CN102558402A - Method for quickly starting polymerization reaction in alpha-olefin gas-phase fluidized bed reactor - Google Patents
Method for quickly starting polymerization reaction in alpha-olefin gas-phase fluidized bed reactor Download PDFInfo
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- CN102558402A CN102558402A CN2011104118992A CN201110411899A CN102558402A CN 102558402 A CN102558402 A CN 102558402A CN 2011104118992 A CN2011104118992 A CN 2011104118992A CN 201110411899 A CN201110411899 A CN 201110411899A CN 102558402 A CN102558402 A CN 102558402A
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Abstract
The invention relates to a method for quickly starting polymerization reaction in an alpha-olefin gas-phase fluidized bed reactor, belongs to a method for preparing alpha-olefin homopolymer or copolymer, and in particular relates to a method for preparing corresponding polymer by ethylene polymerization or copolymerization of ethylene and other alpha-olefins. The method is characterized by comprising the following steps of: displacing trace water in the gas-phase fluidized bed reactor by using nitrogen and ethylene, initiating to start alpha-olefin polymerization reaction or alpha-olefin copolymerization reaction by using a metallocene catalyst, switching to the conventional chromium catalyst alpha-olefin polymerization or alpha-olefin copolymerization reaction system, stopping adding the metallocene catalyst, and switching to the conventional alpha-olefin gas-phase fluidized bed reactor for polymerization reaction. By the method for quickly starting continuous polymerization reaction in the alpha-olefin gas-phase fluidized bed reactor, the trace water is quickly removed, time for establishing continuous and stable polymerization reaction is short, and the consumption of the ethylene for displacement is low; and production accidents are avoided, the consumption of the ethylene is reduced, and the production period is shortened.
Description
Technical field
The present invention is a kind of terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method.The preparation method who belongs to alpha-olefin homo or multipolymer.Be particularly related to vinyl polymerization or ethene and close the preparation method of emergencing copolymer mutually with other alpha-olefin copolymers.
Background technology
The homopolymerization of present most of terminal olefin or the production of multipolymer, the for example polymerization of ethylene copolymer is carried out in gas-phase fluidized bed reactor drum.U.S. Pat 4,302 566 discloses typical fluidized-bed reactor, and it is used for the production of ethylene homo and ethylene copolymer.The gas fluidised bed polymerisation reaction is on the surface of granules of catalyst, to have formed olefin polymer, comprises that the solid particulate of granules of catalyst and polymkeric substance is suspended in the fluidized bed region, promptly obtains polymkeric substance with the particulate form.So, after polyreaction, there is no need into to be provided with the particulate deposition, technological processs such as particulate separation have been simplified production technique.Therefore, gas-phase fluidized bed polymerization technique is simple, convenient and be widely used in the poly suitability for industrialized production with it.
Adopt chromium-based catalysts, produce the high density polyethylene(HDPE) product, when alpha-olefin polymerization carried out in gas-phase fluidized bed reactor drum, the micro-moisture of the ppm order of magnitude that exists in the reactor drum was the objectionable impurities that causes chromium-based catalysts to be poisoned.Therefore, remove the micro-moisture in the fluidized-bed reactor as early as possible, most important to the polyreaction of setting up continous-stable.
Because of H
2O is the serious poisonous substance of chromium-based catalysts, and there is inductive phase in chromium-based catalysts in addition, if displacement is not cut at the end, throws the extremely difficult foundation reaction of catalyzer, can only stop again when serious and change bed.
The method of available technology adopting titration aluminum alkyls consumes micro-moisture, be prone to produce static, knot sheet, and more serious consequence is to influence the subsequent product quality, produces a large amount of transition material.
Being generally used for the method that gas-phase fluidized-bed polymerizing reactor removes minor amount of water, mainly is to adopt nitrogen, ethene replacement dewatering technology.But this method dewatering time is long, and the polyreaction of setting up continous-stable is slow, consumes big content of starting materials ethene, is unfavorable for saving energy and reduce the cost.In the prior art, do not see the reported in literature of terminal olefin gas-phase fluidized-bed reactor successive polymerization reaction quick start method as yet.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art; And provide a kind of micro-moisture to remove soon; The polymerization reaction time of setting up continous-stable is short; Replace fewly, help saving energy and reduce the cost, ideal terminal olefin gas-phase fluidized-bed reactor successive polymerization reaction quick start method with the ethene consumption.
The object of the invention can reach through following measure:
Terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of the present invention; After it is characterized in that adopting nitrogen, ethene with the displacement of the micro-moisture in the gas-phase fluidized bed reactor drum; At first adopt metallocene catalyst; Cause startup alpha-olefin polymerization or alpha-olefin copolymer and close reaction; And then switch to conventional chromium-based catalysts alpha-olefine polymerizing or alpha-olefin copolymer closes reaction system, and stop to add metallocene catalyst simultaneously, change conventional terminal olefin gas-phase fluidized-bed reactor polyreaction over to.
Metallocene catalyst has following characteristics: (1) super-active.In transition metal, its activity is about as much as more than ten times of magnesium chloride support class catalyzer.(2) molecular weight and form distributed pole and kill, its Mw [TX-]/M [TX-] n generally can be lower than 2 (theoretical value is 1), and during with titanium base Ziegler-Natta catalyst, then is 3-8, then is 8-30 when using chrome catalysts; It is also very even to form distribution; It like comonomer macroscopic view content 10% VLDPE; In each molecular chain; The content of its comonomer does not wait from 0-40%, and the polymkeric substance chain length of metallocene catalyst production and side chain all are consistent at interval, thereby each chain all has its essentially identical copolymerization unit content.(3) each transition metal in the metallocene catalyst system all has catalytic activity, active site concentration can reach 100%; And each active site all produces corresponding chain length; And react, and only there is the active site of 1-3% to have activity in the Ziegler-Natta catalyst with the copolymerization unit of same amount.(4) catalyzer is selected for use flexibly, both can use the single component metallocene catalyst, can use the blended metallocene catalyst again, can also be as required and the grafting of Z-N catalyzer, produce the homopolymer of various structures and performance.(5) the polymerization activity life-span long, stable performance.
Contriver of the present invention finds, in fluidized-bed reactor, after the clean and liquid water of system's gaseous state poisonous substance displacement is replaced to a certain degree, sets up initial reaction stage; Add metallocene catalyst, utilize its high reactivity, the characteristics of no inductive phase; Can set up ethylene polymerization efficiently and effectively, utilize the consistency of itself and chromium-based catalysts then, cut again to chromium-based catalysts and change ordinary production over to; Shorten reactor drum and adopt ethene displacement and gas-phase fluidized-bed reactor to drive directly to throw the chromium-based catalysts discharging ethene time, reduced the waste of ethene, cut down the consumption of energy; Shorten device and drive the cycle, lower product cost greatly, remarkable effect is arranged improving product competitiveness.Thereby accomplished task of the present invention.
The object of the invention can also reach through following measure:
Terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of the present invention; Said metallocene catalyst is the bicyclic pentadiene zirconium dichloride; Its add-on is for being benchmark with 100 weight part alpha-olefinic polymer or alpha-olefin copolymer, and catalyst levels is 0.01～0.03 weight part.
Terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of the present invention, said terminal olefin is ethene, propylene, butylene, hexene and octene.
Terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of the present invention comprises following operation steps:
1. displacement
A. nitrogen replacement
Behind the dress bed, control nitrogen pressure 0.7MPa～1.1MPa, system is warming up to 85 ℃～88 ℃; According to the method for replacing of prior art, replace moisture≤5ppm to system;
B. ethene displacement
After the nitrogen replacement water-content was reduced to 5ppm, the ethene displacement was cut by system, and control ethylene pressure 0.7MPa～1.1MPa according to the method for replacing of prior art, replaces moisture≤1ppm to system;
2. metallocene catalyst causes and starts alpha-olefin polymerization or copolymerization
A. set up terminal olefin concentration
System water content be lower than 1ppm and stable after, system feeds terminal olefin, and the terminal olefin concentration that control is fit to according to temperature of reaction;
B. start alpha-olefin polymerization or copolymerization
After the terminal olefin concentration stabilize, feed metallocene catalyst and cause the startup polyreaction, technic index is controlled as follows:
3. switch catalyst system
A. catalyzer switches
After metallocene catalyst initiation startup alpha-olefin polymerization or copolymerization are stable, switch to conventional chromium-based catalysts polymerization reaction system, stop to add metallocene catalyst simultaneously;
B. improve polymerization temperature
Through adjustment 'alpha '-olefin monomers or alpha-olefin comonomer charging,, gradually polymerization temperature is brought up in the normal process indication range along with the chromium-based catalysts polyethylene powder is replaced the metallocene catalyst bed gradually;
C. add hydrogen
After treating that the metallocene catalyst powder is by conventional chromium-based catalysts displacement fully, add hydrogen to hydrogen/'alpha '-olefin monomers molar ratio gradually to normal value;
D. change normal running over to
The add-on of adjustment temperature of reaction and 'alpha '-olefin monomers or alpha-olefin comonomer makes target product qualified; Chromium-based catalysts ordinary production technic index is controlled as follows:
Terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of the present invention, high density polyethylene(HDPE) polyreaction quick start method is produced in the polymerization of a kind of ethene gas-phase fluidized-bed reactor, comprises following operation steps:
1. displacement
A. nitrogen replacement: behind the dress bed, control nitrogen pressure 1.0MPa～1.1MPa, system is warming up to 85 ℃～88 ℃; According to the method for replacing of prior art, replace moisture≤5ppm to system;
B. ethene displacement: after the nitrogen replacement water-content was reduced to 5ppm, the ethene displacement was cut by system, and control ethylene pressure 1.0MPa～1.1MPa according to the method for replacing of prior art, replaces moisture≤1ppm to system;
2. metallocene catalyst startup ethene-hervene copolymer closes reaction
A. set up hexene concentration: system water content be lower than 1ppm and stable after, system feeds hexene, and control hexene/ethene (mol ratio)=0.005～0.010;
B. start ethene-hervene copolymer and close reaction
After setting up the hexene concentration stabilize, feed metallocene catalyst and start polyreaction, technic index is controlled as follows:
3. switch catalyst system
A. after metallocene catalyst startup ethene-hervene copolymer closes stable reaction, switch to conventional chromium-based catalysts polymerization reaction system, stop to add metallocene catalyst simultaneously;
B. substitute the hexene charging by butene monomers, and gradually polymerization temperature is brought up in the normal range;
C. after treating that the metallocene catalyst powder is by conventional chromium-based catalysts displacement fully, add hydrogen to hydrogen/ethylene ratio 0.020～0.030 gradually;
D. change conventional ethene gas-phase fluidized-bed reactor polyreaction over to
The add-on of adjustment temperature of reaction and vinyl monomer makes the high density polyethylene(HDPE) product meet quality standard; Chromium-based catalysts ordinary production technic index is controlled as follows:
It is an optimized technical scheme.
Terminal olefin gas-phase fluidized-bed reactor successive polymerization reaction quick start method of the present invention, disclosed technical scheme, comparing prior art has following positively effect:
1. provide a kind of micro-moisture to remove soon, the polymerization reaction time of setting up continous-stable is short, replace fewly with the ethene consumption, helps saving energy and reduce the cost, and quick start method is reacted in the successive polymerization of ideal terminal olefin gas-phase fluidized-bed reactor.
2. can set up reaction fast, avoid industrial accident; Obviously reduce ethene consumption, shorten the production cycle.It is energy-saving and cost-reducing to help device, improves product market competitiveness.
3. Shandong plastic molding and processing plant theoretical density pilot plant adopts method of the present invention, and about 1 ton of ethene is practiced thrift in each driving, practices thrift about 16 hours of driving time; The HDPE of Shandong plastic molding and processing plant device is driven, and adopts method of the present invention and directly drives than using the S-2 chromium-based catalysts, and about 50 tons of ethene is practiced thrift in each driving, practices thrift about 10 hours of driving time.
Description of drawings
Fig. 1 is gas-phase fluidized bed high density polyethylene(HDPE) process flow diagram
Among the figure
The 1-recycle gas compressor
The 2-recycle gas cooler
The 3-discharge tank
4-product storage tank
5-catalyzer feeder
Embodiment
The present invention below will combine embodiment to make further detailed description:
After adopting nitrogen, ethene with the displacement of the micro-moisture in the gas-phase fluidized bed reactor drum; At first adopt metallocene catalyst; Cause and start polyreaction; And then switch to conventional chromium-based catalysts polymerization reaction system, and stop to add metallocene catalyst simultaneously, change conventional ethene gas-phase fluidized-bed reactor polyreaction over to.Produce high density polyethylene(HDPE).Comprise following operation steps:
1. displacement
A. nitrogen replacement: behind the dress bed, control nitrogen pressure 0.7MPa～1.1MPa, system is warming up to 85 ℃～88 ℃; According to the method for replacing of prior art, replace moisture≤5ppm to system;
B. ethene displacement: after the nitrogen replacement water-content was reduced to 5ppm, the ethene displacement was cut by system, and control ethylene pressure 0.7MPa～1.1MPa according to the method for replacing of prior art, replaces moisture≤1ppm to system;
2. metallocene catalyst startup ethene-hervene copolymer closes reaction
A. set up hexene concentration: system water content be lower than 1ppm and stable after, system feeds hexene, and control hexene/ethene (mol ratio)=0.005～0.010;
B. start ethene-hervene copolymer and close reaction
After setting up the hexene concentration stabilize, feed metallocene catalyst and start polyreaction, technic index is controlled as follows:
3. switch catalyst system
A. after metallocene catalyst startup ethene-hervene copolymer closes stable reaction, switch to conventional chromium-based catalysts polymerization reaction system, stop to add metallocene catalyst simultaneously;
B. substitute the hexene charging by butene monomers, and gradually polymerization temperature is brought up in the normal range;
C. after treating that the metallocene catalyst powder is by conventional chromium-based catalysts displacement fully, add hydrogen to hydrogen/ethylene ratio 0.020～0.030 gradually;
D. change conventional ethene gas-phase fluidized-bed reactor polyreaction over to
The add-on of adjustment temperature of reaction and vinyl monomer makes the high density polyethylene(HDPE) product meet quality standard; Chromium-based catalysts ordinary production technic index is controlled as follows:
About 1 ton of ethene is practiced thrift in each driving, practices thrift about 16 hours of driving time
When Shandong plastic molding and processing plant theoretical density pilot plant carries out chromium-based catalysts product development production, do not react in 2 hours if throw the S-2 chromium-based catalysts, ash content is just abnormally dangerous above 0.06%, has to change again bed when serious.Because of the pilot plant discharge port is designed to 50mm, if displacement is not cut at the end, lean on catalyzer accumulation, virus killing, set up reaction, in case catalyst reaction is prone to caking, and caking is difficult to take out of by discharging, causes the reaction operation not gone down, and can only stop and change bed.
Method and step according to embodiment 1 start polyreaction, and about 1 ton of ethene is practiced thrift in each driving, practices thrift about 16 hours of driving time.
The HDPE of Shandong plastic molding and processing plant device is driven, and also has the long-time nonreactive situation of S-2 chromium-based catalysts of throwing, and sees reaction in normal 4 hours, sees reaction in long 10 hours, opens ethene discharging 4-5t/h, and material consumption is also very high like this.
Method and step according to embodiment 1 start polyreaction, and about 50 tons of ethene is practiced thrift in each driving, practices thrift about 10 hours of driving time.
Claims (5)
1. terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method; After it is characterized in that adopting nitrogen, ethene with the displacement of the micro-moisture in the gas-phase fluidized bed reactor drum; At first adopt metallocene catalyst; Cause startup alpha-olefin polymerization or alpha-olefin copolymer and close reaction; And then switch to conventional chromium-based catalysts alpha-olefine polymerizing or alpha-olefin copolymer closes reaction system, and stop to add metallocene catalyst simultaneously, change conventional terminal olefin gas-phase fluidized-bed reactor polyreaction over to.
2. according to the terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of claim 1; It is characterized in that said metallocene catalyst is the bicyclic pentadiene zirconium dichloride; Its add-on is for being benchmark with 100 weight part alpha-olefinic polymer or alpha-olefin copolymer, and catalyst levels is 0.01～0.03 weight part.
3. according to the terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of claim 1, it is characterized in that said terminal olefin is ethene, propylene, butylene, hexene and octene.
4. according to the terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of claim 1, it is characterized in that comprising following operation steps:
1. displacement
A. nitrogen replacement
Behind the dress bed, control nitrogen pressure 0.7MPa～1.1MPa, system is warming up to 85 ℃～88 ℃; According to the method for replacing of prior art, replace moisture≤5ppm to system;
B. ethene displacement
After the nitrogen replacement water-content was reduced to 5ppm, the ethene displacement was cut by system, and control ethylene pressure 0.7MPa～1.1MPa according to the method for replacing of prior art, replaces moisture≤1ppm to system;
2. metallocene catalyst causes and starts alpha-olefin polymerization or copolymerization
A. set up terminal olefin concentration
System water content be lower than 1ppm and stable after, system feeds terminal olefin, and the terminal olefin concentration that control is fit to according to temperature of reaction;
B. start alpha-olefin polymerization or copolymerization
After the terminal olefin concentration stabilize, feed metallocene catalyst and cause the startup polyreaction, technic index is controlled as follows:
3. switch catalyst system
A. catalyzer switches
After metallocene catalyst initiation startup alpha-olefin polymerization or copolymerization are stable, switch to conventional chromium-based catalysts polymerization reaction system, stop to add metallocene catalyst simultaneously;
B. improve polymerization temperature
Through adjustment 'alpha '-olefin monomers or alpha-olefin comonomer charging,, gradually polymerization temperature is brought up in the normal process indication range along with the chromium-based catalysts polyethylene powder is replaced the metallocene catalyst bed gradually;
C. add hydrogen
After treating that the metallocene catalyst powder is by conventional chromium-based catalysts displacement fully, add hydrogen to hydrogen/'alpha '-olefin monomers molar ratio gradually to normal value;
D. change normal running over to
The add-on of adjustment temperature of reaction and 'alpha '-olefin monomers or alpha-olefin comonomer makes target product qualified; Chromium-based catalysts ordinary production technic index is controlled as follows:
5. according to the terminal olefin gas-phase fluidized-bed reactor polyreaction quick start method of claim 1, it is characterized in that a kind of ethene gas-phase fluidized-bed reactor polyreaction quick start method, comprise following operation steps:
1. displacement
A. nitrogen replacement: behind the dress bed, control nitrogen pressure 1.0MPa～1.1MPa, system is warming up to 85 ℃～88 ℃; According to the method for replacing of prior art, replace moisture≤5ppm to system;
B. ethene displacement: after the nitrogen replacement water-content was reduced to 5ppm, the ethene displacement was cut by system, and control ethylene pressure 1.0MPa～1.1MPa according to the method for replacing of prior art, replaces moisture≤1ppm to system;
2. metallocene catalyst startup ethene-hervene copolymer closes reaction
A. set up hexene concentration: system water content be lower than 1ppm and stable after, system feeds hexene, and control hexene/ethene (mol ratio)=0.005～0.010;
B. start ethene-hervene copolymer and close reaction
After setting up the hexene concentration stabilize, feed metallocene catalyst and start polyreaction, technic index is controlled as follows:
3. switch catalyst system
A. after metallocene catalyst startup ethene-hervene copolymer closes stable reaction, switch to conventional chromium-based catalysts polymerization reaction system, stop to add metallocene catalyst simultaneously;
B. substitute the hexene charging by butene monomers, and gradually polymerization temperature is brought up in the normal range;
C. after treating that the metallocene catalyst powder is by conventional chromium-based catalysts displacement fully, add hydrogen to hydrogen/ethylene ratio 0.020～0.030 gradually;
D. change conventional ethene gas-phase fluidized-bed reactor polyreaction over to
The add-on of adjustment temperature of reaction and vinyl monomer makes the high density polyethylene(HDPE) product meet quality standard; Chromium-based catalysts ordinary production technic index is controlled as follows:
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| CN114621371B (en) * | 2020-12-10 | 2023-11-28 | 中国石油天然气股份有限公司 | On-line rapid switching method from gas-phase polyethylene metallocene catalyst to chromium catalyst |
| CN114965852A (en) * | 2021-02-25 | 2022-08-30 | 中国石油天然气股份有限公司 | Ethylene gas phase polymerization evaluation test device |
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Application publication date: 20120711 |