JPH0482141B2 - - Google Patents
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- Publication number
- JPH0482141B2 JPH0482141B2 JP13080385A JP13080385A JPH0482141B2 JP H0482141 B2 JPH0482141 B2 JP H0482141B2 JP 13080385 A JP13080385 A JP 13080385A JP 13080385 A JP13080385 A JP 13080385A JP H0482141 B2 JPH0482141 B2 JP H0482141B2
- Authority
- JP
- Japan
- Prior art keywords
- extraction
- solvent
- phase
- oil
- water
- 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.)
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- 238000000605 extraction Methods 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- 150000003871 sulfonates Chemical class 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000000638 solvent extraction Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 26
- 239000003208 petroleum Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 150000002763 monocarboxylic acids Chemical class 0.000 description 17
- 239000004530 micro-emulsion Substances 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 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 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 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 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and as a result Substances 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- DVAIYSZTXVOUQZ-UHFFFAOYSA-N diucifon Chemical compound N1C(=O)NC(=O)C(S(=O)(=O)NC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(NS(=O)(=O)C=3C(NC(=O)NC=3C)=O)=CC=2)=C1C DVAIYSZTXVOUQZ-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004391 petroleum recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
〔産業上の利用分野〕
本発明は有機スルフオネート、特に石油スルフ
オネートを抽出精製する方法に関する。
更に詳しく言えば、本発明は数平均分子量300
〜450の石油製品を硫酸または空気希釈の三酸化
イオウでスルフオン化して得られるスルフオン化
物をNaOHで中和したスルフオネート中の未反
応油を、親水性を有し、水より高沸点の炭素数１
〜４の飽和モノカルボン酸と水の混合溶剤を使用
することによつて分離除去することにより所望の
石油スルフオネートを得る有機スルフオネートの
溶剤抽出精製法に関する。
〔従来の技術〕
石油製品をスルフオン化して得られる石油スル
フオネートは、従来より界面活性剤として潤滑油
添加剤、乳化剤、分散剤、清浄剤など、広範な分
野に使用されており、又近年、油井における原油
の二・三次回収法の技術の一つであるマイセラー
ポリマー攻法用界面活性剤として使用され、特に
注目を浴びている。
従来、スルフオン化反応で得られる石油スルフ
オネートの工業的な精製は、アルコール水溶液で
抽出する例が多く、アルコールソーダ液で中和し
てそのアルカリ塩として回収するのが一般的であ
る。
その際使用されるアルコールは、低級アルコー
ル、特にイソプロピルアルコールが主であり、た
とえば、米国特許明細書第3776309号、同第
3956372号などに示されている。
この抽出石油スルフオネートは通常40〜60重量
百分率の含油溶液として製品化されている。
この濃度で製品化される理由は、一つには石油
スルフオネート単体では硬化した固形物状となつ
てしまい取り扱いが困難であるために、油を加え
てスルフオネート濃度を調製したりすることと、
今一つはスルフオネートの溶剤抽出精製法が、次
に述べるようにマイクロエマルジヨン形成による
未反応油分との分離現象を利用したもので、厳密
には単なる溶解抽出とは異なつていることによる
ものである。
この抽出法は未精製石油スルフオネート中の未
反応油を一部包み込んだ石油スルフオネートを飽
和モノカルボン酸の水溶液中にマイクロエマルジ
ヨンを形成させて可溶化させ、濃縮石油スルフオ
ネートを得る技術である。
従つて可溶化されなかつた油分が未反応油分と
して分離され、結果として、石油スルフオネート
が抽出分離される。
ここで抽出相にマイクロエマルジヨンを形成さ
せることの重要性は、乳化粒子の大きさが0.1〜
0.05ミクロンのマイクロエマルジヨン相となつて
均質透明相を示すために、未反応油分と明確な界
面をもつて二相に分離するからであり、これが乳
化粒子径の比較的大きいコロイド相あるいは乳濁
相であると、容易に未反応油分と乳化などの現象
を起こし二相分離を起こさなくなり、結果として
抽出分離操作ができないことになる。
抽出溶剤として使用する先行技術の低級アルコ
ール水溶液中のアルコールは、マイクロエマルジ
ヨン形成における界面活性助剤として作用し重要
な役割を果たたす（マイクロエマルジヨン形成に
関するこれら界面活性助剤の役割については“シ
ヤルマン・エマルジヨンの科学”朝倉書店、第
209頁に詳しく述べられている。）。
しかし先行技術の低級アルコールによる方法で
は、マイクロエマルジヨンを形成た石油スルフオ
ネートを含む抽出相から、溶剤であるアルコール
と水を蒸留回収する段階で、両者は共沸するもの
の、初期には沸点の低いアルコール分の多いもの
が回収され、次に水分の多いものが回収されるこ
とになる。
このとき水が回収されて行くに従い、このマイ
クロエマルジヨン形成相は水が少なくなる為、水
への油の可溶化状態（Ｏ／Ｗ型エマルジヨン）か
ら油中への水の可溶化状態（Ｏ／Ｗ型エマルジヨ
ン）へと連続的に移行する現象を起こす。
この転相時における系は“Winsorの実験”に
示されるごとくゲル状態を示し、極度に高粘度状
態となる（P.A.Winsor；Mfg.Chemist，28，89
（1956）参照。）。
この転相時における高粘度化現象は、石油スル
フオネートを工業規模に移す段階で、溶剤を連続
式方法で回収操作することの困難さというプロセ
ス的制約、製造費の高価格化などの原因となる。
このことは、特に原油の二・三次回収法の一つ
であるマイセラーポリマー攻法用界面活性剤のご
とき大量使用を必要とする需要に対しては大きな
障害となる。
〔発明が解決しようとする問題点〕
従つて、本発明の目的は前述の低級アルコール
を用いる方法のようにエマルジヨン転相時におけ
る高粘度化現象を生じない石油スルフオネートの
溶剤抽出精製法を提供することを目的とする。
〔問題点を解決するための手段及び作用〕
本発明者等は鋭意検討の結果、親水性を有し、
水より高沸点の飽和モノカルボン酸水溶液中の飽
和モノカルボン酸が、従来の低級アルコール水溶
液中のアルコールよりも、マイクロエマルジヨン
形成における界面活性助剤としての能力が高く、
抽出溶剤の原料油に対する体積比（以下、溶剤比
と記す。）がより広い抽出範囲で抽出操作を可能
にすること、また、エマルジヨン転相時に水より
高沸点の界面活性助剤であるこの飽和モノカルボ
ン酸を相内へ残留させることで、ゲル化現象が防
がれることを見出し、前述の問題点を解決した。
すなわち、本発明は有機スルフオネートを製造
する過程で得られる有機スルフオネートと未反応
物の混合物から有機スルフオネートを溶剤抽出す
る方法におて、抽出溶剤として親水性を有し水よ
り高沸点の炭素数１〜４の飽和モノカルボン酸の
水溶液を使用することを特徴とする有機スルフオ
ネートの溶剤精製法である。
飽和モノカルボン酸には炭素数の順によると、
ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉
草酸、イソ吉草酸などがあるが、本発明の抽出条
件に使用しうるのは親水性を有し、かつ水より高
沸点の飽和モノカルボン酸であり、良好な抽出分
離性を有する条件から、ギ酸、酢酸、プロピオン
酸、酪酸に限定される。
このうち、ギ酸は毒性、危険性並びに水との沸
点差の小さいことから、また酪酸は抽出工程にお
いて相分離が完了するまでの所要時間（以下セツ
トリング・タイムと記す。）が長い、などの点か
ら本発明の抽出溶剤として特に好ましい飽和モノ
カルボン酸は、酢酸、プロピオン酸である。
次に、抽出溶剤中の飽和モノカルボン酸濃度
は、マイクロエマルジヨン相を形成するのに適し
た界面活性助剤としての濃度範囲が存在し、濃度
の低い水溶液では溶剤比、抽出温度を変化させて
も白濁乳化状態を示し、明確な界面を生じなくな
る。
濃度の高い水溶液では抽出相、抽残相共に濁り
が生じ、充分な抽出効果が得られない。
従つて、本発明において抽出溶剤として適当な
飽和モノカルボン酸の水溶液濃度は、溶剤比、抽
出温度とも密接な関係があり、10〜90体積百分率
が好ましく、20〜80体積百分率が特に好ましい。
この抽出溶剤中の飽和モノカルボン酸濃度がス
ルフオネート収率に及ぼす傾向について言及すれ
ば、飽和モノカルボン酸濃度が高くなるに従い、
下相に分離されるスルフオネート抽出相の量は減
少するが、その下相を蒸留して得られるスルフオ
ネート抽出物中のスルフオネート濃度は高くな
る。
尚、この際の蒸留操作により回収される飽和モ
ノカルボン酸及び水の混合物を次の抽出操作に用
いる事が可能である。
抽出溶剤の原料油に対する溶剤比についても、
マイクロエマルジヨン相を形成する抽出分離操作
に適する範囲が存在する。
即ち、溶剤比の高い領域では、抽出相、抽残相
共に濁りが生じ充分な抽出効果が得られない。
また、溶剤比の低い領域では、水の油への可溶
化現象、即ちＷ／Ｏ型エマルジヨンの形成が起こ
り、抽出操作は溶剤比が低くなるに従い相分離に
不明瞭な状態を全て界面形成をしなくなり、つい
には完全溶解状態を呈するに至る。
従つて本発明の飽和モノカルボン酸水溶液にお
ける溶剤比は0.1〜1.5の溶剤比が好ましく、0.2〜
1.2が特に好ましい。
抽出温度は、本発明の分離法がマイクロエマル
ジヨン形成によるものであるところから、界面活
性剤である石油スルフオネートの活性能力によつ
て決まり、低温域ではその活性能力および溶剤中
の界面活性助剤の活性能力も低下してマイクロエ
マルジヨン形成が困難となり、結果として相分離
を生じなくなる。
また相分離をした場合であつても低温になる従
いセツトリングタイムに長時間を要することとな
る。また高温域での抽出操作では、使用する溶剤
が水溶液であるために、沸騰を徐々に起こしてき
て分離操作がしにくくなる。
この点で、先行技術のイソプロピルアルコール
の場合は水より低沸点であるため、イソプロピル
アルコールの沸点に制約され更に操作条件中の抽
出温度範囲は狭まるが、本発明の場合は水より高
沸点の飽和モノカルボン酸であるために、操作条
件中の抽出温度範囲はより高温域まで抽出操作す
ることが可能である。
従つて、本発明では20〜95℃の抽出温度が好ま
しく、50〜80℃が特に好ましい。
〔実施例〕
以下に実施例および比較をあげて本発明を具体
的に説明する。
実施例１および比較例１
数平均分子量が300〜450程度の石油系潤滑留分
を原料として、空気希釈の三酸化イオウでスルフ
オン化し、後に当量のNaOHで中和して得られ
た未反応石油を含む石油スルフオネートを抽出操
作に用いる原料油として使用した。
原料油の一般分析値は次の通りであつた。
Na2SO4 1.9 重量百分率
水 分 7.3 重量百分率
結合SO3 3.91 重量百分率
この原料油を使用し、抽出操作条件を以下のご
とく設定した。
原料油 100 ml
酢酸溶液濃度 50 体積百分率
溶剤比 0.1
抽出温度 60 ℃
抽出結果は以下の通りであつた。
セツトリングタイム 51 分
抽残相 25.5 体積百分率
抽出相 74.5 体積百分率
比較例１として行つた先行技術であるイソプロ
ピルアルコール水溶液で使用した分離方法では、
同一条件において、原料油と抽出溶剤が完全溶解
状態となり透明な一相を呈して、相分離を生じな
かつた。
飽和モノカルボン酸として酢酸を使用した本発
明の溶剤抽出精製法では、先行技術におけるイソ
プロピルアルコールのを使用した抽出精製法より
も、低溶剤比領域まで抽出分離が可能であるとい
う特色を示す。
実施例２、３および比較例２
実施例１と同一の原料油を用い、表１に示すよ
うに抽出溶剤として酢酸（実施例２）、プロピオ
ン酸（実施例３）及びイソプロパノール（比較例
２）を使用して60℃にて抽出を行つた。抽出条
件、抽出状態および抽出物の組成を表１に示す。
[Industrial Application Field] The present invention relates to a method for extracting and purifying organic sulfonates, particularly petroleum sulfonates. More specifically, the present invention has a number average molecular weight of 300
~450 petroleum products are sulfonated with sulfuric acid or air-diluted sulfur trioxide, and the unreacted oil in the sulfonate is neutralized with NaOH.
The present invention relates to a method for solvent extraction and purification of organic sulfonates in which a desired petroleum sulfonate is obtained by separation and removal using a mixed solvent of a saturated monocarboxylic acid and water as described above. [Prior Art] Petroleum sulfonates obtained by sulfonating petroleum products have traditionally been used as surfactants in a wide range of fields such as lubricating oil additives, emulsifiers, dispersants, and detergents. It is used as a surfactant for micellar polymer flooding, which is one of the technologies for the secondary and tertiary recovery of crude oil, and is attracting particular attention. Conventionally, petroleum sulfonates obtained by sulfonation reactions have been industrially purified in many cases by extraction with an aqueous alcohol solution, and generally recovered as an alkali salt after neutralization with an alcoholic soda solution. The alcohol used in this case is mainly lower alcohol, especially isopropyl alcohol, for example, US Pat.
This is shown in No. 3956372, etc. This extracted petroleum sulfonate is usually commercialized as a 40 to 60 weight percent oil-containing solution. One of the reasons why products are produced at this concentration is that petroleum sulfonate alone becomes a hardened solid and is difficult to handle, so oil is added to adjust the sulfonate concentration.
Another reason is that the solvent extraction purification method for sulfonate utilizes the separation phenomenon from unreacted oil by forming a microemulsion, as described below, and is strictly different from simple dissolution extraction. This extraction method is a technique for obtaining concentrated petroleum sulfonate by forming a microemulsion in an aqueous solution of a saturated monocarboxylic acid and solubilizing the petroleum sulfonate, which partially encapsulates unreacted oil in unrefined petroleum sulfonate. Therefore, the oil that has not been solubilized is separated as unreacted oil, and as a result, petroleum sulfonate is extracted and separated. Here, the importance of forming a microemulsion in the extraction phase is that the size of the emulsified particles is 0.1~
This is because the microemulsion phase with a diameter of 0.05 microns exhibits a homogeneous transparent phase, which separates into two phases with a clear interface with unreacted oil. If it is a phase, phenomena such as emulsification with unreacted oil easily occur, preventing two-phase separation, and as a result, extraction and separation operations cannot be performed. The alcohols in the prior art lower alcohol aqueous solutions used as extraction solvents play an important role by acting as surfactant auxiliaries in microemulsion formation (About the role of these surfactant auxiliaries on microemulsion formation) “Science of Chalmant Emulsion” Asakura Shoten, Vol.
This is explained in detail on page 209. ). However, in the prior art method using lower alcohols, in the step of distilling and recovering the solvent alcohol and water from the extraction phase containing petroleum sulfonate that formed the microemulsion, although the two are azeotropic, the initial boiling point is low. Those with a high alcohol content will be collected, followed by those with a high water content. At this time, as water is recovered, the amount of water in this microemulsion forming phase decreases, so the state changes from a state in which oil is solubilized in water (O/W emulsion) to a state in which water is solubilized in oil (O/W type emulsion). /W-type emulsion). During this phase inversion, the system exhibits a gel state as shown in "Winsor's experiment" and becomes extremely viscous (PAWinsor; Mfg. Chemist, 28, 89
(1956). ). This phenomenon of high viscosity during phase inversion causes process constraints such as the difficulty of recovering the solvent in a continuous method and increases production costs when petroleum sulfonate is transferred to an industrial scale. . This is a major obstacle, especially for demands that require the use of large amounts of surfactants, such as surfactants for micellar polymer flooding, which is one of the secondary and tertiary recovery methods for crude oil. [Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a method for solvent extraction and purification of petroleum sulfonates that does not cause the phenomenon of increased viscosity during emulsion phase inversion, unlike the above-mentioned method using lower alcohols. The purpose is to [Means and effects for solving the problem] As a result of intensive studies, the present inventors found that
The saturated monocarboxylic acid in the saturated monocarboxylic acid aqueous solution, which has a higher boiling point than water, has a higher ability as a surfactant aid in microemulsion formation than the alcohol in the conventional lower alcohol aqueous solution,
The volume ratio of the extraction solvent to the raw material oil (hereinafter referred to as solvent ratio) enables extraction operations over a wider extraction range, and this saturation, which is a surfactant auxiliary with a higher boiling point than water, during emulsion phase inversion. It was discovered that gelling phenomenon could be prevented by leaving the monocarboxylic acid in the phase, and the above-mentioned problem was solved. That is, the present invention relates to a method for solvent extraction of organic sulfonates from a mixture of organic sulfonates and unreacted substances obtained in the process of producing organic sulfonates, and the extraction solvent is hydrophilic and has a higher boiling point than water and has a carbon number of 1. This is a method for solvent purification of organic sulfonates, characterized by using an aqueous solution of a saturated monocarboxylic acid of 4 to 4. According to the order of carbon number, saturated monocarboxylic acids have:
There are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, etc., but the ones that can be used in the extraction conditions of the present invention are saturated monocarboxylic acids that are hydrophilic and have a higher boiling point than water. The conditions are limited to formic acid, acetic acid, propionic acid, and butyric acid because of the conditions that provide good extraction and separation properties. Among these, formic acid is toxic, dangerous, and has a small boiling point difference with water, while butyric acid requires a long time to complete phase separation in the extraction process (hereinafter referred to as settling time). From this point of view, particularly preferred saturated monocarboxylic acids as extraction solvents in the present invention are acetic acid and propionic acid. Next, there is a concentration range of saturated monocarboxylic acid in the extraction solvent as a surfactant that is suitable for forming a microemulsion phase. However, it shows a cloudy emulsified state and no clear interface is formed. In a highly concentrated aqueous solution, both the extraction phase and the raffinate phase become cloudy, making it impossible to obtain a sufficient extraction effect. Therefore, the concentration of the saturated monocarboxylic acid aqueous solution suitable as an extraction solvent in the present invention is closely related to the solvent ratio and the extraction temperature, and is preferably 10 to 90 volume percent, particularly preferably 20 to 80 volume percent. Regarding the tendency that the saturated monocarboxylic acid concentration in the extraction solvent has on the sulfonate yield, as the saturated monocarboxylic acid concentration increases,
Although the amount of sulfonate extract phase separated into the lower phase is reduced, the sulfonate concentration in the sulfonate extract obtained by distilling the lower phase is increased. Note that the mixture of saturated monocarboxylic acid and water recovered by the distillation operation at this time can be used in the next extraction operation. Regarding the ratio of extraction solvent to raw oil,
There is a range suitable for extractive separation operations to form microemulsion phases. That is, in a region where the solvent ratio is high, both the extraction phase and the raffinate phase become cloudy, making it impossible to obtain a sufficient extraction effect. In addition, in the region where the solvent ratio is low, the phenomenon of solubilization of water into oil, that is, the formation of a W/O emulsion, occurs, and as the solvent ratio becomes lower, the extraction operation eliminates all the states that are unclear in phase separation and forms an interface. and finally reaches a state of complete dissolution. Therefore, the solvent ratio in the saturated monocarboxylic acid aqueous solution of the present invention is preferably 0.1 to 1.5, and preferably 0.2 to 1.5.
1.2 is particularly preferred. Since the separation method of the present invention is based on microemulsion formation, the extraction temperature is determined by the active ability of petroleum sulfonate, which is a surfactant. The active ability of the microemulsion is also reduced, making it difficult to form a microemulsion, and as a result, no phase separation occurs. Furthermore, even if phase separation is performed, the settling time will take a long time due to the low temperature. Furthermore, in extraction operations at high temperatures, since the solvent used is an aqueous solution, it gradually boils, making separation operations difficult. In this respect, in the case of isopropyl alcohol in the prior art, the boiling point is lower than water, so the extraction temperature range in the operating conditions is further narrowed by the boiling point of isopropyl alcohol, but in the case of the present invention, the saturated Since it is a monocarboxylic acid, the extraction temperature range in the operating conditions can be extended to a higher temperature range. Therefore, in the present invention, an extraction temperature of 20 to 95°C is preferred, with 50 to 80°C being particularly preferred. [Example] The present invention will be specifically described below with reference to Examples and comparisons. Example 1 and Comparative Example 1 Unreacted petroleum obtained by sulfonating a petroleum lubricating fraction with a number average molecular weight of about 300 to 450 with air-diluted sulfur trioxide and later neutralizing it with an equivalent amount of NaOH. The petroleum sulfonate containing The general analysis values of the raw oil were as follows. Na 2 SO 4 1.9 Weight percentage Water 7.3 Weight percentage Combined SO 3 3.91 Weight percentage Using this raw material oil, the extraction operation conditions were set as follows. Raw material oil 100 ml Acetic acid solution concentration 50 Volume percentage solvent ratio 0.1 Extraction temperature 60°C The extraction results were as follows. Settling time: 51 minutes Raffinate phase: 25.5 volume percentage Extraction phase: 74.5 volume percentage
Under the same conditions, the raw material oil and the extraction solvent were completely dissolved and presented a single transparent phase, with no phase separation occurring. The solvent extraction and purification method of the present invention using acetic acid as the saturated monocarboxylic acid has the feature that extraction and separation can be carried out to a lower solvent ratio region than the prior art extraction and purification method using isopropyl alcohol. Examples 2, 3 and Comparative Example 2 Using the same raw material oil as in Example 1, acetic acid (Example 2), propionic acid (Example 3) and isopropanol (Comparative Example 2) were used as extraction solvents as shown in Table 1. Extraction was performed at 60°C using Table 1 shows the extraction conditions, extraction state, and composition of the extract.
【表】
表１の実施例２、３および比較例２に示すよう
に、本発明による抽出操作では、先行技術として
の低級アルコールのうちの代表であるイソプロピ
ルアルコールのによる抽出操作で得られた抽出物
と比較して、同一条件下においては有効分である
スルフオネートの高濃度物が得られ、かつ蒸留操
作面において前述したごとくＯ／Ｗ型エマルジヨ
ン相からＷ／Ｏ型エマルジヨン相への相転換の際
に生ずる増粘状態を経ることなく蒸留を完了する
ことができるという点に特徴がみられる。
実施例 ４
本発明の溶剤抽出精製法による石油スルフオネ
ートを用いて原油の二・三次回収法の一つである
マイセラーポリマー攻法用マイセラースラグを調
整し、その基礎的な物性を測定した結果を示す。
＜抽出操作条件＞
抽出溶剤組成酢酸（体積百分率） 50
水（体積百分率） 50
溶剤比 0.5
抽出温度 ℃ 70
上記の条件で溶剤抽出操作を行なつた場合の抽
残相、抽出相の割合は次の通りであつた。
抽残相（体積百分率） 40.5
抽出相（体積百分率） 59.5
抽出相を溶剤回収して得られた石油スルフオネ
ートの一般分析値は以下の通りであつた。
有効分 （重量百分率） 70.9
油 分 （重量百分率） 24.3
水 分 （重量百分率） 0.04
無機塩分 （重量百分率） 4.8
上記の組成の石油スルフオネートを用いて、次
に石油二・三次回収法いわゆるマイセラー・ポリ
マー攻法に、この石油スルフオネートを使用する
ために、その基礎的な物性として相挙動の観察と
界面張力の測定を行なつた。
石油スルフオネートとドデシルベンゼンスルフ
オン酸ナトリウムを種々の割合で混合し、コサー
フアクタントとしてｎ−ブチルアルコールを使用
し、塩分濃度は１％NaCl水、油はケロシンを使
用した。
マイセラースラグ作成温度は50℃であつた。マ
イセラースラグの組成を表２に示す。[Table] As shown in Examples 2 and 3 and Comparative Example 2 in Table 1, in the extraction operation according to the present invention, the extraction obtained in the extraction operation with isopropyl alcohol, which is a representative of lower alcohols, in the prior art Under the same conditions, a product with a high concentration of sulfonate, which is an effective ingredient, can be obtained, and in terms of distillation operation, as mentioned above, the phase transformation from O/W type emulsion phase to W/O type emulsion phase is easy. The feature is that the distillation can be completed without going through the thickening state that occurs during the process. Example 4 Results of preparing Micera slag for Micera polymer flooding, which is one of the secondary and tertiary crude oil recovery methods, using petroleum sulfonate produced by the solvent extraction and refining method of the present invention, and measuring its basic physical properties. shows. <Extraction operation conditions> Extraction solvent composition Acetic acid (volume percentage) 50 Water (volume percentage) 50 Solvent ratio 0.5 Extraction temperature ℃ 70 When the solvent extraction operation is performed under the above conditions, the ratio of the raffinate phase and extraction phase is as follows. It was hot on the street. Raffinate phase (volume percentage) 40.5 Extraction phase (volume percentage) 59.5 General analytical values of petroleum sulfonate obtained by solvent recovery of the extraction phase were as follows. Effective content (weight percentage) 70.9 Oil content (weight percentage) 24.3 Water content (weight percentage) 0.04 Inorganic salt (weight percentage) 4.8 Using the petroleum sulfonate with the above composition, the oil was then processed using the secondary and tertiary petroleum recovery method, the so-called micellar polymer. In order to use this petroleum sulfonate in the attack method, we observed its phase behavior and measured its interfacial tension as its basic physical properties. Petroleum sulfonate and sodium dodecylbenzenesulfonate were mixed in various proportions, n-butyl alcohol was used as a cosurfactant, 1% NaCl water was used as the salt concentration, and kerosene was used as the oil. The temperature for creating the micellar slag was 50°C. The composition of the micellar slag is shown in Table 2.
【表】
ジヨン相
〔発明の効果〕
本発明は、石油製品をスルフオン化して得られ
る石油スルフオネートと未反応物の混合物を、親
水性を有し水より高沸点の炭素数１〜４の飽和モ
ノカルボン酸の水溶液により抽出処理して、石油
スルフオネートを分離する精製方法を提供したも
のであり、従来の低級アルコールを用いる方法に
比較して、溶剤比が広い範囲で抽出操作が可能で
あり、またエマルジヨン転相時によるゲル化現象
を生じない等の特長を有する。[Table] Diyon phase [Effects of the invention] The present invention converts a mixture of petroleum sulfonate obtained by sulfonating petroleum products and unreacted substances into a saturated monomer having 1 to 4 carbon atoms that is hydrophilic and has a higher boiling point than water. This method provides a purification method that separates petroleum sulfonate by extracting it with an aqueous solution of carboxylic acid.Compared to the conventional method using lower alcohols, the extraction operation can be performed over a wider range of solvent ratios, and It has features such as not causing gelation phenomenon due to emulsion phase inversion.
Claims (1)
る有機スルフオネートと未反応物の混合物から有
機スルフオネートを溶剤抽出し精製する方法にお
いて、抽出溶剤として親水性を有し、水より高沸
点の炭素数１〜４の飽和モノカルボン酸の水溶液
を使用することを特徴とする有機スルフオネート
の溶剤精製法。 ２ 抽出溶剤が、飽和モノカルボン酸10〜90体積
百分率と水90〜10体積百分率との混合物である特
許請求の範囲第１項に記載の精製法。 ３ 抽出溶剤の原料油に対する体積比が0.1〜
1.5、抽出温度が20〜95℃の条で抽出を行う特許
請求の範囲第１項または第２項に記載の精製法。[Scope of Claims] 1. In a method for solvent extraction and purification of organic sulfonates from a mixture of organic sulfonates and unreacted substances obtained in the process of producing organic sulfonates, the extraction solvent is hydrophilic and has a boiling point higher than that of water. A method for solvent purification of organic sulfonates, characterized in that an aqueous solution of a saturated monocarboxylic acid having 1 to 4 carbon atoms is used. 2. The purification method according to claim 1, wherein the extraction solvent is a mixture of 10 to 90 volume percent saturated monocarboxylic acid and 90 to 10 volume percent water. 3 Volume ratio of extraction solvent to raw material oil is 0.1~
1.5. The purification method according to claim 1 or 2, wherein the extraction is performed at an extraction temperature of 20 to 95°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13080385A JPS61291561A (en) | 1985-06-18 | 1985-06-18 | Method for purifying organic sulfonate with solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13080385A JPS61291561A (en) | 1985-06-18 | 1985-06-18 | Method for purifying organic sulfonate with solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61291561A JPS61291561A (en) | 1986-12-22 |
| JPH0482141B2 true JPH0482141B2 (en) | 1992-12-25 |
Family
ID=15043074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13080385A Granted JPS61291561A (en) | 1985-06-18 | 1985-06-18 | Method for purifying organic sulfonate with solvent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61291561A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103592375A (en) * | 2012-08-13 | 2014-02-19 | 中国石油天然气股份有限公司 | Analysis method for determining active matter content of petroleum sulfonate by extraction method |
-
1985
- 1985-06-18 JP JP13080385A patent/JPS61291561A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61291561A (en) | 1986-12-22 |
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