CN1010008B - 从链烷与烷基磺酸的混合物中萃取链烷烃的方法 - Google Patents
从链烷与烷基磺酸的混合物中萃取链烷烃的方法Info
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- CN1010008B CN1010008B CN87103209A CN87103209A CN1010008B CN 1010008 B CN1010008 B CN 1010008B CN 87103209 A CN87103209 A CN 87103209A CN 87103209 A CN87103209 A CN 87103209A CN 1010008 B CN1010008 B CN 1010008B
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- extraction
- paraffinic hydrocarbons
- mixture
- alkane
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明是关于从碳原子数为12至18的链烷烃磺化氧化所得到的混合物中萃取链烷烃的方法,其特征在于在超临界条件下使用溶剂CO2。
Description
本发明是关于从链烷烃与烷基磺酸的混合物中萃取链烷烃的方法。
本发明尤其是关于从上述链烷烃与烷基磺酸、硫酸、弱极性醇和水的混合物中萃取链烷烃的方法。
具体地说,烷基磺酸和链烷烃的混合物是由直链烷烃磺化氧化过程得到的,例如,根据德国专利910165。
上述混合物所面临的问题是从用于磺化氧化作用的硫酸和可能过量的SO2中回收烷基磺酸或它们的盐类,以及回收链烷烃。
至于SO2,不存在特殊问题,由于在中等真空中蒸馏或者用氧气汽提,SO2足以从溶液中完全分离,SO2再循环到磺化氧化反应器。
在分离未转变成烷基磺酸的链烷烃和硫酸方面,已经提出了几种方法。其中一种方法(欧洲专利申请131,913)建议在直链烷烃磺化氧化所得到的混合物中加入醇,从磺化链烷烃所得到的混合物中分离出烷基磺酸,或烷基磺酸盐,然后分离出硫酸,醇的碳原子数选择2或3。在该方法中,分离出含有大部分链烷烃的上层液相,用不溶于水的或微溶于水的弱极性有机溶剂从混合物中分离硫酸。
含有可能成盐的烷基磺酸的产物经过加热分离溶剂和残留的链烷烃,如果存在过氧化氢,残留的链烷烃可能变白。
在上述欧洲专利申请所提出的已知技术的方法中有一个缺点,当所用的醇的碳原子数选择为2或3时,链烷烃的分离效果很差,以至后来的加热阶段必须进行很长时间,必然消耗大量热能,同时会使烷基磺酸或烷基磺酸盐变质。
用在超临界状态下的CO2萃取链烷烃能够克服已知技术的缺点是惊人的发现。
根据本发明的方法,原料含有碳原子数为12至18的烷基磺酸、按重量计在水中溶解度低于7%的一种或多种脂肪醇、硫酸、碳原子数为12至18的链烷烃和水。原料在超临界条件下由二氧化碳萃取,分离的萃取相除CO2之外,还含有链烷烃和存在的醇或醇类,精制相含有烷基磺酸、硫酸和水。
于是,根据已知方法,通过中和或除去硫酸回收烷基磺酸,或它们的盐类。
就萃取操作条件而论,萃取条件为:温度为32℃至80℃;操作压力从CO2的临界压力(73.8巴)至某一与操作温度有关的压力值,在该操作温度下超临界状态的CO2的密度稍低于萃取的混合物的密度,一般压力为75至350巴;二氧化碳处于超临界状态;CO2/SAS比率最好为1/1至50/1(SAS=仲烷基磺酸盐或烷基磺酸)。
脂肪醇在水中的溶解度低于7%,脂肪醇可以是直链的,枝链的或环状的,而碳原子数为5至12,尤其是选择1-戊醇、1-己醇、1-庚醇、1-辛醇、1-癸醇、1-十二(烷)醇、2-乙基-1-丁醇、2-甲基-1-戊醇、2-乙基-1-己醇、2,6-二甲基-4-庚醇、3-乙基-1-己醇、2,7-二甲基辛醇、2-辛醇、环己醇、环辛醇和这些醇类的混合物。
就分离硫酸来说,可以使用一种分离剂,最好是使用如上所述的在水中的溶解度低于7%的相同的脂肪醇。
本发明的方法,可以是一种连续方法或者是一种间歇的方法,用以下实施例图解说明,但本发明并不限于这方面。
实施例1
使用如图1中所示的试验室规模的萃取装置。
该装置包括由热交换器(8)冷凝CO2的冷却循环系统。液态CO2(1)由薄膜泵(2)输送到预热器(3),然后,送到萃取装置(4),用恒温槽的循环水使(3)和(4)的温度保持恒定和保持同样的数值。用调节器(5)和控制阀(6)使(4)中的压力恒定在所需的数值。
含有自原料中萃取的产物的CO2注入(4),从(6)流出,CO2在分离装置(7)的超临界区内蒸发,并在(8)中冷凝,然后将CO2送回上述循环系统。可以通过(9)来补充CO2。
分离装置(7)有两个完全相对的玻璃窗,用作液位目视检查,通过第二恒温槽水温的作用,保持液位恒定,用控制冷却循环系统的压力开关使(7)中的压力保持恒定。在萃取装置(4)内,有一个圆柱容器,容器的盖板和底板由多孔烧结钢制造,在容器中注入产物进行萃取。在最佳方案中,把不锈钢物质装进萃取装置,用去雾器保持封闭。
在连续操作状态时,第二个泵(10)输送所萃取的粗产物,在这种情况下,精制产物通过阀(11)排出。
在萃取装置(4)的容器内,注入126.1克(C12-C18)链烷烃磺酸(仲烷基磺酸=SAS)的粗混合物,粗混合物中除了磺酸和二磺酸外,还含有:
1-己醇 =17.06%按重量计
(C12-C18)-正-链烷烃 =36.72%按重量计
H2O =11.22%按重量计
H2SO4=0.78%按重量计
用超临界状态的CO2在40℃和150巴条件下萃取1小时(CO2/粗SAS重量比=14.5)。
在试验末期,在分离装置(7)(萃取相)和萃取装置(4)(精制相)中的产物分别经(12)和(11)排出,经过分析,所萃取的链烷烃量相当于注入的粗SAS中链烷烃含量的99.4%,1-己醇则为91.9%。
实施例2
使用如实施例1所描述的装置。125克具有实施例1所述成分的SAS粗混合物,用超临界的CO2在50℃和150巴条件下萃取3小时(CO2/粗SAS重量比=43.8)。在试验末期,通过分析萃取相和精制相表明,基于注入的粗SAS中所包含的链烷烃,萃取链烷烃的萃取率达99.53%,而1-己醇则达到98.87%。
实施例3
使用如实施例1所描述的装置。119.3克具有如实施例1所述成分的链烷烃磺酸用超临界状态的CO2在60℃和150巴条件下萃取2小时(CO2/粗SAS重量比=30.5)。在试验末期,通过分析萃取相和精制相表明,基于注入的粗SAS中所含的链烷烃,链烷烃的萃取率达99.8%,而1-己醇达98.12%。
Claims (2)
1、从链烷烃与烷基磺酸的混合物,尤其是碳原子数为12至18的链烯烃磺化氧化所得到的混合物中萃取链烷烃的方法,其特征在于,在一种或多种5-12碳脂肪醇的存在下,链烷烃、烷基磺酸和硫酸的含水混合物的超临界条件下用CO2萃取链烷轻,其中温度为32℃-80℃,压力为至少73.8巴,CO2/SAS重量比为1∶1-50∶1。
2、根据权利要求1的方法,其特征在于萃取压力为75-350巴。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT19893A/86 | 1986-03-27 | ||
IT19893/86A IT1191720B (it) | 1986-03-27 | 1986-03-27 | Procedimento per la estrazione di paraffine da miscele delle stesse con acidi alcansolfonici |
Publications (2)
Publication Number | Publication Date |
---|---|
CN87103209A CN87103209A (zh) | 1987-11-04 |
CN1010008B true CN1010008B (zh) | 1990-10-17 |
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ID=11162118
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN87103209A Expired CN1010008B (zh) | 1986-03-27 | 1987-03-26 | 从链烷与烷基磺酸的混合物中萃取链烷烃的方法 |
Country Status (21)
Country | Link |
---|---|
US (1) | US4798915A (zh) |
EP (1) | EP0239177B1 (zh) |
JP (1) | JP2540038B2 (zh) |
CN (1) | CN1010008B (zh) |
AR (1) | AR244781A1 (zh) |
AT (1) | ATE57686T1 (zh) |
BR (1) | BR8701987A (zh) |
CA (1) | CA1274854A (zh) |
CS (1) | CS268176B2 (zh) |
DD (1) | DD255732A5 (zh) |
DE (1) | DE3765667D1 (zh) |
DK (1) | DK167115B1 (zh) |
ES (1) | ES2019368B3 (zh) |
GR (1) | GR3001176T3 (zh) |
IN (1) | IN169362B (zh) |
IT (1) | IT1191720B (zh) |
MX (1) | MX172944B (zh) |
NO (1) | NO165919C (zh) |
PT (1) | PT84576B (zh) |
SU (1) | SU1586511A3 (zh) |
ZA (1) | ZA872037B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1213456B (it) * | 1986-07-23 | 1989-12-20 | Eniricerche Spa | Procedimento per l'estrazione di paraffine da loro miscele con acidi paraffinsolfonici. |
IT1196981B (it) * | 1986-07-23 | 1988-11-25 | Eniricerche Spa | Procedimento per la rimozione delle paraffine da miscele delle stesse con acidi paraffinsolfonici |
IT1196982B (it) * | 1986-07-23 | 1988-11-25 | Eniricerche Spa | Procedimento di estrazione di paraffine da miscele contenenti le stesse ed acidi alcansolfonici |
IT1230155B (it) * | 1989-06-15 | 1991-10-14 | Enichem Augusta Spa | Procedimento migliorato per la preparazione di acidi paraffin-solfonici |
FI105080B (fi) * | 1995-10-11 | 2000-06-15 | Rauma Ecoplanning Oy | Uuttomenetelmä |
DE102008032723A1 (de) | 2008-07-11 | 2010-01-14 | Clariant International Limited | Verfahren zur Isolierung von Paraffinsulfonsäuren |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US2228598A (en) * | 1938-06-30 | 1941-01-14 | Charles L Horn | Purification of hydrocarbon-sulphur dioxide-chlorine reaction products |
US2875257A (en) * | 1954-06-15 | 1959-02-24 | Atlantic Refining Co | Preparation of improved alkylate products using a sulfuric acid treatment |
US3033898A (en) * | 1958-08-18 | 1962-05-08 | Bray Oil Co | Sulfonation of oils |
US3681442A (en) * | 1968-12-26 | 1972-08-01 | Universal Oil Prod Co | Alkylaromatic sulfonate detergent process of preparation |
IT1074825B (it) * | 1977-01-11 | 1985-04-20 | Euteco Spa | Procedimento per la purificazione di acidi alchilsolfonici |
US4361520A (en) * | 1979-07-26 | 1982-11-30 | Marathon Oil Company | Refinement of sulfonated hydrocarbons |
US4269789A (en) * | 1979-12-31 | 1981-05-26 | Phillips Petroleum Company | Petroleum sulfonation |
-
1986
- 1986-03-27 IT IT19893/86A patent/IT1191720B/it active
-
1987
- 1987-03-18 US US07/027,548 patent/US4798915A/en not_active Expired - Fee Related
- 1987-03-19 ZA ZA872037A patent/ZA872037B/xx unknown
- 1987-03-20 NO NO871157A patent/NO165919C/no unknown
- 1987-03-24 IN IN211/MAS/87A patent/IN169362B/en unknown
- 1987-03-24 EP EP87200552A patent/EP0239177B1/en not_active Expired - Lifetime
- 1987-03-24 AT AT87200552T patent/ATE57686T1/de active
- 1987-03-24 CA CA000532881A patent/CA1274854A/en not_active Expired - Lifetime
- 1987-03-24 ES ES87200552T patent/ES2019368B3/es not_active Expired - Lifetime
- 1987-03-24 DE DE8787200552T patent/DE3765667D1/de not_active Expired - Lifetime
- 1987-03-26 DD DD87301159A patent/DD255732A5/de unknown
- 1987-03-26 SU SU874202320A patent/SU1586511A3/ru active
- 1987-03-26 PT PT84576A patent/PT84576B/pt not_active IP Right Cessation
- 1987-03-26 CN CN87103209A patent/CN1010008B/zh not_active Expired
- 1987-03-26 DK DK154787A patent/DK167115B1/da not_active IP Right Cessation
- 1987-03-27 AR AR87307148A patent/AR244781A1/es active
- 1987-03-27 MX MX005778A patent/MX172944B/es unknown
- 1987-03-27 BR BR8701987A patent/BR8701987A/pt active Search and Examination
- 1987-03-27 CS CS872147A patent/CS268176B2/cs unknown
- 1987-03-27 JP JP62071945A patent/JP2540038B2/ja not_active Expired - Fee Related
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1990
- 1990-12-07 GR GR90401046T patent/GR3001176T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
CN87103209A (zh) | 1987-11-04 |
NO165919B (no) | 1991-01-21 |
IT8619893A0 (it) | 1986-03-27 |
ATE57686T1 (de) | 1990-11-15 |
JPS62240630A (ja) | 1987-10-21 |
DE3765667D1 (de) | 1990-11-29 |
CA1274854A (en) | 1990-10-02 |
BR8701987A (pt) | 1988-01-12 |
ES2019368B3 (es) | 1991-06-16 |
IT8619893A1 (it) | 1987-09-27 |
NO871157L (no) | 1987-09-28 |
EP0239177A1 (en) | 1987-09-30 |
PT84576B (pt) | 1989-11-30 |
MX172944B (es) | 1994-01-25 |
AR244781A1 (es) | 1993-11-30 |
US4798915A (en) | 1989-01-17 |
GR3001176T3 (en) | 1992-06-30 |
ZA872037B (en) | 1987-09-14 |
DK154787D0 (da) | 1987-03-26 |
DK167115B1 (da) | 1993-08-30 |
JP2540038B2 (ja) | 1996-10-02 |
IN169362B (zh) | 1991-10-05 |
CS214787A2 (en) | 1989-05-12 |
CS268176B2 (en) | 1990-03-14 |
NO165919C (no) | 1991-05-02 |
DD255732A5 (de) | 1988-04-13 |
SU1586511A3 (ru) | 1990-08-15 |
NO871157D0 (no) | 1987-03-20 |
PT84576A (en) | 1987-04-01 |
EP0239177B1 (en) | 1990-10-24 |
DK154787A (da) | 1987-09-28 |
IT1191720B (it) | 1988-03-23 |
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