CN1035062C - 生产润滑油的方法 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明涉及一种粘度指数至少为120，流动点至少为-45℃的润滑油的生产制备方法。本方法在催化剂存在下将含有重量比至少为2.6%的1-癸烯和重量比至少为6%的1-己烯的C5-C20的1-链烯烃混合物齐聚。这样制得的润滑油可在氢气的存在下加氢以改善其氧化稳定性，本方法尤其适用于用一氧化碳和氢气通过加热的催化剂的Fischer-Fropsch合成法中生成的链烯烃原料。
Description
本发明涉及以含有5-20个碳原子的1-链烯烃为原料制备润滑油的方法。
大家都知道，将1-链烯烃齐聚得到高分子量的碳氢化合物，然后再经加氢或异构此齐聚物就得到了润滑油(见US-A-3763244)。这种情况的大多数中，1-链烯烃最初从乙烯而来(即所谓“乙烯链的增长和取代”方法)而乙烯对1-链烯烃来说是较昂贵的原料，更何况，润滑油都是从较纯的1-链烯烃中经齐聚制得的(见US-A-3780128和EP-A-0 468109)。后一文件还指出一旦齐聚物生成，在制备有所需一定性质如粘度指数和流动点的润滑油的加氢或异构化的步骤之前或之后，将各种1-链烯烃的齐聚物混合。这种混合技术有一个问题就是最终的齐聚物是不同分子量的一种混合物，如C20，C30和C40碳氢化合物的混合物，因而这种混合物由于没有密切相关或相称的齐聚物连续次渐地混杂而缺乏性质的一致性。我们也知道用Fischer Tropsch合成法齐聚链烯烃产物接着加氢或异构此齐聚物而制得润滑油(见例如：单链烯烃，化学和技术，作者是F Asinger，第900和1089页(1968)，由Pergamon出版社出版)。然而，把FischerTropsch产物作为原料来齐聚的公开并不表明混合产物能获得所需的齐聚物或者催化剂适用于齐聚反应的步骤。
例如，现在我们发现，那些从常规Fischer Tropsch方法中可商业化制得的1-链烯烃的一种特定混合物对于齐聚反应是特别适宜的原料，而由此得到的齐聚物可加氢制得润滑油。
因此，本发明是一种制备有粘度数至少为120，流动点至少为-45℃的润滑油的方法，该方法包括：
a)将含有重量比至少为2.6％的1-癸烯和重量比至少为6％的1-己烯的C5-C20 1-链烯烃混合物在齐聚反应催化剂的存在下齐聚生成润滑油；
b)从齐聚反应催化剂中分离润滑油；
c)在氢气存在下可选择地催化加氢润滑油以改善其氧化稳定性。
d)回收上述b)或c)中制得的润滑油。
混合的1-链烯烃原料以含有4-18个碳原子的链烯烃较适宜，以含有5-12个碳原子的更好。这样，原料尤其值得一提的是从Fischer Tropsch合成法中生成的链烯烃蒸汽。
通常在Fischer Tropsch合成法(下称“FTS”)中，将一氧化碳和氢气的混合物通过或穿过一个加热的催化床可以制得多种多样的碳氢化合物。当反应混合物中氢气含量较高，反应产物以链烯烃的碳氢化合物为主，然而，如果反应混合物中氢气的比例较低，反应产物则以链烯烃的碳氢化合物为主。
然而重要的是，即便在FTS的反应产物主要是链烯烃的情况下，FTS法的反应条件也必须控制好才能获得所需的1-链烯烃。譬如，从FTS法中衍生得到的汽油，含有约50％的丁-2-烯(“单链烯烃化学和技术”作者是F.Asinger，第1089页(1968)，由Pergamon出版社出版)并指出在三氯化铝存在下聚合得到极少的润滑物质。由此，非特定的FTS法的非特定的产物混合物看起来并不适宜作为本发明方法的原料。实际上，如果用FTS法的产物作为原材料，则必须使FTS法在一定操作状态下以便合成的链烯烃产物包含有重量比至少为2.6％的1-癸烯，至少为7％更好，以及重量比为6％的1-己烯，至少为13％更好。这样的产物混合物能用常规的FTS法制得，其操作工艺条件应该被控制在使产品有一个从0.6-0.9的Schulz-Floryα值，0.7-0.8则更好。这个Schulz-Floryα值是公认的概念，并被如P.J.Flory在“J.Am.Chem.Soc”中，58，1877(1950)所定义，或被G.V.Schulz在“Z Phys Chem”，B43，25(1935)中所定义。这个值可以用下列等式定义：
Log[Wn/n]＝nLogα+[(1-α)/α]其中Wn为重量分数，n是碳原子数，α是链增长的概率。
在此，齐聚反应所用的催化剂的选择也是重要的。尽管任一种常用阳离子聚合反应催化剂都可以使用，但采用有机铝化合物和卤代烃的组合作为催化剂会更好。这样，这种有机铝化合物适于用通式RnAlX3来表示，其中R为C1-C4的伯、仲或叔烷基，以伯或仲烷基较好，最好是氯化烷基铝(下称“AAH”)；其中X是一个卤素原子可以是氯、溴或碘，以氯较好；n是从1到3的整数，以1和2较好。催化剂中的卤代烃成分以式R3X为宜，其中R和X意义同上，最好是叔烷基如叔丁基氯(下称“TBC”)。AAH最好是二氯化乙基铝(下称“EADC”)齐聚催化剂中TBC与AAH的相对摩尔比适于在2.0∶1到20∶1的范围内，以2.5∶1到15∶1更好。
同样重要的是控制原料中催化成分与1-链烯烃的比例。譬如：如果原料混合物中的1-链烯烃包括C-C的1-链烯烃混合物，那么链烯烃与TBC的摩尔比适于在15∶1到80∶1的范围内变化，以18∶1到75∶1范围更好；同时1-链烯烃与AAH的摩尔比适于在75∶1到500∶1的范围内变化，以85∶1到470∶1更好。
两种被选定的催化成分的精确浓度将有赖于最后得到的润滑油所要求的特定性质如粘度。
齐聚反应适于在环境温度下进行如温度从-30℃到150℃，优选0-20℃左右更好。反应压力可以是环境压力或更高的压力。
齐聚反应在反应条件下适于在惰性溶液存在下发生，以一种链烷烃的碳氢化合物较好，如正己烷。
较适宜的方法是先在1-链烯烃的惰性溶剂溶液中加入所需量的TBC，然后将溶液温度升至反应温度。然后，将AAH溶液，最好是用同一种惰性溶剂在不断搅拌下逐滴加入1-链烯和TBC的溶液中，过一段时间。在加完EADC溶液后再持续一段时间，反应混合物可以用如加入氨水等予以中和，洗涤，过滤。那时，有机产物可以用如蒸馏的方法除去惰性溶剂。如果有必要，上述步骤可以连续操作。
产物的残渣是一种齐聚物，该齐聚物是一种有重要的和所需性质的润滑油，但也可能含有少量的链烯烃基团。
本发明一个重要方面就是通过选择合适的原料，齐聚催化剂和齐聚条件，有可能使得链烯烃基团中齐聚物非常少，也就实质上避免了随后的可选的加氢步骤的需要。
当使用加氢步骤(如果需要)时以保证齐聚物中任一链烯烃基团都是饱和的为适宜。这样做的效果就是能改善经步骤(b)制得的润滑油的氧化稳定性。在现状态下加氢步骤可以用任一种常用的加氢催化剂实现，如Raney镍或者门捷列夫周期表中VII族或VIII族的任一金属。该步骤的反应压力(包括氢气分压)适于在20到1000KPa的范围内，最好是在350到750KPa内。加氢反应的反应温度适于在0到350℃的范围
加氢产物可用较熟悉的技术如分馏从催化剂和其他副产物中分离出来。
本发明的加氢产物是优异的润滑剂，可以在润滑油中单独使用或与其它添加剂混合使用。本方法的产物的流动点最高为-65℃，粘度指数值大于155，如160。
从这些油的合成来源看，它们是可生物降解的，因此也是对环境污染更少的。
本发明可用下述实施例作进一步的说明。例：
将1-己烯(31g)、1-庚烯(27g)、1-辛烯(24g)，1-壬烯(20g)和1-癸烯(17g)的混合物在一容器中与正己烯(217g)混合(1-链烯烃的总量为119g)。将叔丁基氯(TBC，6g)加入此混合物，反应温度设定在20℃。
将二氯化乙基铝(EADC，13ml 1.0M的溶液)溶于“己烷”的溶液(如Aldrich化学公司生产)于2小时内在不断搅拌下逐滴加入1-链烯烃/TBC混合物中。在加入EADC的4个小时后，用加入足够的无水氨使催化剂失活来停止该反应。在加氢后，经洗涤和过滤反应混合物，分离得到主要含有氢氧化铝的白色固体沉淀物。含有有机产物的产物滤出液置于蒸溜盘中，静置过夜以蒸发己烷溶剂。
在有机产物(滤出液)的己烷蒸发后残留的物质为一种润滑油(110g)，其对于1-链烯烃的产率为92％W/W，该润滑油的粘度在40℃时为93.4cSt，100℃时为12.33cSt，粘度指数为124，流动点为-54℃。
下表总结了按照下述用不同工艺条件(如示)的方法实现的一些实验结果，以研究不同变化的条件对产物的影响。
将己烯-1(205g)，辛烯-1(158g)，癸烯-1(116g)和正己烷(215g)与叔丁基氯以标出的数量按表中所示的温度混合。一定量的(如表所示)的一摩尔二氯化乙基铝的己烷(例如Aldrich化学公司产品)溶液在不断搅拌下缓慢加入上述混合物。当所需的反应时间完成后，该反应用加入无水氨来终止并用水洗涤反应混合物，经过滤可以从反应混合物中分离出一种白色固体物(可能是氢氧化铝)。将滤液的水相和碳氢化合物相分离并将碳氢化合物相中的己烷蒸发一晚，除去己烷后残余物就是如下表1中所示性质的润滑油。
工艺条件对生成润滑物的影响。
表1
| 反应条件AAH，TBC，温度，时间 | 粘度 (cst)40℃ 100℃ | VI | 流动点(℃) | 产率(％) | |
| 25ml，13g，20℃，4h | 78.1 | 10.77 | 125 | -45 | 97 |
| 25ml，13g，0℃，2h | 84.25 | 12.15 | 139 | -57 | 98 |
| 25ml，6g，0℃，4h | 60.59 | 10.32 | 160 | -45 | 98 |
| 10ml，13g，20℃，2h | 30.38 | 5.82 | 138 | ＜-63 | 52 |
| 10ml，6g，20℃，4h | 6.07 | 2.08 | 160 | ＜-66 | 45 |
另一套实验是在反应混合物组成一定时进行的。将己烯-1(240g)，辛烯-1(158)，癸烯-1(113g)和庚烯(213g)在一容器中混合。
将所需量的氯代叔丁烷加入容器并将温度设定到所需的反应温度。充分搅拌混合物。逐滴加入二氯化乙基铝(1.0M的己烷)溶液直到指定量滴完。在加入过程中，可观察到放热现象。以手动法控制加入速度，这样可使放热中通常温度不能超过10℃，绝不允许超过20℃。
经必要的反应时间后通入氨水给反应混合物以终止该反应，然后加入约300毫升的蒸馏水，容器中的物料须连续充分地搅拌。反应时间被定义为从加入二氯化乙基铝开始到终止反应为止的全部时间。
在水处理时反应混合物分成水相和有机相，将有机相通过无水磷酸镁以回收和过滤。随后将过滤后的有机相置于一蒸发器以使庚烷蒸发过夜。得到的润滑物分析其40℃和100℃时的粘度，粘度指数和流动点。在这一次不需要分馏，获得的数据列于下表2。
在表2中表示的样品条件以下列顺序列出：1.0M二氯化己基铝的体积，叔丁基氯的质量；温度(℃)和时间(小时)，粘度用cSt表示，每个例子的流动点均＜-53℃。
表2
*-未测量，无量度值**-流动点小于-63℃。#-流动点为-54℃。
| 试样条件 | 粘度 cst40℃ 100℃ | VI | 产率 | |
| 5ml，26g，0℃，3h | 3.3 | 1.29 | - | 19 |
| 50ml，26g，30℃，3h | 44.35 | 7.07 | 119 | 97 |
| 5ml，3g，30℃，3h | 2.54 | 1.06 | * | 17 |
| 50ml，3g，30℃，6h | 55.6 | 8.49 | 127 | 80 |
| 50ml，3g，0℃，6h | 71.3 | 11.53 | 156 | 89 |
| 5ml，26g，0℃，3h | 1.68 | 0.85 | * | 27 |
| 50ml，26g，0℃，6h | 28.0 | 5.95 | 165 | 100 |
| 5ml，3g，0℃，6h | 12.45 | 3.4 | 158 | 39 |
| 15ml，10g，10℃，3.5h | 56.6 | 9.66 | 156 | 93 |
| 5ml，10g，10℃，3.5h | 3.54 | 1.42 | * | 33 |
| 15ml，10g，10℃，2h | 56.8 | 9.74 | 157 | 92 |
| 15ml，26g，10℃，3.5h | 50.6 | 8.48 | 144 | 92 |
| 15ml，10g，30℃，3.5h | 36.45 | 6.61 | 138 | 93 |
| 15ml，10g，0℃，3.5h | 45.55 | 8.1 | 152** | 98 |
| 15ml，10g，10℃，6h | 83.1 | 11.34 | 126# | 84 |
Claims (7)
1.一种生产粘度指数至少为120，流动占至少为-45℃的润滑油的方法，该方法包括：
a)在低于30℃的温度下，将可通过费-托合成操作衍生的C5-C20 1-链烯烃混合物在齐聚反应催化剂的存在下齐聚生成润滑油，所述费-托合成的烯烃产物含有至少2.6％(W/W)1-癸烯和至少6％(W/W)1-己烯，并且其Schulz-Floryα值为0.6-0.9，所述催化剂包含卤化烷基铝和叔丁基氯。其中叔丁基氯与卤化烷基铝的相对摩尔比为2.0∶1至20∶1；
b)从齐聚反应催化剂中分离润滑油；
c)在氢气存在下可选择地催化氢化润滑油以改善其氧化稳定性；和
d)回收上述b)或c)中制得的润滑油。
2.权利要求1的方法，其中混合的1-链烯烃原料包括含有4-18个碳原子的链烯烃。
3.权利要求1的方法，其中用于齐聚反应的1-链烯烃原料包括C6-C10的1-链烯烃混合物，链烯烃和催化剂成分的摩尔比是：1-链烯烃与叔丁基氯之比为15∶1到80∶1，而且1-链烯烃与卤化烷基铝之比为75∶1到500∶1。
4.权利要求1的方法，其中在反应条件下齐聚反应在惰性溶剂中进行。
5.权利要求1的方法，其中用氢化反应以保证润滑油中的任一链烯烃基团均为饱和烃。
6.权利要求1的方法，其中氢化反应是用催化剂Raney镍或者门捷列夫周期表中VII族和VIII族的其它金属进行的。
7.权利要求1的方法，其中氢化反应是在包括氢气分压的反应压力为20-1000KPa、反应温度为0-350℃时进行的。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9216014.2 | 1992-07-28 | ||
| GB929216014A GB9216014D0 (en) | 1992-07-28 | 1992-07-28 | Lubricating oils |
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| Publication Number | Publication Date |
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| CN1081705A CN1081705A (zh) | 1994-02-09 |
| CN1035062C true CN1035062C (zh) | 1997-06-04 |
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| CN93109367A Expired - Fee Related CN1035062C (zh) | 1992-07-28 | 1993-07-28 | 生产润滑油的方法 |
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| Country | Link |
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| US (1) | US5382739A (zh) |
| EP (1) | EP0583072B1 (zh) |
| JP (1) | JPH06172759A (zh) |
| CN (1) | CN1035062C (zh) |
| CA (1) | CA2100704A1 (zh) |
| DE (1) | DE69315274T2 (zh) |
| DK (1) | DK0583072T3 (zh) |
| GB (1) | GB9216014D0 (zh) |
| NO (1) | NO932705L (zh) |
| ZA (1) | ZA935130B (zh) |
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- 1993-07-14 DE DE69315274T patent/DE69315274T2/de not_active Expired - Fee Related
- 1993-07-14 DK DK93305499.1T patent/DK0583072T3/da active
- 1993-07-14 EP EP93305499A patent/EP0583072B1/en not_active Expired - Lifetime
- 1993-07-15 ZA ZA935130A patent/ZA935130B/xx unknown
- 1993-07-16 CA CA002100704A patent/CA2100704A1/en not_active Abandoned
- 1993-07-20 JP JP5179258A patent/JPH06172759A/ja active Pending
- 1993-07-27 NO NO932705A patent/NO932705L/no unknown
- 1993-07-28 CN CN93109367A patent/CN1035062C/zh not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| NO932705L (no) | 1994-01-31 |
| US5382739A (en) | 1995-01-17 |
| EP0583072B1 (en) | 1997-11-19 |
| ZA935130B (en) | 1995-01-16 |
| NO932705D0 (no) | 1993-07-27 |
| CA2100704A1 (en) | 1994-01-29 |
| DK0583072T3 (da) | 1997-12-22 |
| CN1081705A (zh) | 1994-02-09 |
| GB9216014D0 (en) | 1992-09-09 |
| DE69315274D1 (de) | 1998-01-02 |
| EP0583072A1 (en) | 1994-02-16 |
| DE69315274T2 (de) | 1998-03-12 |
| JPH06172759A (ja) | 1994-06-21 |
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