CN1010477B - 从烷烃和烷基磺酸混合物中萃取烷烃的方法 - Google Patents
从烷烃和烷基磺酸混合物中萃取烷烃的方法Info
- Publication number
- CN1010477B CN1010477B CN87105310A CN87105310A CN1010477B CN 1010477 B CN1010477 B CN 1010477B CN 87105310 A CN87105310 A CN 87105310A CN 87105310 A CN87105310 A CN 87105310A CN 1010477 B CN1010477 B CN 1010477B
- Authority
- CN
- China
- Prior art keywords
- mixture
- alkane
- normal paraffin
- sulfonic acid
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 title abstract description 21
- -1 alkyl sulfonic acid Chemical compound 0.000 title description 2
- 239000012188 paraffin wax Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 230000005855 radiation Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 235000011089 carbon dioxide Nutrition 0.000 claims 1
- 230000005484 gravity Effects 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 20
- 239000002253 acid Substances 0.000 abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 abstract description 2
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000006277 sulfonation reaction Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
在使用紫外线辐射激发反应(光—水法)磺化氧化C12-C18正构烷烃时，得到一能自然分离出大量未转化正构烷烃的混合物。自然分离出烷烃的混合物含烷基磺酸，还有水、硫酸和正构烷烃。将一种或多种含4个或少于4个碳原子的醇，最好是异丙醇加到上述混合物中形成一两相混合物。用超临界CO2萃取该两相混合物，萃取出的正构烷烃经循环用于磺化氧化工艺。脱除了烷烃的产物适用于用适当的碱中合制备所需要的烷基磺酸盐。
Description
本发明涉及从烷烃和烷基磺酸混合物中萃取出烷烃的方法。说明书中“烷基磺酸”与石蜡磺酸是同义的。
含有12个至18个碳原子的烷基磺酸通常是用SO2和O2磺化氧化C12-C18正构烷烃制取的，采用紫外线辐射以引发反应。从磺化氧化反应器得到的反应产物含少量烷基磺酸，水和硫酸，但大部分为未反应的正构烷烃。
大部分正构烷烃能从所说的混合物中容易地分离出来，但它们中有相当一部分是和硫酸，水和烷基磺酸一起存在的。
需要指出，必须最大限度地分离出烷烃，不仅是由于明显的经济上的原因，还因为它们保留在烷基磺酸中是不希望的。
已知的技术提出了一些建议使所说的烷烃从它们与硫酸、烷基磺酸和水的混合物中分离出来，欧洲专利申请131913中包括这样的建议，尤其在例1中;据介绍，含有烷基磺酸，未反应烷烃，水和硫酸的混合物，用15%的异丙醇处理，使混合物分离为三个明显的相，上部相主要含烷烃，下部相含水，硫酸和异丙醇，中间相含烷基磺酸，硫酸，水，烷烃和异丙醇。之后，中间相与二氯甲烷混合以便将含异丙醇和少量二氯甲烷的含水硫酸相与含有烷基磺酸，烷烃，水，二氯甲烷和硫酸的相分离。后者用苏打中和并浓缩，最后在高至200℃下蒸发，以分离出烷烃。
这种脱除烷烃的程序显然是复杂的，而且尽管采用了多种萃取阶段，最后仍就需要用高温处理。这种高温处理在所有场合下都会损害得到的产品。
故用这种已知的方法不可能制备游离烷基磺酸或它们与弱酸生成的盐类，因为这些在高温下是不稳定的。
惊奇地发现，上述关于分离正构烷烃的已知技术的缺点可以用一种很简单的方式避免，即从正构烷烃磺化氧化反应器出来的混合物，用已知方法除去其中溶解的二氧化硫以后，用有限数量的含四个碳或少于四个碳原子的醇类与之混合直至生成两相混合物，然后用超临界CO2萃取两相混合物。
本发明提供了从烷烃与烷基磺酸混合物中萃取烷烃的方法，包括预先除去过剩的SO2;澄清用SO2和O2在紫外线辐射作用下和水存在下，在25～50℃温度间对C12-C18正构烷烃进行磺化氧化作用得到的反应产物，以从中自然地分离出大部分未反应的正构烷烃;且将所说的反应产物的剩余部分与含有四个碳或少于四碳原子的脂肪醇，以异丙醇更为可取，进行混合;该方法的特征在于脂肪醇的用量以能生成两相混合物所需要的量而定，且这两相混合物在超临界条件下用CO2萃取，以从烷基磺酸以及硫酸和水中分离出烷烃。
所得到的混合物然后以选好了的碱用已知的方式进行中和，这样就得到了所需型态的烷基磺酸盐。
如果需要，能用已知的方法将硫酸与脱除了烷烃的烷基磺酸分离，如用适当的物质混合或使之沉淀生成不溶性的盐类。
所用醇以异丙醇更为可取，根据本发明，用以生成两相混合物的醇的用量是使其在混合物中的浓度在3%～8.5%（重），最好是大约5%（重）。
用超临界CO2萃取的条件是：温度在32～80℃，压力在73～350巴，用于萃取的CO2对烷基磺酸的重量比在1∶1和50∶1之间。
为了更好地阐述本发明，下面举一些实例，但无意使发明局限在那里或在那一点上。
采用的实验室萃取装置表示在附图中。
它含有一个致冷循环，以冷凝换热器8中的CO2。液体CO2l由隔膜泵2送至预热器3，然后进入萃取器4。利用可控制温度的水槽使水循环以保持温度3和
4的恒定，并且固定在同一值上。用调节器5和控制阀6使4的压力保持在需要的数值上。含有从4的粗混合物中萃取出来的产物的CO2，经过6离开超临界场，进入分离器7;CO2在7中蒸发，在8中冷凝后又回到上述的循环中去，而萃取物仍留在7中。任何需要补充的CO2经9供给。
分离器7设有两个径向相反的观察镜以目测检查界面。
从第二个可控制温度的水槽的水循环来调整这里的温度使之恒定。用一个压力继电器操纵致冷循环，使7中的压力保持恒定。
萃取器中装有不锈钢填料，用一个破沫网压住。
第二个泵10用来连续供给要萃取的粗产品。在这里，精制产品经阀11排出。
124.3克粗混合物（已澄清正构烷烃，除去SO2）与6.4克异丙醇一起送入萃取器4。粗混合物含有
C12-C18烷基磺酸 24.74%（重）
C12-C18正构烷烃 26.46%（重）
水 40.94%（重）
硫酸 7.86%（重）
萃取器4中的温度控制在45℃，然后CO2以通入量为1.46kg/h进入，萃取器压力维持在200巴。
萃取1小时后停止供给CO2，放出萃取器中的产物并分析。
萃取的烷烃量是进料粗产品中含量的96%。
例2（比较例，不加异丙醇）
123.9克粗烷基磺酸具有如例1中同样的组成，用超临界CO2萃取，条件和时间为例1所述。
精制产物的分析表明，被萃取的烷烃是进料的粗产品中含量的67.5%。
Claims (2)
1、一种从含有未反应的C12-C18烷烃与C12-C18链烷基磺酸、水和硫酸的混合物中脱除C12-C18正构烷烃的方法，该混合物是用SO2和O2在紫外线辐射和水存在下，温度为25-50℃磺化氧化C12-C18正构烷烃所得的，该方法包括脱除过剩的二氧化硫，使剩余混合物沉淀经重力自然分离出大部分未反应的C12-C18正构烷烃，该方法的特征在于使剩余混合物与含4个或低于4个碳原子的脂族醇混合，使混合物中的醇浓度为3-8.5%(重量)，从而形成两相混合物，然后用超临界二氧化碳在温度32°-80℃，压力75-350巴条件下处理该两相混合物，所用的二氧化碳对链烷基磺酸的重量比在1∶1至50∶1之间。
2、权利要求1的方法，其特征在于混合物中的醇浓度为5%（重量）。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21225A/86 | 1986-07-23 | ||
| IT21225/86A IT1196982B (it) | 1986-07-23 | 1986-07-23 | Procedimento di estrazione di paraffine da miscele contenenti le stesse ed acidi alcansolfonici |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87105310A CN87105310A (zh) | 1988-05-11 |
| CN1010477B true CN1010477B (zh) | 1990-11-21 |
Family
ID=11178662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87105310A Expired CN1010477B (zh) | 1986-07-23 | 1987-07-23 | 从烷烃和烷基磺酸混合物中萃取烷烃的方法 |
Country Status (21)
| Country | Link |
|---|---|
| US (1) | US4827078A (zh) |
| EP (1) | EP0254368B1 (zh) |
| JP (1) | JP2540046B2 (zh) |
| CN (1) | CN1010477B (zh) |
| AR (1) | AR245691A1 (zh) |
| AT (1) | ATE57375T1 (zh) |
| BR (1) | BR8704130A (zh) |
| CA (1) | CA1296359C (zh) |
| CS (1) | CS272777B2 (zh) |
| DD (1) | DD257836A5 (zh) |
| DE (1) | DE3765484D1 (zh) |
| DK (1) | DK166351C (zh) |
| ES (1) | ES2018819B3 (zh) |
| GR (1) | GR3001131T3 (zh) |
| IN (1) | IN169787B (zh) |
| IT (1) | IT1196982B (zh) |
| MX (1) | MX168755B (zh) |
| NO (1) | NO165920C (zh) |
| PT (1) | PT85390B (zh) |
| RU (1) | RU1780532C (zh) |
| ZA (1) | ZA875104B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI105080B (fi) * | 1995-10-11 | 2000-06-15 | Rauma Ecoplanning Oy | Uuttomenetelmä |
| US9108906B2 (en) * | 2012-03-22 | 2015-08-18 | Uop Llc | Production of alkane sulfonates |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US228598A (en) * | 1880-06-08 | Chaunoey buckley | ||
| 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 |
| IT1191720B (it) * | 1986-03-27 | 1988-03-23 | Eniricerche Spa | Procedimento per la estrazione di paraffine da miscele delle stesse con acidi alcansolfonici |
-
1986
- 1986-07-23 IT IT21225/86A patent/IT1196982B/it active
-
1987
- 1987-07-10 US US07/071,926 patent/US4827078A/en not_active Expired - Fee Related
- 1987-07-13 ZA ZA875104A patent/ZA875104B/xx unknown
- 1987-07-14 IN IN496/MAS/87A patent/IN169787B/en unknown
- 1987-07-17 ES ES87201364T patent/ES2018819B3/es not_active Expired - Lifetime
- 1987-07-17 EP EP87201364A patent/EP0254368B1/en not_active Expired - Lifetime
- 1987-07-17 AT AT87201364T patent/ATE57375T1/de not_active IP Right Cessation
- 1987-07-17 DE DE8787201364T patent/DE3765484D1/de not_active Expired - Lifetime
- 1987-07-21 NO NO873057A patent/NO165920C/no unknown
- 1987-07-21 DK DK379487A patent/DK166351C/da not_active IP Right Cessation
- 1987-07-22 DD DD87305254A patent/DD257836A5/de not_active IP Right Cessation
- 1987-07-22 RU SU874203003A patent/RU1780532C/ru active
- 1987-07-22 BR BR8704130A patent/BR8704130A/pt not_active Application Discontinuation
- 1987-07-22 CA CA000542773A patent/CA1296359C/en not_active Expired - Lifetime
- 1987-07-22 MX MX007466A patent/MX168755B/es unknown
- 1987-07-23 PT PT85390A patent/PT85390B/pt not_active IP Right Cessation
- 1987-07-23 JP JP62182435A patent/JP2540046B2/ja not_active Expired - Fee Related
- 1987-07-23 AR AR87308249A patent/AR245691A1/es active
- 1987-07-23 CN CN87105310A patent/CN1010477B/zh not_active Expired
- 1987-07-23 CS CS557187A patent/CS272777B2/cs unknown
-
1990
- 1990-11-29 GR GR90400993T patent/GR3001131T3/el unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2540046B2 (ja) | 1996-10-02 |
| NO165920B (no) | 1991-01-21 |
| ES2018819B3 (es) | 1991-05-16 |
| MX168755B (es) | 1993-06-07 |
| AR245691A1 (es) | 1994-02-28 |
| BR8704130A (pt) | 1988-04-12 |
| US4827078A (en) | 1989-05-02 |
| DK166351C (da) | 1993-09-06 |
| DE3765484D1 (de) | 1990-11-15 |
| NO165920C (no) | 1991-05-02 |
| JPS6339851A (ja) | 1988-02-20 |
| ATE57375T1 (de) | 1990-10-15 |
| DK379487A (da) | 1988-01-24 |
| GR3001131T3 (en) | 1992-06-25 |
| ZA875104B (en) | 1988-01-13 |
| IN169787B (zh) | 1991-12-21 |
| DK166351B (da) | 1993-04-13 |
| IT8621225A1 (it) | 1988-01-23 |
| DK379487D0 (da) | 1987-07-21 |
| NO873057L (no) | 1988-01-25 |
| EP0254368B1 (en) | 1990-10-10 |
| CN87105310A (zh) | 1988-05-11 |
| IT1196982B (it) | 1988-11-25 |
| CS272777B2 (en) | 1991-02-12 |
| IT8621225A0 (it) | 1986-07-23 |
| CA1296359C (en) | 1992-02-25 |
| RU1780532C (ru) | 1992-12-07 |
| CS557187A2 (en) | 1990-06-13 |
| PT85390B (pt) | 1990-04-30 |
| DD257836A5 (de) | 1988-06-29 |
| EP0254368A1 (en) | 1988-01-27 |
| PT85390A (en) | 1987-08-01 |
| NO873057D0 (no) | 1987-07-21 |
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