CN104109068B - A kind of method of ethylene oligomerization - Google Patents
A kind of method of ethylene oligomerization Download PDFInfo
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- CN104109068B CN104109068B CN201310133250.8A CN201310133250A CN104109068B CN 104109068 B CN104109068 B CN 104109068B CN 201310133250 A CN201310133250 A CN 201310133250A CN 104109068 B CN104109068 B CN 104109068B
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Abstract
The present invention relates to a kind of ethylene oligomerization method, comprising: step a: kettle in placing in reactor, wherein interior kettle outer wall and reactor inwall suitable; Step b: reaction solvent is placed in interior kettle, arranging temperature of reaction is 0-40 DEG C, and controlling reaction pressure by reducing valve is 0-6MPa; Step c: the feed stream containing ethene is passed in reaction solvent and reacts; Steps d: stopped reaction, discharges reaction solution.In the method for the invention, when interior kettle wall built-up is to after to a certain degree, can proceed to react, without the need to the cleaning taken time and effort at the reactor of Industrial processes to wall built-up by changing rapidly interior kettle next time, save time and cost, enhance productivity; And unconventional efficient method can be used easily to process the polymkeric substance of inner wall of kettle wall built-up in changing, avoid using a large amount of solvent to clean, reduce solvent loss.
Description
Technical field
The present invention relates to olefin oligomerization field, be specifically related to a kind of method of ethylene oligomerization.
Background technology
In ethylene oligomerization reaction, under the effect of catalyst system, feed ethylene realizes oligomerisation in a solvent.Due to the effect of catalyzer, in ethylene oligomerization reaction process except generating target product, also along with the generation of side reaction, the polyethylene by product of a certain amount of high molecular can be generated.The polymkeric substance of these high molecular is not soluble, and is attached to reactor inwall gradually, forms more long-pending thicker polymer layer, and this phenomenon is so-called reactor polymkeric substance wall cling phenomenon.The polymer layer of attachment not only can affect reaction heat transfer, simultaneously also can adsorptive catalyst component, thus causes side reaction further, produces more byproduct of reaction, has a strong impact on normally carrying out of reaction.
After reactor superpolymer wall built-up, the general treatment process adopted is solvent soaking, heats up and wash or adopt speciality tool to carry out mechanicalness cleaning.But solvent soaking and the washing that heats up need the longer treatment time, but also will consume relatively large cleaning solvent, affect production efficiency, waste solvent, thus increase production cost.The method adopting speciality tool to carry out mechanicalness cleaning, except needing the longer time, also can cause damage to reactor, if especially after sealing face damage, reactor there will be leakage phenomenon, and reactor can be caused time serious to reuse.Therefore, these methods all can not tackle the superpolymer wall built-up problem in olefin oligomerization process well, and production efficiency still can be subject to larger impact.
Summary of the invention
The invention provides the method for a kind of ethylene oligomerization reaction, by making reaction carry out in the reactor being provided with interior kettle, solving wall built-up superpolymer in ethylene oligomerization reaction process and being difficult to cleaning, and affecting the problem of production efficiency.In the present invention, this interior kettle can realize quick-replaceable, unconventional mode can be used easily to remove polymkeric substance, both protected reactor, and do not affect again the mass-and heat-transfer of reactor, ensures normally carrying out of reaction.
The invention provides a kind of ethylene oligomerization method, comprising: step a: kettle in placing in reactor, wherein interior kettle outer wall and reactor inwall suitable; Step b: reaction solvent is placed in interior kettle, arranging temperature of reaction is 0-40 DEG C, and is preferably 20-40 DEG C, and reaction pressure is 0-6MPa, and is preferably 2-6MPa; Step c: the feed stream containing ethene is passed in reaction solvent and reacts; Steps d: stopped reaction, discharges reaction solution.
The polymkeric substance of high molecular is produced owing to usually side reaction can be there is in ethylene oligomerization reaction process; wherein a part of polymkeric substance is attached on interior kettle wall; when the polymkeric substance built up reaches certain thickness; need to change interior kettle; therefore method of the present invention also comprises step e: kettle in taking out, the polymkeric substance of inner wall of kettle attachment in removing.
The present invention by kettle in placing in reactor, as the generation place of ethylene oligomerization reaction, when polymkeric substance wall built-up extremely to a certain degree time, only reactor need be opened, the interior kettle of rapid taking-up wall built-up, and change new interior kettle, can proceed to react next time.In the process solving wall built-up problem, directly need not process reactor, avoid series of problems as above, especially can not delay the reaction times, production efficiency is improved.
Above-described solvent soaking can be selected to the processing mode of wall built-up, heat up and wash or adopt speciality tool to carry out mechanicalness cleaning.In addition, after interior kettle is taken out, can clear up it separately, therefore other can also be used not to be suitable for the mode directly processed reactor, such as burnt by internal kettle, or interior kettle is put into High Temperature Furnaces Heating Apparatus heating (being such as heated to 150-350 DEG C makes wall built-up polymer melt come off), or rinse with high pressure water (operating pressure is such as 50-100MPa) polymkeric substance removing the attachment of interior inner wall of kettle.These processing modes more thoroughly, efficiently can not only remove wall built-up polymkeric substance, and can not internally damage by kettle, can reuse in multiple times.
In the present invention, the material of interior kettle can be identical with reactor material, and other also can be adopted to possess the material be suitable for of better heat conductivility than reactor material.Interior kettle thickness is preferably 0.5-2mm.In order to the heat transfer in realization response process better, the gap L EssT.LTssT.LT1mm preferably between kettle outer wall and reactor inwall, even if the inwall of the outer wall of interior kettle and reactor close contact as much as possible, but does not affect it and puts into and take out.
In one embodiment, the edge of opening of interior kettle or inwall circumference evenly arrange at least two shackles, adopts and comprise the extracting piece of grabbing bar that at least two ends are provided with hook, make hook fasten shackle, interior kettle is put into or takes out reactor.
In another embodiment, the inwall circumference of interior kettle evenly arranges at least two projections, adopt and comprise the extracting piece of grabbing bar that at least two ends are provided with shackle, shackle is made to fasten projection, put into by interior kettle or take out reactor, the diameter of the circumference convexed to form described in the circle diameter ratio that wherein shackle of grabbing boom end of extracting piece is formed is large.When extracting piece only has two to grab bar, circle diameter refers to two slant ranges of grabbing between the shackle of boom end, and this distance is greater than the slant range between two projections; When extracting piece comprise more than three grab bar time, circle diameter refers to the diameter of the circumference that the shackle of respectively grabbing boom end is formed, and this diameter is greater than the diameter of the circumference that respective bump is formed.Like this, after making the shackle of extracting piece fasten projection, by grabbing the power that the inside inner wall of kettle of bar struts, ensure can not depart from projection mentioning shackle in process, guarantee safety take out in kettle.In use grabbing to strengthen extracting piece the tension force that the inside inner wall of kettle of bar struts, can arrange in extracting piece and can outwards strut the spring of grabbing bar when extracting piece works.
In the present invention, described reaction solvent is preferably toluene and/or heptane; Reactor is preferably batch reactor.
In the method for the invention, the molecular weight distribution of the by-product polymer that reaction produces is 3000-6000000, and the content of polymkeric substance is the 0.1-6 % by weight based on reaction solution weighing scale.
The present invention is by before ethylene oligomerization reaction, add in reactor one suitable with reactor reaction chamber inwall in kettle, and reaction is carried out in interior kettle, thus make byproduct of reaction wall built-up occur over just on interior inner wall of kettle, by changing rapidly interior kettle, can react rapidly next time.Therefore, in the present invention, without the need to the cleaning taken time and effort at the reactor of Industrial processes to wall built-up, save time and cost, enhance productivity.The use of interior kettle, does not affect the heat transfer of reaction process reactor, and the polymkeric substance of unconventional efficient method to wall built-up can be used easily to process, and avoids using a large amount of solvent to clean, and reduces solvent loss.
Accompanying drawing explanation
Fig. 1 is the assembling schematic diagram of reactor and interior kettle;
Fig. 2 is the schematic diagram of extracting piece.
Embodiment
Also by reference to the accompanying drawings the present invention is further described below by specific embodiment, but should be appreciated that scope of the present invention is not subject to the restriction of following examples and accompanying drawing.
Embodiment 1
As shown in Figure 1, first interior kettle 2 is placed in reactor 1.Reaction solvent toluene is placed in interior kettle 2, and setting temperature of reaction is 30 DEG C, and reaction pressure is 3.0MPa.After solvent is preheated to design temperature, with mass space velocity for 30 ~ 60gh
-1pass into reaction raw materials ethene to react.React after 30 minutes, stop heating, termination reaction, opens reactor, and reactor is tilted to discharge reaction solution.
In interior kettle 2, reload reaction solvent, then repeat above-mentioned steps, carry out the 2nd secondary response.When proceeding to the 5th reaction, on the inwall of the interior kettle 2 of discovery, polymkeric substance wall built-up is thicker, now uses extracting piece 20(Fig. 2) interior kettle is taken out.As shown in Figure 2, extracting piece 20 comprises at least two and grabs bar 21, grabs bar 21 end and is provided with shackle 22.In addition, in a preferred embodiment, extracting piece 20 mention position and each grab to be provided with between bar 21 can increase when extracting piece in use time grab the spring (see figure 2) of the outside tension force of bar 21.Shackle 22 is fastened and is located at interior kettle 2 inwall equally distributed at least two protruding 3(are as shown in Figure 1 in the circumferential), wherein when extracting piece 20 be only provided with two grab bar time, slant range between two shackles of grabbing boom end is greater than the slant range between two projections, when extracting piece 20 be provided with more than three grab bar time, the diameter of circumference that the circle diameter that the shackle of respectively grabbing boom end is formed is formed than respective bump is large.After the shackle 22 of extracting piece 20 fastens protruding 3, by grabbing the bar 21 inwardly power that struts of kettle 2 inwall, make can not depart from protruding 3 mentioning shackle 22 in process, thus kettle 2 in can successfully taking out from reactor 1.
In a similar fashion kettle in new is put into reactor, can prepare to proceed to react next time.Can start only to need about 30 minutes to reaction next time from starting to change interior kettle.
Kettle in changing is put into High Temperature Furnaces Heating Apparatus (temperature is 200 DEG C) heating, the polymer melted that inwall adheres to is come off.The polymkeric substance that collection splits away off also is weighed, and polymer weight is 2% of reaction solution gross weight, and the molecular weight distribution of polymkeric substance is 3000-5500000.
Embodiment 2
Concrete operation step is roughly the same with embodiment 1, and difference is, reaction pressure is for being 5.0MPa; When proceeding to the 3rd secondary response, on the inwall of the interior kettle 2 of discovery, polymkeric substance wall built-up is thicker, kettle in now changing; Adopt the mode that high pressure water (operating pressure is 70MPa) rinses, polymkeric substance is come off, collect the polymkeric substance that splits away off to be positioned in loft drier and to be warming up to 100 DEG C and to dry and weigh, polymer weight is 3% of reaction solution gross weight, and the molecular weight distribution of polymkeric substance is 3500-6000000.
Embodiment 3
Concrete operation step is roughly the same with embodiment 1, and difference is, reaction solvent is heptane; When proceeding to the 3rd secondary response, on the inwall of the interior kettle 2 of discovery, polymkeric substance wall built-up is thicker, kettle in now changing; Adopt the mode that high pressure water (operating pressure is 55MPa) rinses, polymkeric substance is come off, collect the polymkeric substance that splits away off to be positioned in loft drier and to be warming up to 100 DEG C and to dry and weigh, polymer weight is 3.5% of reaction solution gross weight, and the molecular weight of polymkeric substance is 2500-6000000.
Claims (9)
1. an ethylene oligomerization method, comprising:
Step a: kettle in placing in reactor, wherein interior kettle outer wall and reactor inwall suitable;
Step b: reaction solvent is placed in interior kettle, arranging temperature of reaction is 0-40 DEG C, and reaction pressure is 0-6MPa;
Step c: the feed stream containing ethene is passed in reaction solvent and reacts;
Steps d: stopped reaction, discharges reaction solution; With
Step e: kettle in taking out, the polymkeric substance of inner wall of kettle attachment in removing.
2. method according to claim 1, is characterized in that, is burnt by internal kettle, or interior kettle is put into High Temperature Furnaces Heating Apparatus heats, or removes the polymkeric substance of interior inner wall of kettle attachment with high pressure water washing.
3. method according to claim 1, is characterized in that, the material of described interior kettle is identical with reactor material.
4. method according to claim 1, is characterized in that, described interior kettle thickness is 0.5-2mm.
5. method according to claim 1, is characterized in that, the gap L EssT.LTssT.LT1mm between interior kettle outer wall and reactor inwall.
6. the method according to any one of claim 1-5, it is characterized in that, the edge of opening of described interior kettle or inwall circumference evenly arrange at least two shackles, adopt and comprise the extracting piece of grabbing bar that at least two ends are provided with hook, make hook fasten shackle, interior kettle is put into or takes out reactor.
7. the method according to any one of claim 1-5, it is characterized in that, the inwall circumference of described interior kettle evenly arranges at least two projections, adopt and comprise the extracting piece of grabbing bar that at least two ends are provided with shackle, shackle is made to fasten projection, put into by interior kettle or take out reactor, the diameter of the circumference convexed to form described in the circle diameter ratio that wherein shackle of grabbing boom end of extracting piece is formed is large.
8. the method according to any one of claim 1-5, is characterized in that, described reaction solvent is toluene and/or heptane; Described reactor is batch reactor.
9. method according to claim 1, is characterized in that, the molecular weight distribution of the by-product polymer that reaction produces is 3000-6000000, and the content of polymkeric substance in reaction solution is the 0.1-6 % by weight based on reaction solution weighing scale.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159307A (en) * | 1976-02-24 | 1979-06-26 | Matsuyama Petrochemicals Inc. | Apparatus for producing aromatic dicarboxylic acids |
| US5741874A (en) * | 1994-09-12 | 1998-04-21 | Mitsubishi Chemical Corporation | Method for producing poly(vinyl chloride) |
| CN1549830A (en) * | 2001-08-28 | 2004-11-24 | 出光石油化学株式会社 | Process for producing low polymer of alpha-olefin |
| CN101291726A (en) * | 2005-10-20 | 2008-10-22 | 林德股份公司 | Method for oligomerization of ethylene and reactor system therefor with removal of heavy molecular weight oligomers |
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2013
- 2013-04-17 CN CN201310133250.8A patent/CN104109068B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4159307A (en) * | 1976-02-24 | 1979-06-26 | Matsuyama Petrochemicals Inc. | Apparatus for producing aromatic dicarboxylic acids |
| US5741874A (en) * | 1994-09-12 | 1998-04-21 | Mitsubishi Chemical Corporation | Method for producing poly(vinyl chloride) |
| CN1549830A (en) * | 2001-08-28 | 2004-11-24 | 出光石油化学株式会社 | Process for producing low polymer of alpha-olefin |
| CN101291726A (en) * | 2005-10-20 | 2008-10-22 | 林德股份公司 | Method for oligomerization of ethylene and reactor system therefor with removal of heavy molecular weight oligomers |
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Effective date of registration: 20230413 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Beijing) Chemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA PETROLEUM & CHEMICAL Corp. |