WO2013150840A1 - 亜硝酸エステルの製造方法、並びにシュウ酸ジアルキル及び炭酸ジアルキルの製造方法 - Google Patents
亜硝酸エステルの製造方法、並びにシュウ酸ジアルキル及び炭酸ジアルキルの製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- the present invention relates to a method for producing nitrite by reacting nitric oxide, oxygen and alcohol, and a method for producing dialkyl oxalate and dialkyl carbonate.
- nitrite As a method of producing nitrite by reacting nitrogen monoxide, oxygen and alcohol, alcohol is supplied to the upper part of the reaction tower and allowed to flow from the upper part to the lower part of the reaction tower.
- a method is known in which nitrogen monoxide, oxygen, and alcohol are reacted to produce nitrite ester while supplying the mixed gas at the bottom of the reaction tower, and nitrite is extracted from the top of the reaction tower (patent) Reference 1 and Patent Reference 2).
- the present invention has been made in view of the above circumstances, and provides a method for producing a nitrite capable of reducing the loss of nitrogen as a raw material by further reducing the concentration of nitric acid in the waste liquid.
- the task is to do.
- Another object of the present invention is to provide a method for producing dialkyl oxalate and dialkyl carbonate capable of reducing the loss of nitrogen used as a raw material by applying the above method for producing nitrite.
- the inventors of the present invention have used a nitric acid concentration tower to concentrate the reaction liquid in the nitric acid conversion reactor, and return the concentrated reaction liquid to the nitric acid conversion reactor. It has been found that the above-described problems can be solved by increasing the concentration of nitric acid therein.
- the present invention specifically has the following configuration.
- alcohol is supplied to the upper part of a reaction tower for producing nitrite ester (hereinafter also referred to as “reaction tower”) to flow down from the upper part to the lower part of the reaction tower.
- reaction tower for producing nitrite ester
- a column bottom liquid containing water, nitric acid and alcohol is extracted from the bottom of the reaction tower and supplied to a nitric acid conversion reactor (hereinafter also referred to as “reactor”).
- a reaction liquid containing water, nitric acid and alcohol is supplied to the nitric acid concentration tower from the lower part of the reactor, and the alcohol concentration in the concentrated liquid generated at the bottom of the nitric acid concentration tower is less than 4.0% by weight.
- the nitrite obtained in the reactor it is preferable to supply the nitrite obtained in the reactor to any height below the middle part of the reaction tower. Further, in the present invention, it is preferable that the bottom liquid of the reaction tower extracted from the bottom of the reaction tower is led to a cooler to be cooled, and the cooled bottom liquid of the reaction tower is circulated and supplied to an intermediate part of the reaction tower. .
- the inside of the nitric acid concentration tower is depressurized from the atmospheric pressure.
- the reaction solution is preferably supplied to the upper part of the nitric acid concentration tower.
- the bottom temperature of the nitric acid concentration tower is preferably 90 ° C. or lower.
- the gas supplied to the reactor is carbon monoxide, and it is preferable to contact the carbon monoxide and the reaction liquid in the presence of a platinum group catalyst in the reactor.
- the present invention provides a method for producing a dialkyl oxalate, in which a nitrite produced by the above-described method for producing a nitrite and carbon monoxide are reacted in the presence of a catalyst to produce a dialkyl oxalate.
- the present invention also provides a method for producing a dialkyl carbonate, wherein a dialkyl carbonate is produced by reacting a nitrite produced by the above-described method for producing a nitrite with carbon monoxide in the presence of a catalyst.
- the nitric acid concentration in the waste liquid can be sufficiently reduced by effectively reusing the nitric acid compound by-produced. Thereby, the loss of the nitrogen content used as a raw material can be reduced.
- FIG. 1 It is a figure showing the schematic structure of the nitrite ester manufacturing device to which one embodiment of the manufacturing method of the nitrite of the present invention is applied. It is a figure which shows schematic structure of the nitrite ester manufacturing apparatus with which another embodiment of the manufacturing method of the nitrite of this invention is applied. It is a figure which shows schematic structure of the nitrite ester manufacturing apparatus with which another embodiment of the manufacturing method of the nitrite of this invention is applied. It is a figure which shows schematic structure of the manufacturing apparatus with which one Embodiment of the manufacturing method of the oxalic acid diester of this invention and the manufacturing method of carbonic acid diester is applied. It is a figure which shows schematic structure of the manufacturing apparatus with which another embodiment of the manufacturing method of the oxalic acid diester of this invention and the manufacturing method of carbonic acid diester is applied.
- the nitrite production method of the present embodiment is a method for producing nitrite by a nitric acid reduction process using carbon monoxide.
- This method for producing nitrite can be suitably applied to a method for producing oxalic acid diester and a method for producing carbonic acid diester.
- FIG. 1 is a view showing a nitrite production apparatus for performing the nitrite production method of the present embodiment.
- the liquid alcohol is also referred to as a reaction tower 1 (hereinafter referred to as “reaction tower 1”) for producing nitrite from an alcohol supply line 11 (hereinafter also referred to as “piping 11”). ) Is supplied at the top.
- the upper part of the reaction tower 1 means a part above the middle part in the vertical direction of the reaction tower 1.
- the intermediate portion of the reaction tower 1 refers to a section having a height of 40 to 60, where the height of the reaction tower 1 is 100.
- the lower part of the reaction tower 1 refers to a part below the intermediate part in the vertical direction of the reaction tower 1.
- a supply port for supplying alcohol is provided in the upper part of the reaction tower 1.
- a pipe 11 is connected to the supply port. The alcohol flowing through the pipe 11 and supplied to the upper part of the reaction tower 1 from this supply port flows downward from the upper part of the reaction tower 1.
- a supply port for supplying nitric oxide to the reaction tower 1 is provided below the middle part of the reaction tower 1.
- a raw material gas supply line 12 (hereinafter also referred to as “pipe 12”) is connected to the supply port. Nitric oxide flowing through the pipe 12 is supplied to the lower part of the reaction tower 1 from this supply port. Nitric oxide supplied to the lower part of the reaction tower 1 rises upward from the lower part of the reaction tower 1.
- the oxygen supply line 15 (hereinafter also referred to as “pipe 15”) is connected to the pipe 12.
- the pipe 15 may be connected to the lower part of the reaction tower 1, or may be connected to both the lower part of the reaction tower 1 and the pipe 12.
- Oxygen is supplied to the lower part of the pipe 12 and / or the reaction tower 1 through the pipe 15.
- oxygen is preferably supplied to the pipe 12 from the viewpoint of reaction efficiency.
- a mixed gas of nitrogen monoxide and oxygen is supplied to the lower part of the reaction tower 1.
- a first reaction gas extraction line 13 (hereinafter also referred to as “pipe 13”) is connected to the top of the reaction tower 1.
- the first reaction gas containing the nitrite produced by the following formula (1) or the like is obtained by extracting from the reaction tower 1 using the pipe 13.
- a reaction represented by the following formula (2) may proceed.
- R represents an alkyl group. 2NO + 2ROH + 1 / 2O 2 ⁇ 2RONO + H 2 O (1) NO + 3 / 4O 2 + 1 / 2H 2 O ⁇ HNO 3 (2)
- the bottom liquid of the reaction tower 1 contains at least water, unreacted alcohol and nitric acid.
- This bottom liquid is withdrawn from the lower part of the reaction tower 1 by using a bottom bottom liquid extraction line 14 (hereinafter also referred to as “piping 14”), and a nitric acid conversion reactor 2 (hereinafter referred to as “reactor 2”). (Also called).
- the pipe 14 only needs to be connected to a position at which the reaction solution at the lower part of the reaction tower 1 can be extracted.
- the pipe 14 is preferably connected to the bottom of the reaction tower 1.
- the position where the pipe 14 is connected to the reactor 2 is not particularly limited, and is preferably connected to the upper part of the reactor 2 from the viewpoint of easy supply of the column bottom liquid to the reactor 2.
- the bottom liquid supplied to the reactor 2 via the pipe 14 is brought into contact with carbon monoxide and / or nitrogen monoxide, and, for example, by the reaction represented by the formulas (3) and (4), nitrous acid. Esters are produced. That is, nitric acid, alcohol, carbon monoxide and / or nitric oxide react to generate nitrite.
- R represents an alkyl group. HNO 3 + 2NO + 3ROH ⁇ 3RONO + 2H 2 O (3) HNO 3 + CO + ROH ⁇ RONO + H 2 O + CO 2 (4)
- the second reaction gas containing nitrite produced in the reactor 2 is extracted from a second reaction gas extraction line 18 (hereinafter also referred to as “pipe 18”) and supplied to the reaction tower 1.
- the pipe 18 is connected to a supply port provided above an intermediate portion in the vertical direction of the reaction tower 1. As a result, the second reaction gas is supplied to the upper part of the reaction tower 1.
- the reaction liquid in the reactor 2 is preferably controlled at 10 to 60 ° C.
- the amount of platinum group metal supported in such a catalyst is preferably 0.01 to 10% by weight, more preferably 0.2 to 2% by weight, based on the carrier.
- the carrier constituting the catalyst include inert carriers such as activated carbon, alumina, silica, diatomaceous earth, pumice, zeolite, and molecular sieve. Among these, alumina is preferable, and ⁇ -alumina is particularly preferable.
- the carbon monoxide is supplied to the reactor 2 using a carbon monoxide supply line 16 (hereinafter also referred to as “pipe 16”).
- the pipe 16 is preferably connected to the lower part of the reactor 2. That is, it is preferable that the pipe 16 is connected to a supply port provided below the intermediate part in the vertical direction of the reactor 2.
- the pipe 18 is connected to an intermediate portion in the height direction of the reaction tower 1 as shown in FIG. 1. Thereby, the oxidation of carbon monoxide in the second reaction gas can be reduced.
- the upper part of the reactor 2 refers to a part above the middle part in the vertical direction of the reactor 2.
- the middle part of the reactor 2 in this specification refers to a section having a height of 40 to 60, where the height of the reactor 2 is 100.
- the lower part of the reactor 2 refers to a part below the intermediate part in the vertical direction of the reactor 2.
- Carbon monoxide supplied to the reactor 2 via the pipe 16 and carbon monoxide supplied using the second carbon monoxide supply line 32 described later are supplied from the same carbon monoxide source. Or may be supplied from different carbon monoxide sources.
- FIG. 2 is a diagram showing another embodiment of the nitrite production apparatus for performing the nitrite production method.
- FIG. 3 is a view showing still another embodiment of the nitrite production apparatus for performing the nitrite production method.
- a nitric oxide supply line 17 (hereinafter also referred to as “pipe 17”) is connected to the reactor 2.
- the pipe 17 is preferably connected to the lower part of the reactor 2.
- Nitric oxide may be supplied to the reactor 2 using a separate pipe from a nitric oxide gas tank or the like.
- the second reaction gas is returned to the pipe 12 using a second reaction gas extraction line 31 (hereinafter also referred to as “pipe 31”).
- pipe 31 a second reaction gas extraction line 31
- the nitric oxide in the second reaction gas can be reacted more efficiently by returning the second reaction gas to a position upstream of the connection portion between the piping 15 and the piping 12 for supplying oxygen. .
- the second reaction gas can be supplied to the reaction tower 1 using a pipe 18.
- nitrite can be generated more efficiently from the second reaction gas.
- the tower bottom liquid extracted from the lower part of the reaction tower 1 using the pipe 14 is partly or entirely circulated through a tower bottom liquid circulation line 19 (hereinafter “pipe 19”). And also circulate to the reaction tower 1 via the cooler 4. This is preferably performed when it is necessary to control the reaction temperature in the reaction tower 1.
- the reaction temperature in the reaction tower 1 is preferably 0 to 100 ° C., more preferably 5 to 80 ° C., and further preferably 10 to 60 ° C.
- the circulating liquid flowing through the pipe 19 is preferably supplied to the middle part of the reaction tower 1.
- the reaction liquid extracted from the reactor 2 using the reaction liquid extraction line 21 (hereinafter also referred to as “pipe 21”) is supplied to the nitric acid concentration tower 3.
- the pipe 21 only needs to be connected to a position where the reaction solution of the reactor 2 can be extracted.
- the piping 21 is preferably connected to the lower part of the reactor 2 and more preferably connected to the bottom from the viewpoint of the efficiency of extracting the reaction liquid.
- the piping 21 should just be connected to the position which can supply a reaction liquid to the nitric acid concentration tower 3.
- FIG. It is preferable that the piping 21 is connected to the upper part of the nitric acid concentration tower 3 from the viewpoint of the concentration efficiency of the reaction solution.
- the upper part of the nitric acid concentration tower 3 in this specification refers to a part above the middle part in the vertical direction of the nitric acid concentration tower 3.
- the intermediate part of the nitric acid concentration tower 3 refers to a section having a height of 40 to 60, where the height of the reaction tower 1 is 100.
- the lower part of the nitric acid concentration tower 3 refers to a part below the intermediate part in the vertical direction of the nitric acid concentration tower 3.
- the alcohol contained in the reaction liquid can be distilled off until the reaction liquid reaches the bottom of the nitric acid concentration tower.
- the reaction solution can be prevented from coming into contact with the concentrated solution having a high nitric acid concentration in a state where the alcohol concentration is high, and the production of alkyl nitrate can be suppressed. Since alkyl nitrate is an explosive liquid, it is preferable to reduce the amount accumulated in the process.
- nitric acid concentration tower 3 a reaction liquid containing at least water, alcohol and nitric acid is heated and concentrated, and a part or all of low boiling water and alcohol are distilled as a distillate. As a result, a concentrated liquid in which nitric acid is concentrated can be obtained.
- the alcohol concentration in the concentrated liquid generated at the bottom of the nitric acid concentration tower 3 is controlled to be less than 4.0% by weight. Thereby, it can suppress that nitric acid and alcohol react with the bottom part of the nitric acid concentration tower 3, and nitric ester is produced
- the concentration of alcohol in the concentrate produced at the bottom of the nitric acid concentration tower 3 can be controlled by adjusting the size of the nitric acid concentration tower 3, the temperature at the bottom, the pressure, the number of theoretical plates, the extraction amount of the concentrate, and the like.
- the alcohol concentration in the concentrate may be measured by, for example, sampling the concentrate extracted through the pipe 22 and performing a gas chromatographic distillation test, or using an online analyzer.
- a control unit for transmitting an output signal for adjusting the pressure of the nitric acid concentrating tower 3, the temperature of the bottom, the pressure, and the amount of the concentrated liquid extracted based on the input signal of the detection result of the alcohol concentration in the online analyzer May be provided. That is, the control unit changes the operation state of the nitric acid concentration tower 3 based on a signal related to the alcohol concentration from the online analyzer (for example, control of the flow rate of alcohol supplied to the nitric acid concentration tower 3, in the nitric acid concentration tower 3. Temperature control, or cooling efficiency control of the cooler 4). By automatically controlling the alcohol concentration of the concentrate in this way, the operation efficiency can be increased.
- the pressure in the nitric acid concentration tower 3 is not particularly limited, and is preferably reduced to less than atmospheric pressure. By concentrating the reaction solution under reduced pressure, the alcohol concentration in the concentrate can be further reduced.
- the pressure in the nitric acid concentration tower 3 may be, for example, 6 to 70 kPa, or 10 to 50 kPa.
- the temperature at the bottom of the nitric acid concentration tower 3 may be, for example, 30 to 90 ° C. or 40 to 85 ° C.
- the production of methyl nitrate can be suppressed by lowering the temperature at the bottom of the nitric acid concentration tower 3.
- the distillate is extracted from a distillate extraction line 24 (hereinafter also referred to as “pipe 24”) connected to the upper part of the nitric acid concentration tower 3. It is also possible to reuse the alcohol separated by distilling the distillate extracted from the pipe 24.
- the alcohol to be reused can be temporarily stored in an alcohol tank as needed, and can be supplied into the reaction system from a pipe 11 or the like connected to the upper part of the reaction tower 1.
- the nitrate ester in the distillate tends to accumulate in the alcohol. For this reason, the amount of nitrate accumulated in the alcohol can be reduced by reducing the concentration of nitrate in the distillate. If the distillate is distilled to neutralize the alcohol after neutralizing the distillate, the nitrate concentration in the alcohol to be reused can be further reduced.
- the concentration of the nitrate ester in the distillate is preferably less than 50 ppm by weight, more preferably less than 30 ppm by weight, and even more preferably less than 20 ppm by weight.
- the concentrate concentrated in the nitric acid concentration tower 3 is supplied to the reactor 2 using a concentrate extraction line 22 (hereinafter also referred to as “pipe 22”) and a concentrate circulation line 23 (hereinafter also referred to as “pipe 23”).
- the pipe 22 is preferably connected to the lower part of the nitric acid concentration tower 3, and more preferably connected to the bottom.
- the pipe 23 is preferably connected to the upper part of the reactor 2, and more preferably connected to the top.
- a part of the concentrated liquid can be treated as waste liquid using a waste liquid extraction line 25 (hereinafter also referred to as “pipe 25”). Since the waste liquid of this embodiment has a sufficiently reduced nitric acid concentration, even if it is treated as a waste liquid, a nitrogen source such as nitrogen monoxide used as a raw material can be sufficiently reduced.
- the nitric acid concentration tower 3 is preferably filled with a packing material such as a regular packing or an irregular packing to improve the number of theoretical plates of distillation.
- the theoretical plate number of the nitric acid concentration tower 3 is preferably 1 or more, and more preferably 5 or more.
- the theoretical plate number of the nitric acid concentration tower 3 may be, for example, 1 to 20, or 5 to 10.
- a part of the reaction gas or the like can be purged out of the reaction system using a purge line 20 (hereinafter also referred to as “piping 20”).
- piping 20 a purge line 20 is connected to the pipe 13.
- the purge line may be connected anywhere as long as it is a pipe through which gas flows.
- the nitrite production apparatuses 100, 101, 102 are all equipped with a nitric acid concentration tower for distilling off low-boiling components from the reaction solution from the reactor 2 and concentrating the nitric acid content. And by maintaining the alcohol concentration in the nitric acid concentrate from this nitric acid concentration tower at 4% by mass or less, it is possible to sufficiently reduce the nitric acid content such as alkyl nitrate mixed in the low boiling point content. As a result, the amount of nitric acid to be treated in the waste liquid can be sufficiently reduced. Then, the nitric acid concentrate is circulated to the reactor 2 to effectively use the nitric acid component. Therefore, nitric oxide used as a raw material can be sufficiently reduced.
- FIG. 4 is a diagram showing a schematic configuration of a manufacturing apparatus to which the manufacturing method of oxalic acid diester or the manufacturing method of carbonic acid diester of the present embodiment is applied.
- FIG. 5 is a diagram showing a schematic configuration of a manufacturing apparatus to which the manufacturing method of oxalic acid diester or the manufacturing method of carbonic acid diester of another embodiment is applied.
- the oxalic acid diester or carbonic acid diester production apparatus 200 shown in FIG. 4 includes the nitrite production apparatus 100 shown in FIG.
- An oxalic acid diester or carbonic acid diester production apparatus 201 shown in FIG. 5 includes a nitrite ester production apparatus 101 shown in FIG.
- oxalic acid diester and carbonic acid diester can be produced using the first reaction gas containing nitrite extracted from the pipe 13.
- the pipe 13 is connected to the reactor 5 for producing oxalic acid diester and / or carbonic acid diester (hereinafter also referred to as “reactor 5”).
- the first reaction gas is supplied to the reactor 5 (hereinafter also referred to as “reactor 5”) via the pipe 13.
- a carbon monoxide supply line 32 hereinafter also referred to as “pipe 32” is connected to the pipe 13.
- the first reaction gas flowing through the pipe 13 is supplied to the reactor 5 together with the carbon monoxide supplied from the pipe 32.
- the nitrite contained in the first reaction gas reacts with carbon monoxide to produce an oxalic acid diester and / or a carbonic acid diester.
- R represents an alkyl group.
- Carbon monoxide supplied using the carbon monoxide supply lines (pipes 16 and 32) may be pure, diluted with an inert gas such as nitrogen, or may contain hydrogen gas or methane gas. Good.
- the reactor 5 is not particularly limited, and a single-tube or multi-tube heat exchanger type reactor is preferable. In the reactor 5, it is preferable to react nitrite and carbon monoxide in the presence of a catalyst for producing an oxalic acid diester and / or a catalyst for producing a carbonic acid diester.
- a catalyst for producing oxalic acid diester and the catalyst for producing carbonic acid diester a known catalyst such as palladium can be used, and a catalyst supported on a carrier such as alumina may be used.
- Known conditions can also be adopted for the reaction temperature and pressure in the reactor 5.
- the oxalic acid diester produced by the production method of the present embodiment is preferably a dialkyl oxalate.
- the two alkyl groups in the dialkyl oxalate molecule may be the same or different.
- Examples of the dialkyl oxalate include dimethyl oxalate, diethyl oxalate, dipropyl oxalate, diisopropyl oxalate, dibutyl oxalate, dipentyl oxalate, dihexyl oxalate, diheptyl oxalate, dioctyl oxalate, dinonyl oxalate, and oxalic acid.
- dialkyl oxalates such as ethylmethyl and ethylpropyl oxalate.
- dialkyl oxalates having a linear or branched alkyl group having 1 to 10 carbon atoms are preferred from the viewpoint of the reaction rate of the transesterification reaction and the ease of removing the by-produced alkyl alcohol. More preferred is dimethyl oxalate or diethyl oxalate.
- the carbonate ester produced by the production method of the present embodiment is preferably a dialkyl carbonate.
- the two alkyl groups in the dialkyl carbonate molecule may be the same or different.
- the dialkyl carbonate include dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, ethyl methyl carbonate, and ethyl propyl carbonate. It is done.
- dialkyl carbonates having a linear or branched alkyl group having 1 to 10 carbon atoms are preferable from the viewpoint of the reaction rate of the transesterification reaction and the ease of removing the by-produced alkyl alcohol. More preferred is dimethyl carbonate or diethyl carbonate.
- the third reaction gas containing oxalic acid diester and / or carbonic acid diester obtained in the reactor 5 passes through the third reaction gas extraction line 26 (hereinafter also referred to as “pipe 26”) to the absorption tower 6. Supplied.
- an absorption liquid supply line 27 (hereinafter also referred to as “pipe 27”) is connected to the absorption tower 6.
- An absorption liquid for absorbing oxalic acid diester or carbonic acid diester in the third reaction gas is supplied to the absorption tower 26 from the pipe 27.
- the pipe 26 is connected to the lower part of the absorption tower 6, and the pipe 27 is connected to the upper part of the absorption tower 6.
- the absorbing liquid is preferably alcohol and / or oxalic acid diester.
- the oxalic acid diester and / or the carbonic acid diester absorbed by the absorption liquid in the absorption tower 6 is supplied from a condensate extraction line 28 (hereinafter also referred to as “pipe 28”) connected to the bottom of the absorption tower 6 together with the absorption liquid. Extracted.
- the absorption liquid containing oxalic acid diester and / or carbonic acid diester extracted from the absorption tower 6 is purified by a purification step such as distillation. Thereby, an oxalic acid diester and / or a carbonic acid diester is obtained.
- the gas component that has not been absorbed by the absorption liquid in the absorption tower 6 is supplied to the reaction tower 1 as a raw material gas via the raw material gas supply line 12 connected to the upper part of the absorption tower 6.
- the carbonic acid diester and the oxalic acid diester may be produced separately, and the carbonic acid diester is adjusted by adjusting the content ratio of carbon monoxide and nitrite in the first reaction gas. And oxalic acid diester may be produced simultaneously to obtain a mixture thereof.
- Example 1 A distillation process was performed using an apparatus including the reactor 2 and the nitric acid concentration tower 3 as shown in FIG.
- the nitric acid concentration tower 3 was a continuous distillation apparatus having the following configuration. That is, a container having a spherical part of about 100 ml forming the bottom of the nitric acid concentration tower 3 and a cylindrical part having a diameter of 25 mm and a height of 275 mm connected to the opening at the top of the spherical part was prepared.
- the cylindrical portion was filled with 5 pieces of Sulzer Lab Packing EX (trade name, manufactured by Sumitomo Heavy Industries, Ltd.) as a filler.
- the spherical portion of the container was configured to be heated with a heating oil bath.
- a pipe 21 was connected to the upper side of the filler in the cylindrical part (upper part of the nitric acid concentration tower 3), and a pipe 24 was connected to the upper end of the cylindrical part, that is, the top of the tower.
- a pipe 22 was connected to the lower part of the spherical portion.
- reaction solution having the following composition was continuously supplied from the reactor 2 to the upper part of the nitric acid concentration tower 3 through the pipe 21 at a flow rate of 199.2 g / h.
- Composition of reaction solution methanol 30.8% by weight, nitric acid 1.6% by weight, water 61.7% by weight, other 5.9% by weight
- the reaction liquid was heated and concentrated under the conditions of 300 Torr (about 40 kPa), a bottom temperature of 78 ° C., and a tower top temperature of 69 ° C.
- a distillate was extracted from the top of the nitric acid concentration tower 3 through the pipe 24 at a distillation rate of 169.4 g / h.
- the concentrate was extracted at a rate of 29.8 g / h through the pipe 22.
- composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 0.2 ppm by weight.
- the composition of the distillate and the concentrate was analyzed by a gas chromatographic distillation test.
- Composition of distillate 36.2% by weight of methanol, 57.6% by weight of water, 6.2% by weight of other components
- Composition of concentrated liquid 0.006% by weight of methanol, 10.7% by weight of nitric acid, 85.0% by weight of water, and other residue (about 4.3% by weight)
- Example 1 The results of Example 1 are summarized in Table 1.
- the methyl nitrate concentration in the distillate could be sufficiently reduced. That is, in Example 1, the nitric acid compound (methyl nitrate) conventionally contained in the waste liquid can be circulated and reused in the reactor 2. This makes it possible to effectively use the nitrogen component supplied into the apparatus.
- Example 2 Example 1 except that the flow rate of the reaction solution supplied from the reactor 2 to the nitric acid concentration tower 3 was 200.1 g / h, and the amount of the concentrated liquid extracted from the nitric acid concentration tower 3 was 17.8 g / h. The distillation process was carried out. The results of Example 2 are summarized in Table 1.
- the temperature at the bottom of the nitric acid concentration tower 3 was 80 ° C., and the composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 0.6 ppm by weight.
- Composition of distillate 33.8% by weight of methanol, 60.1% by weight of water, 6.1% by weight of others
- Composition of concentrate methanol 0.105% by weight, nitric acid 18.0% by weight, water 78.0% by weight, other residue (about 3.9% by weight)
- Example 3 The number of Sulzer Lab Packing EX packed in the cylindrical portion of the nitric acid concentration tower 3 was set to one, the flow rate of the reaction solution supplied from the reactor 2 to the nitric acid concentration tower 3 was 199.8 g / h, A distillation process was performed in the same manner as in Example 1 except that the amount of the concentrated liquid extracted from the nitric acid concentration tower 3 was 17.8 g / h.
- the results of Example 3 are summarized in Table 1.
- the temperature at the bottom of the nitric acid concentration tower 3 was 81 ° C., and the composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 8 ppm by weight.
- Composition of distillate 33.7% by weight of methanol, 60.3% by weight of water, 6.0% by weight of other
- Composition of concentrate methanol 0.9 wt%, nitric acid 18.0 wt%, water 76.0 wt%, other 5.1 wt%
- Example 4 The connection position of the pipe 21 was changed from the upper part of the nitric acid concentration tower 3 to the lower part of the nitric acid concentration tower 3. Specifically, the piping 21 was connected to the lower side (lower part of the nitric acid concentration tower 3) than the filling position of the packing material in the nitric acid concentration tower 3. Thereby, the reaction liquid from the reactor 2 was continuously supplied to the lower part of the nitric acid concentration tower 3.
- Example 4 the pressure of the nitric acid concentration tower 3 is set to 100 Toor (about 13 kPa), the flow rate of the reaction solution supplied from the reactor 2 to the nitric acid concentration tower 3 is 200.2 g / h, The distillation process was performed in the same manner as in Example 1 except that the amount of the concentrated liquid extracted was 20.0 g / h.
- the results of Example 4 are summarized in Table 1.
- the temperature at the bottom of the nitric acid concentration tower 3 was 51 ° C., and the composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 2 ppm by weight.
- Composition of distillate 33.8% by weight of methanol, 60.2% by weight of water, 6.0% by weight of others
- Composition of concentrate 3.6% methanol, 16.0% nitric acid, 75.0% water, 5.4% other
- Example 5 As in Example 4, the reaction liquid was continuously supplied to the lower part of the nitric acid concentration tower 3, the flow rate of the reaction liquid supplied from the reactor 2 to the nitric acid concentration tower 3 was 199.9 g / h, and the nitric acid concentration tower 3 A distillation process was performed in the same manner as in Example 1 except that the amount of the concentrated liquid extracted from the mixture was 32.0 g / h. The results of Example 5 are summarized in Table 1.
- the temperature at the bottom of the nitric acid concentration tower 3 was 76 ° C., and the composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 13 ppm by weight.
- Composition of distillate 36.1% by weight methanol, 57.6% by weight water, 6.3% by weight other
- Composition of concentrate methanol 2.9% by weight, nitric acid 10.0% by weight, water 83.0% by weight, other 4.1% by weight
- Comparative Example 1 The same as Example 5 except that the flow rate of the reaction solution supplied from the reactor 2 to the nitric acid concentration tower 3 was 201.0 g / h, and the amount of the concentrate extracted from the nitric acid concentration tower 3 was 20.1 g / h. I went there.
- the results of Comparative Example 1 are summarized in Table 1.
- the temperature at the bottom of the nitric acid concentration tower was 78 ° C., and the composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 500 ppm by weight.
- Composition of distillate 33.8% by weight of methanol, 60.2% by weight of water, 6.0% by weight of others
- Composition of concentrate methanol 4.0 wt%, nitric acid 16.0 wt%, water 75.0 wt%, other 5.0 wt%
- Comparative Example 2 The pressure in the nitric acid concentration tower 3 was set to normal pressure, the flow rate of the reaction liquid supplied from the reactor 2 to the nitric acid concentration tower 3 was 199.5 g / h, and the extraction amount of the concentrated liquid from the nitric acid concentration tower 3 was 31. The distillation process was performed in the same manner as in Example 5 except that the amount was 9 g / h. The results of Comparative Example 2 are summarized in Table 1.
- the temperature at the bottom of the nitric acid concentration tower was 98 ° C., and the composition of the distillate and the concentrate was as follows.
- the methyl nitrate concentration in the distillate was 150 ppm by weight.
- Composition of distillate 35.5% by weight of methanol, 58.2% by weight of water, 6.3% by weight of other components
- Composition of concentrate 6.2 wt% methanol, 10.0 wt% nitric acid, 80.0 wt% water, 3.8 wt% other
- Example 1 and Example 5 in which the methanol concentration in the concentrate is controlled to less than 4.0% by weight, it can be seen that the methyl nitrate concentration in the distillate is sufficiently low and the loss of nitrogen content is small. Moreover, when Example 1 and Example 5 are compared, when the supply position to a nitric acid concentration tower is an upper part, compared with the case where a supply position is a lower part, the density
- a method for producing a nitrite that can sufficiently reduce the concentration of nitric acid in the waste liquid and reduce the loss of nitrogen.
- Such a method for producing a nitrite ester can be suitably used for producing dialkyl oxalate, dialkyl carbonate and the like.
- SYMBOLS 1 Reaction tower for nitrite ester production, 2 ... Reactor for nitric acid conversion, 3 ... Nitric acid concentration tower, 4 ... Cooler, 5 ... Reactor for oxalic acid diester and / or carbonic acid diester production, 6 ... Absorption tower, 11 DESCRIPTION OF SYMBOLS ... Alcohol supply line, 12 ... Raw material gas supply line, 13 ... 1st reaction gas extraction line, 14 ... Tower bottom liquid extraction line, 15 ... Oxygen supply line, 16 ... Carbon monoxide supply line, 17 ... Nitric oxide supply line , 18, 31 ... second reaction gas extraction line, 19 ... tower bottom liquid circulation line, 20 ... purge line, 21, 32 ...
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Abstract
Description
上記反応塔の底部から、水と硝酸とアルコールとを含有する塔底液を抜き出して硝酸変換用反応器(以下、「反応器」ともいう。)に供給すると共に、反応器に一酸化窒素及び/又は一酸化炭素を供給し、反応器中で塔底液と一酸化窒素及び/又は一酸化炭素とを接触させて亜硝酸エステルを生成させる工程と、
反応器で得られた亜硝酸エステルを反応塔に供給する工程と、
反応器の下部から、水と硝酸とアルコールとを含有する反応液を硝酸濃縮塔に供給すると共に、硝酸濃縮塔の底部に生じる濃縮液中のアルコール濃度が4.0重量%未満となるように制御しながら低沸点分を蒸留分離する工程と、
硝酸濃縮塔の下部から濃縮液を抜き出し、反応器に導入する工程と、を有する亜硝酸エステルの製造方法である。
2NO+2ROH+1/2O2 → 2RONO+H2O (1)
NO+3/4O2+1/2H2O → HNO3 (2)
HNO3+2NO+3ROH → 3RONO+2H2O (3)
HNO3+CO+ROH → RONO+H2O+CO2 (4)
CO+2RONO → ROC(=O)OR+2NO (5)
2CO+2RONO → (RCO2)2+2NO (6)
図1に示すような反応器2及び硝酸濃縮塔3を備える装置を用いて、蒸留プロセスを行った。硝酸濃縮塔3は、以下のような構成を有する連続蒸留装置とした。すなわち、硝酸濃縮塔3の底部をなす約100mlの球状部分と、該球状部分の上部の開口に連結された、直径25mm、高さ275mmの円筒状部分とからなる容器を準備した。円筒状部分には、充填材として、スルーザーラボパッキングEX(商品名、住友重機械工業社製)を5個充填した。容器の球状部分を、加熱用のオイルバスで加熱可能な構成とした。円筒状部分の充填材の上側(硝酸濃縮塔3の上部)には配管21を接続し、円筒状部分の上端、すなわち塔頂には配管24を接続した。また、球状部分の下部には配管22を接続した。
反応液の組成:メタノール30.8重量%、硝酸1.6重量%、水61.7重量%、その他5.9重量%
留出液の組成:メタノール36.2重量%、水57.6重量%、その他6.2重量%
濃縮液の組成:メタノール0.006重量%、硝酸10.7重量%、水85.0重量%、その他残余(約4.3重量%)
反応器2から硝酸濃縮塔3に供給する反応液の流量を200.1g/h、硝酸濃縮塔3からの濃縮液の抜き出し量を17.8g/hとしたこと以外は、実施例1と同様にして蒸留プロセスを行った。実施例2の結果を表1に纏めて示す。
留出液の組成:メタノール33.8重量%、水60.1重量%、その他6.1重量%
濃縮液の組成:メタノール0.105重量%、硝酸18.0重量%、水78.0重量%、その他残余(約3.9重量%)
硝酸濃縮塔3の円筒状部分に充填するスルーザーラボパッキングEXの個数を1個にしたこと、反応器2から硝酸濃縮塔3に供給する反応液の流量を199.8g/hにしたこと、硝酸濃縮塔3からの濃縮液の抜き出し量を17.8g/hとしたこと以外は、実施例1と同様にして蒸留プロセスを行った。実施例3の結果を表1に纏めて示す。
留出液の組成:メタノール33.7重量%、水60.3重量%、その他6.0重量%
濃縮液の組成:メタノール0.9重量%、硝酸18.0重量%、水76.0重量%、その他5.1重量%
配管21の接続位置を、硝酸濃縮塔3の上部から硝酸濃縮塔3の下部に変更した。具体的には、硝酸濃縮塔3における充填材の充填位置よりも下側(硝酸濃縮塔3の下部)に配管21を接続した。これによって、反応器2からの反応液を硝酸濃縮塔3の下部に連続的に供給した。この変更点に加えて、硝酸濃縮塔3の圧力を100Toor(約13kPa)としたこと、反応器2から硝酸濃縮塔3に供給する反応液の流量を200.2g/h、硝酸濃縮塔3からの濃縮液の抜き出し量を20.0g/hとしたこと以外は、実施例1と同様にして蒸留プロセスを行った。実施例4の結果を表1に纏めて示す。
留出液の組成:メタノール33.8重量%、水60.2重量%、その他6.0重量%
濃縮液の組成:メタノール3.6重量%、硝酸16.0重量%、水75.0重量%、その他5.4重量%
実施例4と同様に、反応液を硝酸濃縮塔3の下部に連続的に供給したこと、反応器2から硝酸濃縮塔3に供給する反応液の流量を199.9g/h、硝酸濃縮塔3からの濃縮液の抜き出し量を32.0g/hとしたこと以外は、実施例1と同様にして蒸留プロセスを行った。実施例5の結果を表1に纏めて示す。
留出液の組成:メタノール36.1重量%、水57.6重量%、その他6.3重量%
濃縮液の組成:メタノール2.9重量%、硝酸10.0重量%、水83.0重量%、その他4.1重量%
反応器2から硝酸濃縮塔3に供給する反応液の流量を201.0g/h、硝酸濃縮塔3からの濃縮液の抜き出し量を20.1g/hとしたこと以外は、実施例5と同様にして行った。比較例1の結果を表1に纏めて示す。
留出液の組成:メタノール33.8重量%、水60.2重量%、その他6.0重量%
濃縮液の組成:メタノール4.0重量%、硝酸16.0重量%、水75.0重量%、その他5.0重量%
硝酸濃縮塔3内の圧力を常圧としたこと、反応器2から硝酸濃縮塔3に供給する反応液の流量を199.5g/h、硝酸濃縮塔3からの濃縮液の抜き出し量を31.9g/hとしたこと以外は、実施例5と同様にして蒸留プロセスを行った。比較例2の結果を表1に纏めて示す。
留出液の組成:メタノール35.5重量%、水58.2重量%、その他6.3重量%
濃縮液の組成:メタノール6.2重量%、硝酸10.0重量%、水80.0重量%、その他3.8重量%
Claims (10)
- アルコールを亜硝酸エステル製造用の反応塔の上部に供給して該反応塔の上部から下部に流下させると共に、一酸化窒素と酸素又はそれらの混合ガスを該反応塔の下部に供給して、前記一酸化窒素と前記酸素と前記アルコールとを反応させて亜硝酸エステルを生成させる、亜硝酸エステルの製造方法であって、
前記反応塔の底部から、水と硝酸とアルコールとを含有する塔底液を抜き出して反応器に供給すると共に、前記反応器に一酸化窒素及び/又は一酸化炭素を供給する工程と、
前記反応器中で前記塔底液と前記一酸化炭素及び/又は前記一酸化窒素とを接触させて亜硝酸エステルを生成させる工程と、
前記反応器で得られた前記亜硝酸エステルを前記反応塔に供給する工程と、
前記反応器の下部から、水と硝酸とアルコールとを含有する反応液を硝酸濃縮塔に供給する工程と、
前記硝酸濃縮塔において、前記硝酸濃縮塔の底部に生じる濃縮液中のアルコール濃度を4.0重量%未満に制御しながら、前記反応液から低沸点分を蒸留分離し、前記硝酸濃縮塔の下部から前記濃縮液を抜き出して前記反応器に導入する工程と、を有する亜硝酸エステルの製造方法。 - 前記反応器で得られた前記亜硝酸エステルは、前記反応塔の中間部、下部又はこれらの間に設けられた供給口から前記反応塔に供給される、請求項1に記載の亜硝酸エステルの製造方法。
- 前記反応塔の下部から抜き出した前記塔底液を冷却器に導入して冷却し、冷却された前記塔底液を前記反応塔の中間部に循環供給する、請求項1又は2に記載の亜硝酸エステルの製造方法。
- 前記硝酸濃縮塔内の圧力が大気圧未満である、請求項1~3のいずれか一項に記載の亜硝酸エステルの製造方法。
- 前記反応液は、前記硝酸濃縮塔の中間部よりも上側に設けられた供給口から前記硝酸濃縮塔に供給される、請求項1~4のいずれか一項に記載の亜硝酸エステルの製造方法。
- 前記硝酸濃縮塔で蒸留分離された低沸点分を精製して得られるアルコールは、前記反応塔の中間部よりも上側に設けられた供給口から前記反応塔に供給される、請求項1~5のいずれか一項に記載の亜硝酸エステルの製造方法。
- 前記硝酸濃縮塔の底部の温度が90℃以下である、請求項1~6のいずれか一項に記載の亜硝酸エステルの製造方法。
- 前記反応器に一酸化炭素を含むガスを供給し、前記反応器中で、前記一酸化炭素と前記反応液とを白金族触媒存在下で接触させる、請求項1~7のいずれか一項に記載の亜硝酸エステルの製造方法。
- 請求項1~8のいずれか一項に記載の方法で製造した亜硝酸エステルと一酸化炭素とを触媒存在下で反応させて、シュウ酸ジアルキルを製造する工程を有するシュウ酸ジアルキルの製造方法。
- 請求項1~8のいずれか一項に記載の方法で製造した亜硝酸エステルと一酸化炭素とを触媒存在下で反応させて、炭酸ジアルキルを製造する工程を有する炭酸ジアルキルの製造方法。
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