patent Document 2 describes a method for producing biodiesel and glycerin using high-temperature methanol near the critical temperature without using an alkali catalyst.
- impurities such as alkali and neutralizing agent are not required, so that biodiesel and glycerol can be easily purified.
- this production method has a problem that a large amount of energy is required as compared with the alkali catalyst method, and a large amount of cost is required to produce an inexpensive material.
- Patent Documents 1 and 2 In addition to the production methods described in Patent Documents 1 and 2, there are known methods for obtaining high-purity glycerin by enzymatic methods, supercritical methods, etc., but both production methods are costly and economically established. Is difficult to industrially use.
- glycerin as a chemical product includes use as a raw material for producing acrolein used as a raw material for acrylic acid and 1,3-propanediol.
- Non-Patent Document 1 describes a method for producing acrolein by adding sulfuric acid to glycerin and treating with supercritical water.
- acrolein can be obtained from glycerin in a yield of 70% or more because supercritical water protons have a high catalytic action.
- Non-Patent Document 1 In the technology of Non-Patent Document 1, only the condition where the glycerin concentration in the reaction mixture subjected to the supercritical reaction is as low as around 1.0% is examined. However, for industrialization, it is necessary to use high-concentration glycerin as a raw material from the viewpoint of efficiently using energy input when obtaining supercritical water.
- Non-Patent Document 2 in a method of synthesizing acrolein from glycerin by treatment with acid and supercritical water, in order to maintain a high raw material yield for acrolein synthesis even under high glycerin concentration conditions, the concentration is increased. It is described that an appropriate reaction time corresponding to the above and a catalyst assistant (acid) concentration are required.
- the triglyceride raw material for producing biodiesel fuel it is preferable to use waste of animal and vegetable oils and fats discharged from the food industry and general households.
- the waste of animal and vegetable oils and fats includes impurities such as water generated during cooking, and the content thereof is not constant.
- glycerin produced as a by-product in the production of biodiesel using waste of animal and vegetable oils and fats as a triglyceride raw material contains an unsteady amount of water and the like.
- Non-Patent Document 2 in the conversion reaction from glycerin to acrolein by treatment with supercritical water and acid, in order to suppress by-products such as tar and carbon, glycerin concentration and hydrogen ion concentration Precise control is required. For this reason, it is difficult to apply this conversion reaction to acrolein production from glycerin derived from wastes of animal and vegetable oils and fats.
- an alkali catalyst when used as a catalyst in the production of biodiesel fuel, the alkali catalyst is mixed in the by-product glycerin. For this reason, when an acid is added to by-product glycerol, there exists a problem that the salt of an alkali catalyst is formed. It is difficult to remove the salt in glycerin.
- the present invention provides an industrially applicable method for producing acrolein by treatment with supercritical water from glycerin by-produced in the production process of biodiesel fuel from animal and vegetable oil waste using an alkali catalyst. Providing is a problem to be solved.
- the present inventors measured the hydrogen ion concentration in glycerin by-produced in the biodiesel extraction process, and added and mixed the acid so as to obtain an appropriate acid concentration. Then, the inventors have found a method by which acrolein can be synthesized without reacting with supercritical water and dehydrating glycerol to acrolein without using any special measures to increase the purity of glycerol.
- the present invention includes the following inventions.
- the water content of glycerin subjected to the precipitate removing step is less than the stoichiometric amount of water in which the total amount of the salt in the glycerin can be hydrated.
- the method further includes a water adjustment step of cooling the glycerin and / or removing the water ( Method 4).
- Water used in the supercritical water treatment process is added as glycerin after the acid addition process, or water in a pressure condition lower than the critical pressure of water to the glycerin in the precipitate removal process when performing the precipitate removal process.
- the high-temperature and high-pressure treatment step is a step of treating the mixture of glycerin and water after the acid addition under the condition that the water in the mixture has a temperature of 374 ° C. or higher and a pressure of 22.06 MPa or higher. 7) Method.
- the water content of glycerin subjected to the precipitate removing step is less than the stoichiometric amount of water in which the total amount of the salt in the glycerin can be hydrated, (10) Method.
- the method further includes a water adjusting step of cooling the glycerin and / or removing the water ( 11) The method.
- the water used in the high-temperature and high-pressure treatment step is added to the glycerin after the acid addition step or to the glycerin in the precipitate removal step as water having a pressure condition lower than the critical pressure of water.
- An apparatus for producing acrolein by allowing supercritical water to act on glycerin Means for measuring the hydrogen ion concentration of the raw material glycerin;
- An acid addition tank for adding an acid to the raw material glycerin comprising a means for supplying the raw material glycerin, a means for supplying an acid, and a stirring means;
- An apparatus comprising: supercritical water treatment means that is located downstream of the acid addition tank and causes supercritical water to act on glycerin supplied from the acid addition tank.
- a water addition tank for adding water to the glycerin after removing the precipitate, and a stirring means, and the glycerin added with water in the water addition tank is supplied to the supercritical water treatment means.
- An apparatus comprising: a high-temperature high-pressure water treatment unit which is located downstream of the acid addition tank and causes high-temperature high-pressure water to act on glycerin supplied from the acid addition tank.
- the glycerin is separated and removed from the glycerin supplied from the acid addition tank, which is disposed downstream of the acid addition tank and upstream of the high-temperature and high-pressure water treatment means.
- the apparatus of (17) further provided with the sediment removal means which supplies this to a high temperature / high pressure water treatment means.
- the crude acrolein obtained by the method and apparatus of the present invention has a low boiling point and is easily purified. After purification, it can be used as a raw material for acrolein derivatives such as acrylic acid, 1,3-propanediol and methionine.
- Acrylic acid can be easily obtained by air oxidation of acrolein.
- 1,3-propanediol can be obtained by hydrogenating 3-hydroxypropionaldehyde obtained by hydrating acrolein in the presence of a catalyst such as Pt and Ni.
- Methionine can be obtained by Michael addition of methyl mercaptan to acrolein to produce 3-methylmercaptopropionaldehyde, followed by reaction and hydrolysis using hydrogen cyanide, ammonia and carbon dioxide.
- the acrolein production method of the present invention comprises a monohydric alcohol and a fatty acid obtained by transesterifying a waste oil and a monohydric alcohol mainly composed of an ester of a fatty acid and glycerin in the presence of an alkali catalyst.
- the glycerin separated from the mixture containing ester and glycerin is used as a starting material.
- the glycerin contains water derived from fat and oil waste, water generated by transesterification, alkali catalyst, and other impurities, and the content thereof is not constant.
- the step until the glycerin is obtained is preferably performed simultaneously with the method of the present invention, but glycerin produced as a by-product by separately carrying out the biodiesel production step may be used as a starting material of the present invention. .
- Oils and fats are ester compounds of higher fatty acids and glycerin, and are mainly composed of triglycerides.
- Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid.
- Oils and fats are either one of vegetable oils or animal fats or a mixture of both.
- Animal fats and oils include beef oil, pork oil, whale oil, fish oil, and vegetable oils include soybean oil, rapeseed oil, sesame oil, olive oil, corn oil, coconut oil, peanut oil, and the like.
- the oil and fat waste refers to the oil and fat waste that is used and discharged for the purpose of cooking and the like in the food industry such as the food and beverage industry and the food manufacturing and processing industry, and in general households.
- fat and oil waste may generally contain impurities such as water, lipid hydroperoxides, free fatty acids, solid impurities such as deep-fried rice cakes, trace metals and proteins.
- Examples of the monohydric alcohol used in the transesterification reaction with fat and oil waste include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, with methanol being preferred.
- the alkaline catalyst is not particularly limited as long as the aqueous solution is a catalyst made of a substance exhibiting an alkaline pH value (pH> 7.0).
- a catalyst made of a substance exhibiting an alkaline pH value for example, sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide And alkali metal hydroxides or oxides such as calcium oxide, and alkaline earth metal oxides or hydroxides such as calcium oxide.
- potassium hydroxide or sodium hydroxide is preferred.
- the alkali catalyst can also be used in a form supported on a suitable carrier such as zeolite.
- one embodiment of the method of the present invention may include a transesterification step of mixing fat and oil waste, an alkali catalyst, and a monohydric alcohol, and transesterifying the fat with a monohydric alcohol.
- the mixing and transesterification steps may be performed simultaneously or alternately, but are preferably performed simultaneously.
- There are also means for mixing in piping such as line mixers and static mixers as mixing means, but since it is difficult to adjust the mixing time, the raw materials, alkali catalyst and monohydric alcohol are continuously or batch-fed into the stirring tank and stirred. It is preferable to stir by means.
- stirring means examples include one in which one or two or more stirring blades such as a circle, an oval, a triangle, a quadrangle, and a multi-leaf are installed on the rotation shaft.
- the stirring means may be uniaxial or biaxial or more, but in the present invention, uniaxial stirring means is preferred.
- a mixture containing an ester compound of monohydric alcohol and fatty acid and glycerin is formed.
- the ester compound and glycerin are separated by a glycerin separation step.
- the glycerin separation step may be performed by any method of stationary separation such as decanter and forced separation such as centrifugation, but when the amount of processing becomes large, forced separation is preferable from the viewpoint of cost.
- biodiesel (based on an ester compound) is separated into a light phase and glycerin is separated into a heavy phase.
- Biodiesel is made into biodiesel by adding purification treatment such as distillation.
- the glycerin thus separated is used as a starting material for the acrolein production method of the present invention.
- the measurement step in the present invention is a step of measuring the hydrogen ion concentration in the glycerin (containing water, alkali catalyst, and other impurities) as a starting material.
- the hydrogen ion concentration ([H + ] R ) (under normal temperature and normal pressure conditions) of the reaction mixture subjected to the supercritical reaction is preferably 0.1 to 500 mM, and particularly 5 to 5 when the glycerol concentration is 1.5 to 15 wt%.
- Non-patent document 2 describes that 18 mM is more preferable.
- the hydrogen ion concentration is higher than 500 mM, the reaction becomes too fast to control, and the amount of by-products such as tar and carbon accompanying the side reaction increases, making it difficult to design the production apparatus. If it is lower than 0.1 mM, the reactivity is conversely reduced, resulting in an increase in operating cost accompanying an increase in reaction time.
- the hydrogen ion concentration of the reaction mixture subjected to the supercritical reaction is particularly preferably 1 to 100 mM.
- the glycerin concentration ([G] R ) of the reaction mixture subjected to the supercritical reaction is preferably 15 to 30 wt%. This is because if the glycerin concentration is less than 15 wt%, energy efficiency decreases and the operating cost increases, so it is not appropriate from the viewpoint of product value. If it is higher than 30 wt%, coordinating water that acts on glycerin is secured. This is because it becomes impossible to increase the influence of the side reaction and the raw material yield decreases. Thus, there are various demands on the supercritical reaction conditions.
- the hydrogen ion concentration in the glycerin of the starting material is measured, and based on the measurement result, the amount of acid to be added in the following acid addition step to satisfy the above request, and the reaction of the supercritical reaction Guide the amount of water to be included in the mixture.
- Examples of the method for measuring the hydrogen ion concentration include a method using a pH meter that measures a pH value by a potential difference using a quinhydrone electrode, an antimony electrode, a glass electrode, a hydrogen electrode, and the like.
- a method for measuring the pH value is preferred.
- the hydrogen ion concentration may be measured by titration by a colorimetric method using an indicator.
- the indicator used for titration Congo red, methyl orange, bromcresol green, methyl red, bromcresol purple or the like is preferably used if glycerin is alkaline.
- a small amount of the raw material glycerin is sampled, diluted with water, the hydrogen ion concentration of the diluted solution is measured, and the hydrogen ion concentration of the raw material glycerin can be calculated based on the hydrogen ion concentration of the diluted solution.
- Acid addition step is a step of adding, to the raw material glycerin, an amount of acid derived from the result of the measurement step so as to make the raw material glycerin acidic.
- “acidic” refers to conditions where the pH value at normal temperature and pressure is less than 7.0.
- the level of hydrogen ions required in the acidic region is determined so that the hydrogen ion concentration in the mixture finally subjected to the supercritical reaction satisfies the conditions described in detail in “2. Measurement step” above. Can be determined as appropriate.
- the means for adding an acid to the raw material glycerin the same means as described above for the transesterification step can be adopted. It is preferable that raw material glycerin and acid are charged continuously or batchwise into the stirring tank and stirred by the stirring means.
- the added acid neutralizes the alkali catalyst and acts as a catalyst in the supercritical reaction.
- the acid either an organic acid or an inorganic acid can be selected.
- the organic acid include methanesulfonic acid, benzenesulfonic acid, and alkylsulfonic acid
- the inorganic acid include sulfuric acid, phosphoric acid, acetic acid, nitric acid, and the like, and sulfuric acid having a strong dehydrating action and catalytic action is preferable.
- a salt is formed from the alkali catalyst and the acid when the glycerin is neutralized in the acid removal step of the precipitate removal step .
- the kind of salt is decided by the combination of an alkali catalyst and an acid, typically sodium sulfate, potassium sulfate, calcium sulfate, calcium chloride, etc. are mentioned.
- the salt is precipitated in the form of a hydrate salt or an anhydride salt after the time when the glycerin in the acid addition step is neutralized or after the completion of the step and before the supercritical water treatment step. It is preferable to avoid the above risk by removing the salt by ordinary separation means such as filtration and centrifugation. By removing the precipitate, the operation efficiency of the supercritical water treatment step can be improved.
- the precipitate may be separated and removed after the glycerin is neutralized, and then the acid addition step may be completed by further adding an acid to the glycerin from which the precipitate has been removed. The precipitate may be separated and removed after completion of the acid addition step.
- the amount of water of 10 mol, 1 mol, 2 mol, and 6 mol, respectively is “the chemistry of water in which the total amount of salt can be hydrated. It corresponds to “stoichiometric amount”.
- the weight of the alkali metal or alkaline earth metal hydroxide added is 2.25 times, 0.16 times, 0.49 times, and 1.46 times the weight, respectively.
- Water is taken into the salt as crystal water.
- the amount of water contained in the raw material glycerin or the acid to be added is smaller than these amounts, the hydrate of each salt will theoretically precipitate as a solid in the glycerin / acid mixed solution.
- a separating means such as centrifugal separation, it becomes possible to remove the alkali metal or alkaline earth metal of the remaining catalyst with high efficiency.
- the amount of water in glycerin is less than the stoichiometric amount of water that the total amount of salt in the glycerin can be hydrated means that a precipitate is deposited and an anhydride salt is present in the precipitate. It can be confirmed by being included.
- the presence or absence of an anhydride salt can be determined by ordinary means such as an X-ray diffraction pattern.
- the glycerin after acid addition has the above water content by a method such as increasing the acid concentration of the aqueous solution when the acid is added in the form of an aqueous solution. It is possible.
- a water regulation step of cooling glycerin and / or removing water is performed.
- the glycerin is cooled, the crystal phase transition occurs as described above, and a hydrate is formed. Therefore, the water in the glycerin is taken in and precipitated in the hydrate salt, and the excess salt is an anhydrous salt. It will precipitate as.
- the method for removing moisture include moisture adsorption with zeolite and moisture absorbent resin, separation with a separation membrane, and distillation. After removal, the moisture concentration in glycerin can be measured with a Karl Fischer moisture meter or the like.
- the deposited salt deposits can be removed by ordinary means such as filtration and centrifugation.
- the type of filter used for filtration includes, for example, a porous structure such as ceramics and activated carbon, a mesh structure made of metal, a fiber structure made of fiber, and the like, which are appropriately selected according to the particle diameter of the precipitate.
- the supercritical water treatment step is a step of producing acrolein by allowing supercritical water to act on the glycerin that has been acid-added in the acid addition step, preferably glycerin from which the precipitate has been removed.
- supercritical water refers to water in a state where the temperature is equal to or higher than the critical temperature (Tc) of water and the pressure is equal to or higher than the critical pressure (Pc) of water.
- Tc critical temperature
- Pc critical pressure
- the mixture of glycerin and water is treated under high temperature and high pressure conditions in which the water in the mixture can be at a temperature of 374 ° C. or higher and a pressure of 22.06 MPa or higher.
- the water temperature condition (that is, the reaction temperature condition) is preferably in the range of 380 ° C. to 550 ° C., more preferably in the range of 400 to 500 ° C. When the temperature is lower than 380 ° C., there is a problem that side reactions tend to proceed.
- the water pressure condition (that is, the reaction pressure condition) is preferably in the range of 25 to 50 MPa, more preferably in the range of 30 to 45 MPa.
- the pressure condition is less than 25 MPa, there is a problem that the proton concentration in the reaction mixture decreases and the reaction does not proceed easily.
- the pressure is higher than 50MPa, there is little merit of increasing the pressure, but on the other hand, it increases the cost for securing the structural strength of filter equipment when removing by-products, etc. There is a problem that it is not suitable.
- the reaction time and acid concentration (hydrogen ion concentration) of the supercritical water treatment step have an optimum solution according to the concentration of glycerin as a raw material as described in “2. Measurement step” above.
- the optimum acid concentration is proportional to the half power of the glycerin concentration.
- the optimum reaction time is inversely proportional to the glycerin concentration. Accordingly, the reaction time is preferably from 0.1 to 100 seconds, and more preferably from 0.5 to 10 seconds.
- the types of reactors used in the supercritical water treatment step include a tube type and a tank type, but a tube type is preferable in consideration of a short reaction time.
- the glycerin mixed with the supercritical water is heated to the reaction temperature by an external heating means such as a heater or a heating medium when passing through the tube, and a dehydration reaction to acrolein occurs.
- Water addition step The water concentration in the reaction mixture at the start of the supercritical reaction is determined so as to satisfy various requirements described in “2. Measurement step” above.
- water water from the pipe 25
- supercritical water
- the amount of water added can be finely adjusted, and an industrially suitable method is provided.
- the mass flow rate of supercritical water is M sc
- the mass of water for fine adjustment including water derived from acid neutralization
- the mass of water for fine adjustment based on the pH value of the raw material glycerin measured in the measurement process that can be calculated and the flow rate M W and amount M H of the acid present inventors have found.
- FIG. 1 shows a model of a method for calculating the concentration of acid to be added to glycerin from the measured pH.
- FIG. 1 shows a model in which an acid and water are added to raw material glycerin whose pH is measured and reacted with supercritical water.
- T is the temperature of the fluid
- [H + ] is the hydrogen ion concentration
- [G] is the glycerin concentration
- ⁇ is the density
- M is the mass flow rate
- Cp is the specific heat.
- the subscripts (sc, H, w, G, R) at the lower right of the symbol represent each line.
- water used in the supercritical water treatment step is glycerin after the acid addition step, or glycerin in the precipitate removal step when the precipitate removal step is performed.
- a step of adding as water and a step of adding as water having a pressure condition equal to or higher than the critical pressure of water is usually added without using a high-pressure pump or the like, and is usually added at a pressure of 0.1 MPa to 3.0 MPa and a temperature of 5 ° C. to 40 ° C.
- Water under a pressure condition higher than the critical pressure of water is usually added under pressure by a high-pressure pump or the like, and the pressure at the time of addition is preferably 30 MPa to 45 MPa, and the temperature is 400 ° C. to 550 ° C. It is preferable.
- various conditions such as mass flow rate M sc , target acid concentration, glycerin concentration, etc. of ⁇ water with a pressure condition higher than the critical pressure of water '', based on the hydrogen ion concentration in glycerin measured in the measurement process the equation of equation 8, it is possible to determine the mass flow rate M w of "water pressure conditions below the critical pressure of water”.
- the present invention can comprise the step of cooling the acrolein produced by supercritical reaction. Since the supercritical reaction is stopped by cooling, the cooling time needs to be much shorter than the reaction time from the viewpoint of reaction control. Therefore, the cooling time is preferably 0.01 to 10 seconds, and more preferably 0.05 to 1 Seconds. Although a heat exchanger may be used as the cooling means, in view of the cooling time described above, direct contact by mixing of refrigerants is preferable, and water is more preferable for the purpose of preventing contamination due to mixing.
- the method includes a step of removing solids produced by a side reaction of a supercritical reaction from cooled acrolein.
- a sedimentation separation system such as a decanter may be used, but simple filtration with a filter is preferable because of shortening of processing time.
- the type of filter include a porous structure such as ceramics and activated carbon, a mesh structure made of metal, a fiber structure made of fiber, and the like, which are appropriately selected according to the particle diameter of the precipitate.
- the method may further include a step of purifying the filtered acrolein.
- the crude acrolein contains unreacted glycerin, acid, tar and allyl alcohol due to side reactions, etc., all of which are high-boiling components for acrolein, so separation by distillation is desirable.
- a hydration step of purified acrolein can be further included.
- acrolein containing water is passed through a column packed with a cation exchange resin.
- the reaction temperature is 30 to 150 ° C, preferably 40 to 100 ° C.
- 3-Hydroxypropanal can be obtained by hydrating acrolein.
- a hydrogenation step of 3-hydroxypropanal obtained by hydration can be further included.
- hydrogen is added to the raw material and then reacted under a catalyst.
- the reaction temperature is 40 to 200 ° C, preferably 70 to 180 ° C.
- the reaction pressure is 0.5 to 20 MPa, preferably 5 to 15 MPa.
- the catalyst in the hydrogenation step include metals such as nickel, platinum, and tungsten. Platinum is preferably used to increase the yield.
- Hydrogenation of hydroxypropanal gives 1,3-propanediol. Unreacted acrolein, unreacted hydroxypropanal and the like are purified and separated from the obtained crude 1,3-propanediol to obtain the product 1,3-propanediol.
- FIG. 2 shows an embodiment of an apparatus for carrying out the method of the present invention, but the apparatus of the present invention is not limited to this.
- the 1,3-propanediol production process shown in Fig. 2 consists of raw oil and fat mixing / BDF (biodiesel fuel) process, BDF separation process, pH measurement / acid addition process, precipitate separation process, water addition process, supercritical It consists of 10 steps: water treatment step, solid matter separation step, acrolein purification step, hydration step, and hydrogenation step.
- BDF biodiesel fuel
- pH measurement / acid addition process pH measurement / acid addition process
- precipitate separation process precipitate separation process
- water addition process supercritical It consists of 10 steps: water treatment step, solid matter separation step, acrolein purification step, hydration step, and hydrogenation step.
- the raw oil / fat mixing / BDF conversion step the raw oil / fat is supplied from the tank 1, the alkali catalyst is supplied from the tank 2, and the monohydric alcohol is supplied from the tank 3 to the BDF conversion tank 7 via the pipes 4, 5, 6.
- the piping 4, 5, 6 is provided with a transport mechanism such as a pump as necessary.
- the BDF process proceeds with mixing.
- the reactant passes through the pipe 8 and is transferred to the separation process.
- a forced separation device 9 such as a centrifugal separator is provided, and the continuously supplied crude BDF is separated into light BDF and heavy glycerin aqueous solution.
- the separated BDF passes through the pipe 10 and is purified by the purification tower 11, and a product BDF is obtained from the pipe 12.
- the separated aqueous glycerin solution is transferred to the acid addition tank 15 through the pipe 14.
- the pH of the glycerin aqueous solution is measured.
- the pH measurement can be performed by usual means. 2 and 3, the pH meter 100 is provided, but the invention is not limited to this.
- a small amount of the glycerin aqueous solution is sampled from the tank 15, diluted with water, the pH concentration of the diluted solution is measured, and the pH value of the glycerin aqueous solution in the tank 15 can be calculated based on the pH value of the diluted solution.
- the acid concentration and the amount of water added necessary for the reaction mixture to be subjected to the supercritical reaction performed in the subsequent stage to have the target hydrogen ion concentration and glycerin concentration are calculated. .
- the acid is transferred from the tank 16 to the tank 15 through the pipe 17 and mixed by the stirrer 101 provided in the tank 15. When the inside of the tank 15 reaches an appropriate pH, the transfer of the acid from the tank 16 is stopped.
- the pH-adjusted glycerin aqueous solution passes through the pipe 18 and is transferred to the filter 19.
- the filter 19 removes precipitates generated by acid addition or the like.
- the aqueous glycerin solution is transferred to the water addition tank 50 through the pipe 20.
- the tank 50 an amount of water calculated based on the pH value in the tank 15 is transferred from the tank 51 via the pipe 52 to the tank 50 and mixed by the stirrer 201 provided in the tank 50.
- the transfer of water from the tank 51 is stopped.
- the glycerin aqueous solution after water addition is supplied to the high-pressure pump 21 through the pipe 53.
- the glycerin aqueous solution is pressurized to the critical pressure of water by the pump 21 and then mixed with the water supplied from the tank 22 in the pipe 28.
- Water from the tank 22 passes through the pipe 23 and is pressurized by the high-pressure pump 24.
- a heat exchanger 26 is installed in the pipe 25 and heated to near the critical temperature of water.
- the mixed glycerin aqueous solution and water are transferred to the supercritical reactor 28.
- the reactor 28 is equipped with an electric heater and is heated to the reaction temperature.
- the supercritical water treatment means means a supercritical water generation means comprising a tank 22, a pipe 23, a high pressure pump 24, a heat exchanger 26, and a pipe 25, and a high pressure pump.
- a supercritical water generation means comprising a tank 22, a pipe 23, a high pressure pump 24, a heat exchanger 26, and a pipe 25, and a high pressure pump.
- 21 and a supercritical reactor 28 supercritical water (or high-temperature high-pressure water) is supplied from a pipe 25 of supercritical water generation means to a portion 27 of a pipe connecting the high-pressure pump 21 and the supercritical reactor 28. It is configured to merge.
- the mixture containing acrolein generated by the supercritical reaction is discharged from the pipe 32. Cooling water from the tank 22 is mixed in the pipe 32. In order to mix with the high-pressure fluid, the cooling water is pressurized by the high-pressure pump 30 and mixed by the pipe 32.
- the filter 33 Since solid matter precipitates when the mixture is cooled, the solid matter is removed by the filter 33.
- the mixture is then depressurized by a pressure reducing valve 34 and transferred to a purification tower 35 for purifying acrolein.
- high-boiling components such as glycerin and acid are removed from the tower bottom and discharged through the pipe 36, and acrolein as a low-boiling component is obtained from the tower top.
- the purified acrolein is transferred to the hydration reactor 38 through the pipe 37.
- the reactor 38 is composed of an ion exchange resin and a heating device, and has a mechanism in which a hydration reaction proceeds by passing acrolein through the reactor 38.
- Propionaldehyde generated by hydration is transferred to the hydrogenation process through the pipe 39.
- the tank 40 is filled with hydrogen and mixed with propionaldehyde in the pipe 39 through the pipe 41. Since the hydrogenation reaction is carried out under high pressure, a high-pressure pump 42 is installed in the pipe, and the pressure is increased to the reaction pressure and supplied to the hydrogenation reactor 44 through the pipe 43.
- the reactor 44 is composed of a column packed with a catalyst and a heating device. By passing through the reactor 44, 1,3-propanediol can be obtained.
- FIG. 3 Another embodiment of an apparatus for carrying out the method of the present invention is shown in FIG.
- the embodiment of FIG. 3 has the same configuration as the apparatus shown in FIG. 2 except that the water addition tank 50, the tank 51, and the pipes 52 and 53 are not included.
- the glycerin aqueous solution in the tank 15 is adjusted by adjusting the amount of water supplied from the tank 22 through the pipe 23, the high-pressure pump 24, and the pipe 25 under pressure conditions equal to or higher than the critical pressure of water.
- the amount of water necessary for the reaction mixture to be subjected to the supercritical reaction which is calculated based on the pH value, to be the target hydrogen ion concentration and glycerin concentration is realized.
- the functions and structures of the other components in the apparatus shown in FIG. 3 are the same as the functions and configurations of the components having the same reference numerals described in detail with reference to FIG.
- Example 1 Soybean oil was selected as the BDF feedstock.
- the fatty acid composition excluding the glycerin component was 8 wt% palmitic acid, 5 wt% stearic acid, 27 wt% oleic acid, 53 wt% linoleic acid, and 7 wt% linolenic acid.
- the glycerin concentration ([G] R ) of the reaction mixture at the start of the supercritical reaction is set to 15 wt% and the hydrogen ion concentration ([H + ] R ) is set to 18 mM.
- Acrolein was purified by removing high boiling components such as sulfuric acid, unreacted glycerin and tar from the solution using a batch single distillation apparatus. As a result, 1.4 L of acrolein solution was obtained.
- ⁇ Hydration> The water concentration of the acrolein solution was measured using a Karl Fischer moisture meter, and the amount of water necessary for the hydration process was calculated. After adding 5.1 L of water to the acrolein solution so that the acrolein concentration becomes 20 wt%, the acrolein aqueous solution was circulated at a flow rate of 0.35 mL / s through the column packed with the ion exchange resin, and the outlet liquid temperature was 50 ° C. It heated with the heater so that it might become. As a result, acrolein could be converted to 3-hydroxypropionaldehyde with a conversion rate of 76%.
- Example 2 ⁇ Glycerin concentration>
- the glycerin concentration ([G] R ) of the reaction mixture at the start of the supercritical reaction is set to 50 wt%
- the hydrogen ion concentration ([H + ] R ) is set to 18 mM.
- Example 1 In ⁇ pH adjustment> in Example 1, 4 g of concentrated sulfuric acid was added so that the hydrogen ion concentration was 18 mM, and in the case of ⁇ Add water>, 2.5 L of water was added so that the glycerin concentration was 50 wt%. The reaction was carried out under the same reaction conditions as in 1.
- the yield of acrolein was 10%.
- a large amount of tar and carbon particles were confirmed in the solution after the reaction.
- Example 3 ⁇ Hydrogen ion concentration>
- the glycerin concentration ([G] R ) of the reaction mixture at the start of the supercritical reaction is set to 15 wt%
- the hydrogen ion concentration ([H + ] R ) is set to 6 mM.
- Example 1 In ⁇ pH adjustment> of Example 1, 9.7 g of sulfuric acid was added after titration, and the reaction was performed under the same reaction conditions as in Example 1. The hydrogen ion concentration in the aqueous solution obtained by adding water to the mixed solution of glycerin / sulfuric acid was 6 mM, which is 1/3 of Example 1. As a result, the yield of acrolein was 40%. A comparison with Example 1 is shown in FIG.
- the method for producing acrolein from waste oil according to the present invention can reduce the raw material cost of product acrolein by using glycerin removed from biodiesel as a raw material for a high value-added product without purifying it with high purity. Therefore, industrial applicability is high.
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Abstract
Description
グリセリン中の水素イオン濃度を測定する測定工程と、
前記測定の結果から導かれる、前記グリセリンを酸性とするための量の酸を前記グリセリンに添加する酸添加工程と、
酸添加後のグリセリンに超臨界水を作用させ、グリセリンからアクロレインを製造する超臨界水処理工程と
を含むことを特徴とする、アクロレインの製造方法。
グリセリン中の水素イオン濃度を測定する測定工程と、
前記測定の結果から導かれる、前記グリセリンを酸性とするための量の酸を前記グリセリンに添加する酸添加工程と、
酸添加後のグリセリンに水を加え、得られた混合物を高温高圧条件で処理する、グリセリンからアクロレインを製造する高温高圧処理工程と
を含むことを特徴とする、アクロレインの製造方法。
原料グリセリンの水素イオン濃度を測定する手段と、
原料グリセリンを供給する手段と、酸を供給する手段と、攪拌手段とを備えた、原料グリセリンに酸を添加するための酸添加槽と、
酸添加槽の下流側に位置し、酸添加槽から供給されるグリセリンに超臨界水を作用させる超臨界水処理手段と
を備えることを特徴とする装置。
原料グリセリンの水素イオン濃度を測定する手段と、
原料グリセリンを供給する手段と、酸を供給する手段と、攪拌手段とを備えた、原料グリセリンに酸を添加するための酸添加槽と、
酸添加槽の下流側に位置し、酸添加槽から供給されるグリセリンに高温高圧水を作用させる高温高圧水処理手段と
を備えることを特徴とする装置。
100・・・pH計(水素イオン濃度測定手段)
16・・・タンク(酸)
101・・・攪拌機
19・・・フィルタ(沈殿物除去手段)
50・・・水添加槽
51・・・タンク(水)
201・・・攪拌機
28・・・超臨界反応器(高温高圧反応器)
22・・タンク(超臨界水生成用)
2000・・・アクロレイン製造装置
3000・・・アクロレイン製造装置
本発明のアクロレイン製造方法は、脂肪酸とグリセリンとのエステルを主成分とする油脂の廃棄物と一価アルコールとをアルカリ触媒存在下においてエステル交換させることで得られる、一価アルコールと脂肪酸とのエステルおよびグリセリンを含む混合物から分離されたグリセリンを出発原料とする。
本発明における測定工程は、出発原料の上記グリセリン(水、アルカリ触媒、その他の不純物を含有する)中の水素イオン濃度を測定する工程である。
酸添加工程は、上記測定工程の結果に基づき導かれた、原料グリセリンを酸性とするための量の酸を原料グリセリンに添加する工程である。本発明において「酸性」とは常温常圧におけるpH値が7.0未満の条件を指す。酸性領域のなかでもどの程度の水素イオン濃度が必要であるかは、最終的に超臨界反応に供される混合物中の水素イオン濃度が上記「2.測定工程」において詳述した条件を満たすように適宜決定することができる。原料グリセリンに酸を添加する手段は、エステル交換工程に関して上記したものと同様の手段が採用できる。攪拌槽に原料グリセリンおよび酸を連続または回分で投入し、上記撹拌手段により攪拌するのが好ましい。
酸添加工程においてグリセリンが中和された時点で、アルカリ触媒と酸とから塩が形成される。塩の種類はアルカリ触媒と酸との組み合わせにより決まるが、典型的には、硫酸ナトリウム、硫酸カリウム、硫酸カルシウム、塩化カルシウムなどが挙げられる。
超臨界水処理工程は、上記の酸添加工程により酸添加されたグリセリン、好ましくは更に沈殿物が除去されたグリセリンに超臨界水を作用させ、アクロレインを生成する工程である。
超臨界反応の開始時の反応混合物中の水分濃度は、上記「2.測定工程」に記載された種々の要請を満たすように決定される。後述する図3におけるように、酸添加工程後(好ましくは沈殿物除去工程後)のグリセリンと混合される、水の臨界条件に近い温度圧力の水(配管25からの水)(以下「超臨界水」と呼ぶ)の流量を制御することにより、反応混合物の水分濃度を制御することが可能である。しかしながら、図2に示すように、超臨界水(配管25からの水)を合流させる流路以外に、酸添加工程後(好ましくは沈殿物除去工程後)のグリセリンに水を添加する手段(図2の符号50~53)を、沈殿物除去手段の下流側であって超臨界水処理手段の上流側の位置に配置すれば、超臨界水(配管25からの水)の流量を固定したままで水添加量の微調整が可能となり、工業的に適した方法が提供される。
本発明においては、超臨界反応によって生成したアクロレインを冷却する工程を含むことができる。冷却することによって超臨界反応を停止させるので、反応制御の側面から、冷却時間は反応時間よりも遥かに短い必要があり、従って冷却時間は0.01~10秒が好ましく、またより好ましくは0.05~1秒とする。冷却手段は熱交換器を用いても良いが、前述した冷却時間との関係上、冷媒の混合による直接接触が好ましく、また混合によるコンタミネーションを防ぐ目的で、水を用いるのがより好ましい。
<BDF製造>
BDFの原料油として大豆油を選定した。グリセリン成分を除いた脂肪酸組成は、パルミチン酸8wt%、ステアリン酸5wt%、オレイン酸27wt%、リノール酸53wt%、リノレン酸7wt%であった。
グリセリン溶液にpH指示薬のメチルレッドを2滴加え、攪拌した。溶液は黄色を呈した。溶液の攪拌を続けながら、濃硫酸(濃度90wt%、以下同じ)を1滴ずつ加えていった。溶液が赤色になった時点で一旦添加を停止した。この時点でのグリセリン溶液のpH値は7である。
室温20℃の環境下、中和によって硫酸ナトリウム十水和物と無水物の混合物が無色透明のスラリー状沈殿として、グリセリン/硫酸混合溶液中に析出した。これをろ過することでナトリウムの除去を行った。分離した沈殿物の重量は130gであった。沈殿物をX線回折装置にかけ、沈殿物が硫酸ナトリウム十水和物と無水物の混合物であることを確認した。なお、溶液中の酸濃度は0.15M程度と希硫酸相当の濃度である。ろ過用フィルターは腐食等の影響のない耐酸性合金、布、または紙製のものが望ましい。
沈殿物除去後のグリセリン/硫酸の混合溶液に、グリセリン濃度が15wt%、水素イオン濃度が18mMとなるように蒸留水を14.3L添加し、グリセリン水溶液を作った。
水素イオン濃度18mMの15wt%グリセリン水溶液を高圧ポンプにより35MPaまで昇圧し、250℃にて流量を安定させた。圧力が安定したら、反応器中の液温度が瞬時に400℃になるように反応器に設置したヒーターを調整した。調整した反応器に、反応時間が2秒となるように、水溶液を流通させた。
流通させた水溶液を瞬時に200℃に冷却するために20℃の蒸留水を6mL/sの流量で配管中に加えた。
溶液中にはカーボンの沈殿物が生じた。フィルタを用いて沈殿物の除去を行った。更に冷却した後、減圧弁を通じて、常圧に戻した。この結果、収率70%でグリセリンをアクロレインに転換することができた。
回分単式蒸留装置を用いて溶液から硫酸、未反応グリセリン、タールなどの高沸成分の除去を行い、アクロレインを精製した。この結果、1.4Lのアクロレイン溶液を得た。
アクロレイン溶液の水分濃度をカールフィッシャー水分計を用いて測定し、水和工程に必要な水分量を算出した。アクロレイン濃度が20wt%となるように、アクロレイン溶液中に水を5.1L添加した後に、イオン交換樹脂を充填したカラム中にアクロレイン水溶液を0.35mL/sの流量で流通させ、出口液温度を50℃となるようにヒーターで加熱した。この結果、転換率76%でアクロレインを3-ヒドロキシプロピオンアルデヒドに転換できた。
水和によって得られた3-ヒドロキシプロピオンアルデヒド水溶液を高圧ポンプにより15MPaまで昇圧し、流量を安定させた。配管途中で水素ボンベから水素を7.5NmL/sの流量で添加し、混合物を白金とニッケルを充填したカラムに1.7mL/sの流量で流通させた。カラムにはヒーターを備え付け、出口温度が60℃となるように設定した。この結果、転換率99%で3-ヒドロキシプロピオンアルデヒドを1,3-プロパンジオール (1,3-PDO) に転換することができた。以上のことから、原料グリセリンから収率53%で1,3-PDOを合成することができた。
<グリセリン濃度>
本実験では、超臨界反応開始時の反応混合物のグリセリン濃度([G]R)を50wt%、水素イオン濃度([H+]R)を18mMとすることを目標とする。このグリセリン濃度、水素イオン濃度のとき、[H+]R 2/[G]R= 182 / 50 = 6.48 mM2/wt%となる。
<水素イオン濃度>
本実験では、超臨界反応開始時の反応混合物のグリセリン濃度([G]R)を15wt%、水素イオン濃度([H+]R)を6mMとすることを目標とする。このグリセリン濃度、水素イオン濃度のとき、[H+]R 2/[G]R= 62 / 15 = 2.4 mM2/wt%となる。
Claims (19)
- 脂肪酸とグリセリンとのエステルを主成分とする油脂の廃棄物と一価アルコールとをアルカリ触媒存在下においてエステル交換させることで得られる、一価アルコールと脂肪酸とのエステルおよびグリセリンを含む混合物から分離されたグリセリンに超臨界水を作用させてアクロレインを製造する方法であって、
グリセリン中の水素イオン濃度を測定する測定工程と、
前記測定の結果から導かれる、前記グリセリンを酸性とするための量の酸を前記グリセリンに添加する酸添加工程と、
酸添加後のグリセリンに超臨界水を作用させ、グリセリンからアクロレインを製造する超臨界水処理工程と
を含むことを特徴とする、アクロレインの製造方法。 - アルカリ触媒が、アルカリ金属またはアルカリ土類金属の酸化物または水酸化物である、請求項1の方法。
- 酸添加工程におけるグリセリンが中和された時点以降または該工程終了後であって、超臨界水処理工程よりも前に、アルカリ触媒と酸とで形成される塩の沈殿物をグリセリン中に析出させ、分離除去する沈殿物除去工程を更に含む、請求項1または2の方法。
- 沈殿物除去工程に供されるグリセリンの水分量が、該グリセリン中の前記塩の全量が水和することのできる水の化学量論量より少ないことを特徴とする、請求項3の方法。
- 沈殿物除去工程に供されるグリセリン中の水分量を請求項4に規定される量とするために、グリセリンを冷却する、および/または水分を除去する水分調節工程を更に含む、請求項4の方法。
- 超臨界水処理工程に用いられる水が、酸添加工程後のグリセリン、または沈殿物除去工程を行う場合は沈殿物除去工程のグリセリンに、水の臨界圧力未満の圧力条件の水として添加される工程と、水の臨界圧力以上の圧力条件の水として添加される工程とを含む、請求項1~5のいずれかに記載の方法。
- 脂肪酸とグリセリンとのエステルを主成分とする油脂の廃棄物と一価アルコールとをアルカリ触媒存在下においてエステル交換させることで得られる、一価アルコールと脂肪酸とのエステルおよびグリセリンを含む混合物から分離されたグリセリンに高温高圧水を作用させてアクロレインを製造する方法であって、
グリセリン中の水素イオン濃度を測定する測定工程と、
前記測定の結果から導かれる、前記グリセリンを酸性とするための量の酸を前記グリセリンに添加する酸添加工程と、
酸添加後のグリセリンに水を加え、得られた混合物を高温高圧条件で処理する、グリセリンからアクロレインを製造する高温高圧処理工程と
を含むことを特徴とする、アクロレインの製造方法。 - 高温高圧処理工程が、酸添加後のグリセリンと水との混合物を、該混合物中の水が374℃以上の温度、22.06MPa以上の圧力となる条件により処理する工程である、請求項7の方法。
- アルカリ触媒が、アルカリ金属またはアルカリ土類金属の酸化物または水酸化物であることを特徴とする、請求項7または8の方法。
- 酸添加工程におけるグリセリンが中和された時点以降または該工程終了後であって、高温高圧処理工程よりも前に、アルカリ触媒と酸とで形成される塩の沈殿物をグリセリン中に析出させ、分離除去する沈殿物除去工程を更に含む、請求項7~9のいずれかの方法。
- 沈殿物除去工程に供されるグリセリンの水分量が、該グリセリン中の前記塩の全量が水和することのできる水の化学量論量より少ないことを特徴とする、請求項10の方法。
- 沈殿物除去工程に供されるグリセリン中の水分量を請求項11に規定される量とするために、グリセリンを冷却する、および/または水分を除去する水分調節工程を更に含む、請求項11の方法。
- 高温高圧処理工程に用いられる水が、酸添加工程後のグリセリン、または沈殿物除去工程を行う場合は沈殿物除去工程のグリセリンに、水の臨界圧力未満の圧力条件の水として添加される工程と、水の臨界圧力以上の圧力条件の水として添加される工程とを含む、請求項7~12のいずれかに記載の方法。
- グリセリンに超臨界水を作用させてアクロレインを製造するための装置であって、
原料グリセリンの水素イオン濃度を測定する手段と、
原料グリセリンを供給する手段と、酸を供給する手段と、攪拌手段とを備えた、原料グリセリンに酸を添加するための酸添加槽と、
酸添加槽の下流側に位置し、酸添加槽から供給されるグリセリンに超臨界水を作用させる超臨界水処理手段と
を備えることを特徴とする装置。 - 酸添加槽の下流側であって超臨界水処理手段の上流側の位置に配置される、酸添加槽から供給されるグリセリン中の沈殿物を分離除去し、沈殿物除去後のグリセリンを超臨界水処理手段に供給する沈殿物除去手段を更に備える、請求項14の装置。
- 沈殿物除去手段の下流側であって超臨界水処理手段の上流側の位置に配置される、沈殿物除去後のグリセリンを沈殿物除去手段から供給する手段と、水を供給する手段と、攪拌手段とを備えた、沈殿物除去後のグリセリンに水を添加するための水添加槽を更に備え、水添加槽において水が添加されたグリセリンが超臨界水処理手段に供給される、請求項15の装置。
- グリセリンに高温高圧水を作用させてアクロレインを製造するための装置であって、
原料グリセリンの水素イオン濃度を測定する手段と、
原料グリセリンを供給する手段と、酸を供給する手段と、攪拌手段とを備えた、原料グリセリンに酸を添加するための酸添加槽と、
酸添加槽の下流側に位置し、酸添加槽から供給されるグリセリンに高温高圧水を作用させる高温高圧水処理手段と
を備えることを特徴とする装置。 - 酸添加槽の下流側であって高温高圧水処理手段の上流側の位置に配置される、酸添加槽から供給されるグリセリン中の沈殿物を分離除去し、沈殿物除去後のグリセリンを高温高圧水処理手段に供給する沈殿物除去手段を更に備える、請求項17の装置。
- 沈殿物除去手段の下流側であって高温高圧水処理手段の上流側の位置に配置される、沈殿物除去後のグリセリンを沈殿物除去手段から供給する手段と、水を供給する手段と、攪拌手段とを備えた、沈殿物除去後のグリセリンに水を添加するための水添加槽を更に備え、水添加槽において水が添加されたグリセリンが高温高圧水処理手段に供給される、請求項18の装置。
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JP2013159599A (ja) * | 2012-02-08 | 2013-08-19 | Hitachi Plant Technologies Ltd | アクロレインの製造方法 |
WO2020059887A1 (ja) * | 2018-09-20 | 2020-03-26 | バイオ燃料技研工業株式会社 | 重合体の製造方法 |
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JP5632787B2 (ja) * | 2011-04-05 | 2014-11-26 | 株式会社日立製作所 | 超臨界水を用いた反応プロセス |
JP5755995B2 (ja) * | 2011-10-26 | 2015-07-29 | 株式会社日立製作所 | 超臨界水を用いた反応プロセス |
US9329159B2 (en) * | 2013-03-08 | 2016-05-03 | Ecolab Usa Inc. | Methods and systems for analyzing a liquid medium |
US10870805B2 (en) * | 2018-02-12 | 2020-12-22 | Saudi Arabian Oil Company | Removal of olefins from hydrothermally upgraded heavy oil |
FR3122103A1 (fr) * | 2021-04-27 | 2022-10-28 | Ipsomedic | Cascade de réacteur Gaz - Liquide - Solide pour la réalisation de réactions chimiques en flux continu sous haute pression |
FR3134996A1 (fr) * | 2022-04-27 | 2023-11-03 | Ipsomedic | Cascade de réacteur Gaz - Liquide – Solide et Liquide-Solide pour la réalisation de réactions chimiques en flux continu sous pression ou haute pression |
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JP2009057289A (ja) * | 2007-08-29 | 2009-03-19 | Showa Denko Kk | アクロレインの製造方法およびアクリル酸の製造方法 |
JP2009132663A (ja) * | 2007-11-30 | 2009-06-18 | National Institute Of Advanced Industrial & Technology | アクロレイン類の製造法とその装置 |
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JPWO2020059887A1 (ja) * | 2018-09-20 | 2021-11-25 | バイオ燃料技研工業株式会社 | 重合体の製造方法 |
JP7417271B2 (ja) | 2018-09-20 | 2024-01-18 | バイオ燃料技研工業株式会社 | ポリ乳酸の製造方法 |
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