WO2018198428A1 - Method for recovering tar acid salt and method for producing tar acid - Google Patents
Method for recovering tar acid salt and method for producing tar acid Download PDFInfo
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- WO2018198428A1 WO2018198428A1 PCT/JP2017/045760 JP2017045760W WO2018198428A1 WO 2018198428 A1 WO2018198428 A1 WO 2018198428A1 JP 2017045760 W JP2017045760 W JP 2017045760W WO 2018198428 A1 WO2018198428 A1 WO 2018198428A1
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- oil
- tar
- naphthalene
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/04—Working-up tar by distillation
- C10C1/08—Winning of aromatic fractions
Definitions
- the present invention relates to a method for recovering tar acid salt and a method for producing tar acid.
- the tar oil (coal acid) is contained in the light oil obtained by distilling coal tar generated when carbonizing carbon.
- a method for producing tar acid from coal tar among fractionated oils obtained by distillation of coal tar, carbol oil and naphthalene oil containing a large amount of tar acid are brought into contact with an alkaline aqueous solution to form tar acid salt. Extracted and recovered on the water layer side, and the recovered tarate is decomposed with carbon dioxide and / or sulfuric acid to obtain crude tar acid, followed by purification and distillation, tar containing phenol, cresol, xylenol, etc. as the main component Methods for obtaining acids are known.
- the tar acid obtained in this way is useful as a raw material for various products such as synthetic resins, flame retardants, semiconductor sealants, insulating varnishes, etc., so studies have been conducted to efficiently obtain tar acid from coal tar. ing.
- Patent Document 1 discloses an extract washing oil obtained by extracting a hydrocarbon oil mixture containing tar acids obtained in a tar distillation step with a caustic aqueous solution, and washing the obtained tar acid extract with a tar-based light oil.
- a method for treating a tar acid extract washing oil that can efficiently recover both tar acids and tar light oils with high purity by charging them into a tar distillation step is disclosed.
- An object of the present invention is to provide a method for recovering a tartrate that has a higher recovery rate of the tartrate.
- a coal tar distillation process obtained by distilling coal tar to separate naphthalene oil and carbol oil, and an alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation process, and contained in the naphthalene oil.
- the tar acid is a tar acid salt
- the oil layer 1 from which the tar acid has been removed and the water layer 1 containing the tar acid salt are separated, and the oil layer 1 separated in the first separation process is Distillation to obtain naphthalene gas oil Naphthalene distillation step, carboru oil obtained in the coal tar distillation step, aqueous layer 1 separated in the first separation step, and naphthalene obtained in the naphthalene distillation step
- Gas oil is mixed, and tar acid contained in the carbol oil and naphthalene gas oil is changed to tarate, and separated into oil layer 2 from which tar acid has been removed and aqueous layer 2 containing tarate.
- tarate can be recovered from coal tar at a higher recovery rate.
- tar acid can be obtained from coal tar with higher yield.
- FIG. 1 is a schematic diagram showing the flow of one embodiment of the method for recovering a tartrate of the present invention.
- FIG. 2 is a schematic diagram showing a flow of a method for recovering a tartrate according to Example 1.
- FIG. 3 is a schematic diagram showing a flow of a method for recovering a tartrate according to Comparative Example 1.
- FIG. 1 is a schematic diagram showing the flow of one embodiment of the method for recovering a tartrate of the present invention.
- the tarate recovery method of the present invention includes a coal tar distillation step obtained by distilling coal tar to separate naphthalene oil and carbol oil, and an alkaline aqueous solution in the naphthalene oil obtained in the coal tar distillation step.
- the first separation step of separating the tar acid contained in the naphthalene oil into a tartrate and separating the oil layer 1 from which the tar acid has been removed and the aqueous layer 1 containing the tartrate and the first separation
- the oil layer 1 separated in the step is distilled to obtain a naphthalene light oil, a naphthalene distillation step, the carbol oil obtained in the coal tar distillation step, the water layer 1 separated in the first separation step, and the The naphthalene gas oil obtained in the naphthalene distillation step is mixed, the tar acid contained in the carbol oil and the naphthalene gas oil is changed to a tar acid salt, and the oil layer 2 from which the tar acid has been removed and the tar A second separation step of separating the water layer 2 containing salt,.
- coal tar distillation process In the coal tar distillation step, coal tar as a raw material is distilled to obtain naphthalene oil and carbol oil.
- coal tar is charged into a tar distillation column and distilled to separate naphthalene oil and carbol oil.
- the naphthalene oil is obtained as a fraction of about 200 to 250 ° C.
- the carbol oil is obtained as a fraction of about 170 to 200 ° C.
- the naphthalene oil usually contains a large amount of naphthalene (boiling point 218 ° C.), and also includes a high-boiling tar acid and base such as xylenolic acid.
- the carbol oil contains a large amount of tar acid.
- the temperature of the fraction, boiling point and the like means a temperature at normal pressure unless otherwise specified.
- First separation step In the first separation step, an alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation step, and the tar acid contained in the naphthalene oil is changed to a tar acid salt. Is separated into an oil layer 1 from which water is removed and an aqueous layer 1 containing tartrate. In the example of FIG. 1, a process of separating the oil layer 1 and the water layer 1 in the extraction tank 1 is performed.
- the tar acid contained in the naphthalene oil becomes a tar acid salt (taric acid alkali salt) and is extracted into the aqueous layer (in the alkaline aqueous solution). That is, in the example of FIG. 1, in the extraction tank 1, the mixed solution containing tartrate is converted into naphthalene oil (oil layer 1) from which taric acid has been removed (deoxidized) and water layer 1 containing tartrate. Processing to separate is performed.
- the oil layer 1 only needs to remove at least a part of the tar acid contained in the naphthalene oil. Therefore, tar acid may remain in the oil layer 1.
- Tar acids are, for example, phenol, o-cresol, m, p-cresol, xylenol and the like.
- the tar acid is one or more selected from the group consisting of phenol, o-cresol, m, p-cresol and xylenol.
- the alkaline aqueous solution is not particularly limited, and a known alkaline aqueous solution can be used, and a caustic soda aqueous solution is preferable.
- the concentration of the aqueous alkali solution is adjusted as appropriate, and is about 10 to 12% by mass as an example.
- the addition amount of the alkaline aqueous solution in the first separation step is adjusted as appropriate, but it is possible to add an alkaline aqueous solution in an amount that is excessive with respect to the content of tar acid contained in naphthalene oil in molar equivalents. preferable. In addition, it is preferable to adjust the addition amount of the alkaline aqueous solution in consideration of the mixing ratio of carbol oil and naphthalene gas oil mixed in the second separation step described later.
- naphthalene distillation process In the naphthalene distillation step, the oil layer 1 separated in the first separation step is distilled to obtain naphthalene light oil.
- the oil layer 1 In the example of FIG. 1, the oil layer 1 is charged into a naphthalene distillation tower and subjected to distillation treatment to obtain naphthalene light oil.
- naphthalene gas oil has a lower boiling point than naphthalene.
- the naphthalene gas oil has a boiling point of 200 to 210 ° C.
- the oil layer 1 usually contains tar acid that has not been transferred to the water layer 1 in the first separation step.
- the oil layer 1 is distilled to obtain naphthalene gas oil, so that tar acid can be concentrated in the naphthalene gas oil and other components can be removed from the naphthalene gas oil.
- tar acid can be concentrated in the naphthalene gas oil and other components can be removed from the naphthalene gas oil.
- components other than the naphthalene gas oil obtained in the naphthalene distillation step are transported to other steps and processed.
- the process of distilling components other than the said naphthalene light oil and obtaining naphthalene is mentioned, for example.
- ⁇ Second separation step> carboru oil obtained in the coal tar distillation step, the water layer 1 separated in the first separation step, and the naphthalene light oil obtained in the naphthalene distillation step are mixed,
- the tar acid contained in the carboruyl oil and the naphthalene light oil is used as a tar salt, and the mixed solution containing the tar acid salt is separated into an oil layer 2 from which the tar acid has been removed and an aqueous layer 2 containing the tar acid salt.
- the extraction tank 2 performs a process of separating the mixed solution containing the tartrate into an oil layer 2 and an aqueous layer 2.
- the carboxylic acid, the aqueous layer 1 and the naphthalene gas oil are mixed to form tar acid contained in the carbol oil and naphthalene gas oil as a tar acid salt. Extract into aqueous layer 2 and collect. That is, in the example of FIG. 1, in the extraction tank 2, the mixed solution containing tarates is mixed with carboru oil and naphthalene gas oil (oil layer 2) from which tar acid has been removed (deoxidized), and the extracted tarates. The process which isolate
- an aqueous alkaline solution may or may not be added to a mixture obtained by mixing carboru oil, aqueous layer 1 and naphthalene light oil.
- aqueous alkaline solution may not be added to the above mixture.
- the mixing ratio of carborub oil, water layer 1 and naphthalene gas oil in the second separation step is appropriately adjusted in consideration of the extraction rate of tartrate and the like.
- the volume ratio is 1: 0.8 to 1: 1.2.
- the tar acid contained in the carbol oil and naphthalene oil is extracted as a tartrate, and in addition to the naphthalene light oil (or the oil layer 1) that has not been recovered in the past.
- the tar acid contained is also extracted as a tartrate salt. Therefore, according to the tarate recovery method of this embodiment, the tarate can be recovered from the raw coal tar at a higher recovery rate.
- the oil layer 2 (naphthalene light oil) separated in the second separation step is conveyed to another step and processed.
- the process of obtaining the indene by distilling the said oil layer 2 is mentioned, for example.
- the method for producing tar acid according to the present invention includes a crude tar obtained by decomposing a tarate contained in the aqueous layer 2 obtained in the second separation step of the tarate recovery method with carbon dioxide and / or sulfuric acid.
- the crude tar acid production step and the tar acid purification step are not particularly limited, and can be performed, for example, in the same manner as in the conventional method.
- An arbitrary step such as a dehydration step may be provided between the crude tar acid production step and the tar acid purification step.
- various tar acid products may be distilled to produce by one or more purification distillations.
- tar acid can be produced from the tar acid salt contained in the aqueous layer 2 collected at a high recovery rate, the tar acid can be obtained with a higher yield.
- FIG. 2 is a schematic diagram showing a flow of the method for recovering a tartrate according to the present invention.
- FIG. 2 shows the relative value of the tar acid content in each step when the content of tar acid contained in the raw coal tar is 100.
- the final tar acid content is determined by the amount of tar acid 0.5 (relative value) contained in addition to the naphthalene gas oil conveyed from the naphthalene distillation step to another step, and the amount of tar acid in the aqueous layer 2.
- 97 (relative value) and the total amount of tar acid 2.5 (relative value) in the oil layer 2 is 100 (relative value).
- ⁇ Coal tar distillation process> As shown in FIG. 2, the raw coal tar was distilled and separated into naphthalene oil and carbol oil. ⁇ First separation step> Next, an aqueous caustic soda solution (concentration: 10 to 15% by mass, average addition amount: 0.8 m 3 / hr) is added to the naphthalene oil, and the tar acid contained in the naphthalene oil is changed to a tar salt, so that the oil layer 1 and the water layer 1 And separated. The tar acid concentration in the oil layer 1 was 0.40% by mass.
- the tar acid concentration in the naphthalene gas oil was 5.8% by mass. From this, it was found that the tar acid concentration in the naphthalene gas oil can be increased by about 15 times the tar acid concentration in the oil layer 1 by subjecting the oil layer 1 to the distillation treatment in the naphthalene distillation step.
- FIG. 3 is a schematic diagram showing a flow of a method for recovering a tartrate according to Comparative Example 1.
- the flow of the tartrate recovery method shown in FIG. 3 is the same as the flow of the tartrate recovery method of Example 1 except that naphthalene gas oil is not mixed in the second separation step.
- FIG. 3 also shows the relative value of the tar acid content in each step when the content of tar acid contained in the raw coal tar is 100 (relative value).
- Example 2 In the same manner as in Example 1, the raw coal tar was distilled and separated into naphthalene oil and carbol oil (coal tar distillation step). Next, in the same manner as in Example 1, a sodium hydroxide aqueous solution was added to the naphthalene oil, and the tar acid contained in the naphthalene oil was converted into a tartrate to separate the oil layer 1 and the water layer 1 (first separation step). . Thereafter, 480 mL of the aqueous layer 1 was added to 200 mL of the carboru oil, and the tar acid contained in the carboru oil was converted to a tart acid salt to separate the oil layer 2 ′ and the aqueous layer 2 ′.
- the content of tarate in the aqueous layer 2 ′ obtained as described above is 89 (relative value), which is based on the taric acid contained in the raw coal tar.
- the recovery rate was 89% in terms of tar acid.
- Example 1 the oil layer 1 is distilled in the naphthalene distillation step, and the obtained naphthalene light oil is mixed with the carboru oil and the water layer 1 in the second separation step.
- the tar acid contained in the oil layer 1 that could not be recovered in the flow of Comparative Example 1 can be recovered in the water layer 2 as a tar salt.
- the final tarate recovery rate could be increased to 97% (in terms of tar acid).
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Abstract
Provided is a method for recovering tar acid salts in a higher recovery. The method for recovering tar acid salts comprises: a coal tar distillation step in which coal tar is distilled to separately obtain naphthalene oil and carbolic oil; a first separation step, in which an aqueous alkali solution is added to the naphthalene oil obtained in the coal tar distillation step, thereby converting tar acids contained in the naphthalene oil into tar acid salts, and the naphthalene oil is separated into oil layer 1, from which the tar acids have been removed, and aqueous layer 1, which contains the tar acid salts; a naphthalene distillation step in which the oil layer 1 separated in the first separation step is distilled to obtain naphthalene light oil; and a second separation step, in which the carbolic oil obtained in the coal tar distillation step is mixed with the aqueous layer 1 separated in the first separation step and with the naphthalene light oil obtained in the naphthalene distillation step, thereby converting tar acids contained in both the carbolic oil and the naphthalene light oil into tar acid salts, and the mixture is separated into oil layer 2, from which the tar acids have been removed, and aqueous layer 2, which contains the tar acid salts.
Description
本発明は、タール酸塩の回収方法およびタール酸の製造方法に関する。
The present invention relates to a method for recovering tar acid salt and a method for producing tar acid.
石炭を乾留する際に発生するコールタールを蒸留して得られる軽質油分中には、タール酸（石炭酸）が含まれている。従来、コールタールからタール酸を製造する方法としては、コールタールを蒸留して得られる分留油のうち、タール酸を多く含有するカルボル油、ナフタリン油をアルカリ水溶液と接触させてタール酸塩として水層側に抽出して回収し、回収したタール酸塩を炭酸ガスおよび／または硫酸で分解して粗製タール酸とした後、精製蒸留して、フェノール、クレゾール、キシレノール等を主成分とするタール酸を得る方法が知られている。
The tar oil (coal acid) is contained in the light oil obtained by distilling coal tar generated when carbonizing carbon. Conventionally, as a method for producing tar acid from coal tar, among fractionated oils obtained by distillation of coal tar, carbol oil and naphthalene oil containing a large amount of tar acid are brought into contact with an alkaline aqueous solution to form tar acid salt. Extracted and recovered on the water layer side, and the recovered tarate is decomposed with carbon dioxide and / or sulfuric acid to obtain crude tar acid, followed by purification and distillation, tar containing phenol, cresol, xylenol, etc. as the main component Methods for obtaining acids are known.
このようにして得られるタール酸は、合成樹脂、難燃剤、半導体封止剤、絶縁ワニス等の各種製品の原料として有用であるため、コールタールからタール酸を効率よく得るための検討が行われている。
The tar acid obtained in this way is useful as a raw material for various products such as synthetic resins, flame retardants, semiconductor sealants, insulating varnishes, etc., so studies have been conducted to efficiently obtain tar acid from coal tar. ing.
特許文献１には、タール蒸留工程で得られたタール酸類を含有する炭化水素油混合物を苛性アルカリ水溶液で抽出し、得られたタール酸抽出液をタール系軽質油で洗浄処理した抽出液洗浄油をタール蒸留工程に装入することで、タール酸類とタール系軽質油をともに高純度で効率よく回収できるタール酸抽出液洗浄油の処理方法が開示されている。
Patent Document 1 discloses an extract washing oil obtained by extracting a hydrocarbon oil mixture containing tar acids obtained in a tar distillation step with a caustic aqueous solution, and washing the obtained tar acid extract with a tar-based light oil. A method for treating a tar acid extract washing oil that can efficiently recover both tar acids and tar light oils with high purity by charging them into a tar distillation step is disclosed.
本発明は、タール酸塩の回収率がより優れるタール酸塩の回収方法を提供することを目的とする。
An object of the present invention is to provide a method for recovering a tartrate that has a higher recovery rate of the tartrate.
本発明は、以下の態様を有する。
［１］コールタールを蒸留して、ナフタリン油とカルボル油とを分離して得るコールタール蒸留工程と、前記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する第１の分離工程と、前記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得るナフタリン蒸留工程と、前記コールタール蒸留工程で得られたカルボル油と、前記第１の分離工程で分離された水層１と、前記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する第２の分離工程と、を有するタール酸塩の回収方法。
［２］前記［１］に記載の水層２に含まれるタール酸塩を炭酸ガスおよび／または硫酸で分解して、粗製タール酸を得る粗製タール酸製造工程と、前記粗製タール酸製造工程で得られた粗製タール酸を蒸留して精製タール酸を得るタール酸精製工程と、を有するタール酸の製造方法。 The present invention has the following aspects.
[1] A coal tar distillation process obtained by distilling coal tar to separate naphthalene oil and carbol oil, and an alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation process, and contained in the naphthalene oil. The tar acid is a tar acid salt, the oil layer 1 from which the tar acid has been removed and the water layer 1 containing the tar acid salt are separated, and the oil layer 1 separated in the first separation process is Distillation to obtain naphthalene gas oil Naphthalene distillation step, carboru oil obtained in the coal tar distillation step, aqueous layer 1 separated in the first separation step, and naphthalene obtained in the naphthalene distillation step Gas oil is mixed, and tar acid contained in the carbol oil and naphthalene gas oil is changed to tarate, and separated into oil layer 2 from which tar acid has been removed and aqueous layer 2 containing tarate. Method for recovering tar acid salt having a second separation step, the that.
[2] In the crude tar acid production step of decomposing the tarate contained in the aqueous layer 2 described in [1] with carbon dioxide gas and / or sulfuric acid to obtain a crude tar acid, and the crude tar acid production step And a tar acid purification step for obtaining a purified tar acid by distilling the obtained crude tar acid.
［１］コールタールを蒸留して、ナフタリン油とカルボル油とを分離して得るコールタール蒸留工程と、前記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する第１の分離工程と、前記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得るナフタリン蒸留工程と、前記コールタール蒸留工程で得られたカルボル油と、前記第１の分離工程で分離された水層１と、前記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する第２の分離工程と、を有するタール酸塩の回収方法。
［２］前記［１］に記載の水層２に含まれるタール酸塩を炭酸ガスおよび／または硫酸で分解して、粗製タール酸を得る粗製タール酸製造工程と、前記粗製タール酸製造工程で得られた粗製タール酸を蒸留して精製タール酸を得るタール酸精製工程と、を有するタール酸の製造方法。 The present invention has the following aspects.
[1] A coal tar distillation process obtained by distilling coal tar to separate naphthalene oil and carbol oil, and an alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation process, and contained in the naphthalene oil. The tar acid is a tar acid salt, the oil layer 1 from which the tar acid has been removed and the water layer 1 containing the tar acid salt are separated, and the oil layer 1 separated in the first separation process is Distillation to obtain naphthalene gas oil Naphthalene distillation step, carboru oil obtained in the coal tar distillation step, aqueous layer 1 separated in the first separation step, and naphthalene obtained in the naphthalene distillation step Gas oil is mixed, and tar acid contained in the carbol oil and naphthalene gas oil is changed to tarate, and separated into oil layer 2 from which tar acid has been removed and aqueous layer 2 containing tarate. Method for recovering tar acid salt having a second separation step, the that.
[2] In the crude tar acid production step of decomposing the tarate contained in the aqueous layer 2 described in [1] with carbon dioxide gas and / or sulfuric acid to obtain a crude tar acid, and the crude tar acid production step And a tar acid purification step for obtaining a purified tar acid by distilling the obtained crude tar acid.
本発明のタール酸塩の回収方法によれば、コールタールから、より高い回収率でタール酸塩を回収できる。
また、本発明のタール酸の製造方法によれば、コールタールから、より高い収率でタール酸を得ることができる。 According to the tarate recovery method of the present invention, tarate can be recovered from coal tar at a higher recovery rate.
Moreover, according to the method for producing tar acid of the present invention, tar acid can be obtained from coal tar with higher yield.
また、本発明のタール酸の製造方法によれば、コールタールから、より高い収率でタール酸を得ることができる。 According to the tarate recovery method of the present invention, tarate can be recovered from coal tar at a higher recovery rate.
Moreover, according to the method for producing tar acid of the present invention, tar acid can be obtained from coal tar with higher yield.
以下、本発明のタール酸塩の回収方法およびタール酸の製造方法の一実施形態について、図面を参照しながら説明する。ただし、本発明は、以下の実施形態に限定されない。
Hereinafter, an embodiment of a method for recovering a tartrate and a method for producing a tar acid according to the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments.
（タール酸塩の回収方法）
図１は、本発明のタール酸塩の回収方法の一実施形態のフローを示す概略図である。本発明のタール酸塩の回収方法は、コールタールを蒸留して、ナフタリン油とカルボル油とを分離して得るコールタール蒸留工程と、前記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する第１の分離工程と、前記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得るナフタリン蒸留工程と、前記コールタール蒸留工程で得られたカルボル油と、前記第１の分離工程で分離された水層１と、前記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する第２の分離工程と、を有する。 (Tarrate recovery method)
FIG. 1 is a schematic diagram showing the flow of one embodiment of the method for recovering a tartrate of the present invention. The tarate recovery method of the present invention includes a coal tar distillation step obtained by distilling coal tar to separate naphthalene oil and carbol oil, and an alkaline aqueous solution in the naphthalene oil obtained in the coal tar distillation step. In addition, the first separation step of separating the tar acid contained in the naphthalene oil into a tartrate and separating the oil layer 1 from which the tar acid has been removed and the aqueous layer 1 containing the tartrate, and the first separation The oil layer 1 separated in the step is distilled to obtain a naphthalene light oil, a naphthalene distillation step, the carbol oil obtained in the coal tar distillation step, the water layer 1 separated in the first separation step, and the The naphthalene gas oil obtained in the naphthalene distillation step is mixed, the tar acid contained in the carbol oil and the naphthalene gas oil is changed to a tar acid salt, and the oil layer 2 from which the tar acid has been removed and the tar A second separation step of separating the water layer 2 containing salt,.
図１は、本発明のタール酸塩の回収方法の一実施形態のフローを示す概略図である。本発明のタール酸塩の回収方法は、コールタールを蒸留して、ナフタリン油とカルボル油とを分離して得るコールタール蒸留工程と、前記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する第１の分離工程と、前記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得るナフタリン蒸留工程と、前記コールタール蒸留工程で得られたカルボル油と、前記第１の分離工程で分離された水層１と、前記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する第２の分離工程と、を有する。 (Tarrate recovery method)
FIG. 1 is a schematic diagram showing the flow of one embodiment of the method for recovering a tartrate of the present invention. The tarate recovery method of the present invention includes a coal tar distillation step obtained by distilling coal tar to separate naphthalene oil and carbol oil, and an alkaline aqueous solution in the naphthalene oil obtained in the coal tar distillation step. In addition, the first separation step of separating the tar acid contained in the naphthalene oil into a tartrate and separating the oil layer 1 from which the tar acid has been removed and the aqueous layer 1 containing the tartrate, and the first separation The oil layer 1 separated in the step is distilled to obtain a naphthalene light oil, a naphthalene distillation step, the carbol oil obtained in the coal tar distillation step, the water layer 1 separated in the first separation step, and the The naphthalene gas oil obtained in the naphthalene distillation step is mixed, the tar acid contained in the carbol oil and the naphthalene gas oil is changed to a tar acid salt, and the oil layer 2 from which the tar acid has been removed and the tar A second separation step of separating the water layer 2 containing salt,.
＜コールタール蒸留工程＞
コールタール蒸留工程では、原料となるコールタールを蒸留して、ナフタリン油とカルボル油とを分離して得る。図１の例では、コールタールをタール蒸留塔に装入して蒸留処理し、ナフタリン油とカルボル油とを分離している。この際、前記ナフタリン油は、約２００～２５０℃の留分として得られ、前記カルボル油は、約１７０～２００℃の留分として得られる。前記ナフタリン油には、通常、ナフタリン（沸点２１８℃）が多く含まれ、キシレノール酸等の高沸点のタール酸や塩基も含まれる。また、前記カルボル油には、タール酸が多く含まれる。なお、本明細書における留分、沸点等の温度は、特に断らない限り常圧での温度を意味する。 <Coal tar distillation process>
In the coal tar distillation step, coal tar as a raw material is distilled to obtain naphthalene oil and carbol oil. In the example of FIG. 1, coal tar is charged into a tar distillation column and distilled to separate naphthalene oil and carbol oil. At this time, the naphthalene oil is obtained as a fraction of about 200 to 250 ° C., and the carbol oil is obtained as a fraction of about 170 to 200 ° C. The naphthalene oil usually contains a large amount of naphthalene (boiling point 218 ° C.), and also includes a high-boiling tar acid and base such as xylenolic acid. The carbol oil contains a large amount of tar acid. In the present specification, the temperature of the fraction, boiling point and the like means a temperature at normal pressure unless otherwise specified.
コールタール蒸留工程では、原料となるコールタールを蒸留して、ナフタリン油とカルボル油とを分離して得る。図１の例では、コールタールをタール蒸留塔に装入して蒸留処理し、ナフタリン油とカルボル油とを分離している。この際、前記ナフタリン油は、約２００～２５０℃の留分として得られ、前記カルボル油は、約１７０～２００℃の留分として得られる。前記ナフタリン油には、通常、ナフタリン（沸点２１８℃）が多く含まれ、キシレノール酸等の高沸点のタール酸や塩基も含まれる。また、前記カルボル油には、タール酸が多く含まれる。なお、本明細書における留分、沸点等の温度は、特に断らない限り常圧での温度を意味する。 <Coal tar distillation process>
In the coal tar distillation step, coal tar as a raw material is distilled to obtain naphthalene oil and carbol oil. In the example of FIG. 1, coal tar is charged into a tar distillation column and distilled to separate naphthalene oil and carbol oil. At this time, the naphthalene oil is obtained as a fraction of about 200 to 250 ° C., and the carbol oil is obtained as a fraction of about 170 to 200 ° C. The naphthalene oil usually contains a large amount of naphthalene (boiling point 218 ° C.), and also includes a high-boiling tar acid and base such as xylenolic acid. The carbol oil contains a large amount of tar acid. In the present specification, the temperature of the fraction, boiling point and the like means a temperature at normal pressure unless otherwise specified.
＜第１の分離工程＞
第１の分離工程では、上記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸塩を含む混合溶液を、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する。図１の例では、抽出槽１で油層１と水層１とに分離する処理が行われる。 <First separation step>
In the first separation step, an alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation step, and the tar acid contained in the naphthalene oil is changed to a tar acid salt. Is separated into an oil layer 1 from which water is removed and an aqueous layer 1 containing tartrate. In the example of FIG. 1, a process of separating the oil layer 1 and the water layer 1 in the extraction tank 1 is performed.
第１の分離工程では、上記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸塩を含む混合溶液を、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する。図１の例では、抽出槽１で油層１と水層１とに分離する処理が行われる。 <First separation step>
In the first separation step, an alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation step, and the tar acid contained in the naphthalene oil is changed to a tar acid salt. Is separated into an oil layer 1 from which water is removed and an aqueous layer 1 containing tartrate. In the example of FIG. 1, a process of separating the oil layer 1 and the water layer 1 in the extraction tank 1 is performed.
ナフタリン油にアルカリ水溶液を加えることで、ナフタリン油に含まれるタール酸は、タール酸塩（タール酸アルカリ塩）となり、水層（アルカリ水溶液中）に抽出される。すなわち、図１の例では、抽出槽１では、タール酸塩を含む混合溶液を、タール酸が除去（脱酸）されたナフタリン油（油層１）と、タール酸塩を含む水層１とに分離する処理が行われる。
By adding an alkaline aqueous solution to naphthalene oil, the tar acid contained in the naphthalene oil becomes a tar acid salt (taric acid alkali salt) and is extracted into the aqueous layer (in the alkaline aqueous solution). That is, in the example of FIG. 1, in the extraction tank 1, the mixed solution containing tartrate is converted into naphthalene oil (oil layer 1) from which taric acid has been removed (deoxidized) and water layer 1 containing tartrate. Processing to separate is performed.
油層１は、ナフタリン油に含まれるタール酸の少なくとも一部が除去されていればよい。したがって、油層１にはタール酸が残っていてもよい。
The oil layer 1 only needs to remove at least a part of the tar acid contained in the naphthalene oil. Therefore, tar acid may remain in the oil layer 1.
タール酸は、例えば、フェノール、ｏ－クレゾール、ｍ，ｐ－クレゾールおよびキシレノールなどである。一実施形態では、タール酸は、フェノール、ｏ－クレゾール、ｍ，ｐ－クレゾールおよびキシレノールからなる群より選択される１種以上である。
Tar acids are, for example, phenol, o-cresol, m, p-cresol, xylenol and the like. In one embodiment, the tar acid is one or more selected from the group consisting of phenol, o-cresol, m, p-cresol and xylenol.
前記アルカリ水溶液としては、特に限定されず、公知のアルカリ水溶液を用いることができ、苛性ソーダ水溶液が好ましい。
The alkaline aqueous solution is not particularly limited, and a known alkaline aqueous solution can be used, and a caustic soda aqueous solution is preferable.
前記アルカリ水溶液の濃度は、適宜に調整されるが、一例として、１０～１２質量％程度である。
The concentration of the aqueous alkali solution is adjusted as appropriate, and is about 10 to 12% by mass as an example.
第１の分離工程でのアルカリ水溶液の添加量は、適宜に調整されるが、モル当量で、ナフタリン油に含まれるタール酸の含有量に対して過剰となる量のアルカリ水溶液を添加することが好ましい。また、後述の第２の分離工程で混合されるカルボル油とナフタリン軽油との混合比等を考慮して、アルカリ水溶液の添加量を調整することが好ましい。
The addition amount of the alkaline aqueous solution in the first separation step is adjusted as appropriate, but it is possible to add an alkaline aqueous solution in an amount that is excessive with respect to the content of tar acid contained in naphthalene oil in molar equivalents. preferable. In addition, it is preferable to adjust the addition amount of the alkaline aqueous solution in consideration of the mixing ratio of carbol oil and naphthalene gas oil mixed in the second separation step described later.
＜ナフタリン蒸留工程＞
ナフタリン蒸留工程では、上記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得る。図１の例では、油層１を、ナフタリン蒸留塔に装入して蒸留処理してナフタリン軽油を得ている。通常、ナフタリン軽油は、ナフタリンよりも低沸点である。一例として、前記ナフタリン軽油は２００～２１０℃の沸点を有する。 <Naphthalene distillation process>
In the naphthalene distillation step, the oil layer 1 separated in the first separation step is distilled to obtain naphthalene light oil. In the example of FIG. 1, the oil layer 1 is charged into a naphthalene distillation tower and subjected to distillation treatment to obtain naphthalene light oil. Usually, naphthalene gas oil has a lower boiling point than naphthalene. As an example, the naphthalene gas oil has a boiling point of 200 to 210 ° C.
ナフタリン蒸留工程では、上記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得る。図１の例では、油層１を、ナフタリン蒸留塔に装入して蒸留処理してナフタリン軽油を得ている。通常、ナフタリン軽油は、ナフタリンよりも低沸点である。一例として、前記ナフタリン軽油は２００～２１０℃の沸点を有する。 <Naphthalene distillation process>
In the naphthalene distillation step, the oil layer 1 separated in the first separation step is distilled to obtain naphthalene light oil. In the example of FIG. 1, the oil layer 1 is charged into a naphthalene distillation tower and subjected to distillation treatment to obtain naphthalene light oil. Usually, naphthalene gas oil has a lower boiling point than naphthalene. As an example, the naphthalene gas oil has a boiling point of 200 to 210 ° C.
上記油層１には、通常、第１の分離工程で水層１に移行されなかったタール酸が含まれている。このナフタリン蒸留工程で、油層１を蒸留処理してナフタリン軽油を得ることで、該ナフタリン軽油中にタール酸を濃縮でき、かつ他の成分を該ナフタリン軽油中から除去することができる。これにより、後述の第２の分離工程でナフタリン軽油からタール酸塩を抽出しやすくなり、タール酸塩の回収率をより高めることができる。
The oil layer 1 usually contains tar acid that has not been transferred to the water layer 1 in the first separation step. In this naphthalene distillation step, the oil layer 1 is distilled to obtain naphthalene gas oil, so that tar acid can be concentrated in the naphthalene gas oil and other components can be removed from the naphthalene gas oil. Thereby, it becomes easy to extract a tartrate from naphthalene light oil in the second separation step described later, and the recovery rate of tartrate can be further increased.
一実施形態では、このナフタリン蒸留工程で得られる前記ナフタリン軽油以外の成分は、他工程へ搬送され処理される。前記他工程としては、例えば、前記ナフタリン軽油以外の成分を蒸留処理してナフタリンを得る工程が挙げられる。
In one embodiment, components other than the naphthalene gas oil obtained in the naphthalene distillation step are transported to other steps and processed. As said other process, the process of distilling components other than the said naphthalene light oil and obtaining naphthalene is mentioned, for example.
＜第２の分離工程＞
第２の分離工程では、上記コールタール蒸留工程で得られたカルボル油と、上記第１の分離工程で分離された水層１と、上記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸塩を含む混合溶液を、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する。図１の例では、抽出槽２で、タール酸塩を含む混合溶液を、油層２と水層２とに分離する処理が行われる。 <Second separation step>
In the second separation step, carboru oil obtained in the coal tar distillation step, the water layer 1 separated in the first separation step, and the naphthalene light oil obtained in the naphthalene distillation step are mixed, The tar acid contained in the carboruyl oil and the naphthalene light oil is used as a tar salt, and the mixed solution containing the tar acid salt is separated into an oil layer 2 from which the tar acid has been removed and an aqueous layer 2 containing the tar acid salt. In the example of FIG. 1, the extraction tank 2 performs a process of separating the mixed solution containing the tartrate into an oil layer 2 and an aqueous layer 2.
第２の分離工程では、上記コールタール蒸留工程で得られたカルボル油と、上記第１の分離工程で分離された水層１と、上記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸塩を含む混合溶液を、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する。図１の例では、抽出槽２で、タール酸塩を含む混合溶液を、油層２と水層２とに分離する処理が行われる。 <Second separation step>
In the second separation step, carboru oil obtained in the coal tar distillation step, the water layer 1 separated in the first separation step, and the naphthalene light oil obtained in the naphthalene distillation step are mixed, The tar acid contained in the carboruyl oil and the naphthalene light oil is used as a tar salt, and the mixed solution containing the tar acid salt is separated into an oil layer 2 from which the tar acid has been removed and an aqueous layer 2 containing the tar acid salt. In the example of FIG. 1, the extraction tank 2 performs a process of separating the mixed solution containing the tartrate into an oil layer 2 and an aqueous layer 2.
この第２の分離工程では、上記カルボル油と、上記水層１と、上記ナフタリン軽油とを混合することで、カルボル油およびナフタリン軽油中に含まれるタール酸をタール酸塩とし、タール酸塩を水層２中に抽出して回収する。すなわち、図１の例では、抽出槽２では、タール酸塩を含む混合溶液を、タール酸が除去（脱酸）されたカルボル油およびナフタリン軽油（油層２）と、前記抽出されたタール酸塩を含む水層２とに分離する処理が行われる。
In this second separation step, the carboxylic acid, the aqueous layer 1 and the naphthalene gas oil are mixed to form tar acid contained in the carbol oil and naphthalene gas oil as a tar acid salt. Extract into aqueous layer 2 and collect. That is, in the example of FIG. 1, in the extraction tank 2, the mixed solution containing tarates is mixed with carboru oil and naphthalene gas oil (oil layer 2) from which tar acid has been removed (deoxidized), and the extracted tarates. The process which isolate | separates into the water layer 2 containing is performed.
第２の分離工程では、カルボル油と、水層１と、ナフタリン軽油とを混合した混合物に、アルカリ水溶液を添加してもよいし、添加しなくてもよい。例えば、第１の分離工程で、ナフタリン油に含まれるタール酸の含有量に対して過剰量のアルカリ水溶液を添加した場合、水層１中にはアルカリが存在するため、第２の分離工程では、上記混合物にアルカリ水溶液を添加しなくてもよい。
In the second separation step, an aqueous alkaline solution may or may not be added to a mixture obtained by mixing carboru oil, aqueous layer 1 and naphthalene light oil. For example, in the first separation step, when an excessive amount of alkaline aqueous solution is added to the content of tar acid contained in naphthalene oil, alkali is present in the aqueous layer 1, and therefore in the second separation step The alkaline aqueous solution may not be added to the above mixture.
第２の分離工程におけるカルボル油と、水層１と、ナフタリン軽油との混合比は、タール酸塩の抽出率等を考慮して適宜に調整される。一例として、カルボル油とナフタリン軽油の合計と、水層１との体積比は、（カルボル油とナフタリン軽油の合計：水層１）＝１：０．６～１：１．４であり、別の例では、当該体積比は、１：０．８～１：１．２である。
The mixing ratio of carborub oil, water layer 1 and naphthalene gas oil in the second separation step is appropriately adjusted in consideration of the extraction rate of tartrate and the like. As an example, the volume ratio of the total of carbol oil and naphthalene light oil to the water layer 1 is (total of carbol oil and naphthalene light oil: water layer 1) = 1: 0.6 to 1: 1.4. In the example, the volume ratio is 1: 0.8 to 1: 1.2.
カルボル油と、ナフタリン軽油との体積比は、一例では、カルボル油：ナフタリン軽油＝１：０．５～１：５であり、別の例では、当該体積比は、１：１～１：２である。
In one example, the volume ratio of carbol oil to naphthalene gas oil is carbol oil: naphthalene gas oil = 1: 0.5 to 1: 5, and in another example, the volume ratio is 1: 1 to 1: 2. It is.
このようにして得られた水層２には、カルボル油およびナフタリン油に含まれるタール酸がタール酸塩として抽出されていることに加え、従来回収されていなかったナフタリン軽油（あるいは油層１）に含まれるタール酸もタール酸塩として抽出されている。そのため、本実施形態のタール酸塩の回収方法によれば、原料のコールタールから、より高い回収率でタール酸塩を回収することができる。
In the aqueous layer 2 thus obtained, the tar acid contained in the carbol oil and naphthalene oil is extracted as a tartrate, and in addition to the naphthalene light oil (or the oil layer 1) that has not been recovered in the past. The tar acid contained is also extracted as a tartrate salt. Therefore, according to the tarate recovery method of this embodiment, the tarate can be recovered from the raw coal tar at a higher recovery rate.
一実施形態では、この第２の分離工程で分離された油層２（ナフタリン軽油）は、他工程へ搬送され処理される。前記他工程としては、例えば、前記油層２を蒸留処理してインデンを得る工程が挙げられる。
In one embodiment, the oil layer 2 (naphthalene light oil) separated in the second separation step is conveyed to another step and processed. As said other process, the process of obtaining the indene by distilling the said oil layer 2 is mentioned, for example.
（タール酸の製造方法）
本発明のタール酸の製造方法は、上記タール酸塩の回収方法の第２の分離工程で得られた水層２に含まれるタール酸塩を炭酸ガスおよび／または硫酸で分解して、粗製タール酸を得る粗製タール酸製造工程と、前記粗製タール酸製造工程で得られた粗製タール酸を蒸留して精製タール酸を得るタール酸精製工程と、を有する。 (Production method of tar acid)
The method for producing tar acid according to the present invention includes a crude tar obtained by decomposing a tarate contained in the aqueous layer 2 obtained in the second separation step of the tarate recovery method with carbon dioxide and / or sulfuric acid. A crude tar acid production step for obtaining an acid; and a tar acid purification step for obtaining a purified tar acid by distilling the crude tar acid obtained in the crude tar acid production step.
本発明のタール酸の製造方法は、上記タール酸塩の回収方法の第２の分離工程で得られた水層２に含まれるタール酸塩を炭酸ガスおよび／または硫酸で分解して、粗製タール酸を得る粗製タール酸製造工程と、前記粗製タール酸製造工程で得られた粗製タール酸を蒸留して精製タール酸を得るタール酸精製工程と、を有する。 (Production method of tar acid)
The method for producing tar acid according to the present invention includes a crude tar obtained by decomposing a tarate contained in the aqueous layer 2 obtained in the second separation step of the tarate recovery method with carbon dioxide and / or sulfuric acid. A crude tar acid production step for obtaining an acid; and a tar acid purification step for obtaining a purified tar acid by distilling the crude tar acid obtained in the crude tar acid production step.
前記粗製タール酸製造工程およびタール酸精製工程は、特に限定されないが、例えば従来の方法と同様に実施することができる。
The crude tar acid production step and the tar acid purification step are not particularly limited, and can be performed, for example, in the same manner as in the conventional method.
粗製タール酸製造工程と、タール酸精製工程との間に、脱水工程等の任意の工程が設けられてもよい。
An arbitrary step such as a dehydration step may be provided between the crude tar acid production step and the tar acid purification step.
上記タール酸精製工程では、１回または複数回の精製蒸留により各種タール酸製品（フェノール、オルトクレゾール、メタクレゾール、キシレノール等）を留出させ製造してもよい。
In the tar acid purification step, various tar acid products (phenol, orthocresol, metacresol, xylenol, etc.) may be distilled to produce by one or more purification distillations.
本発明のタール酸の製造方法によれば、高い回収率で回収された水層２に含まれるタール酸塩からタール酸を製造できるため、より高い収率でタール酸を得ることができる。
According to the method for producing tar acid of the present invention, since tar acid can be produced from the tar acid salt contained in the aqueous layer 2 collected at a high recovery rate, the tar acid can be obtained with a higher yield.
コールタールからタール酸塩を回収する工程を想定したラボ試験を実施した。
（実施例１）
図２は、本発明のタール酸塩の回収方法のフローを示す概略図である。図２には、原料のコールタールに含まれるタール酸の含有量を１００とした場合の、各工程でのタール酸の含有量の相対値を示してある。図２の場合、最終的なタール酸の含有量は、ナフタリン蒸留工程から他工程へ搬送されるナフタリン軽油以外に含まれるタール酸量０．５（相対値）と、水層２のタール酸量９７（相対値）と、油層２のタール酸量２．５（相対値）との合計１００（相対値）である。 A laboratory test was conducted assuming a process for recovering tar tartrate from coal tar.
Example 1
FIG. 2 is a schematic diagram showing a flow of the method for recovering a tartrate according to the present invention. FIG. 2 shows the relative value of the tar acid content in each step when the content of tar acid contained in the raw coal tar is 100. In the case of FIG. 2, the final tar acid content is determined by the amount of tar acid 0.5 (relative value) contained in addition to the naphthalene gas oil conveyed from the naphthalene distillation step to another step, and the amount of tar acid in the aqueous layer 2. 97 (relative value) and the total amount of tar acid 2.5 (relative value) in the oil layer 2 is 100 (relative value).
（実施例１）
図２は、本発明のタール酸塩の回収方法のフローを示す概略図である。図２には、原料のコールタールに含まれるタール酸の含有量を１００とした場合の、各工程でのタール酸の含有量の相対値を示してある。図２の場合、最終的なタール酸の含有量は、ナフタリン蒸留工程から他工程へ搬送されるナフタリン軽油以外に含まれるタール酸量０．５（相対値）と、水層２のタール酸量９７（相対値）と、油層２のタール酸量２．５（相対値）との合計１００（相対値）である。 A laboratory test was conducted assuming a process for recovering tar tartrate from coal tar.
Example 1
FIG. 2 is a schematic diagram showing a flow of the method for recovering a tartrate according to the present invention. FIG. 2 shows the relative value of the tar acid content in each step when the content of tar acid contained in the raw coal tar is 100. In the case of FIG. 2, the final tar acid content is determined by the amount of tar acid 0.5 (relative value) contained in addition to the naphthalene gas oil conveyed from the naphthalene distillation step to another step, and the amount of tar acid in the aqueous layer 2. 97 (relative value) and the total amount of tar acid 2.5 (relative value) in the oil layer 2 is 100 (relative value).
＜コールタール蒸留工程＞
図２に示すように、原料のコールタールを蒸留し、ナフタリン油と、カルボル油とに分離した。
＜第１の分離工程＞
次いで、上記ナフタリン油に苛性ソーダ水溶液（濃度１０～１５質量％、添加量平均０．８ｍ3／ｈｒ）を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、油層１と水層１とに分離した。油層１中のタール酸濃度は、０．４０質量％であった。
＜ナフタリン蒸留工程＞
上記第１の分離工程で分離した油層１を蒸留処理し、ナフタリン軽油を得た。このナフタリン軽油中のタール酸濃度は、５．８質量％であった。このことから、ナフタリン蒸留工程で油層１を蒸留処理することで、ナフタリン軽油中のタール酸濃度を油層１中のタール酸濃度より１５倍程度高められることがわかった。
＜第２の分離工程＞
次に、上記実施形態の抽出槽２内を想定したタール酸塩の抽出試験を行った。上記カルボル油２００ｍＬに、上記ナフタリン軽油３００ｍＬを加え、これに上記水層１を４８０ｍＬ加えて、カルボル油およびナフタリン軽油に含まれるタール酸をタール酸塩とした。そして、このタール酸塩を含む混合溶液を、油層２と水層２とに分離した。
以上のようにして得られた水層２中のタール酸塩の含有量（タール酸換算）は、９７（相対値）であり、原料のコールタール中に含まれていたタール酸に対してタール酸換算で回収率９７％であった。 <Coal tar distillation process>
As shown in FIG. 2, the raw coal tar was distilled and separated into naphthalene oil and carbol oil.
<First separation step>
Next, an aqueous caustic soda solution (concentration: 10 to 15% by mass, average addition amount: 0.8 m 3 / hr) is added to the naphthalene oil, and the tar acid contained in the naphthalene oil is changed to a tar salt, so that the oil layer 1 and the water layer 1 And separated. The tar acid concentration in the oil layer 1 was 0.40% by mass.
<Naphthalene distillation process>
The oil layer 1 separated in the first separation step was subjected to distillation treatment to obtain naphthalene light oil. The tar acid concentration in the naphthalene gas oil was 5.8% by mass. From this, it was found that the tar acid concentration in the naphthalene gas oil can be increased by about 15 times the tar acid concentration in the oil layer 1 by subjecting the oil layer 1 to the distillation treatment in the naphthalene distillation step.
<Second separation step>
Next, a tartrate extraction test was performed assuming the inside of the extraction tank 2 of the above embodiment. 300 mL of the above-mentioned naphthalene light oil was added to 200 mL of the above-mentioned carboll oil, and 480 mL of the above water layer 1 was added thereto, so that tar acid contained in the carbol oil and naphthalene light oil was used as a tartrate. Then, the mixed solution containing the tartrate was separated into an oil layer 2 and an aqueous layer 2.
The content of tarate in the aqueous layer 2 obtained as described above (in terms of tar acid) is 97 (relative value), and tar is contained in the tar acid contained in the raw coal tar. The recovery was 97% in terms of acid.
図２に示すように、原料のコールタールを蒸留し、ナフタリン油と、カルボル油とに分離した。
＜第１の分離工程＞
次いで、上記ナフタリン油に苛性ソーダ水溶液（濃度１０～１５質量％、添加量平均０．８ｍ3／ｈｒ）を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、油層１と水層１とに分離した。油層１中のタール酸濃度は、０．４０質量％であった。
＜ナフタリン蒸留工程＞
上記第１の分離工程で分離した油層１を蒸留処理し、ナフタリン軽油を得た。このナフタリン軽油中のタール酸濃度は、５．８質量％であった。このことから、ナフタリン蒸留工程で油層１を蒸留処理することで、ナフタリン軽油中のタール酸濃度を油層１中のタール酸濃度より１５倍程度高められることがわかった。
＜第２の分離工程＞
次に、上記実施形態の抽出槽２内を想定したタール酸塩の抽出試験を行った。上記カルボル油２００ｍＬに、上記ナフタリン軽油３００ｍＬを加え、これに上記水層１を４８０ｍＬ加えて、カルボル油およびナフタリン軽油に含まれるタール酸をタール酸塩とした。そして、このタール酸塩を含む混合溶液を、油層２と水層２とに分離した。
以上のようにして得られた水層２中のタール酸塩の含有量（タール酸換算）は、９７（相対値）であり、原料のコールタール中に含まれていたタール酸に対してタール酸換算で回収率９７％であった。 <Coal tar distillation process>
As shown in FIG. 2, the raw coal tar was distilled and separated into naphthalene oil and carbol oil.
<First separation step>
Next, an aqueous caustic soda solution (concentration: 10 to 15% by mass, average addition amount: 0.8 m 3 / hr) is added to the naphthalene oil, and the tar acid contained in the naphthalene oil is changed to a tar salt, so that the oil layer 1 and the water layer 1 And separated. The tar acid concentration in the oil layer 1 was 0.40% by mass.
<Naphthalene distillation process>
The oil layer 1 separated in the first separation step was subjected to distillation treatment to obtain naphthalene light oil. The tar acid concentration in the naphthalene gas oil was 5.8% by mass. From this, it was found that the tar acid concentration in the naphthalene gas oil can be increased by about 15 times the tar acid concentration in the oil layer 1 by subjecting the oil layer 1 to the distillation treatment in the naphthalene distillation step.
<Second separation step>
Next, a tartrate extraction test was performed assuming the inside of the extraction tank 2 of the above embodiment. 300 mL of the above-mentioned naphthalene light oil was added to 200 mL of the above-mentioned carboll oil, and 480 mL of the above water layer 1 was added thereto, so that tar acid contained in the carbol oil and naphthalene light oil was used as a tartrate. Then, the mixed solution containing the tartrate was separated into an oil layer 2 and an aqueous layer 2.
The content of tarate in the aqueous layer 2 obtained as described above (in terms of tar acid) is 97 (relative value), and tar is contained in the tar acid contained in the raw coal tar. The recovery was 97% in terms of acid.
（比較例１）
次に、本発明の比較例として、図３に示すフローでタール酸塩の回収試験を行った結果を示す。図３は、比較例１のタール酸塩の回収方法のフローを示す概略図である。図３に示すタール酸塩の回収方法のフローは、第２の分離工程でナフタリン軽油を混合しないこと以外は、実施例１のタール酸塩の回収方法のフローと同様である。なお、図３にも、原料のコールタールに含まれるタール酸の含有量を１００（相対値）とした場合の、各工程でのタール酸の含有量の相対値を示してある。 (Comparative Example 1)
Next, as a comparative example of the present invention, the result of a tarate recovery test performed according to the flow shown in FIG. 3 is shown. FIG. 3 is a schematic diagram showing a flow of a method for recovering a tartrate according to Comparative Example 1. The flow of the tartrate recovery method shown in FIG. 3 is the same as the flow of the tartrate recovery method of Example 1 except that naphthalene gas oil is not mixed in the second separation step. FIG. 3 also shows the relative value of the tar acid content in each step when the content of tar acid contained in the raw coal tar is 100 (relative value).
次に、本発明の比較例として、図３に示すフローでタール酸塩の回収試験を行った結果を示す。図３は、比較例１のタール酸塩の回収方法のフローを示す概略図である。図３に示すタール酸塩の回収方法のフローは、第２の分離工程でナフタリン軽油を混合しないこと以外は、実施例１のタール酸塩の回収方法のフローと同様である。なお、図３にも、原料のコールタールに含まれるタール酸の含有量を１００（相対値）とした場合の、各工程でのタール酸の含有量の相対値を示してある。 (Comparative Example 1)
Next, as a comparative example of the present invention, the result of a tarate recovery test performed according to the flow shown in FIG. 3 is shown. FIG. 3 is a schematic diagram showing a flow of a method for recovering a tartrate according to Comparative Example 1. The flow of the tartrate recovery method shown in FIG. 3 is the same as the flow of the tartrate recovery method of Example 1 except that naphthalene gas oil is not mixed in the second separation step. FIG. 3 also shows the relative value of the tar acid content in each step when the content of tar acid contained in the raw coal tar is 100 (relative value).
実施例１と同様にして、原料のコールタールを蒸留し、ナフタリン油と、カルボル油とに分離した（コールタール蒸留工程）。次いで、実施例１と同様に、前記ナフタリン油に苛性ソーダ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、油層１と水層１とに分離した（第１の分離工程）。その後、前記カルボル油２００ｍＬに、前記水層１を４８０ｍＬ加えて、カルボル油に含まれるタール酸をタール酸塩とし、油層２'と水層２'とに分離した。
以上のようにして得られた水層２'中のタール酸塩の含有量（タール酸換算）は、８９（相対値）であり、原料のコールタール中に含まれていたタール酸に対してタール酸換算で回収率８９％であった。 In the same manner as in Example 1, the raw coal tar was distilled and separated into naphthalene oil and carbol oil (coal tar distillation step). Next, in the same manner as in Example 1, a sodium hydroxide aqueous solution was added to the naphthalene oil, and the tar acid contained in the naphthalene oil was converted into a tartrate to separate the oil layer 1 and the water layer 1 (first separation step). . Thereafter, 480 mL of the aqueous layer 1 was added to 200 mL of the carboru oil, and the tar acid contained in the carboru oil was converted to a tart acid salt to separate the oil layer 2 ′ and the aqueous layer 2 ′.
The content of tarate in the aqueous layer 2 ′ obtained as described above (in terms of taric acid) is 89 (relative value), which is based on the taric acid contained in the raw coal tar. The recovery rate was 89% in terms of tar acid.
以上のようにして得られた水層２'中のタール酸塩の含有量（タール酸換算）は、８９（相対値）であり、原料のコールタール中に含まれていたタール酸に対してタール酸換算で回収率８９％であった。 In the same manner as in Example 1, the raw coal tar was distilled and separated into naphthalene oil and carbol oil (coal tar distillation step). Next, in the same manner as in Example 1, a sodium hydroxide aqueous solution was added to the naphthalene oil, and the tar acid contained in the naphthalene oil was converted into a tartrate to separate the oil layer 1 and the water layer 1 (first separation step). . Thereafter, 480 mL of the aqueous layer 1 was added to 200 mL of the carboru oil, and the tar acid contained in the carboru oil was converted to a tart acid salt to separate the oil layer 2 ′ and the aqueous layer 2 ′.
The content of tarate in the aqueous layer 2 ′ obtained as described above (in terms of taric acid) is 89 (relative value), which is based on the taric acid contained in the raw coal tar. The recovery rate was 89% in terms of tar acid.
実施例１および比較例１の各工程でのタール酸の濃度を詳細に検討すると、図２、図３に示すように、ナフタリン油に苛性ソーダ水溶液を加えて分離した油層１には、水層１にタール酸塩として抽出されなかったタール酸が１０．５（相対値）含まれていた。図３に示す比較例１のフローでは、この油層１に含まれるタール酸はタール酸として回収されずロス分となる。
When the concentration of tar acid in each step of Example 1 and Comparative Example 1 is examined in detail, as shown in FIGS. 2 and 3, the oil layer 1 separated by adding a sodium hydroxide aqueous solution to naphthalene oil has an aqueous layer 1. Contained 10.5 (relative value) of tar acid that was not extracted as a tartrate. In the flow of Comparative Example 1 shown in FIG. 3, the tar acid contained in the oil layer 1 is not recovered as tar acid but becomes a loss.
これに対し、図２に示す実施例１のフローでは、油層１をナフタリン蒸留工程で蒸留し、得られたナフタリン軽油を、第２の分離工程で、カルボル油および水層１と混合する。これにより、比較例１のフローでは回収できなかった油層１に含まれるタール酸をタール酸塩として水層２中に回収できる。その結果、実施例１のフローでは、最終のタール酸塩の回収率を９７％（タール酸換算）まで高めることができた。
On the other hand, in the flow of Example 1 shown in FIG. 2, the oil layer 1 is distilled in the naphthalene distillation step, and the obtained naphthalene light oil is mixed with the carboru oil and the water layer 1 in the second separation step. Thereby, the tar acid contained in the oil layer 1 that could not be recovered in the flow of Comparative Example 1 can be recovered in the water layer 2 as a tar salt. As a result, in the flow of Example 1, the final tarate recovery rate could be increased to 97% (in terms of tar acid).
以上の結果から、本発明のタール酸塩の回収方法を適用することにより、コールタールから、より高い回収率でタール酸塩を回収できることがわかる。
From the above results, it can be seen that by applying the tarate recovery method of the present invention, tarrate can be recovered from coal tar at a higher recovery rate.
Claims (2)
- コールタールを蒸留して、ナフタリン油とカルボル油とを分離して得るコールタール蒸留工程と、
前記コールタール蒸留工程で得られたナフタリン油にアルカリ水溶液を加えて、前記ナフタリン油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層１とタール酸塩を含む水層１とに分離する第１の分離工程と、
前記第１の分離工程で分離された油層１を蒸留して、ナフタリン軽油を得るナフタリン蒸留工程と、
前記コールタール蒸留工程で得られたカルボル油と、前記第１の分離工程で分離された水層１と、前記ナフタリン蒸留工程で得られたナフタリン軽油とを混合し、前記カルボル油および前記ナフタリン軽油に含まれるタール酸をタール酸塩とし、タール酸が除去された油層２とタール酸塩を含む水層２とに分離する第２の分離工程と、を有するタール酸塩の回収方法。 A coal tar distillation process obtained by distilling coal tar to separate naphthalene oil and carbol oil;
An alkaline aqueous solution is added to the naphthalene oil obtained in the coal tar distillation step, the tar acid contained in the naphthalene oil is changed to a tar salt, the oil layer 1 from which the tar acid has been removed, and the water layer 1 containing the tar salt, A first separation step of separating into
Naphthalene distillation step of distilling the oil layer 1 separated in the first separation step to obtain naphthalene gas oil;
The carboru oil obtained in the coal tar distillation step, the aqueous layer 1 separated in the first separation step, and the naphthalene light oil obtained in the naphthalene distillation step are mixed, and the carbol oil and the naphthalene light oil are mixed. And a second separation step of separating the tar acid contained in the oil layer 2 from which the tar acid has been removed into the oil layer 2 from which the tar acid has been removed and the aqueous layer 2 containing the tar acid salt. - 請求項１に記載の水層２に含まれるタール酸塩を炭酸ガスおよび／または硫酸で分解して、粗製タール酸を得る粗製タール酸製造工程と、
前記粗製タール酸製造工程で得られた粗製タール酸を蒸留して精製タール酸を得るタール酸精製工程と、を有するタール酸の製造方法。 A crude tar acid production step for obtaining a crude tar acid by decomposing the tarate contained in the aqueous layer 2 according to claim 1 with carbon dioxide gas and / or sulfuric acid
And a tar acid purification step for obtaining a purified tar acid by distilling the crude tar acid obtained in the crude tar acid production step.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61136589A (en) * | 1984-12-06 | 1986-06-24 | Osaka Gas Co Ltd | Preparation of tar acid |
| JPH0931472A (en) * | 1995-07-24 | 1997-02-04 | Nippon Steel Chem Co Ltd | Recovering tar acid |
| JP2017210500A (en) * | 2016-05-23 | 2017-11-30 | Ｊｆｅケミカル株式会社 | Tar treatment method and tar treatment equipment |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61136589A (en) * | 1984-12-06 | 1986-06-24 | Osaka Gas Co Ltd | Preparation of tar acid |
| JPH0931472A (en) * | 1995-07-24 | 1997-02-04 | Nippon Steel Chem Co Ltd | Recovering tar acid |
| JP2017210500A (en) * | 2016-05-23 | 2017-11-30 | Ｊｆｅケミカル株式会社 | Tar treatment method and tar treatment equipment |
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