CN104056583A - Control method for ethylene oligomerization loop reactor - Google Patents
Control method for ethylene oligomerization loop reactor Download PDFInfo
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- CN104056583A CN104056583A CN201310089671.5A CN201310089671A CN104056583A CN 104056583 A CN104056583 A CN 104056583A CN 201310089671 A CN201310089671 A CN 201310089671A CN 104056583 A CN104056583 A CN 104056583A
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- thermal medium
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Abstract
The invention provides a control method for an ethylene oligomerization loop reactor. The control method both adjusts the flow of a thermal medium in real time and accordingly adjusts the flow of an ethylene feed so as to allow the actual reaction temperature in the reactor to approach set reaction temperature as much as possible, thereby guaranteeing stable running of the reactor. According to the invention, the double parameters of the flow of the thermal medium and the flow of the ethylene feed are controlled together so as to regulate and control the loop reactor, and the phenomenon of cavitation erosion or vapor lock in the reactor can be effectively reduced so as to allow operation of the reactor to be stable.
Description
Technical field
The object of this invention is to provide a kind of reactor control method of ethylene oligomerization; Specifically, be a kind of control method of the ethylene oligomerization annular-pipe reactor in ethylene oligomerization for prepn. of alpha-olefines production process.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry, cheap small-numerator olefin can be changed into and has high value-added product, as 1-hexene and 1-octene by oligomerisation reaction.Wherein, 1-hexene is the important comonomer of producing LLDPE and HDPE, is also the raw material of some fine chemicals.The LLDPE resin of 1-hervene copolymer compared with the copolymer of 1-butylene, its hot strength, impact strength, tear resistance and property durable in use are all obviously excellent, are particularly suitable for the agricultural mulch films such as packaging film and greenhouse, canopy chamber.
In CN1160700A, report that a kind of ethylene oligomerization prepares the serialization production process of low-carbon alpha-alkene.Use a kind of zirconium quaternary system catalyst, under specific reaction condition, catalyst solution, ethylene raw material gas and quencher are added respectively to corresponding course of reaction continuously, oligomerization product draws product through continuous rectification.In this application, also point out to react actual conditions, this catalyst is selectively higher to carbon ten following alkene, but its catalytic activity is not high.
Above-mentioned prior art all lays particular emphasis on the research of ethylene oligomerization production technology and catalyst, and reaction is carried out substantially in common autoclave.CN102272684A has introduced a kind of method that is related to control fluidized-bed polymerization reactor by pressure and productive rate, regulates by the productive rate of polymer in reactor and the relation of pressure the charging rate that enters monomer in reactor.US7329712B2 has reported that one is for olefinic polyreaction, and the variation of fluctuating by reaction is diluted material in reactor, thereby reaches the method for controlling reaction process.DE3122561A1 has reported a kind of by changing the method for gas-liquid mixture pressure drop control reaction in circulation flow reactor.KR1093470B1 has reported a kind of polymerization technique of the variation control weight of otefi pi polymer by hydrogen and monomer ratio.
Features such as (kiss-coatings) that annular-pipe reactor has that heat transfer area is large, mass transfer intensity is high, wall is less scaling, is widely used in generating in the exothermic reaction of the high strength such as polypropylene and polyethylene.Mobile, the mixing of reaction mass in annular-pipe reactor drives by axial-flow pump, thereby the reaction mass only existing with liquid phase state can participate in polymerisation; In addition, in order to maintain the selective of higher reaction speed and target product, need the ethene liquid concentration that keeps higher; And when gas phase ratio exceedes certain value in reactor, just there will be " cavitation erosion " or " vapour lock " phenomenon, make the reactor can not stable operation; In reactor, the permissible value of gas phase content depends on the characterisitic parameter of axial-flow pump.
Ethylene oligomerization reaction refers to the alkene (C that by catalyst action, ethene is changed into larger molecular weight in solvent
4～C
12) process.Adopting annular-pipe reactor to carry out ethylene oligomerization when reaction, in course of reaction, all chargings in a continuous manner such as solvent and ethene, are first full of for full liquid phase in reactor, and this course of reaction is strong exothermal reaction, nC
2h
4→ C
2nh
4n+ △ H, wherein △ H=-17.47Kcal/mol C
2h
4, because ethene mainly exists (critical-temperature of ethene is as 9 DEG C) taking gas phase state under oligomerisation reaction condition, in the time that ethylene contents in reactor exceedes its saturated concentration, will produce gas phase; And the existence of too many gaseous phase materials can cause the fluctuation of service of reactor, be unfavorable for the continuous and steady operation of commercial plant.Therefore, in ethylene oligomerization annular-pipe reactor, the control of gas content is to ensure that reactor is stablized, the essential condition of efficient operation, thereby need to find a kind of effectively control method, realizes safe, the steadily production of ethylene oligomerization.
Summary of the invention
The reaction heat of chemical reaction is directly proportional to the reacting dose of raw material, and the flow of removing thermal medium changes with the variation of reaction heat; Rare in prior art have a report in ethylene oligomerization operation by this application of principle.The inventor is considering after this ATM layer relationsATM, both that reaction heat in reactor is associated with the flow of removing thermal medium, again that it is associated with ethylene feed flow; Stable and control ethylene feed flow and remove the flow of thermal medium two-parameter in order to control reactor temperature, and then reach the object of controlling ethylene polymerization process and realization response device energy stable and high effective operation.
Therefore, the invention provides a kind of control method of ethylene oligomerization annular-pipe reactor, it is characterized in that, not only regulated in real time thermal medium flow size, but also corresponding adjusting ethylene feed flow size to make real reaction temperature in reactor approach the reaction temperature of setting as far as possible, and then ensure reactor steady running.Particularly, when real reaction temperature in reactor higher than set reaction temperature time, manually or automatically (computer program control) regulate in real time thermal medium flow to make it become large, and corresponding adjusting ethylene feed flow makes it become large, is regulated and is impelled real reaction temperature to return as early as possible design temperature by biparametric.Ethylene oligomerization in annular-pipe reactor of the present invention, makes real reaction temperature in reactor approach as much as possible the reaction temperature of setting, and the ethene solubility in reactor is stable, thereby wherein the stable reactor pressure of gas content is stable; Temperature and pressure stable guaranteed reactor steady running.
The present invention in conjunction with thermal medium flow and ethylene feed flow two-parameter regulate and control annular-pipe reactor, can effectively reduce reactor occur " cavitation erosion " or " vapour lock " phenomenon, make reactor stable operation.
In detailed description of the invention of the present invention, according to set design parameter and condition, first find out by experiment the empirical relation between thermal medium flow and the ethylene feed flow size that can make reactor steady running; Then in control loop pipe reactor process, regulate thermal medium flow and ethylene feed flow size to make reactor steady running according to this empirical relation simultaneously.This empirical relation is for example rule-of-thumb relation, empirical relation curve map or the form be made up of some empirical data points.Preferably, after the empirical relation of finding out between thermal medium flow and ethylene feed flow size; In control loop pipe reactor process, ethylene feed flow size regulates according to thermal medium flow size.Preferably described set design parameter and condition comprise reaction temperature, reaction pressure, anti-solvent-applied and the flow thereof of setting, anti-applications catalyst and flow thereof, thermal medium outlet and the inlet temperature in reactor.More preferably, described solvent is heptane or hexene-1.
In the present invention, the reaction temperature of described setting is for example the arbitrary data between 100～135 DEG C.
In the present invention, more preferably, use automatic control equipment, automatically regulate thermal medium flow size according to real reaction temperature in reactor.
In the present invention, more preferably, use automatic control equipment, automatically regulate ethylene feed flow size according to thermal medium flow size.
The present invention also provides a kind of computer-controlled program, when this program is moved on computers, will provide technology controlling and process to reactor according to the method described in aforementioned any one.
Brief description of the drawings
Fig. 1 is ethylene oligomerization annular-pipe reactor and control flow chart thereof.
Detailed description of the invention
Below be only the preferred embodiment of the present invention, protection scope of the present invention is not limited to this, and any those skilled in the art is in technical scope disclosed by the invention, within can being easy to the change carried out or changing and be encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Embodiment 1
Fig. 1 is the reactor in the present embodiment, and in figure, 1,2 and 3 represent respectively heat exchanger, axial-flow pump and flowmeter; In figure, FIC and TIC are that DCS controls term, and FIC represents flow-control, the control of TIC representation temperature; Ethylene oligomerization reaction heat for example, is shifted out by thermal medium (being hot water), and the temperature of thermal medium is controlled by the cooling water circulating (adjusting cooling water flow).Setting reactor temperature is certain steady state value, carrys out the aperture control thermal medium flow of automatic adjusting control valve (valves on flowmeter 3 sides) by the fluctuation of actual temperature in reactor; According in flowmeter 3, read thermal medium flow size of data automatically regulate the inlet amount of the aperture control ethene of ethene control valve (valve in the lower left corner in figure), thereby make the operation that reactor can stability and high efficiency.
In the present embodiment, above-mentioned reactor is for ethylene trimer hexene-1 processed, and solvent is heptane, and its inlet amount is 150Kg/ hour; Reaction pressure is 5.0MPa, and reaction temperature is set as 125 DEG C, and now the saturation solubility of ethene in reactor is 14%; The initial flow of ethene is 110Kg/ hour; Catalyst is chromium complex, and its flow is 5Kg/ hour; The inlet temperature of thermal medium water in reactor is 90 DEG C, and outlet temperature is 93 DEG C.Under above-mentioned condition, in order to make liquid phase ethylene in reactor approach to greatest extent its saturated concentration, draw thermal medium discharge Q
hot waterwith ethylene feed amount Q
etheneempirical relation data as table 1.In concrete course of reaction, pass through Q according to the empirical relation shown in table 1
hot waterand Q
ethenebiparametric real-time monitoring, makes the operation that reactor can stability and high efficiency.
Table 1
| Data point sequence number | Q Hot water(Kg/h) | Q Ethene(Kg/h) |
| 1 | 20 | 117 |
| 2 | 25 | 138 |
| 3 | 30 | 160 |
| 4 | 35 | 182 |
| 5 | 40 | 203 |
Embodiment 2
In the present embodiment, the reactor identical with embodiment 1 is for ethylene trimer hexene-1 processed, and solvent is hexene-1, and its inlet amount is 150Kg/ hour; Reaction pressure is 5.0MPa, and reaction temperature is set as 125 DEG C, and now the saturation solubility of ethene in reactor is 14%; The initial flow of ethene is 80Kg/ hour; Catalyst is chromium complex, and its flow is 5Kg/ hour; The inlet temperature of thermal medium water in reactor is 90 DEG C, and outlet temperature is 96 DEG C.Under above-mentioned condition, in order to make liquid phase ethylene in reactor approach to greatest extent its saturated concentration, draw thermal medium discharge Q
hot waterwith ethylene feed amount Q
etheneempirical relation data as table 2.In concrete course of reaction, pass through Q according to the empirical relation shown in table 2
hot waterand Q
ethenebiparametric real-time monitoring, makes the operation that reactor can stability and high efficiency.
Table 2
| Data point sequence number | Q Hot water(Kg/h) | Q Ethene(Kg/h) |
| 1 | 10 | 87 |
| 2 | 15 | 130 |
| 3 | 20 | 173 |
| 4 | 25 | 217 |
| 5 | 30 | 260 |
Claims (9)
1. the control method of ethylene oligomerization annular-pipe reactor, it is characterized in that, not only regulated in real time thermal medium flow size, but also corresponding adjusting ethylene feed flow size to make real reaction temperature in reactor approach the reaction temperature of setting as far as possible, and then ensure reactor steady running.
2. control method according to claim 1, is characterized in that, according to set design parameter and condition, first finds out by experiment the empirical relation between thermal medium flow and the ethylene feed flow size that can make reactor steady running; Then in control loop pipe reactor process, regulate thermal medium flow and ethylene feed flow size to make reactor steady running according to this empirical relation simultaneously.
3. control method according to claim 2, is characterized in that, after the empirical relation of finding out between thermal medium flow and ethylene feed flow size; In control loop pipe reactor process, ethylene feed flow size regulates according to thermal medium flow size.
4. according to the control method described in claim 2 or 3, it is characterized in that, described set design parameter and condition comprise reaction temperature, reaction pressure, anti-solvent-applied and the flow thereof of setting, anti-applications catalyst and flow thereof, thermal medium outlet and the inlet temperature in reactor.
5. control method according to claim 4, is characterized in that, described solvent is heptane or hexene-1.
6. according to the control method described in any one in claim 1～5, it is characterized in that, the reaction temperature of described setting is the arbitrary data between 100～135 DEG C.
7. according to the control method described in any one in claim 1～5, it is characterized in that, use automatic control equipment, automatically regulate thermal medium flow size according to real reaction temperature in reactor.
8. according to the control method described in any one in claim 1～7, it is characterized in that, use automatic control equipment, automatically regulate ethylene feed flow size according to thermal medium flow size.
9. computer-controlled program, will provide technology controlling and process to reactor according to the method described in any one in claim 1～8 when this program is moved on computers.
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| CN201310089671.5A CN104056583A (en) | 2013-03-20 | 2013-03-20 | Control method for ethylene oligomerization loop reactor |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240666A (en) * | 2019-05-10 | 2019-09-17 | 中国神华煤制油化工有限公司 | The load adjustment method and system of high-pressure polyethylene device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060852A (en) * | 1990-10-20 | 1992-05-06 | 中国石油化工总公司兰州炼油化工总厂 | Polyethers preparation manipulation Variable Control and optimization method |
-
2013
- 2013-03-20 CN CN201310089671.5A patent/CN104056583A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060852A (en) * | 1990-10-20 | 1992-05-06 | 中国石油化工总公司兰州炼油化工总厂 | Polyethers preparation manipulation Variable Control and optimization method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240666A (en) * | 2019-05-10 | 2019-09-17 | 中国神华煤制油化工有限公司 | The load adjustment method and system of high-pressure polyethylene device |
| CN110240666B (en) * | 2019-05-10 | 2021-12-17 | 中国神华煤制油化工有限公司 | Load adjustment method and system for high-pressure polyethylene device |
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Application publication date: 20140924 |