WO2015166706A1 - Procédé de production d'acide acétique et d'acétaldéhyde - Google Patents

Procédé de production d'acide acétique et d'acétaldéhyde Download PDF

Info

Publication number
WO2015166706A1
WO2015166706A1 PCT/JP2015/056507 JP2015056507W WO2015166706A1 WO 2015166706 A1 WO2015166706 A1 WO 2015166706A1 JP 2015056507 W JP2015056507 W JP 2015056507W WO 2015166706 A1 WO2015166706 A1 WO 2015166706A1
Authority
WO
WIPO (PCT)
Prior art keywords
acetic acid
acetaldehyde
ethyl acetate
producing
liquid
Prior art date
Application number
PCT/JP2015/056507
Other languages
English (en)
Japanese (ja)
Inventor
河辺正人
三浦裕幸
Original Assignee
株式会社ダイセル
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ダイセル filed Critical 株式会社ダイセル
Priority to JP2016515884A priority Critical patent/JP6723151B2/ja
Publication of WO2015166706A1 publication Critical patent/WO2015166706A1/fr

Links

Images

Classifications

    • 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
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/06—Acetaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/08—Acetic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds

Definitions

  • the present invention relates to a method for producing acetic acid and acetaldehyde from methanol.
  • This application claims the priority of Japanese Patent Application No. 2014-092590 for which it applied to Japan on April 28, 2014, and uses the content here.
  • Acetic acid and acetaldehyde are industrially important intermediates.
  • Acetic acid is used as a raw material for acetates such as vinyl acetate, acetic anhydride, and ethyl acetate, and as a solvent for producing terephthalic acid and the like.
  • Acetaldehyde is used in large quantities as a raw material for ethyl acetate, peracetic acid, pyridine derivatives, pentaerythritol, crotonaldehyde, paraaldehyde, and the like.
  • Acetic acid is produced by oxidation of acetaldehyde, oxidation of alkane, oxidation of ethylene, etc., but for economic reasons, a method of carbonylating methanol with carbon monoxide has become the mainstream at present.
  • Acetaldehyde is mainly produced by Wacker oxidation of ethylene.
  • acetic acid can be produced at a lower cost than methanol and carbon monoxide, and due to the rise in ethylene prices, the production of acetaldehyde by hydrogenation of acetic acid is becoming an option, realizing this process. What can be done depends on how the economy can be improved.
  • Patent Document 1 As a method for producing acetaldehyde by hydrogenation of acetic acid, a method for producing acetaldehyde by hydrogenating acetic acid in the presence of conical hydrogen on an iron oxide catalyst containing 2.5 to 90% by weight of palladium is disclosed. (Patent Document 1). Also disclosed is a method for producing acetaldehyde by reacting acetic acid and hydrogen on a hydrogenation catalyst supported on a catalyst carrier (Patent Document 2).
  • acetic acid is produced by carbonylation of methanol with carbon monoxide separated from synthesis gas as shown in FIG.
  • Syngas is produced by steam reforming or partial oxidation of hydrocarbons such as methane, natural gas, and petroleum, and gasification of coal with steam. Therefore, only carbon monoxide is necessary for the production of acetic acid among the synthesis gas, and hydrogen is to be disposed of by combustion or used for other purposes.
  • acetaldehyde has been studied to be produced by hydrogenating acetic acid with hydrogen separated from synthesis gas.
  • synthesis gas only hydrogen is required for the production of acetaldehyde, and carbon monoxide is either combusted or used for other purposes.
  • the present inventors have found a new method for producing acetic acid and aldehyde that can efficiently use raw materials such as hydrogen and carbon monoxide by integrating the production process of acetic acid and the production process of acetaldehyde.
  • the present invention has been completed.
  • the present invention is a method for producing acetic acid and acetaldehyde from methanol and synthesis gas, step 1 for producing synthesis gas, removing impurities such as carbon dioxide from synthesis gas, and separating them into carbon monoxide and hydrogen. Characterized in that it comprises step 2, step 3 for producing acetic acid from the carbon monoxide obtained in step 2 and methanol, step 4 for producing acetaldehyde from hydrogen obtained in step 2 and acetic acid obtained in step 3.
  • a method for producing acetic acid and acetaldehyde is provided.
  • the present invention also provides the above-mentioned method for producing acetic acid and acetaldehyde, which comprises step 5 of producing ethyl acetate from acetic acid produced in step 3 and ethanol produced as a by-product in step 4.
  • a method for producing acetic acid and acetaldehyde from methanol and synthesis gas which comprises the following steps 1 to 4.
  • Process 1 Process for producing synthesis gas
  • Process 2 Process for removing impurities such as carbon dioxide from the synthesis gas obtained in Process 1 and separating into carbon monoxide and hydrogen
  • Process 3 Process of monoxide obtained in Process 2 Step 4 for producing acetic acid from carbon and methanol
  • Step 4 Step for producing acetaldehyde from hydrogen obtained in Step 2 and acetic acid obtained in Step 3
  • Process 5 Process for producing ethyl acetate from acetic acid produced in process 3 and ethanol by-produced in process 4
  • acetaldehyde when acetaldehyde is produced by hydrogenating acetic acid, acetaldehyde can be produced at low cost because hydrogen and carbon monoxide in the synthesis gas are efficiently used without waste.
  • acetic acid and acetaldehyde can be produced industrially efficiently and at low cost from synthesis gas and methanol.
  • FIG. 5 is a schematic flow diagram showing an example of a method for producing acetaldehyde and ethyl acetate of the present invention [Purification system and reaction system-2 (reaction of ethanol and acetic acid); continuation of FIG. 4].
  • FIG. 6 is a schematic flow diagram [Purification system and reaction system-2 (reaction of ethanol and acetic acid); continuation of FIG. 4] showing another example of the method for producing acetaldehyde and ethyl acetate of the present invention.
  • the method for producing acetic acid and acetaldehyde according to the present invention is a method for producing acetic acid and acetaldehyde from methanol and synthesis gas.
  • step 2 for separating acetic acid and hydrogen step 3 for producing acetic acid from carbon monoxide and methanol obtained in step 2
  • step 4 for producing acetaldehyde from hydrogen obtained in step 2 and acetic acid obtained in step 3 It is characterized by including.
  • the method for producing acetic acid and acetaldehyde of the present invention is characterized by comprising Step 5 of producing ethyl acetate from acetic acid produced in Step 3 and ethanol by-produced in Step 4.
  • Step 5 is an optional step provided as necessary.
  • FIG. 3 shows an integrated process of acetic acid and acetaldehyde.
  • ethanol is also produced as a by-product
  • FIG. 3 a process for producing ethyl acetate by esterifying this ethanol with acetic acid is also added.
  • the integrated process is a process for producing acetic acid and acetaldehyde from methanol and synthesis gas.
  • the production of the synthesis gas as step 1 is not particularly limited, but is performed by a known and conventional method such as steam reforming or partial oxidation of hydrocarbons such as methane, natural gas, and petroleum, and gasification of coal with steam. Thereby, a synthesis gas containing carbon monoxide and hydrogen gas used in the production of acetic acid and acetaldehyde is obtained.
  • step 2 impurities such as carbon dioxide are removed from the synthesis gas obtained in step 1 and separated into carbon monoxide and hydrogen gas, respectively.
  • the separation is not particularly limited, but is performed by a known and common method such as a cryogenic separation method, a pressure swing adsorption method, or a membrane separation method.
  • the separated carbon monoxide is used in the next step 3, and hydrogen gas is used in the production of acetaldehyde in step 4.
  • step 3 acetic acid is produced by the carbonylation reaction of carbon monoxide obtained in step 2 and methanol. Production of acetic acid is carried out by a known and commonly used method such as Monsanto method or Katiba method. Part or all of the acetic acid obtained in step 3 is supplied to step 4. The remaining acetic acid other than that supplied to step 4 can be distributed to the market as a product.
  • Step 4 acetaldehyde is produced by performing a hydrogenation reaction of acetic acid from the hydrogen obtained in Step 2 and the acetic acid obtained in Step 3. In this hydrogenation reaction, ethanol is obtained as a by-product and used as a raw material for the next step 5, which is an optional step.
  • the hydrogenation reaction of acetic acid can be performed using, for example, a known catalyst.
  • the produced acetaldehyde can be purified and separated by distillation through, for example, absorption and release processes. In the distillation, acetaldehyde is allowed to flow out from the top of the column, and unreacted acetic acid, by-product water, ethanol, and the like are recovered from the bottom of the column. Unreacted acetic acid can be recycled to the reaction system.
  • By-produced ethanol can be converted into ethyl acetate by reacting with acetic acid, for example. This ethyl acetate can be used as an azeotropic solvent for separating acetic acid and water from a mixture of unreacted acetic acid and water.
  • reaction system-1 reaction between acetic acid and hydrogen
  • FIG. 4 A reaction system for producing acetaldehyde by the hydrogenation reaction of acetic acid is shown in FIG.
  • hydrogen gas is supplied from P (hydrogen storage equipment obtained in step 2) through line 1, pressurized by compressor I-1, and then passed through buffer tank J-1 to the circulating gas in line 2.
  • evaporator A acetic acid evaporator
  • the evaporator A is supplied with acetic acid from the line 4 using the pump N-1 from K-1 (the acetic acid storage tank obtained in step 3), and the evaporated acetic acid together with hydrogen gas is a heat exchanger (heater).
  • reactor B Heated at L-1 and L-2 and charged into reactor B filled with catalyst from line 5.
  • the evaporator A is provided with a circulation pump N-2.
  • acetic acid is hydrogenated to produce ethanol, non-condensable methane, ethane, ethylene, carbon dioxide, condensable acetone, ethyl acetate, diethyl acetal and the like in addition to aldehydes as main products.
  • the catalyst used in the hydrogenation reaction of acetic acid is not particularly limited as long as it produces acetaldehyde by hydrogenating acetic acid.
  • metal oxides such as iron oxide, germanium oxide, tin oxide, vanadium oxide, and zinc oxide Etc. can be used.
  • noble metals such as palladium and platinum
  • the amount of the precious metal added is, for example, about 0.5 to 90% by weight with respect to the whole catalyst.
  • a preferable catalyst is iron oxide to which a noble metal such as palladium or platinum is added.
  • the catalyst Before the catalyst is used for hydrogenation of acetic acid, the catalyst may be subjected to a reduction treatment by, for example, contacting with hydrogen in advance.
  • the reduction treatment is performed under conditions of, for example, 50 to 500 ° C. and 0.1 to 5 MPa.
  • the reaction temperature of hydrogenation is not particularly limited, but is preferably 200 to 350 ° C, more preferably 260 to 330 ° C.
  • by-products such as alcohols, ketones and hydrocarbons can be suppressed while maintaining the reaction rate at a certain level or higher.
  • the bottoms of the absorption tower C is divided into a line 14 supplied to the purification process and a line 8 charged into the stripping tower D.
  • the bottoms of the line 14 are stored as a reaction crude liquid in the reaction crude liquid tank K-2 and used for a purification process.
  • the line 8 is depressurized by the diffusion tower D, and hydrogen, methane, ethane, ethylene and carbon dioxide, which are non-condensable gases dissolved in the absorption liquid, are diffused from the line 10, and the liquid after the non-condensable gas is diffused is from the line 9.
  • Q-2 is a vent.
  • the entire amount of the effluent of the absorption tower C can be charged into the diffusion tower D, a part of the liquid after the non-condensable gas emission can be recycled to the absorption tower, and the remainder can be used as a crude reaction liquid used for the purification process. Good.
  • the pressure of the bottoms of the absorption tower is reduced to dissipate the non-condensable gas dissolved in the absorption liquid.
  • Gas can be separated efficiently. This is due to the difference in solubility between hydrogen and other non-condensable gases. For example, at 30 ° C., the solubility of hydrogen and methane in ethyl acetate when the partial pressure is 1 atm is 0.01 NL / L and 0.48 NL / L, respectively. Is 48 times easier to dissolve than hydrogen.
  • the liquid after the non-condensable gas is diffused is recycled to the absorption tower, so that the non-condensable gas other than hydrogen gas is efficiently absorbed and dissolved, and as a result, the purge loss of hydrogen gas is greatly reduced. it can.
  • the non-condensable gas that has not been absorbed and dissolved in the absorption liquid in the absorption tower C is pressurized by the compressor I-2 through the buffer tank J-3 from the top of the absorption tower C through the line 12, and is then supplied to the buffer tank J-2. Then, the hydrogen gas in the line 1 is merged by the line 2 and supplied to the evaporator A from the line 3. The non-condensable gas is purged from the line 13 as necessary.
  • Q-1 is a vent.
  • This distillate upper phase liquid contains a large amount of ethyl acetate.
  • the distillate lower phase liquid of the acetic acid recovery tower F contains a large amount of water and forms an aqueous phase.
  • the absorption liquid charged into the absorption tower C may be only the bottom liquid (circulating liquid) of the absorption tower C, but the bottom liquid of the absorption tower C contains a lot of acetaldehyde having a low boiling point of 21 ° C.
  • an absorption liquid not containing acetaldehyde is preferable.
  • an ethyl acetate-containing liquid distilled liquid from the acetic acid recovery tower F is used as a decanter for separation of unreacted acetic acid and by-product water by azeotropic distillation as in the above example.
  • an acetic acid aqueous solution (a mixed liquid containing acetic acid and water; for example, an acetaldehyde product described later) such as a liquid after separation of acetaldehyde from the bottoms of the absorption tower C
  • a liquid containing 10% by weight or more preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 75% by weight or more
  • ethyl acetate is preferable.
  • the acetic acid content in the aqueous acetic acid solution is, for example, 10 to 95% by weight, preferably 50 to 90% by weight, and more preferably 60 to 80% by weight.
  • methane which is the main component of the non-condensable gas, dissolves better in ethyl acetate having a lower polarity than a highly polar acetic acid aqueous solution, ethyl acetate is suitable as an absorbing solution.
  • the number of plates (theoretical plate number) of the absorption tower C is, for example, 1 to 20, preferably 3 to 10.
  • the temperature in the absorption tower C is, for example, 0 to 70 ° C.
  • the pressure in the absorption tower C is, for example, 0.1 to 5 MPa (absolute pressure).
  • the temperature in the diffusion tower D is, for example, 0 to 70 ° C.
  • the pressure in the stripping tower D may be lower than the pressure in the absorption tower C, for example, 0.05 to 4.9 MPa (absolute pressure).
  • the difference between the pressure in the absorption tower C and the pressure in the diffusion tower D (the former-the latter) can be appropriately selected from the viewpoint of the emission efficiency of the non-condensable gas and the suppression of the loss of acetaldehyde, and is, for example, 0.05 to 4.9 MPa.
  • the pressure is preferably 0.5 to 2 MPa.
  • the reaction crude liquid obtained in the reaction system is supplied to a purification step (purification system), and acetaldehyde is obtained as a product. Further, unreacted acetic acid and by-product components can be collected and recycled to the reactor as necessary.
  • the purification system includes a step of separating acetaldehyde from the reaction crude liquid obtained by hydrogenating acetic acid in the first distillation column (hereinafter sometimes referred to as “acetaldehyde purification step”), a liquid after separation of acetaldehyde. It is preferable to include a step of separating unreacted acetic acid in the second distillation column (hereinafter sometimes referred to as “acetic acid recovery step”).
  • the reaction crude liquid is charged into a first distillation column (acetaldehyde product column), and acetaldehyde is separated and recovered from the top of the column. From the bottom of the column, an acetic acid aqueous solution containing unreacted acetic acid and by-produced water (usually further containing other products such as ethanol and ethyl acetate) is discharged.
  • a first distillation column acetaldehyde product column
  • the number of plates (theoretical plate number) of the acetaldehyde product column is, for example, 10 to 50, preferably 20 to 40. Distillation may be performed under normal pressure, reduced pressure, or increased pressure.
  • the bottom liquid (bottom liquid) in the acetaldehyde product tower is charged into the second distillation tower (acetic acid recovery tower), and a liquid containing ethyl acetate is introduced from the top of the tower.
  • the column top distillate is introduced into a decanter (in this case, ethyl acetate may be replenished) and separated into an upper phase (ethyl acetate phase) and a lower phase (aqueous phase).
  • a part of the distillate upper phase liquid is refluxed into the distillation tower, but as described above, a part of the upper liquid may be used as the absorbing liquid in the absorption tower.
  • the remainder of the distillate upper phase liquid and the distillate lower phase liquid are supplied to, for example, a delow boiling tower described later.
  • Acetic acid is recovered from the bottom of the acetic acid recovery tower. This acetic acid can be recycled to the reaction system.
  • the number of plates (theoretical plate number) of the acetic acid recovery tower is, for example, 10 to 50, preferably 10 to 30. Distillation may be performed under normal pressure, reduced pressure, or increased pressure.
  • the liquid after separation of acetaldehyde and unreacted acetic acid from the reaction crude liquid contains (a) low-boiling components having a lower boiling point than ethyl acetate such as acetone, (b) ethanol and ethyl acetate, and (c) water. ing.
  • a method for separating these components for example, there are the following two methods.
  • a low-boiling component having a boiling point lower than that of ethyl acetate is separated (a) in the third distillation column from the unreacted acetic acid-separated liquid, and then the low-boiling component is removed.
  • B) A mixture of ethanol and ethyl acetate and (c) water are separated from the liquid after the boiling point component separation in the fourth distillation column (ethanol / ethyl acetate recovery step).
  • the de-low boiling step a part (if necessary) of the distillate upper phase liquid of the acetic acid recovery tower and the distillate lower phase liquid are charged into the third distillation column (delow boiling tower), The boiling component is recovered, and a liquid containing ethanol, ethyl acetate, and water is discharged from the bottom of the tower.
  • the column bottom liquid is supplied to a fourth distillation column (ethanol / ethyl acetate recovery column) described later.
  • the number of plates (theoretical plate number) of the third distillation column (delow boiling column) is, for example, 10 to 50, preferably 20 to 40. Distillation may be performed under normal pressure, reduced pressure, or increased pressure.
  • the bottom liquid of the third distillation tower (delow boiling tower) is charged into the fourth distillation tower (ethanol / ethyl acetate recovery tower), and ethanol and ethyl acetate are mixed from the top of the tower.
  • the liquid is recovered and water is discharged from the bottom of the tower.
  • the number of plates (theoretical plate number) of the fourth distillation column is, for example, 5 to 50, preferably 10 to 20. Distillation may be performed under normal pressure, reduced pressure, or increased pressure.
  • a part (if necessary) of the distillate upper phase liquid of the second distillation column (acetic acid recovery column) and the distillate lower phase solution are charged into a third distillation column (water separation column), A low-boiling component having a boiling point lower than that of ethyl acetate, ethanol and ethyl acetate are distilled from the top of the column, and water is discharged from the bottom of the column.
  • the column top liquid is supplied to a fourth distillation column (low boiling point component recovery column) described later.
  • the number of plates (theoretical plate number) of the third distillation column (water separation column) is, for example, 5 to 50, preferably 10 to 20. Distillation may be performed under normal pressure, reduced pressure, or increased pressure.
  • the top liquid of the third distillation column (water separation column) is charged into the fourth distillation column (low boiling point component recovery column), and the boiling point is higher than ethyl acetate such as acetone from the top of the column.
  • Low low boiling point components are recovered, and a mixture of ethanol and ethyl acetate is recovered from the bottom of the column.
  • the number of plates (theoretical plate number) of the fourth distillation column (low boiling point component recovery column) is, for example, 10 to 50, preferably 20 to 40. Distillation may be performed under normal pressure, reduced pressure, or increased pressure.
  • Step 5 ethyl acetate is produced from the acetic acid produced in step 3 and the ethanol produced as a by-product in step 4.
  • Step 5 an example of the reaction system in Step 5 which is an optional step will be described in detail.
  • reaction system-2 reaction of ethanol and acetic acid
  • ethanol and ethyl acetate azeotrope in order to separate ethanol and ethyl acetate from a by-product mixture of ethanol and ethyl acetate, a complicated process is required, and ethanol obtained as a valuable resource is obtained. And the cost of ethyl acetate increases.
  • acetic acid is added to a part or all of a mixed solution of ethanol and ethyl acetate after separation of acetaldehyde, unreacted acetic acid and water from the reaction crude liquid by distillation, and the presence of an acidic catalyst.
  • the ethanol is preferably converted to ethyl acetate.
  • Examples of the mixed solution of ethanol and ethyl acetate include a mixed solution of ethanol and ethyl acetate obtained from the top of the fourth distillation column in the first method, and the bottom of the fourth distillation column in the second method. And a mixed solution of ethanol and ethyl acetate containing a low-boiling component obtained from the top of the third distillation column.
  • the acidic catalyst may be a homogeneous catalyst or a solid catalyst as long as it is an acidic catalyst capable of esterifying ethanol and acetic acid.
  • a mineral acid such as sulfuric acid or phosphoric acid, or an organic acid such as p-toluenesulfonic acid or methanesulfonic acid is selected.
  • an ion exchange resin or zeolite is selected.
  • the reactor may be a complete mixing tank, a plug flow, or a combination of these. Furthermore, in order to further promote the reaction, part or all of the product water and ethyl acetate may be separated on the way. Further, the reactor may be a fixed bed filled with a solid catalyst, or the catalyst may be present in the distillation column, and the esterification reaction and the product may be separated at the same time. When the esterification reaction solution contains an acidic catalyst, the acidic catalyst can be separated by a conventional method.
  • the reaction temperature in the esterification reaction is, for example, 30 to 150 ° C., preferably 40 to 100 ° C.
  • the reaction may be carried out under any conditions of reduced pressure, normal pressure and increased pressure.
  • the product ethyl acetate can be obtained by recovering and recycling the unreacted raw material by using a normal separation and purification method of the ethyl acetate reaction solution.
  • FIG. 5 is a schematic flow diagram illustrating a purification system (including the reaction system-2) including the first method
  • FIG. 6 illustrates a purification system (including the reaction system-2) including the second method.
  • the reaction crude liquid is charged from the reaction crude liquid tank K-2 to the first distillation column (acetaldehyde product column) E through the line 16 using the pump N-4.
  • the first distillation column (acetaldehyde product column) E the non-condensable gas is purged from the line 17 from the top of the column, and the product acetaldehyde is distilled from the line 18.
  • the bottoms of the first distillation column (acetaldehyde product column) E is supplied to the second distillation column (acetic acid recovery column) F through the line 19.
  • M-5 and M-6 are coolers
  • R-1 is a receiver
  • N-5 and N-6 are pumps
  • Q-3 is a vent
  • O-1 is a reboiler
  • K-3 is a product acetaldehyde tank.
  • acetic acid recovery column F an ethyl acetate-containing liquid is charged to the top of the column from the line 23, and unreacted acetic acid is recovered from the bottoms of the line 24, and the recovered acetic acid tank K-4 is recovered. Stored and recycled to the reaction system. Acetone, ethanol, ethyl acetate, and water are distilled off at the top of the second distillation column (acetic acid recovery column) F, separated by a decanter S, and a part of the upper phase liquid of the line 20 (if necessary). The lower phase water of the line 21 is charged into the third distillation column (delow boiling column) G.
  • the decanter S is supplied with the ethyl acetate in the ethyl acetate tank K-5 from the line 25.
  • a part of the upper phase liquid of the decanter S is stored in the absorption liquid tank K-6 from the line 22, and is also charged into the absorption tower C from the line 15 and the line 11 as described above to absorb acetaldehyde.
  • a part of the upper phase liquid of the decanter S is refluxed into the distillation column by the line 23.
  • M-7 is a cooler
  • N-7, N-8, N-9, N-10, N-11 are pumps
  • O-2 is a reboiler.
  • Low boiling components such as acetone are distilled from the top of the third distillation column (delow boiling column) G from the line 26, and the bottoms of the line 28 are charged into the fourth distillation column (ethanol / ethyl acetate recovery column) H. It is. A part of the column top distillate is refluxed into the distillation column via line 27.
  • M-8 is a cooler
  • R-2 is a receiver
  • N-12 and N-13 are pumps
  • O-3 is a reboiler
  • K-7 is a low boiling point component tank.
  • a mixed liquid of ethanol and ethyl acetate is recovered from the line 29, and the bottom liquid (water) is drained from the line 31.
  • a part of the column top distillate is refluxed into the distillation column via line 30.
  • M-9 and M-10 are coolers
  • R-3 is a receiver
  • N-14 and N-15 are pumps
  • O-4 is a reboiler
  • K-8 is a recovered ethanol / ethyl acetate tank.
  • Part or all of the ethanol / ethyl acetate mixture in the line 35 is added with acetic acid from the line 36, heated to the esterification reaction temperature by the heater O-5, and the esterification reactor in which an acidic catalyst is present from the line 37.
  • the reaction crude liquid is charged from the reaction crude liquid tank K-2 to the first distillation column (acetaldehyde product column) E through the line 16 using the pump N-4.
  • the first distillation column (acetaldehyde product column) E the non-condensable gas is purged from the line 17 from the top of the column, and the product acetaldehyde is distilled from the line 18.
  • the bottoms of the first distillation column (acetaldehyde product column) E is supplied to the second distillation column (acetic acid recovery column) F through the line 19.
  • M-5 and M-6 are coolers
  • R-1 is a receiver
  • N-5 and N-6 are pumps
  • Q-3 is a vent
  • O-1 is a reboiler
  • K-3 is a product acetaldehyde tank.
  • acetic acid recovery column F an ethyl acetate-containing liquid is charged to the top of the column from the line 23, and unreacted acetic acid is recovered from the bottoms of the line 24, and the recovered acetic acid tank K-4 is recovered. Stored and recycled to the reaction system. Acetone, ethanol, ethyl acetate, and water are distilled off at the top of the second distillation column (acetic acid recovery column) F, separated by a decanter S, and a part of the upper phase liquid of the line 20 (if necessary). The lower phase water of the line 21 is charged into a third distillation column (in this case, functioning as a water separation column) G.
  • a third distillation column in this case, functioning as a water separation column
  • the decanter S is supplied with the ethyl acetate in the ethyl acetate tank K-5 from the line 25.
  • a part of the upper phase liquid of the decanter S is stored in the absorption liquid tank K-6 from the line 22, and is also charged into the absorption tower C from the line 15 and the line 11 as described above to absorb acetaldehyde.
  • a part of the upper phase liquid of the decanter S is refluxed into the distillation column by the line 23.
  • M-7 is a cooler
  • N-7, N-8, N-9, N-10, N-11 are pumps
  • O-2 is a reboiler.
  • a low boiling point component such as acetone is recovered from the line 29 from the top of the fourth distillation column (low boiling point recovery column) H, and a mixed solution of ethanol and ethyl acetate is recovered from the line 28 from the line bottom.
  • a part of the column top distillate is refluxed into the distillation column via line 30.
  • M-9 is a cooler
  • R-3 is a receiver
  • N-12 and N-15 are pumps
  • O-4 is a reboiler
  • K-7 is a low boiling point component tank
  • K-8 is a recovered ethanol / ethyl acetate tank. is there.
  • acetic acid and acetaldehyde which are industrially important intermediates from the synthesis gas and methanol, are industrially efficient and low cost. Can be manufactured.
  • a Evaporator B Reactor C Absorption tower C-1 Scrubber D Stripping tower E First distillation tower (acetaldehyde product tower) F Second distillation column (acetic acid recovery column) G Third distillation column H Fourth distillation column I-1 to I-2 Compressor J-1 to J-3 Buffer tank K-1 Acetic acid tank (Acetic acid storage tank obtained in step 3) K-2 Reaction crude liquid tank K-3 Acetaldehyde product tank K-4 Recovery acetic acid tank K-5 Ethyl acetate tank K-6 Absorption liquid tank K-7 Low boiling point tank K-8 Recovery ethanol / ethyl acetate tank K-9 Absorption liquid tank L-1 to L-2 Heater M-1 to M-12 Cooler (cooler) N-1 to N-18 pump (liquid feed pump) O-1 to O-4 Reboiler O-5 Heater P Hydrogen equipment (Hydrogen storage equipment obtained in Step 2) Q-1 to Q-3 Vent R-1 to R-3 Receiver (tank) S Decanter T Drainage equipment U Gas-liquid separator V Esterification

Abstract

La présente invention aborde le problème concernant la fourniture d'un procédé de production d'acétaldéhyde par hydrogénation d'acide acétique, de façon qu'il soit de ce fait possible d'utiliser efficacement une matière première sans gaspiller la matière première, et de produire de l'acétaldéhyde à un faible coût. La présente invention aborde aussi le problème concernant la fourniture d'un procédé pour la production d'acide acétique et d'acétaldéhyde à partir de méthanol à l'échelle industrielle, avec un rendement élevé et à faible coût. Le procédé de production d'acide acétique et d'acétaldéhyde selon la présente invention est un procédé de production d'acide acétique et d'acétaldéhyde à partir de méthanol et d'un gaz de synthèse, ledit procédé étant caractérisé en ce qu'il comprend une étape (1) de production du gaz de synthèse, une étape (2) d'élimination des impuretés, y compris le dioxyde de carbone, à partir du gaz de synthèse, et de séparation du gaz de synthèse en monoxyde de carbone et hydrogène, une étape (3) de production d'acide acétique à partir du monoxyde de carbone produit dans l'étape (2) et du méthanol, et une étape (4) de production d'acétaldéhyde à partir de l'hydrogène produit dans l'étape (2) et de l'acide acétique produit dans l'étape (3).
PCT/JP2015/056507 2014-04-28 2015-03-05 Procédé de production d'acide acétique et d'acétaldéhyde WO2015166706A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016515884A JP6723151B2 (ja) 2014-04-28 2015-03-05 酢酸とアセトアルデヒドと酢酸エチルの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014092590 2014-04-28
JP2014-092590 2014-04-28

Publications (1)

Publication Number Publication Date
WO2015166706A1 true WO2015166706A1 (fr) 2015-11-05

Family

ID=54358447

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/056507 WO2015166706A1 (fr) 2014-04-28 2015-03-05 Procédé de production d'acide acétique et d'acétaldéhyde

Country Status (2)

Country Link
JP (1) JP6723151B2 (fr)
WO (1) WO2015166706A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010071016A1 (fr) * 2008-12-19 2010-06-24 ダイセル化学工業株式会社 Procédé de fabrication d'acide acétique et d'ammoniac
JP2010241765A (ja) * 2009-04-09 2010-10-28 Daicel Chem Ind Ltd カルボン酸エステルの製造方法
JP2011529494A (ja) * 2008-07-31 2011-12-08 セラニーズ・インターナショナル・コーポレーション 担持金属触媒を用いる酢酸からのアセトアルデヒドの直接及び選択的な製造

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6121498A (en) * 1998-04-30 2000-09-19 Eastman Chemical Company Method for producing acetaldehyde from acetic acid
CN102421734B (zh) * 2010-02-02 2015-11-25 国际人造丝公司 生产变性乙醇的方法
US9150474B2 (en) * 2010-07-09 2015-10-06 Celanese International Corporation Reduction of acid within column through esterification during the production of alcohols

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011529494A (ja) * 2008-07-31 2011-12-08 セラニーズ・インターナショナル・コーポレーション 担持金属触媒を用いる酢酸からのアセトアルデヒドの直接及び選択的な製造
WO2010071016A1 (fr) * 2008-12-19 2010-06-24 ダイセル化学工業株式会社 Procédé de fabrication d'acide acétique et d'ammoniac
JP2010241765A (ja) * 2009-04-09 2010-10-28 Daicel Chem Ind Ltd カルボン酸エステルの製造方法

Also Published As

Publication number Publication date
JPWO2015166706A1 (ja) 2017-04-20
JP6723151B2 (ja) 2020-07-15

Similar Documents

Publication Publication Date Title
US20110224462A1 (en) Hydrogenation of ethanoic acid to produce ethanol
EA017325B1 (ru) Способ получения спирта из углеродсодержащего сырья
ES2624629T3 (es) Procedimiento para recuperar compuestos reductores de permanganato de un procedimiento de producción de ácido acético
JP6700327B2 (ja) アセトアルデヒドの製造方法
KR20130115274A (ko) 아세트산의 제조 방법
JP2011516552A (ja) ジクロロヒドリン類の効率的回収のための方法及び装置
JP2007529517A (ja) 他のプロセスプラントにおける酢酸反応熱の利用
JP2010523703A (ja) ジクロロヒドリンの共沸回収方法及び装置
KR102355059B1 (ko) 아세트산 제조 유닛에서 오프가스를 처리하기 위한 방법 및 장치
JP2010523704A (ja) ポリヒドロキシ脂肪族炭化水素化合物の塩化水素処理中の蒸気相精製の方法および装置
CN104661991A (zh) 在羰基化工艺中改进催化剂稳定性
BR112021011508A2 (pt) Processo de produção de butadieno a partir de etanol com regeneração in situ do catalisador da segunda etapa reacional
JP6502951B2 (ja) アセトアルデヒドの製造方法
US8637698B2 (en) Production of acetic acid with an increased production rate
US20170137395A1 (en) Process for the production of furan and its derivatives
WO2015166706A1 (fr) Procédé de production d'acide acétique et d'acétaldéhyde
JP6405367B2 (ja) アセトアルデヒドの製造方法
CS198231B2 (en) Method of the partial separation of water from gas mixture arising in vinyl acetate preparation
JP2011506419A (ja) １，２−プロパンジオールの製造方法
US10508062B2 (en) Conversion of butanediol into butadiene, with scrubbing using diesters
KR102039403B1 (ko) 고순도 테레프탈산 제조 시 반응기에서 배출되는 부산물로부터 초산을 분리하는 방법 및 장치
US20210363091A1 (en) Electric heating of boiler feedwater in the manufacture of purified aromatic carboxylic acids
WO2018069441A1 (fr) Procede de production de 1,3-butadiene et purification
JP2021151976A (ja) 酢酸の製造方法および酢酸製造装置
JP2023542375A (ja) 多管式反応器におけるエタノールの脱水素方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15785513

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016515884

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15785513

Country of ref document: EP

Kind code of ref document: A1