CN114426590A - On-line switching method of metallocene catalyst and Ziegler-Natta catalyst - Google Patents
On-line switching method of metallocene catalyst and Ziegler-Natta catalyst Download PDFInfo
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- CN114426590A CN114426590A CN202011044838.2A CN202011044838A CN114426590A CN 114426590 A CN114426590 A CN 114426590A CN 202011044838 A CN202011044838 A CN 202011044838A CN 114426590 A CN114426590 A CN 114426590A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Abstract
The invention discloses an on-line switching method of a metallocene catalyst and a Ziegler-Natta catalyst, which realizes switching in an original bed layer without complete reaction and shutdown, opening a reactor and replacing a seed bed, greatly reduces the switching difficulty, avoids the risk of exposing a reaction system in the air, reduces the operation risk, has short time consumption, only needs about 48 hours, and effectively reduces the cost. The invention also uses CO2And O2As the terminator of the Ziegler-Natta catalyst, the two terminators are easy to obtain, have low use cost, have irreversible termination effect on the Ziegler-Natta catalyst, are more beneficial to the catalytic reaction of the subsequent metallocene catalyst and are also beneficial to the smooth operation of the switching process. The switching method of the invention does not need to use the existing raw materialsThe refining system, the catalyst filling system, the raw material feeding control system, the electrostatic control system and the like are transformed on a large scale, so that the cost of transformation investment is greatly reduced, and the running state of the reactor before and after switching is stable.
Description
Technical Field
The invention belongs to the technical field of polymerization catalyst on-line switching, and particularly relates to an on-line switching method of a metallocene catalyst and a Ziegler-Natta catalyst.
Background
The metallocene catalyst is a single-active-center catalyst, has high activity, can precisely customize the molecular structure of the polyethylene resin, comprises relative molecular mass distribution, comonomer content, comonomer distribution on a molecular chain and the like, and is the development direction of polyolefin products in the future.
In the production and operation of a gas phase polyethylene device, the switching between a Ziegler-Natta (titanium system or chromium system) catalyst and a metallocene catalyst is realized. The prior art generally employs an off-line bed change process to switch between Ziegler-Natta and metallocene catalysts, i.e., the reaction is stopped, the existing seedbed is emptied, a new type of seedbed to be changed is loaded, the components are reestablished, and a new catalyst to be changed is added to initiate the reaction. The off-line switching method has long processing time, consumes about 96 hours, can reduce the capacity of the device, is difficult to control the balance of reaction materials, is difficult to realize industrial application of the metallocene catalyst, and has high consumption because a reactor needs to be opened for cleaning and maintenance in the switching process.
To this end, another switching method has been developed, such as "switching between incompatible catalysts" disclosed in CN107207649A, which requires discharging and refilling the reactor with a seedbed, and de-watering and de-aerating the newly filled seedbed to clean up catalyst poisons, since almost all of the polymer in the reactor has to be removed. Thus, this catalyst changeover process is time consuming and expensive, and in commercial operation it typically takes 96 hours or more to shut down the reactor until the polymerization reaction can be initiated again with fresh catalyst. In addition, there are other switching methods, such as "a method of converting incompatible catalysts to each other" see U.S. Pat. Nos. 5442019, 5672665, 5753786 and 5747612. The method comprises the following steps: a) stopping the addition of one of the incompatible catalyst or catalyst system to the reactor; b) adding a catalyst killer; c) a second catalyst or catalyst system incompatible with the first catalyst system is added to the reactor. Since this conversion process does not have a specific systematic replacement method, resulting in inefficient replacement of the reaction components, the reactor contents after reinitiation are susceptible to the formation of polymers of unacceptable properties. For example, in the manufacture of polyethylene with an MI of 1.0, the Ziegler-Natta catalyst needs to operate at high hydrogen concentrations (about 6 mol% hydrogen in the reactor), while the metallocene catalyst must operate at low hydrogen concentrations (about 500 ppm). If the Ziegler-Natta catalyst is operated at low hydrogen conditions, very high molecular weight polymers are formed, and if the Ziegler-Natta catalyst and metallocene catalyst are combined and operated at 500ppm hydrogen, the reaction product will contain ultra high molecular weight polymers and hard particles, and the handling of such polymers will be difficult. In addition, the catalyst killer used in the method is a special organic terminator, is not easy to obtain and has high use cost.
Disclosure of Invention
To overcome the above-mentioned drawbacks and deficiencies of the prior art, it is an object of the present invention to provide a method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst. The on-line switching method of the invention does not need to completely react and stop, does not need to open a reactor, does not need to replace a seed bed, has low switching difficulty, higher safety and short time consumption, is about 0.5 time of the existing off-line switching method, has lower cost and better switching effect.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides CO2And/or O2Use in the inhibition of Ziegler-Natta catalyst activity. Preferably in the catalyst-switching process, CO2And/or O2Use as irreversible terminator for inhibiting the activity of Ziegler-Natta catalysts.
The invention also provides a terminator for irreversible deactivation of a Ziegler-Natta catalyst, comprising CO2And/or O2。
In a second aspect, the present invention provides a method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst, comprising switching from a polymerization reaction a catalyzed by a catalyst a to a polymerization reaction B catalyzed by a catalyst B, said catalyst a and said catalyst B being of different types and being selected from the group consisting of metallocene catalysts and Ziegler-Natta catalysts, comprising the following steps:
(1) stopping injecting the catalyst A into the gas phase reactor, and maintaining the polymerization reaction A to continue to consume the catalyst A in the reactor;
(2) injecting an irreversible terminator for inactivating the catalyst A into the reactor, and maintaining the temperature, pressure and fluidization state of the reaction in the reactor;
(3) continuously maintaining the reaction temperature in the reactor, reducing the reaction pressure, and then injecting water for hydrolysis reaction;
(4) continuously maintaining the reaction temperature in the reactor, introducing nitrogen, and replacing the material used for the polymerization reaction A in the reactor by flowing pressure;
(5) re-establishing circulation in the reactor, and then adjusting the temperature and establishing reaction components according to the requirements of the polymerization reaction B;
(6) an antistatic agent is injected into the reactor, and then a catalyst B is injected to initiate a polymerization reaction B.
Further, the online switching method further comprises a step a introduced after the step (4) and before the step (5): and stopping the circulating fan, and replacing the residual material for the polymerization reaction A in the reactor at zero pressure to ensure that the material for the polymerization reaction A is completely replaced and the condition for subsequently carrying out the polymerization reaction B meets the requirement. Preferably, the number of zero-pressure substitutions is 2 to 8. The zero pressure displacement process should prevent the distribution plate from leaking out of the bed.
It will be understood by those skilled in the art that the term "zero pressure metathesis" refers to the depressurization of the internal pressure of the reactor to zero gauge pressure during the metathesis process.
Preferably, during said polymerization reaction A of step (1), the reactor is maintained in a low load operating condition. The reaction process should keep the material proportion as stable as possible to ensure the product quality.
It will be understood by those skilled in the art that the term "low load operation" refers to the state of production operation at the minimum ethylene feed rate required to maintain back flushing throughout the reactor, i.e., to ensure proper operation of the reactor.
Preferably, in the step (1), the injection of the cocatalyst of the catalyst a is stopped within two hours before the injection of the catalyst a into the gas phase reactor is stopped.
Preferably, the step (1) further comprises the step b before stopping injecting the cocatalyst of the catalyst a: the condensing mode is exited and the amount of induced condensing agent in the reactor is reduced.
Preferably, in the step (2), after the reaction load cannot be maintained, the irreversible terminator is injected into the reactor.
It will be understood by those skilled in the art that the term "reaction load is not maintained" means that blow back cannot continue to decrease throughout the reactor and ethylene feed cannot continue to be down-regulated.
In the step (3), the pressure inside the reactor is reduced to maintain a substantially fluidized state.
It will be understood by those skilled in the art that the term "substantially fluidized state" refers to a state in which the reaction recycle gas flow rate is slightly greater than the minimum fluidizing gas flow rate, just enough to maintain the fluidization capability of the reactor, and no falling or falling out of bed occurs.
Preferably, in the step (3), the injection amount of water is 100 to 1000 ppm.
Preferably, in the step (3), the inside of the reactor is maintained in a sealed state during the hydrolysis reaction, and the circulation is maintained for more than 4 hours. In the present invention, the hydrolysis reaction can completely deactivate the cocatalyst in the reactor to prevent the cocatalyst from affecting the reaction of the metallocene catalyst.
And (4) analyzing the content change condition of each material component in the reactor in the replacement process of the step (4) so as to track the replacement condition in real time. After the hydrolysis reaction is finished, the pressure of the reactor is released to the lowest pressure at which the circulating fan can operate, and then nitrogen is introduced for flowing pressure replacement. The flowing pressure replacement can replace the water and oxygen absorbed by the powder in the reactor relatively quickly.
Preferably, the method for establishing the loop in the step (5) is as follows: introducing nitrogen into the reactor, establishing proper nitrogen pressure, and starting a circulating fan to reestablish the fluidized state of the reactor.
And (5) after the circulation is reestablished, analyzing the impurity content in the reactor (namely the content of the material for the polymerization reaction A), and continuing the next step when the impurity content reaches the ppm level or below, or continuing the replacement of the reactor until the reactor is qualified.
Preferably, in step (6), the antistatic agent is injected in an amount of 20ppm by weight of the reactor bed.
Preferably, the injection position of the antistatic agent is the middle position of the bed.
Preferably, in the step (6), before the catalyst B is injected, the promoter of the catalyst B is injected into the reactor to establish a concentration. When the catalyst B is injected, a small amount of the catalyst B is injected to establish a reaction, and then the injection amount is gradually increased to improve the reaction yield. During the polymerization reaction B, inert heavy component hydrocarbon after refining treatment can be added to assist the reaction control.
In the invention, the catalyst A is consumed by reaction, and then the irreversible terminator is added to inactivate the residual catalyst A. Therefore, the addition amount of the terminating agent can be reduced, the treatment cost of the catalyst A is reduced, the treatment time is shortened, and the treatment is more thorough.
Preferably, the catalyst A is a Ziegler-Natta catalyst, the catalyst B is a metallocene catalyst, and the irreversible terminator is CO2And/or O2. Because some components in the Ziegler-Natta catalyst can become poisons of the metallocene catalyst and are not beneficial to the metallocene catalyst to promote the polymerization reaction, the Ziegler-Natta catalyst in the reactor needs to be completely inactivated before introducing the metallocene catalyst, and the irreversible terminator can completely and irreversibly inactivate the catalyst A to ensure that the catalyst A does not participate in the reaction in the later period.
Compared with the prior art, the invention has the beneficial effects that:
1. the switching method of the invention has short time consumption, only needs about 48 hours, effectively reduces the time cost and realizes the quick switching of the metallocene catalyst.
2. The switching method of the invention does not need to completely react and stop, open the reactor and replace the seed bed, but realizes switching in the original bed layer, thereby greatly reducing the switching difficulty, avoiding the risk of exposing the reaction system in the air and reducing the operation risk.
3. The invention uses CO2And O2As the terminator of the Ziegler-Natta catalyst, the two terminators are easy to obtain, have low use cost, have irreversible termination effect on the Ziegler-Natta catalyst, are more beneficial to the catalytic reaction of the subsequent metallocene catalyst and are also beneficial to the smooth operation of the switching process.
4. The switching method has better reliability and stability, the state in the reactor is easy to control in the switching process, the running state of the reactor before and after switching is stable, the production running is stable after switching, the activity of the catalyst is good, and the switching requirement of the gas-phase polyethylene process can be met.
5. The switching method of the invention does not need to carry out large-scale reconstruction on the prior raw material refining system, the catalyst filling system, the raw material feeding control system, the static control system and the like, thereby greatly reducing the cost of reconstruction investment.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. The starting materials used in the examples are commercially available, and the methods used are conventional in the art unless otherwise specified. It will be understood by those skilled in the art that the polymerization reactions A and B in the polymerization reaction A and the polymerization reaction B described in the present invention are only to distinguish two polymerization reactions.
Examples
An on-line switching method of a metallocene catalyst and a Ziegler-Natta catalyst comprises the following steps of switching a polymerization reaction A catalyzed by the Ziegler-Natta catalyst into a polymerization reaction B catalyzed by the metallocene catalyst:
(1) reducing the operation load of the reactor, exiting a condensation mode, reducing the content of an induced condensing agent in the reactor, stopping injecting a cocatalyst (aluminum alkyl and the like) within two hours before stopping the Ziegler-Natta catalyst, stopping injecting the Ziegler-Natta catalyst, adjusting the feeding amount of each reaction component, and keeping the ratio of each reaction component stable so as to ensure that the product quality is in a qualified range, maintain the polymerization reaction A to operate in a low-load state, and consume the existing Ziegler-Natta catalyst and cocatalyst in the reactor as much as possible;
(2) after the reaction load could not be maintained, the reactor was filled with CO stored in a high pressure cylinder2Or O2The reaction is terminated by the irreversible terminator, and the temperature, the pressure and the fluidization state of the reaction are maintained in the reactor after the terminator is injected;
(3) after the reaction is ended and the circulation is carried out for a period of time, continuously maintaining the reaction temperature in the reactor, reducing the pressure to a state of maintaining basic fluidization, then injecting trace water (100-1000 ppm) for hydrolysis reaction, and maintaining the circulation for more than 4 hours without pressure relief and discharge in the reactor during the hydrolysis reaction;
(4) after the hydrolysis reaction is finished, the pressure of the reactor is released to the lowest pressure at which a circulating fan can operate, the reaction temperature is continuously maintained, nitrogen is introduced, reaction components (including hydrogen, comonomers (butylene-1 and hexylene-1), induced condensing agents (isopentane, hexane and the like)) in the reactor are replaced by flowing pressure, and the components (including H) are analyzed in the process2O) content variation;
(5) when the content of the comonomer and the induced condensing agent in the reactor is reduced to the extent that the comonomer and the induced condensing agent cannot be condensed at the bottom of the reactor due to the cooling of the reactor, stopping the circulating fan, and performing zero-pressure replacement on the reactor for 2-8 times to ensure that reaction components in the reactor are completely replaced, wherein the leakage of a distribution plate is prevented in the replacement process;
(6) introducing nitrogen into the reactor to increase the pressure, starting a circulating fan, reestablishing the fluidized state of the reactor, heating the temperature of the reactor to meet the operating conditions of the polymerization reaction B under the condition of the nitrogen, analyzing the impurity content (namely, reaction components for the polymerization reaction A) in the reactor, controlling the impurity content to be in the ppm level, otherwise, continuously replacing the reactor, and establishing the reaction components according to the requirements of the metallocene catalyst after the reactor is qualified;
(7) introducing each reaction component of the polymerization reaction B into the reactor, strictly controlling the content of each component, and then adding an accurate flow control valve on a feed line of each material (such as hydrogen, comonomer and the like), wherein an accurate chromatograph is added to the reaction circulating gas to monitor the content of each component in the reactor;
(8) injecting an antistatic agent into the reactor half an hour before the metallocene catalyst is injected to establish the concentration of the antistatic agent, wherein the injection amount of the antistatic agent is 20ppm of the weight of the reactor bed, and the injection position of the antistatic agent is the middle position of the bed layer;
(9) injecting a cocatalyst into a reactor to establish concentration, then adding a small amount of metallocene catalyst, observing the temperature of a bed layer and electrostatic change, and gradually increasing the addition of the metallocene catalyst after establishing a reaction to improve the reaction yield; according to the analysis data, the feeding quantity, reaction temperature, static electricity and the like of the reaction components are controlled to generate qualified target products, and the refined inert heavy component hydrocarbon can be added to assist reaction control.
Through statistics, the total time consumption of the whole switching process of the embodiment is 47h, the switching effect is good, the operation of the switching process is simple, the control is easy, and no new impurity is introduced into the polymerization reaction B.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst, which is characterized by comprising the step of switching a polymerization reaction A catalyzed by a catalyst A to a polymerization reaction B catalyzed by a catalyst B, wherein the catalyst A and the catalyst B are different in type and are selected from the group consisting of metallocene catalysts and Ziegler-Natta catalysts, and the method comprises the following specific steps:
(1) stopping injecting the catalyst A into the gas phase reactor, and maintaining the polymerization reaction A to continue to consume the catalyst A in the reactor;
(2) injecting an irreversible terminator for inactivating the catalyst A into the reactor, and maintaining the temperature, pressure and fluidization state of the reaction in the reactor;
(3) continuously maintaining the reaction temperature in the reactor, reducing the reaction pressure, and then injecting water for hydrolysis reaction;
(4) continuously maintaining the reaction temperature in the reactor, introducing nitrogen, and replacing the material used for the polymerization reaction A in the reactor by flowing pressure;
(5) re-establishing circulation in the reactor, and then adjusting the temperature and establishing reaction components according to the requirements of the polymerization reaction B;
(6) an antistatic agent is injected into the reactor, and then a catalyst B is injected to initiate a polymerization reaction B.
2. The method for the on-line switching of a metallocene catalyst with a Ziegler-Natta catalyst according to claim 1, characterized in that it further comprises a step a, introduced after step (4) and before step (5): the circulating fan is stopped and the residual material for the polymerization reaction A in the reactor is replaced under zero pressure.
3. The method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst according to claim 1, wherein in step (1), the polymerization a process reactor is maintained in a low-load operation state, and the co-catalyst injection of catalyst a is stopped within two hours before the injection of catalyst a into the gas phase reactor is stopped.
4. The method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst according to claim 3, wherein the step (1) further comprises the step of b: the condensing mode is exited and the amount of induced condensing agent in the reactor is reduced.
5. The method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst according to claim 1, wherein in the step (3), the injection amount of water is 100 to 1000 ppm; preferably, the hydrolysis reaction process reactor is kept in a sealed state and is kept for circulation for more than 4 hours.
6. The method for the on-line switching of a metallocene catalyst with a Ziegler-Natta catalyst according to claim 1, wherein the step (5) of establishing a cycle comprises: introducing nitrogen into the reactor, establishing nitrogen pressure, and starting a circulating fan to reestablish the fluidized state of the reactor.
7. The method for on-line switching of a metallocene catalyst and a Ziegler-Natta catalyst according to claim 1, wherein in the step (6), the antistatic agent is injected in an amount of 20ppm based on the weight of the reactor bed; preferably, the injection position of the antistatic agent is the middle position of the bed.
8. The method for on-line switching between a metallocene catalyst and a Ziegler-Natta catalyst according to claim 1, wherein in step (6), the cocatalyst of catalyst B is injected into the reactor to establish the concentration before the catalyst B is injected.
9. In the catalyst switching method, CO2And/or O2Use as irreversible terminator for inhibiting the activity of Ziegler-Natta catalysts.
10. A terminator for the irreversible deactivation of a Ziegler-Natta catalyst comprising CO2And/or O2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117567676A (en) * | 2024-01-16 | 2024-02-20 | 新疆独山子石油化工有限公司 | Production method of titanium-series polyethylene converted metallocene polyethylene |
| CN117567676B (en) * | 2024-01-16 | 2024-04-16 | 新疆独山子石油化工有限公司 | Production method of titanium-series polyethylene converted metallocene polyethylene |
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