CN107098991B - A kind of olefine polymerizing process and device - Google Patents
A kind of olefine polymerizing process and device Download PDFInfo
- Publication number
- CN107098991B CN107098991B CN201710232955.3A CN201710232955A CN107098991B CN 107098991 B CN107098991 B CN 107098991B CN 201710232955 A CN201710232955 A CN 201710232955A CN 107098991 B CN107098991 B CN 107098991B
- Authority
- CN
- China
- Prior art keywords
- fluidized
- bed reactor
- gas
- hydrogen
- reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of polyene hydrocarbon synthesis process and devices, and the method provides fluidized-bed reactor, and olefin polymerization occurs in a fluidized bed reactor.The present invention utilizes membrane separation device separation and concentration hydrogen, utilize condensation, gas-liquid separation device separation and concentration comonomer, under the effect of the second-order separation of membrane separation device and gas-liquid separator, the concentration gradient of temperature gradient and hydrogen is strengthened in fluidized-bed reactor, can produce the polyolefin products for having both good moulding processability and physical property.
Description
Technical field
The invention discloses a kind of converging operation method and devices.More particularly to use fluidized-bed reactor produce molecular weight
It is distributed the method and device of the polyolefin and polyolefin copolymer with bimodal/broad peak.
Background technique
It is specifically exactly unreacted from fluidized-bed reactor outlet the present invention relates to a kind of olefinic polymerization operating method
Enrichment and separate section hydrogen in material, and by the middle part of isolated hydrogen Returning reactor or top, the structure in single reactor
The high region of density of hydrogen and the low region of density of hydrogen are built, so that the continuous polymerization reaction of polymerized monomer generates molecular weight distribution
Wider or molecular weight distribution is in the method for the polyolefin copolymer or polyolefin copolymer of bimodal distribution.
For polyolefin, especially polyethylene, molecular weight and molecualr weight distribution greatly influences the mechanical performance of polymer
And processing performance.In the research of this field, it has been recognized that, molecular weight is higher, and the mechanical performance is higher.However there is height
The mobility of the polyolefin of molecular weight is bad, it is difficult to process, be difficult to blow under high shearing and squeeze.It is known in the art,
The molecular weight distribution for expanding polyethylene may be implemented improvement rheological property while maintain the purpose of the mechanical performance of final products；Its
Middle high molecular weight moieties guarantee that the mechanical performance of product, low molecular weight part help to improve the processing performance of product.
This field it has been recognized that, by catalyst or the polymer with activated centre be placed in two or more difference
Reaction condition or gas composition in, make its successive reaction, just can produce with wide/double peak distribution polyethylene.However
The mixing of single-reactor polymer pellets inside is more abundant, and the temperature in reactor is almost the same, therefore, certain single catalysis
The molecular weight distribution for the polymer that agent produces at the stable a certain temperature in single-reactor is relatively narrow, using multiple anti-
The device production wider product of molecular weight distribution is answered to obtain extensive research.According to aggregated media difference, series reactor process
It is divided into slurry-slurry, slurry-gas phase, gas phase-vapor mode etc..European patent EP-A-691353 describes two traditional gas
The method that the series connection of phase reaction device produces bimodal/broad peak polyethylene；A kind of first endless tube is disclosed in United States Patent (USP) US 7115687B
Reactor and the concatenated technique of the second gas-phase fluidized-bed reactor；Chinese patent 102060943A disclose one kind be used to prepare it is double
The method of peak polyethylene and gas-phase reactor comprising at least four fluidized beds.
Using single reaction kettle technique, the catalyst with more active sites, perhaps single catalyst multichip carrier or mixing are used
Catalyst, and the research hotspot of production bimodal polyethylene.UCC company, the U.S. is suitable using vapor phase method in Unipol process unit
Synthesize bimodal polyethylene product with composite catalyst.The Prodigy catalyst that Univation company develops, can be in list
Bimodal HDPE is produced in reactor.Chinese patent 103421138A also discloses a kind of method for preparing bimodal/broad peak polyethylene,
A kind of double salicylaldiminato zirconium dichloride catalysts and metallocene catalyst are compound.Composite catalyst produces in single reactor
The technique of polyethylene, cost is relatively low, easy to implement, but to the more demanding of catalyst.
Further, it is also possible to construct different polymerization reaction environment in single reactor, wide/double peak polyethylene is produced.China
Patent 101284889A disclose it is a kind of by the control of fluidized-bed reactor at least there are two temperature differences at 10 DEG C or more
Stable conversion zone method.Patent WO00/02929A1 proposes a kind of multizone circulating reactor technique and device, this
Polymer reactor is connected with each other by the raising section of fast fluidized regime and the descending branch of moving bed state, and control two is passed through
The polymerizing condition of a conversion zone realizes the production of broad peak polyolefin.
The present invention is enriched with and separates hydrogen using membrane separating method, and different polymerization reactions is constructed on space reactor
Environment, so that production has bimodal/broad peak polyethylene product of different distributions width.Process flow of the invention is relatively simple,
Operation is easy, and by the effect of the second-order separation of membrane separation device and gas-liquid separator, enhances temperature gradient in reactor
With the concentration gradient of hydrogen, the polyolefin products for having both good moulding processability and physical property are obtained.
Summary of the invention
The object of the present invention is to provide a kind of methods of new olefinic polymerization, especially for bimodal/broad peak polyethylene
It is applicable in.The present invention using condensation, gas-liquid separation method by comonomer enrichment and separation, using membrane separating method by recycle
Hydrogen-rich and separation in material.Above the reactor distributing plate in the middle part of side wall, lower part different location introduce liquid material, utilize liquid
Body material evaporation absorbs heat to form at least one low-temperature region and low hydrogen gas concentration region；And the gas material rich in hydrogen is anti-
It answers in the middle part of device and top different location introduces reactor, form a high-temperature region in the middle and upper part of reactor and rich in the area of hydrogen
Domain.
The present invention provides a kind of polyolefin synthetic method, which comprises
1) unreacted gas material is exported from fluidized-bed reactor (1) outlet, part or all of gas material enters film
Separator (3)；
2) from the derived gas material rich in hydrogen of membrane separation device (3) through overcompression and cooling, in reactor
Portion and upper area introduce fluidized-bed reactor (1), form circulation loop；
3) less gas material, olefinic monomer and the fluidized-bed reaction of the hydrogen content derived from membrane separation device (3)
The gas material mixing that membrane separation device (3) is exported and do not entered at the top of device (1), into gas-liquid point after overcompression, cooling
From device (6)；
4) liquid material separated in gas-liquid separator (6) passes through condensate tank (7) and pumping unit (8), part or complete
Portion introduces middle part and the lower area of fluidized-bed reactor (1)；Remaining liq material and gas material are from reactor distributing plate (2)
Lower section introduces fluidized-bed reactor (1)；
5) gas material, liquid material are contacted with the catalyst of addition, are reacted and form solid phase in fluidized-bed reactor (1)
Polyolefin；
Wherein, dense-phase fluidized is kept inside the fluidized-bed reactor (1)；Continuously or intermittently from fluidized-bed reaction
Polyolefin is exported in device (1)；And into fluidized-bed reactor (1) or circulation loop introduce olefinic monomer, catalyst, condensing agent,
Co-catalyst, chain-transferring agent, antistatic agent and inert gas；Wherein the circulation loop is fluidized-bed reactor (1) outlet
Material again returns to the fluid line that fluidized-bed reactor (1) is passed through.
Specifically, unreacted gas material from fluidized-bed reactor (1) export export, part or all of gas material into
Enter membrane separation device (3), the hydrogen-rich gas derived from membrane separation device (3) through overcompression, it is cooling after introduce fluidized-bed reactor
(1) middle part and upper area, the few gas of the hydrogen derived from membrane separation device (3), Fresh olefin and part are from fluidisation
After gas mixing derived from the top of reactor (3), enter gas-liquid separator (6) after overcompression, condensation, gas-liquid separator (6)
The liquid material separated is partly or entirely introduced into fluidized reactor (1) from the different location above reactor distributing plate (2)
Portion and lower area；Remaining liq material and gas material enter reactor distributing plate (2) lower space, are distributed by reactor
The laggard fluidized bed reactor (1) of the dispersion of plate (2)；Gas material, liquid material and addition in fluidized-bed reactor (1)
Catalyst contacts to form solid phase polyolefin, and solid phase polyolefin is continuously or intermittently drawn from reactor.Gas rich in hydrogen
It is higher that at least one temperature is formed in the upper area (17) of reactor fluidized bed, hydrogen content is high, the low region of ethylene contents,
The materials such as the less gas of hydrogen, condensed fluid fluidized-bed reactor (1) lower area (16) formed a temperature compared with
Low, hydrogen content is low, the high region of ethylene contents.
In a preferred embodiment of the invention, the catalyst includes ziegler-nata, metallocene or non-cyclopentadienyl gold
Metal catalyst or their mixture, preferably Ziegler-Natta catalyst.
In a preferred embodiment of the invention, the alkene is selected from ethylene and the alpha-olefin less than 18 carbon atoms,
Optimal ethylene, propylene.The comonomer is selected from ethylene and alpha-olefin, and wherein alpha-olefin can be butylene, hexene, octene, the last of the ten Heavenly stems
Alkene etc. is less than the alpha-olefin of 18 carbon atoms, preferably butylene, hexene and octene.
In a preferred embodiment of the invention, the gas material for entering membrane separation device (3) and the fluidisation
The mass ratio of unreacting gas material derived from bed reactor outlet is 0.05:1~1:1, preferably 0.4:1~0.8:1.
In a preferred embodiment of the invention, the gas of hydrogen is rich in described in membrane separation device (3) exit
The ratio between hydrogen quality is 0.2:1~0.95:1 in gas material described in material and the membrane separation device (3) inlet, preferably
0.5:1~0.8:1.
In a preferred embodiment of the invention, the separative efficiency of the gas-liquid separation is 30~100%, preferably 60
~100%.
In a preferred embodiment of the invention, in the polymerization process, can by condensing agent, co-catalyst,
Chain-transferring agent, antistatic agent and inert gas are passed directly into fluidized-bed reactor (1)；It can also be passed directly to circulation loop
In；A portion can also be passed into fluidized-bed reactor (1), other are passed into circulation loop.
In a preferred embodiment of the invention, the condensing agent is selected from the saturated straight chain of C4~C8 or the alkane of branch
At least one of at least one of hydrocarbon and the cycloalkane of C4~C8, preferably pentane, isopentane, hexane.
In a preferred embodiment of the invention, the co-catalyst is that Ziegler-Natta catalyst is anti-in fluidized bed
Answer the co-catalyst needed when using in device (1), for example, alkyl aluminum compound, alkyl lithium compounds, aluminum dialkyl oxygen compound,
Alkyl zinc compound, alkyl boron compound；Preferably alkyl aluminum compound, more preferably triethyl aluminum, triisobutyl aluminium
Or tri-n-hexyl aluminum.
The chain-transferring agent is conventional chain-transferring agent, these compounds include hydrogen and metal alkyl, such as hydrogen.
The antistatic agent is antistatic agent known to those skilled in the art, for example, double stearic acid aluminium, ethoxylation amine,
Polysulfone copolymer, one or more composition such as polymerized polyamines, oil-soluble sulfonic acid.
The inert gas is conventional inert gas, such as nitrogen, ethane, propane, preferably nitrogen.
In a preferred embodiment of the invention, which is characterized in that the reaction pressure of the reaction is 0.5~10MPa,
It is preferred that 1.5~5MPa；Temperature is 40~150 DEG C, preferably 50~120 DEG C；In the gas-liquid mixture liquid content be 5~
50wt%, preferably 10~25wt%.
In this bright preferred embodiment, the manufacture of polyolefins device includes:
Fluidized-bed reactor (1) carries out polymerization reaction for alkene；
Reactor distributing plate (2), the bottom position inside fluidized-bed reactor enter reactor distributing plate for making
(2) gas or liquid material of lower space are evenly dispersed enters fluidized-bed reactor (1)；
Membrane separation device (3) is used to from separating hydrogen in gas material derived from the fluidized-bed reactor (1) top,
Wherein membrane separation device (3) entrance is connected with fluidized-bed reactor (1) top material, membrane separation device (3) outlet
Material rich in hydrogen is connected with compressor (9), membrane separation device (3) outlet hydrogen few material and compressor (4)
It is connected；
First compressor (4), the flowing of the material for maintaining the hydrogen few；
First Heat Exchanger (5) is connected, for removing heat from fluid with the first compressor (4) outlet material；
Gas-liquid separator (6) is connected with the First Heat Exchanger (5) outlet material, cold for separating circulating current part
The solidifying gas and liquid two phases mixture formed；
Condensate tank (7), for storing the liquid material isolated from the gas-liquid separator (6)；
Pumping unit (8), for the liquid material in the condensate tank (7) to be introduced the fluidized-bed reactor (1)；
Second compressor (9), for improving the pressure of the material rich in hydrogen；
Second heat exchanger (10) is connected with the second compressor (9) outlet material, for from the object rich in hydrogen
Heat is removed in material, the second heat exchanger (10) outlet material is connected with the fluidized-bed reactor (1)；
First fluid pipeline (11), for catalyst to be introduced the fluidized-bed reactor (1)；
Second fluid pipeline (12), for taking out solid polyolefin from the fluidized-bed reactor (1)；
Third fluid line (13), for chain-transferring agent to be introduced the circulation loop；
4th fluid line (14), for olefinic monomer, inert component to be introduced the fluidized-bed reactor (1) or described
Circulation loop；
5th fluid line (15), for cooling medium, comonomer etc. to be introduced the fluidized-bed reactor (1) or institute
The circulation loop stated.
Compared with prior art, the present invention has the advantage that
1) bimodal/broad peak polyethylene is produced in single-reactor, process flow is simple, and equipment is less, and operation is easy.
2) by the effect of the second-order separation of membrane separation device and gas-liquid separator, temperature gradient and hydrogen in reactor are enhanced
The concentration gradient of gas obtains the polyolefin products for having both good moulding processability and physical property.
Detailed description of the invention
Fig. 1 is the flow diagram of ethylene polymerization system according to one embodiment of the present invention.
Specific embodiment
The object of the present invention is to provide a kind of new polyolefin productions, and being particularly suitable for production molecular weight distribution has
The polyolefin of bimodal/broad peak distribution.Term " bimodal " used in the present invention refers to molecular weight distribution, and there are two local maximums
Value, " broad peak " refer to that molecular weight distributing index is greater than the molecule of conventional Ziegler Natta polymer obtained in single reactor
Measure profile exponent.The present invention will be described in detail with attached drawing with reference to embodiments, and the embodiment and attached drawing are only used for pair
The present invention is illustratively described, and any restrictions can not be constituted to protection scope of the present invention, all to be included in this hair
Reasonable changes and combinations in bright invention teachings each fall within protection scope of the present invention.
Fig. 1 is the flow diagram of ethylene polymerization system according to embodiment of the present invention, comprising:
The fluidized-bed reactor 1 of polymerization reaction is carried out for alkene；
For making gas or the evenly dispersed reactor distributing plate 2 into fluidized-bed reactor 1 of liquid material；
For from the membrane separation device 3 for separating hydrogen derived from 1 top of fluidized-bed reactor in gas material；
First compressor 4 of the Flow of Goods and Materials for maintaining the hydrogen few；
For removing the First Heat Exchanger 5 of heat from fluid；
For separating the gas-liquid separator 6 of the gas and liquid two phases mixture of circulating current partial condensation formation；
For storing the condensate tank 7 from the isolated liquid material of the gas-liquid separator 6；
For the liquid material in the condensate tank 7 to be introduced to the pumping unit 8 of the fluidized-bed reactor 1；
For improving the second compressor 9 of the material pressure rich in hydrogen；
For removing the second heat exchanger 10 of heat from the material rich in hydrogen；
For catalyst to be introduced to the first fluid pipeline 11 of the fluidized-bed reactor 1；
For taking out solid polyolefin second fluid pipeline 12 from the fluidized-bed reactor 1；
For chain-transferring agent to be introduced to the third fluid line 13 of the circulation loop；
For olefinic monomer, inert component to be introduced to the 4th fluid of the fluidized-bed reactor 1 or the circulation loop
Pipeline 14；
For cooling medium, comonomer etc. to be introduced the 5th of the fluidized-bed reactor 1 or the circulation loop the
Fluid line 15.
Unreacted gas material is exported from fluidized-bed reactor 1 and is exported, and part or all of gas material enters UF membrane
Device 3, the hydrogen-rich gas derived from the membrane separation device 3 through overcompression, it is cooling after introduce 1 middle part of fluidized-bed reactor and upper zone
Domain.The used membrane separation device 3 of the present invention is used to enrichment and separation gas, is used as in membrane separation device using hydrogen film and separates material
Material is low to alkene, the equimolecular selective penetrated property of nitrogen since selective penetrated property of the hydrogen film to hydrogen is high.Hydrogen is in hydrogen film two
Side pressure difference under the action of reach the lower side of pressure, formed hydrogen-rich gas, and the higher side of hydrogen film pressure be hydrogen compared with
Few gas.Term " hydrogen-rich gas " used herein refers to the relatively high gas of hydrogen content.Gas rich in hydrogen
In the formation of upper area 17 of reactor fluidized bed, at least one temperature is higher, and hydrogen content is high, the low region of ethylene contents, should
The polyolefin molecular weight that region clustering generates is low, and melt index is larger, is conducive to the moulding processability for improving polyolefin.In order to
The load of membrane separation device 3 is reduced, preferred operation scheme is that the hydrogen of supplement is introduced circulation loop after the second compressor.
The few gas of the hydrogen derived from the membrane separation device 3, with the Fresh olefin and portion supplemented outside reaction system
After gas mixing derived from dividing at the top of fluidized reactor 3, gas-liquid separator 6, gas-liquid separator are entered after overcompression, condensation
6 liquid materials separated partly or entirely introduce the middle part of fluidized reactor 1 under from different location above reactor distributing plate 2
Portion region；Remaining liq material and gas material enter 2 lower space of reactor distributing plate, by point of reactor distributing plate 2
Dissipate laggard fluidized bed reactor 1；Gas material, liquid material and the catalyst of addition contact shape in fluidized-bed reactor 1
At solid phase polyolefin.The materials such as the less gas of hydrogen, condensed fluid form one in the lower area of fluidized-bed reactor 1
Temperature is lower, and hydrogen content is low, the high region 16 of ethylene contents, and the polyolefin molecular weight which generates is high, and melting refers to
Number is smaller, is conducive to the physical property for improving polyolefin.
Acutely, the polyolefin that region 16 and region 17 generate can achieve good mixing for Granules in Fluidized Bed mixing, according to
The requirement of the molecular weight distribution of actual product by adjusting UF membrane efficiency, and then changes the reaction ring in region 16 and region 17
Border, to produce the polyolefin products that molecular weight has the characteristics that bimodal/broad peak.
Examples 1 to 3 provides the illustrative methods for producing bimodal/broad peak polyolefin, and wherein Examples 1 and 2 are
Ethylene and the butene trade mark produce bimodal/broad peak polyethylene, and embodiment 3 is that ethylene and the hervene copolymer trade mark produce the poly- second of broad peak
Alkene.Comparative example 1 is to produce polyethylene in single fluidised bed reactor.
Embodiment 1
The broad peak polyethylene of a kind of olefine polymerizing process shown in Fig. 1, by ethylene, 1- butylene, hydrogen, nitrogen, isoamyl
Alkane, high active titanium catalyst, TEAL co-catalyst introduce fluidized-bed reactor 1, pressure 2.4MPa, and fluidized-bed reactor 1 is kept
Dense bed state, recycle stock enter in fluidized-bed reactor bottom, and the superficial linear velocity in a column of gas material is 0.63m/s, maintain stream
The fluidisation of polyethylene powder in fluidized bed reactor 1.UF membrane is fully entered from the gas material of 1 Base top contact of fluidized-bed reactor
Device 3, membrane separation device 3 separate 50% hydrogen from recyclegas, are formed and are rich in hydrogen stream stock and hydrogen content
Low stream stock.Fluidized-bed layer, hydrogen are introduced at the middle part of fluidized-bed reactor 1 after stream stock-traders' know-how overcompression rich in hydrogen is cooling
The low stream stock-traders' know-how overcompression of content, cooling, gas-liquid separation are introduced into fluidized-bed reactor 1 from the lower section of reactor distributing plate 2.?
The ratio of the lower hydrogen of fluidized-bed reactor and ethylene is 0.18:1, and the ratio of 1- butylene and ethylene is 0.28:1, reaction temperature
Degree is 76 DEG C, instantaneous melt index 1.33g/10min, density 0.9112g/cm3.In the top hydrogen and ethylene of fluidized bed product
Ratio be 0.32:1, the ratio of 1- butylene and ethylene is 0.26:1, and reaction temperature is 88 DEG C, instantaneous melt index 9.40g/
10min, density 0.9152g/cm3.The melt index of final products is 3.54g/10min, density 0.9132g/cm3, molecular weight
Profile exponent is 6.5.
Embodiment 2
The bimodal polyethylene of a kind of olefine polymerizing process shown in Fig. 1, by ethylene, 1- butylene, hydrogen, nitrogen, isoamyl
Alkane, high active titanium catalyst, TEAL co-catalyst introduce fluidized-bed reactor 1, pressure 2.15MPa, and fluidized-bed reactor 1 is kept
Dense bed state, recycle stock enter in fluidized-bed reactor bottom, and the superficial linear velocity in a column of gas material is 0.65m/s, maintain stream
The fluidisation of polyethylene powder in fluidized bed reactor 1.UF membrane is fully entered from the gas material of 1 Base top contact of fluidized-bed reactor
Device 3, membrane separation device 3 separate 80% hydrogen from recyclegas, are formed and are rich in hydrogen stream stock and hydrogen content
Low stream stock.Fluidized-bed layer, hydrogen are introduced at the middle part of fluidized-bed reactor 1 after stream stock-traders' know-how overcompression rich in hydrogen is cooling
The low stream stock-traders' know-how overcompression of content, cooling, gas-liquid separation are introduced into fluidized-bed reactor 1 from the lower section of reactor distributing plate 2.?
The ratio of the lower hydrogen of fluidized-bed reactor and ethylene is 0.20:1, and the ratio of 1- butylene and ethylene is 0.16:1, reaction temperature
Degree is 80 DEG C, instantaneous melt index 1.22g/10min, density 0.9218g/cm3.In the top hydrogen and ethylene of fluidized bed product
Ratio be 0.79:1, the ratio of 1- butylene and ethylene is 0.13:1, and reaction temperature is 90 DEG C, instantaneous melt index 67.13g/
10min, density 0.9333g/cm3.The melt index of final products is 9.05g/10min, density 0.9275g/cm3, molecular weight
Profile exponent is 8.9.
Embodiment 3
The broad peak polyethylene of a kind of olefine polymerizing process shown in Fig. 1, by ethylene, 1- hexene, hydrogen, nitrogen, isoamyl
Alkane, high active titanium catalyst, TEAL co-catalyst introduce fluidized-bed reactor 1, pressure 2.15MPa, and fluidized-bed reactor 1 is kept
Dense bed state, recycle stock enter in fluidized-bed reactor bottom, and the superficial linear velocity in a column of gas material is 0.72m/s, maintain stream
The fluidisation of polyethylene powder in fluidized bed reactor 1.UF membrane is fully entered from the gas material of 1 Base top contact of fluidized-bed reactor
Device 3, membrane separation device 3 separate 80% hydrogen from recyclegas, are formed and are rich in hydrogen stream stock and hydrogen content
Low stream stock.Fluidized-bed layer, hydrogen are introduced at the middle part of fluidized-bed reactor 1 after stream stock-traders' know-how overcompression rich in hydrogen is cooling
The low stream stock-traders' know-how overcompression of content, cooling, gas-liquid separation are introduced into fluidized-bed reactor 1 from the lower section of reactor distributing plate 2.?
The ratio of the lower hydrogen of fluidized-bed reactor and ethylene is 0.08:1, and the ratio of 1- hexene and ethylene is 0.20:1, reaction temperature
Degree is 74 DEG C, instantaneous melt index 0.15g/10min, density 0.9225g/cm3.In the top hydrogen and ethylene of fluidized bed product
Ratio be 0.33:1, the ratio of butylene and ethylene is 0.17:1, and reaction temperature is 92 DEG C, instantaneous melt index 2.98g/
10min, density 0.9334g/cm3.The melt index of final products is 0.67g/10min, density 0.9279g/cm3, molecular weight
Profile exponent is 7.3.
Comparative example 1
Comparative example produces polyethylene in single vapor phase method reactor, and catalyst is high active titanium catalyst, reaction temperature
It is 90 DEG C, pressure 2.3MPa, the ratio of hydrogen and ethylene is 0.18:1, melt index 1.2g/10min, and density is
0.9267g/cm3, molecular weight distributing index 4.9.
Claims (10)
1. a kind of polyene hydrocarbon synthesis process, which is characterized in that described method includes following steps:
1) unreacted gas material is exported from fluidized-bed reactor (1) outlet, part or all of gas material enters UF membrane
Device (3)；
2) from the derived gas material rich in hydrogen of membrane separation device (3) through overcompression and cooling, reactor middle part and
Upper area introduces fluidized-bed reactor (1), forms circulation loop；
3) the less gas material of the hydrogen content derived from membrane separation device (3), olefinic monomer and fluidized-bed reactor (1) top
Portion exports and does not enter into the gas material mixing of membrane separation device (3), into gas-liquid separator (6) after overcompression, cooling；
4) liquid material separated in gas-liquid separator (6) passes through condensate tank (7) and pumping unit (8), partly or entirely draws
The middle part of fluidized bed reactor (1) and lower area；The remaining liq material of gas-liquid separator (6) and gas material are from reacting
Fluidized-bed reactor (1) is introduced below device distribution grid (2)；
5) gas material, liquid material are contacted with the catalyst of addition, are reacted and form solid phase polyene in fluidized-bed reactor (1)
Hydrocarbon；
Wherein, dense-phase fluidized is kept inside the fluidized-bed reactor (1)；Continuously or intermittently from fluidized-bed reactor
(1) polyolefin is exported in；And into fluidized-bed reactor (1) or circulation loop introduce olefinic monomer, catalyst, comonomer,
Condensing agent, co-catalyst, chain-transferring agent, antistatic agent and inert gas；Wherein the circulation loop is fluidized-bed reactor
(1) outlet material again returns to the fluid line that fluidized-bed reactor (1) is passed through.
2. the method according to claim 1, wherein the olefinic monomer is selected from ethylene or less than 18 carbon atoms
One of alpha-olefin or a variety of.
3. the method according to claim 1, wherein the gas material for entering membrane separation device (3) and institute
Stating fluidized-bed reactor (1) and exporting the mass ratio of derived unreacting gas material is 0.05:1 ~ 1:1.
4. method according to claim 1, which is characterized in that be rich in hydrogen described in membrane separation device (3) exit
The ratio between hydrogen quality and hydrogen quality in gas material described in the membrane separation device (3) inlet are in the gas material of gas
0.95:1~0.2:1。
5. the method according to claim 1, wherein the separative efficiency of the gas-liquid separator (6) be 30~
100%。
6. method according to claim 1-5, which is characterized in that, can will be cold in the polymerization process
Solidifying agent, co-catalyst, chain-transferring agent, antistatic agent and inert gas are passed directly into the fluidized-bed reactor (1)；It can also be with
It is passed directly in circulation loop；A portion can also be passed into the fluidized-bed reactor (1), other are passed into
In circulation loop.
7. the method according to claim 1, wherein the catalyst is ziegler-nata, metallocene or non-cyclopentadienyl
Metallic catalyst or their mixture.
8. the method according to claim 1, wherein the condensing agent is selected from the saturated straight chain or branch of C4 ~ C8
Alkane and at least one of the cycloalkane of C4 ~ C8.
9. the method according to claim 1, wherein the reaction pressure of the reaction is 0.5 ~ 10MPa；Temperature is
40~150 ℃。
10. a kind of manufacture of polyolefins device for implementing method as described in claim 1, which is characterized in that the manufacture of polyolefins
Device includes:
Fluidized-bed reactor (1) carries out polymerization reaction for alkene；
Reactor distributing plate (2), the bottom position inside fluidized-bed reactor enter reactor distributing plate (2) for making
The gas or liquid material of lower space are evenly dispersed to enter fluidized-bed reactor (1)；
Membrane separation device (3), for from separating hydrogen in gas material derived from the fluidized-bed reactor top, wherein described
Membrane separation device (3) entrance is connected with fluidized-bed reactor (1) top material, and membrane separation device (3) outlet is rich in hydrogen
Material be connected with the second compressor (9), the membrane separation device (3) outlet hydrogen few material and the first compressor (4)
It is connected；
First compressor (4), the flowing of the material for maintaining the hydrogen few；
First Heat Exchanger (5) is connected, for removing heat from fluid with the first compressor (4) outlet material；
Gas-liquid separator (6) is connected, for separating circulating current partial condensation shape with the First Heat Exchanger (5) outlet material
At gas and liquid two phases mixture；
Condensate tank (7), for storing the liquid material isolated from the gas-liquid separator (6)；
Pumping unit (8), for the liquid material in the condensate tank (7) to be introduced the fluidized-bed reactor (1)；
Second compressor (9), for improving the pressure of the material rich in hydrogen；
Second heat exchanger (10) is connected, for from the material rich in hydrogen with the second compressor (9) outlet material
Heat is removed, the second heat exchanger (10) outlet material is connected with the fluidized-bed reactor (1)；
First fluid pipeline (11), for catalyst to be introduced the fluidized-bed reactor (1)；
Second fluid pipeline (12), for taking out solid polyolefin from the fluidized-bed reactor (1)；
Third fluid line (13), for chain-transferring agent to be introduced the circulation loop；
4th fluid line (14), for olefinic monomer, inert component to be introduced the fluidized-bed reactor (1) or the circulation
Circuit；
5th fluid line (15), for cooling medium, comonomer etc. to be introduced the fluidized-bed reactor (1) or described
Circulation loop.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710232955.3A CN107098991B (en) | 2017-04-11 | 2017-04-11 | A kind of olefine polymerizing process and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710232955.3A CN107098991B (en) | 2017-04-11 | 2017-04-11 | A kind of olefine polymerizing process and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107098991A CN107098991A (en) | 2017-08-29 |
| CN107098991B true CN107098991B (en) | 2019-04-16 |
Family
ID=59675804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710232955.3A Active CN107098991B (en) | 2017-04-11 | 2017-04-11 | A kind of olefine polymerizing process and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107098991B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11485636B2 (en) | 2018-02-22 | 2022-11-01 | Borealis Ag | Process |
| EP3980177A1 (en) * | 2019-06-04 | 2022-04-13 | Borealis AG | Process and reactor assembly for the enhancement of hydrodynamics in a gas-solids fluidized bed reactor |
| CN112300312B (en) * | 2020-11-05 | 2023-03-14 | 杭州双安科技有限公司 | Synthetic method of polyethylene |
| CN114524893B (en) * | 2021-02-01 | 2024-04-02 | 中国石油化工股份有限公司 | Ethylene polymer and process for producing the same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08151410A (en) * | 1994-11-29 | 1996-06-11 | Ube Ind Ltd | Method of recovering olefin monomer |
| CN1190099A (en) * | 1997-02-06 | 1998-08-12 | 弗纳技术股份有限公司 | Method of olefin polymerization utilizing hydrogen pulsing, products made therefrom, and method of hydrogeation |
| CN1424333A (en) * | 2002-12-06 | 2003-06-18 | 浙江大学 | Polymer composition production |
| CN1684987A (en) * | 2002-09-27 | 2005-10-19 | 联合碳化化学及塑料技术公司 | Improved control of resin properties |
| CN101952328A (en) * | 2007-11-20 | 2011-01-19 | 尤尼威蒂恩技术有限公司 | Methods for making polyolefins |
| CN102037022A (en) * | 2008-05-22 | 2011-04-27 | 埃克森美孚研究工程公司 | Polymerization processes for broadened molecular weight distribution |
| CN102432708A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工集团公司 | Fluidized bed polymerization reactor |
| CN104592426A (en) * | 2014-12-24 | 2015-05-06 | 浙江大学 | Method and device for polymerization of olefins |
| CN104628904A (en) * | 2015-01-28 | 2015-05-20 | 浙江大学 | Method for preparing olefin polymer by utilizing multiple temperature reaction areas |
-
2017
- 2017-04-11 CN CN201710232955.3A patent/CN107098991B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08151410A (en) * | 1994-11-29 | 1996-06-11 | Ube Ind Ltd | Method of recovering olefin monomer |
| CN1190099A (en) * | 1997-02-06 | 1998-08-12 | 弗纳技术股份有限公司 | Method of olefin polymerization utilizing hydrogen pulsing, products made therefrom, and method of hydrogeation |
| CN1684987A (en) * | 2002-09-27 | 2005-10-19 | 联合碳化化学及塑料技术公司 | Improved control of resin properties |
| CN1424333A (en) * | 2002-12-06 | 2003-06-18 | 浙江大学 | Polymer composition production |
| CN101952328A (en) * | 2007-11-20 | 2011-01-19 | 尤尼威蒂恩技术有限公司 | Methods for making polyolefins |
| CN102037022A (en) * | 2008-05-22 | 2011-04-27 | 埃克森美孚研究工程公司 | Polymerization processes for broadened molecular weight distribution |
| CN102432708A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工集团公司 | Fluidized bed polymerization reactor |
| CN104592426A (en) * | 2014-12-24 | 2015-05-06 | 浙江大学 | Method and device for polymerization of olefins |
| CN104628904A (en) * | 2015-01-28 | 2015-05-20 | 浙江大学 | Method for preparing olefin polymer by utilizing multiple temperature reaction areas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107098991A (en) | 2017-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107098991B (en) | A kind of olefine polymerizing process and device | |
| CN105199031B (en) | A kind of olefine polymerizing process and device | |
| CN104592426B (en) | Method and device for polymerization of olefins | |
| CN102639571B (en) | Process for producing polyolefins | |
| JP4467185B2 (en) | Polymerization catalyst | |
| US10266625B2 (en) | Olefin polymerization apparatus and olefin polymerization process | |
| CN107303478B (en) | Fluidized bed reactor, olefin polymerization apparatus, and olefin polymerization method | |
| CA2608318A1 (en) | Process for the gas-phase polymerization of olefins | |
| CN103387628A (en) | Alkene polymerization system and method | |
| CN105732849B (en) | A kind of olefinic polymerization device and method | |
| CN105339393A (en) | Multistage process for producing polyethylene compositions | |
| US20220177609A1 (en) | Olefin polymerization method and system | |
| US11505625B2 (en) | Polymerization process including discharging polyolefin particles from a gas-phase polymerization reactor | |
| US11400428B2 (en) | Fluidized-bed reactor having multiple recycle gas inlet nozzles | |
| CN101378832A (en) | Method for transforming a loop reactor | |
| CN104558332B (en) | A method of preparing polymer | |
| BR112019008570B1 (en) | OLEFIN POLYMERIZATION PROCESS IN A GAS PHASE REACTOR THAT HAS THREE OR MORE POLYMERIZATION ZONES | |
| CN104558349A (en) | Method for performing olefin polymerization by fluidized bed facility, olefin polymer prepared by method and application of olefin polymer | |
| KR102333339B1 (en) | Method for improving cooling performance of gas solid olefin polymerization reactor | |
| CN106957382B (en) | A kind of method and apparatus of dynamic operation production polyolefin | |
| CN112300312B (en) | Synthetic method of polyethylene | |
| CN104558333B (en) | A method of preparing olefin polymer | |
| CN115073634B (en) | Process for producing poly-1-butene and poly-1-butene | |
| CN106928383B (en) | Olefinic polymerization device and method | |
| US20230016760A1 (en) | Apparatus and process for the gas-phase polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |