JPS6155191A - Refining of tar acid - Google Patents
Refining of tar acidInfo
- Publication number
- JPS6155191A JPS6155191A JP17813684A JP17813684A JPS6155191A JP S6155191 A JPS6155191 A JP S6155191A JP 17813684 A JP17813684 A JP 17813684A JP 17813684 A JP17813684 A JP 17813684A JP S6155191 A JPS6155191 A JP S6155191A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- tar
- tar acid
- distillation
- aromatic carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011289 tar acid Substances 0.000 title claims abstract description 38
- 238000007670 refining Methods 0.000 title description 2
- 238000004821 distillation Methods 0.000 claims abstract description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011269 tar Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 13
- 238000009835 boiling Methods 0.000 abstract description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 150000002830 nitrogen compounds Chemical class 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 238000006386 neutralization reaction Methods 0.000 abstract description 3
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 159000000000 sodium salts Chemical class 0.000 abstract 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- -1 cyclic nitrogen compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011847 coal-based material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Working-Up Tar And Pitch (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は石炭乾留ないし石炭ガス化工程から副生ずるタ
ール酸の精製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for purifying tar acid which is a by-product from coal carbonization or coal gasification processes.
タール酸とは、元来フェノール、クレゾール類、キシレ
ノール類を総称していうが、前記タール酸中には、通常
タール塩基と総称せられるアニリン、ピリジン、ピコリ
ン、ルチジン、キノリンな。Tar acid is originally a general term for phenol, cresols, and xylenols, but the tar acid includes aniline, pyridine, picoline, lutidine, and quinoline, which are generally called tar bases.
ど環基性窒素化合物その他の不純物が含有せられ画側と
しての用途もあるが、合成樹脂や可塑剤などの原料に供
用する場合には、上記不純物は可及的に除去されねばな
らな−０しかも、近時資源的な理由から、合成樹脂等の
材料源として、石油系から石炭系へ見かえられて来てい
るので、タール酸精製法の開発は大きな課題となってい
る。It contains cyclic nitrogen compounds and other impurities and is used for painting purposes, but when used as raw materials for synthetic resins and plasticizers, the above impurities must be removed as much as possible. Furthermore, for resource reasons, the source of materials such as synthetic resins has recently been replaced by coal-based materials instead of petroleum-based ones, so the development of a tar acid refining method has become a major issue.
（従来の技術〕
従来、石炭乾留工程からタール酸を取得するには、原料
たるタール軽油、カルポル油、ナフタリン油ないし吸収
油を、希薄苛性ソーダ水溶液で洗滌し、それによって原
料中のタール酸をそのソーダ塩に転化し、ついで、これ
をスチーミング法や軽油洗滌法によって、中性油分、タ
ール塩基を除去したのち、硫酸もしくは炭酸ガスによっ
て中和分解を行い、さらに必要に応じて蒸留等の手段を
採って来た。(Prior art) Conventionally, in order to obtain tar acid from the coal carbonization process, the raw material tar light oil, carpol oil, naphthalene oil or absorption oil is washed with a dilute aqueous solution of caustic soda, thereby removing the tar acid in the raw material. After converting into soda salt, the neutral oil and tar base are removed by steaming or light oil washing, followed by neutralization and decomposition with sulfuric acid or carbon dioxide gas, and if necessary, distillation or other means. I picked it up.
ところが上記方法では、ピリジンのような比較的低沸点
塩基はスチーミング工程で除去され易いがアニリンのよ
うな高沸点塩基は除去が困難であるのみならず、上記方
法では、スチームないし軽油の大量が必要とされ経済採
算上も好ましくない。However, in the above method, relatively low boiling point bases such as pyridine are easily removed in the steaming process, but high boiling point bases such as aniline are difficult to remove. This is not desirable from an economic point of view.
本発明は如上観点から、芳香族アミンないしルチジンの
ような高沸点複素環式化合物を容易に減除するタール酸
の精製法を提供するものである。In view of the above, the present invention provides a method for purifying tar acid that easily removes aromatic amines and high-boiling heterocyclic compounds such as lutidine.
本発明者らは、タール酸に芳香族カルボン酸を添加して
蒸留に付することによって、上記問題点が解決できるこ
とを見出した。The present inventors have discovered that the above problems can be solved by adding an aromatic carboxylic acid to tar acid and subjecting it to distillation.
本発明にいうタール酸とは、従来法で述べたタール酸ソ
ーダ塩の酸による中和分解後の粗タール酸、粗タール酸
を脱水および／または脱ピツチして得られる精製タール
酸、精製タール酸を蒸留して得られるフェノール、０−
クレゾール、ｎ＆・Ｐ−クレゾール、キシレノール等を
いう。換言すれば塩基性窒素化合物を含むタール酸をい
う。The tar acid referred to in the present invention refers to crude tar acid after neutralization and decomposition of sodium tar acid salt with an acid as described in the conventional method, purified tar acid obtained by dehydrating and/or depitching crude tar acid, and purified tar. Phenol obtained by distilling acid, 0-
Cresol, n&P-cresol, xylenol, etc. In other words, it refers to tar acid containing a basic nitrogen compound.
このようなタール酸に添加せられる芳香族カルダン牌と
は、単環もしくは複環の１価もしくは多価カルボン酸類
−切が含まれるが、とくに好ましくは多価カルボン酸、
具体的にはフタール酸、トリメリット酸、ピロメリット
酸などである。The aromatic cardan tile added to such tar acid includes monocyclic or multicyclic monovalent or polyvalent carboxylic acids, and particularly preferably polyvalent carboxylic acids,
Specific examples include phthalic acid, trimellitic acid, and pyromellitic acid.
芳香族カルボン酸の添加量は、タール酸中に含有せられ
るタール塩基、とくに塩基性窒素含有化合物の量と等量
ないしそれ以上である。The amount of aromatic carboxylic acid added is equal to or greater than the amount of tar base, particularly basic nitrogen-containing compound, contained in tar acid.
タール酸に添加後は、よくかきまぜ直ちに蒸留に着手し
て差支えない。蒸留時間内に、蒸留温度でタール塩基と
添加された芳香族カルボン酸とが又応して、高沸点の塩
類に転化し、留出することなくピッチ状の釜残として除
去される。After adding to the tar acid, stir well and begin distillation immediately. During the distillation time, the tar base and the added aromatic carboxylic acid also react at the distillation temperature and are converted into high-boiling salts, which are removed as pitch-like bottoms without distillation.
本発明によるタール塩基の除去は、添加物と塩基とが塩
を形成し、高沸点または高分解温度となることを利用し
ている。これがため蒸留温度は低い方が望ましいが、実
用上は塔底温度２００ ’Ｃ以下の常圧または減圧下で
の蒸留がよい。The removal of tar bases according to the present invention takes advantage of the fact that additives and bases form salts that result in high boiling points or high decomposition temperatures. For this reason, it is desirable that the distillation temperature be low, but in practice it is preferable to distill at a bottom temperature of 200'C or less under normal pressure or reduced pressure.
第１表所載の組成を有する粗タール酸２００１を、２０
０ ｍｔのフラスコに装入し、常圧下ボトム温度１８０
℃で、理論段数・１５段の蒸留塔を用φて脱水を行った
。即ちます塔頂より、水と油分３３．５９を留来した。Crude tar acid 2001 having the composition listed in Table 1 was added to
Pour into a 0 mt flask and keep the bottom temperature at 180 mt under normal pressure.
Dehydration was carried out at .degree. C. using a distillation column with 15 theoretical plates. That is, 33.59 g of water and oil were distilled from the top of the column.
第 １ 表 油分とは水と共沸して留出するフェノールなどである。Table 1 The oil component is phenol, etc., which is azeotropically distilled with water.
ついで、塔底温度を１８０℃に維持したまま減圧蒸留に
付し、最終圧力３０ｍｘＨｙに至らしめた。フラスコ内
にはピッチ状釜残１４ｇが残存し、１４４ノの脱水脱ピ
ツチされたタール酸、換言すれば精製タール酸が留出し
た。なお、ロスは８．５１であった０
〔実施例〕
第１表記載の粗タール酸に、その含有する塩基性窒素化
合物の２倍当量の各種芳香族カルボン酸を添加し、上記
比較例と同様な操作を行い精製タール酸を留取した。物
質収支そのものは比較例の場合と実質的に異らない。Then, the mixture was subjected to vacuum distillation while maintaining the bottom temperature at 180° C. to reach a final pressure of 30 m×Hy. 14 g of pitch-like residue remained in the flask, and 144 g of dehydrated and depitched tar acid, in other words purified tar acid, was distilled out. The loss was 8.510 [Example] To the crude tar acid listed in Table 1, various aromatic carboxylic acids in twice the equivalent amount of the basic nitrogen compound contained therein were added, and the results were compared with the above comparative example. A similar operation was performed to distill purified tar acid. The material balance itself is not substantially different from that of the comparative example.
留取したタール酸中の塩基性窒素化合物の種類およびそ
の含量を、原料粗タール酸の場合を含め第２表に一括表
示する（単位はＭ９／ｋｙ ）。The types and contents of basic nitrogen compounds in the distilled tar acid, including the raw material crude tar acid, are listed in Table 2 (unit: M9/ky).
第 ２ 表
！
第２表の通り、芳香族カルボン酸を添加蒸留することに
より、スチーミング等では除去し難い高沸点塩基性−で
あるアニリン、トルイジンを完全に除去することができ
る。また、窒素環化合物のうちでは、ルチジン、ピコリ
ンを大巾に低減できることも明白である。なお、ピリジ
ン、ピコリンは、通常のスチーミング工程でほとんど除
＊すれるので問題となることはない。Second table! As shown in Table 2, by additive distillation of aromatic carboxylic acids, aniline and toluidine, which are high-boiling basic compounds that are difficult to remove by steaming or the like, can be completely removed. It is also clear that among nitrogen ring compounds, lutidine and picoline can be significantly reduced. Note that pyridine and picoline do not pose a problem as they are almost completely removed in the normal steaming process.
〔発明の効果〕
以上詳述したように、本発明方法によれば少量の芳香族
カルボン酸を添加して蒸留するという簡単な操作だけで
、タール酸中の塩基性窒素化合物の大部分が除去できた
のである。[Effects of the Invention] As detailed above, according to the method of the present invention, most of the basic nitrogen compounds in tar acid can be removed by a simple operation of adding a small amount of aromatic carboxylic acid and distilling it. It was done.
Claims (1)
すことを特徴とするタール酸の精製方法 ２）芳香族カルボン酸の添加量は、タール酸中に含有せ
られるタール塩基と当量ないしそれ以上である特許請求
の範囲１）記載の方法 ３）蒸留は塔底温度２００℃以下の蒸留である特許請求
の範囲１）および２）記載の方法[Claims] 1) A method for purifying tar acid, which is characterized by adding an aromatic carboxylic acid to tar acid and subjecting it to distillation. 2) The amount of aromatic carboxylic acid added is determined according to the amount of the aromatic carboxylic acid contained in the tar acid. The method according to claim 1) is equivalent to or more than the tar base used in the process. 3) The method according to claims 1) and 2) wherein the distillation is distillation at a bottom temperature of 200° C. or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17813684A JPS6155191A (en) | 1984-08-27 | 1984-08-27 | Refining of tar acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17813684A JPS6155191A (en) | 1984-08-27 | 1984-08-27 | Refining of tar acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6155191A true JPS6155191A (en) | 1986-03-19 |
| JPH0145513B2 JPH0145513B2 (en) | 1989-10-03 |
Family
ID=16043278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17813684A Granted JPS6155191A (en) | 1984-08-27 | 1984-08-27 | Refining of tar acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6155191A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014019678A (en) * | 2012-07-20 | 2014-02-03 | Tokyo Ohka Kogyo Co Ltd | Purification method of cresol, production method of novolac resin for photosensitive resin composition, and photosensitive resin composition |
-
1984
- 1984-08-27 JP JP17813684A patent/JPS6155191A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014019678A (en) * | 2012-07-20 | 2014-02-03 | Tokyo Ohka Kogyo Co Ltd | Purification method of cresol, production method of novolac resin for photosensitive resin composition, and photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0145513B2 (en) | 1989-10-03 |
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