JPH0742086B2 - Method for purifying hydrogen chloride gas containing organic acid - Google Patents
Method for purifying hydrogen chloride gas containing organic acidInfo
- Publication number
- JPH0742086B2 JPH0742086B2 JP3321377A JP32137791A JPH0742086B2 JP H0742086 B2 JPH0742086 B2 JP H0742086B2 JP 3321377 A JP3321377 A JP 3321377A JP 32137791 A JP32137791 A JP 32137791A JP H0742086 B2 JPH0742086 B2 JP H0742086B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- hydrogen chloride
- chloride gas
- organic acid
- sulfuric acid
- 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.)
- Expired - Lifetime
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims description 63
- 239000007789 gas Substances 0.000 title claims description 57
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims description 57
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims description 57
- 150000007524 organic acids Chemical class 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 74
- 238000000746 purification Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 54
- 235000011054 acetic acid Nutrition 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 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
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CBWUNQZJGJFJLZ-UHFFFAOYSA-N [Cl].Cl Chemical compound [Cl].Cl CBWUNQZJGJFJLZ-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は塩化水素ガスの精製に関
するものである。さらに詳しくは有機酸を含有する塩化
水素ガスを硫酸で処理することによって該有機酸を分離
する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to purification of hydrogen chloride gas. More specifically, it relates to a method for separating an organic acid by treating hydrogen chloride gas containing the organic acid with sulfuric acid.
【０００２】[0002]
【従来の技術】従来、有機酸を含む塩化水素ガスの精製
法については、いろいろ提案されている。たとえば圧縮
液化蒸留法（特公昭４２−１７４号），抽出法（特公昭
４９−４２７９６号），熱分解法（特公昭５６−１１６
４３）などがあるが、これらは複雑な工程を必要とし、
又使用助剤，エネルギー等の消費が大きく、工業的には
十分満足できるものではない。2. Description of the Related Art Conventionally, various methods for purifying hydrogen chloride gas containing an organic acid have been proposed. For example, compression liquefaction distillation method (Japanese Patent Publication No. 42-174), extraction method (Japanese Patent Publication No. 49-42796), thermal decomposition method (Japanese Patent Publication No. 56-116).
43) etc., but these require complicated steps,
In addition, it consumes a large amount of auxiliary agents, energy, etc., and is not satisfactory industrially.
【０００３】この中で、熱分解法は比較的容易で確実な
精製法であるが、塩素ガスと水素ガスとを反応させ、合
成塩酸を製造する設備が必要であり、合成塩酸を必要と
しないところでは使用できない。又合成塩酸の製造量に
対して、処理できる粗製塩化水素ガスには制限がある。Of these, the thermal decomposition method is a relatively easy and reliable refining method, but a facility for reacting chlorine gas and hydrogen gas to produce synthetic hydrochloric acid is required, and synthetic hydrochloric acid is not required. Not usable by the way. Further, there is a limit to the crude hydrogen chloride gas that can be treated with respect to the production amount of synthetic hydrochloric acid.
【０００４】一方、一部の有機化合物が濃硫酸に溶解す
ることは知られており、濃硫酸に可溶な有機化合物を含
有してなる塩化水素ガスを硫酸と接触させれば、塩化水
素ガスは硫酸にほとんど溶解しないので、塩化水素ガス
中の有機化合物が硫酸に選択的に溶解し、塩化水素ガス
の精製がある程度期待できる。しかしながら、実際に硫
酸との接触によって、塩化水素ガスの高度な精製が行わ
れている例は、ほとんど見当たらない。On the other hand, it is known that some organic compounds dissolve in concentrated sulfuric acid, and if hydrogen chloride gas containing an organic compound soluble in concentrated sulfuric acid is brought into contact with sulfuric acid, hydrogen chloride gas Is almost insoluble in sulfuric acid, organic compounds in hydrogen chloride gas are selectively dissolved in sulfuric acid, and purification of hydrogen chloride gas can be expected to some extent. However, there are few examples in which hydrogen chloride gas is actually highly purified by contact with sulfuric acid.
【０００５】この理由は、塩化水素ガス中の有機化合物
を実際に精製塩化水素ガスと呼べる濃度まで低下させる
事が気液平衡上困難であったり、又硫酸−有機化合物−
塩化水素の３成分系の気液平衡関係が詳しく知られてい
なかったり、さらに又高度の精製が可能でも硫酸の使用
が多量となり、経済上精製技術として成立し得なかった
からと思われる。わずかにこの種の精製法として、塩化
アセチルを含む塩化水素ガスを、水，酢酸及び硫酸から
なる洗液に接触させ、塩化水素ガスから塩化アセチルを
除去する精製法（特開昭５１−１４３５９６）が報告さ
れている。しかし、かかる精製法では塩化水素ガス中の
不純物として、酢酸分が２００ｐｐｍ（体積基準、以下
同じ）程度残存するため、一部の用途を除いて、直接他
の製造工程で使用できない。The reason for this is that it is difficult in terms of vapor-liquid equilibrium to reduce the concentration of organic compounds in hydrogen chloride gas to a concentration that can actually be called purified hydrogen chloride gas, and sulfuric acid-organic compounds-
This is probably because the vapor-liquid equilibrium relationship of the hydrogen chloride ternary system is not known in detail, or even if high-level purification is possible, the amount of sulfuric acid used becomes large and it cannot be economically established as a purification technique. As a slight purification method of this kind, a purification method of removing acetyl chloride from hydrogen chloride gas by bringing hydrogen chloride gas containing acetyl chloride into contact with a washing liquid composed of water, acetic acid and sulfuric acid (JP-A-51-143596). Has been reported. However, in such a purification method, acetic acid content of about 200 ppm (volume basis, the same applies hereinafter) remains as an impurity in hydrogen chloride gas, and therefore cannot be directly used in other manufacturing processes except for some applications.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記欠点、
つまり複雑な設備の使用や使用上の制約といった問題も
なく、きわめて経済的に有機酸を含む粗製塩化水素ガス
を、精製する方法を提供するものである。SUMMARY OF THE INVENTION The present invention has the following drawbacks.
That is, the present invention provides a method for purifying crude hydrogen chloride gas containing an organic acid extremely economically without problems such as the use of complicated equipment and restrictions on use.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、従来詳し
く知られていなかった有機酸と硫酸及び塩化水素との気
液平衡関係を詳細に研究した結果、有機酸を含む塩化水
素ガスを硫酸と接触させる事によって容易に高度かつ経
済的に精製できることを見出した。The present inventors have studied in detail the gas-liquid equilibrium relationship between an organic acid and sulfuric acid and hydrogen chloride, which have not been known in detail, and as a result, have found that hydrogen chloride gas containing an organic acid is It was found that it can be easily and highly refined and economically refined by bringing it into contact with sulfuric acid.
【０００８】即ち、本発明は、５００〜１０００ｐｐｍ
の有機酸を含有する塩化水素ガスを、該有機酸を最大３
０重量％含む濃硫酸溶液に−１０〜３０℃の温度で接触
させて、塩化水素ガス中の該有機酸を１０ｐｐｍ以下に
低減させる事を特徴とする有機酸含有塩化水素ガスの精
製方法である。また、有機酸が酢酸である上記記載の有
機酸含有塩化水素ガスの精製方法である。[0008] That is, the present onset Ming, 500~1000ppm
Up to 3 hydrogen chloride gas containing an organic acid, an organic acid
0 in contact with concentrated sulfuric acid solution containing by weight% at a temperature of -10 to 30 ° C., the organic acid in the hydrogen chloride gas to 10ppm or less
Ru purification method der of an organic acid containing hydrogen chloride gas, characterized in that Ru is reduced. Also, chromatic organic acid is in the above described Ru der acetate
This is a method for purifying hydrogen chloride gas containing organic acid .
【０００９】本発明に適用可能な代表的な有機酸として
は、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草
酸、ピバル酸、ラウリン酸、ミリスチン酸、パルミチン
酸、ステアリン酸、アクリル酸、プロピオル酸、メタク
リル酸、クロトン酸、オレイン酸、安息香酸等のモノカ
ルボン酸、及びシュウ酸、マロン酸、コハク酸、グルタ
ル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライ
ン酸、セバシン酸、マレイン酸、フマル酸、イタコン
酸、フタル酸、イソフタル酸、テレフタル酸等のジカル
ボン酸などが挙げられる。Representative organic acids applicable to the present invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, Monocarboxylic acids such as propiolic acid, methacrylic acid, crotonic acid, oleic acid, benzoic acid, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid And dicarboxylic acids such as fumaric acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid.
【００１０】不純物として上記のような有機酸を５００
〜１０００ｐｐｍ含有してなる粗製塩化水素ガスを、こ
れらの有機酸を０〜３０重量％含む硫酸溶液に、−１０
〜３０℃の温度で、充填塔のような既知の吸収塔を使用
して、効率よく接触させ、塩化水素ガス中の有機酸を選
択的に硫酸に溶解せしめ、塩化水素ガスの精製を行うこ
とができる。As an impurity, 500 of the above-mentioned organic acid is used.
The crude hydrogen chloride gas containing 1000 ppm to 1000 ppm was added to a sulfuric acid solution containing these organic acids in an amount of 0 to 30% by weight.
Using a known absorption tower such as a packed tower at a temperature of -30 ° C. to efficiently bring them into contact with each other to selectively dissolve the organic acid in the hydrogen chloride gas in sulfuric acid to purify the hydrogen chloride gas. You can
【００１１】ここで０〜３０重量％の有機酸を含む濃硫
酸溶液が選ばれるのは、主として経済的な理由と気液平
衡関係からくる制限によるものである。従って、工業的
に有利であるためには、精製塩化水素ガス中の有機酸濃
度を許容される一定濃度以下に保ちながら、吸収液であ
る濃硫酸溶液中に粗製塩化水素ガス中の有機酸を極力溶
解させる事が好ましい。[0011] Here, the concentrated sulfuric <br/> acid solution containing 0 to 30 wt% of the organic acid is chosen is by limiting coming mainly for economic reasons and vapor-liquid equilibrium. Therefore, in order to be industrially advantageous, while keeping the concentration of the organic acid in the purified hydrogen chloride gas below an allowable constant concentration, the organic acid in the crude hydrogen chloride gas is added to the concentrated sulfuric acid solution that is the absorbing liquid. It is preferable to dissolve it as much as possible.
【００１２】本発明者らの研究によれば、塩化水素ガス
中に含まれる有機酸の硫酸溶液への溶解は、これに接触
している硫酸溶液中の有機酸濃度に依存し、塩化水素ガ
ス中の有機酸濃度と硫酸中の有機酸濃度との間には一定
の気液平衡関係が成立している。この為、精製塩化水素
ガス中の有機酸濃度を一定の濃度以下に保つには、吸収
液である硫酸溶液中の有機酸濃度と温度の管理が重要で
ある。According to the research conducted by the present inventors, the dissolution of an organic acid contained in hydrogen chloride gas into a sulfuric acid solution depends on the concentration of the organic acid in the sulfuric acid solution in contact with the hydrogen chloride gas. A certain gas-liquid equilibrium relationship is established between the organic acid concentration in the solution and the organic acid concentration in sulfuric acid. Therefore, in order to keep the concentration of the organic acid in the purified hydrogen chloride gas below a certain concentration, it is important to control the concentration and temperature of the organic acid in the sulfuric acid solution which is the absorbing liquid.
【００１３】硫酸溶液中の有機酸濃度については、３０
重量％以下にすることが好ましく、３０重量％を越える
と精製塩化水素ガス中の有機酸濃度を１０ｐｐｍ以下に
保つ事が困難となる。The organic acid concentration in the sulfuric acid solution is 30
It is preferable to set the content to not more than 30% by weight, and if it exceeds 30% by weight, it becomes difficult to keep the concentration of the organic acid in the purified hydrogen chloride gas below 10 ppm.
【００１４】硫酸溶液の温度については、−１０〜３０
℃に保つ事が必要である。この理由は吸収液の温度を−
１０℃以下に下げる事は吸収液の凍結の危険性，粘度の
上昇、大きな冷凍機が必要等の問題が生じ、また３０℃
以上では精製塩化水素ガス中の有機酸濃度を１０ｐｐｍ
以下に保つ事はきわめて困難となる為である。なお、硫
酸溶液の凍結点は含有される有機酸の濃度によって変化
するので、最適の操作温度は−１０〜３０℃の温度範囲
において、有機酸の種類、精製塩化水素ガス中の許容有
機酸濃度及びユーティリティー使用コスト等を総合的に
考慮して決定される。The temperature of the sulfuric acid solution is -10 to 30.
It is necessary to keep at ℃. The reason for this is that the temperature of the absorbing liquid is
Decreasing the temperature below 10 ° C causes problems such as freezing of the absorption liquid, increase in viscosity, and the need for a large refrigerator.
With the above, the organic acid concentration in the purified hydrogen chloride gas is 10 ppm.
It is very difficult to keep below. Since the freezing point of the sulfuric acid solution changes depending on the concentration of the contained organic acid, the optimum operating temperature is within the temperature range of -10 to 30 ° C, the type of organic acid and the allowable concentration of organic acid in the purified hydrogen chloride gas. Also, it is determined by comprehensively considering the utility usage cost, etc.
【００１５】粗製塩化水素ガスと吸収液との接触方法に
ついては、十分に気液が接触できるものであればどんな
方法でもよいが、通常、吸収塔が用いられる。この吸収
塔は理論段数１０段以上のものであれば、充填塔，棚段
塔等公知のものが使用できる。又この場合塔径は、塩化
水素ガスの空塔速度が０．４ｍ／ｓｅｃ程度に選ぶ事が
大切である。The method of contacting the crude hydrogen chloride gas with the absorbing solution may be any method as long as it can sufficiently contact the gas-liquid, but an absorption tower is usually used. As the absorption tower, known towers such as a packed tower and a tray tower can be used as long as they have a theoretical plate number of 10 or more. Further, in this case, it is important to select the tower diameter such that the superficial velocity of hydrogen chloride gas is about 0.4 m / sec.
【００１６】次に、本発明の方法は、回分法又は連続法
いずれの方法でも実施できる。連続法の場合は吸収液で
ある硫酸溶液中の有機酸濃度が３０重量％を越えないよ
うに、好ましくは２０重量％を越えないように吸収液の
一部を吸収塔から抜き出しながら、濃硫酸を吸収塔に供
給する必要がある。Next, the method of the present invention can be carried out by either a batch method or a continuous method. In the case of the continuous process, while the sulfuric acid solution as the absorbing solution does not exceed 30% by weight of the organic acid concentration, preferably 20% by weight or less, while extracting a part of the absorbing solution from the absorption tower, concentrated sulfuric acid is used. Need to be supplied to the absorption tower.
【００１７】本発明は、特に不純物として１０００ｐｐ
ｍ以下の有機酸を含む塩化水素ガス中の有機酸を１０ｐ
ｐｍ以下に精製する方法として有用である。有機酸を１
０００ｐｐｍ以上含む場合でも本発明の方法を適用する
事が可能であるが、この場合は吸収塔が大きくなり、ま
た硫酸の使用量も多くなる。実際、塩化水素ガス中に１
０００ｐｐｍ以上の有機酸を含む場合には、他の方法た
とえば冷却等によって容易に５００〜１０００ｐｐｍに
低下させる事ができるので、これらの前処理を行ってか
ら、本発明の精製法を適用する事が有利である。The present invention is particularly applicable as an impurity of 1000 pp.
10 p of organic acid in hydrogen chloride gas containing organic acid of m or less
It is useful as a method for purification to pm or less. 1 organic acid
The method of the present invention can be applied even when the content is 000 ppm or more, but in this case, the absorption tower becomes large and the amount of sulfuric acid used also increases. In fact, 1 in hydrogen chloride gas
When the organic acid is contained in an amount of 000 ppm or more, it can be easily reduced to 500 to 1000 ppm by another method such as cooling. Therefore, it is possible to apply the purification method of the present invention after performing these pretreatments. It is advantageous.
【００１８】[0018]
【実施例】以下実施例により本発明を具体的に説明す
る。The present invention will be described in detail with reference to the following examples.
【００１９】実施例１ 不純物として、酢酸を約８００ｐｐｍ含有している塩化
水素ガスを、１Ｎｍ3／Ｈの割合で１リットルの濃硫酸
に２０℃で吹き込み、気液接触させた。吹き込み約１０
０時間後に、気液接触後の塩化水素ガスをガスクロマト
グラフ法で分析した結果、酢酸分は５ｐｐｍであった。
又この時、塩化水素ガス中の酢酸が硫酸に経時的に吸収
され、硫酸中の酢酸濃度は１０重量％まで上昇した。さ
らにこの操作を続け、２００時間後には、硫酸中の酢酸
濃度は２０重量％になっったが、気液接触後の塩化水素
ガス中の酢酸濃度は８ｐｐｍに保たれた。以下、４００
時間までこの操作を続けた結果を表１に示す。Example 1 Hydrogen chloride gas containing about 800 ppm of acetic acid as an impurity was blown into 1 liter of concentrated sulfuric acid at a rate of 1 Nm 3 / H at 20 ° C. for gas-liquid contact. Blowing about 10
After 0 hour, the hydrogen chloride gas after gas-liquid contact was analyzed by gas chromatography, and as a result, the acetic acid content was 5 ppm.
At this time, acetic acid in hydrogen chloride gas was absorbed by sulfuric acid over time, and the concentration of acetic acid in sulfuric acid increased to 10% by weight. This operation was further continued, and after 200 hours, the acetic acid concentration in sulfuric acid became 20% by weight, but the acetic acid concentration in hydrogen chloride gas after the gas-liquid contact was kept at 8 ppm. Below 400
The results of continuing this operation until time are shown in Table 1.
【００２０】実施例２ 次に図１に示すフローを用いて実施した場合について説
明する。不純物として、酢酸と塩素からモノクロル酢酸
を製造する際に副生する、酢酸を５００〜１０００ｐｐ
ｍ含む塩化水素ガス５０ｍ3 ／ｈを導入管２より吸収塔
４（高さ３０００ｍｍ，塔径２００ｍｍの充填塔）の底
部に導入し、塔頂部より導入した、酢酸を２０重量％含
む硫酸溶液３００リットル／ｈと２０℃で連続的に向流
接触させた。吸収塔４の塔底から流出する液はポンプ５
を用いて、熱交換器６を通して温度調整を行い吸収塔４
の塔頂部へ供給した。洗浄塩化水素ガスは導管７〜硫酸
ミスト分離器８を通して精製塩化水素とし導管９より取
り出した。この結果、気液接触後の塩化水素ガス中の酢
酸濃度は、６時間ごとにガスクロマトグラフ分析を実施
したが、９６０時間にわたって１０ｐｐｍ以下であっ
た。なお、硫酸溶液中の酢酸濃度を一定濃度以下に保つ
ため、導管１よりフレッシュな硫酸を補給し、導管３よ
り酢酸を溶解した硫酸溶液の一部を抜き取った。Embodiment 2 Next, a case where the flow is shown in FIG. 1 will be described. As an impurity, 500-1000 pp of acetic acid, which is a by-product of the production of monochloroacetic acid from acetic acid and chlorine
Hydrogen chloride gas containing 50 m 3 / h containing m was introduced into the bottom of the absorption tower 4 (height 3000 mm, tower diameter 200 mm packed tower) from the introduction pipe 2, and the sulfuric acid solution 300 containing 20% by weight of acetic acid introduced from the top of the tower. Continuous countercurrent contact with liter / h at 20 ° C was carried out. The liquid flowing out from the bottom of the absorption tower 4 is pump 5
The temperature is adjusted through the heat exchanger 6 by using the absorption tower 4
Was supplied to the top of the tower. The washed hydrogen chloride gas was made into purified hydrogen chloride through the conduit 7 to the sulfuric acid mist separator 8 and taken out through the conduit 9. As a result, the concentration of acetic acid in hydrogen chloride gas after gas-liquid contact was 10 ppm or less over 960 hours when gas chromatographic analysis was performed every 6 hours. In order to keep the concentration of acetic acid in the sulfuric acid solution below a certain concentration, fresh sulfuric acid was replenished from conduit 1 and part of the sulfuric acid solution in which acetic acid was dissolved was extracted from conduit 3.
【００２１】実施例３ 不純物として、酢酸を５００ｐｐｍ含む塩化水素ガス
を、酢酸を１０重量％含む硫酸溶液と温度−７℃で実施
例２と同じ方法で接触させた。この結果、塩化水素ガス
中の酢酸濃度は１ｐｐｍ以下であった。Example 3 Hydrogen chloride gas containing 500 ppm of acetic acid as an impurity was brought into contact with a sulfuric acid solution containing 10% by weight of acetic acid at a temperature of −7 ° C. in the same manner as in Example 2. As a result, the acetic acid concentration in hydrogen chloride gas was 1 ppm or less.
【００２２】実施例４ 不純物として、クロル酢酸を１００〜１０００ｐｐｍ含
む粗製塩化水素ガスを実施例２と同じ方法によって精製
を行った。精製された塩化水素ガスを一定時間ごとに、
ガスクロマトグラフ分析を実施した結果、クロル酢酸は
検出されなかった。（クロル酢酸の検出限界：１ｐｐ
ｍ）Example 4 Crude hydrogen chloride gas containing 100 to 1000 ppm of chloroacetic acid as an impurity was purified by the same method as in Example 2. Purified hydrogen chloride gas at regular intervals,
As a result of gas chromatographic analysis, chloroacetic acid was not detected. (Detection limit of chloroacetic acid: 1 pp
m)
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明によると、有機酸とくに１００〜
１０００ｐｐｍのカルボン酸を含む粗製塩化水素ガスを
濃硫酸溶液で処理することにより容易かつ経済的に１０
ｐｐｍ以下に精製する事ができる。このため、本発明で
精製された塩化水素ガスは、そのままの状態で、他への
利用が可能である。According to the present invention, an organic acid, especially 100-
Treating crude hydrogen chloride gas containing 1000 ppm of carboxylic acid with concentrated sulfuric acid solution facilitates and economically
It can be purified to below ppm. Therefore, the hydrogen chloride gas purified by the present invention can be used for other purposes as it is.
【図１】本発明の実施の態様を示す工程説明図。FIG. 1 is a process explanatory view showing an embodiment of the present invention.
【符号の説明】 １ 濃硫酸送入口 ２ 粗製塩化水素ガス送入口 ３ 有機酸を溶解した硫酸溶液の排出口 ４ 吸収塔 ５ 硫酸循環ポンプ ６ 水クーラー ７ 洗浄塩化水素ガス排出口 ８ 硫酸ミスト分離器 ９ 精製塩化水素ガス排出口[Explanation of symbols] 1 concentrated sulfuric acid inlet 2 crude hydrogen chloride gas inlet 3 outlet for sulfuric acid solution in which organic acid is dissolved 4 absorption tower 5 sulfuric acid circulation pump 6 water cooler 7 wash hydrogen chloride gas outlet 8 sulfuric acid mist separator 9 Purified hydrogen chloride gas outlet
Claims (2)
する塩化水素ガスを、該有機酸を最大３０重量％含む濃
硫酸溶液に−１０〜３０℃の温度で接触させて、塩化水
素ガス中の該有機酸を１０ｐｐｍ以下に低減させる事を
特徴とする有機酸含有塩化水素ガスの精製方法。1. Containing 500 to 1000 ppm of organic acid
Hydrogen chloride gas, concentrated <br/> by contacting at a temperature of sulfuric acid solution to -10 to 30 ° C. containing up to 30% by weight of organic acid, water chloride
Purification method of an organic acid containing hydrogen chloride gas, characterized in that Ru reduce organic acid in hydrogen gas to 10ppm or less.
酸含有塩化水素ガスの精製方法。Wherein organic according to claim 1, wherein the organic acid is Ru der acetate
Method for purifying acid-containing hydrogen chloride gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3321377A JPH0742086B2 (en) | 1991-11-08 | 1991-11-08 | Method for purifying hydrogen chloride gas containing organic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3321377A JPH0742086B2 (en) | 1991-11-08 | 1991-11-08 | Method for purifying hydrogen chloride gas containing organic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05132302A JPH05132302A (en) | 1993-05-28 |
| JPH0742086B2 true JPH0742086B2 (en) | 1995-05-10 |
Family
ID=18131883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3321377A Expired - Lifetime JPH0742086B2 (en) | 1991-11-08 | 1991-11-08 | Method for purifying hydrogen chloride gas containing organic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742086B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116639657A (en) * | 2023-06-28 | 2023-08-25 | 河南红东方化工股份有限公司 | A kind of hydrochloric acid purifying treatment method containing sulfuric acid impurity |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3133799A1 (en) * | 1981-08-26 | 1983-03-17 | Siemens AG, 1000 Berlin und 8000 München | "CONTACT ARRANGEMENT FOR VACUUM SWITCHES" |
| DE3526801A1 (en) * | 1985-07-26 | 1987-02-05 | Hoechst Ag | METHOD FOR PURIFYING HYDROGEN CHLORINE GAS |
-
1991
- 1991-11-08 JP JP3321377A patent/JPH0742086B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05132302A (en) | 1993-05-28 |
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