CN109517098A - A kind of offline pre-polymerized catalyst and propylene homo close and the method for combined polymerization - Google Patents
A kind of offline pre-polymerized catalyst and propylene homo close and the method for combined polymerization Download PDFInfo
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- CN109517098A CN109517098A CN201710845013.2A CN201710845013A CN109517098A CN 109517098 A CN109517098 A CN 109517098A CN 201710845013 A CN201710845013 A CN 201710845013A CN 109517098 A CN109517098 A CN 109517098A
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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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Abstract
The present invention provides a kind of offline pre-polymerized catalyst, it is prepared using following steps: will first be suitable for the Ziegler-Natta catalyst component of olefinic polymerization, organic aluminum cocatalyst, optionally uses external electron donor, offline prepolymerization occurs at -20~60 DEG C with propylene, obtains the control of pre-polymerization multiple in 0.1~15g polypropylene/g catalyst pre-polymerized catalyst；Then time not shorter than 2 seconds in -20~50 DEG C of environment are stored at before being used for polymerization reaction, storage form is dry powder or is scattered in the slurries of atent solvent.During preparing olefin polymer in gas phase polymerization apparatus using the offline pre-polymerized catalyst, it can effectively avoid that pipeline scaling caused by propylene polymerization, blocking occur in the feed pipe of gas phase polymerization apparatus, it can further solve in gas-phase polymerization that polymeric reaction temperature fluctuation is big, is easy to produce hot spot, lead to that polymer lumps, fine powder content is high in polymer powders.
Description
Technical field
The present invention relates to a kind of propylene polymerization or the methods of combined polymerization, specifically, being related to a kind of low naked using low power number
The offline pre-polymerized catalyst of catalyst activity, and the method for carrying out in gas-phase apparatus propylene homo conjunction or combined polymerization.
Background technique
High activity polyolefin catalyst is at present in polyolefin industry large-scale use, but at the beginning of the catalyst of the type
The activity that begins is relatively high, often brings that polymerization reaction initial stage temperature fluctuation is larger, polymerization reaction is easy to produce hot spot, causes to polymerize
Object agglomeration, catalyst breakage, lead to problems such as fine powder content in polymer powders high.To solve the problems, such as this, it is necessary to reduce
The initial activity of catalyst, while improving the intensity of catalyst particle.
Thus industrially applying more extensive method at present is to introduce " online " pre-polymerization reactor, such as Spheripol
Technique, Spherizone etc. take " online " prepolymerization technology substantially.The case where industrial application, shows using prepolymerization
The polymarization method for prodcing polyacrylates of technique, polymeric reaction temperature control is steady, polymerization reaction without hot spot, do not generate block, polymer powder substantially
Fine powder content is lower in material.But since the residence time of catalyst particle in continuous pre-polymerization reactor, there are bigger differences
Different, the residence time is longer in the reactor for some particles, and other is then relatively short, so obtained catalyst granules is simultaneously
It is not the prepolymer comprising equivalent.For example, the catalyst that continuous pre-polymerization reactor obtains in patent CN200880019432.X
The content of prepolymer is not consistent in particle, but an average value.Therefore, always some catalyst particle prepolymerization
Degree causes later period decay of activity serious very much deeply, and some catalyst particle is almost without prepolymerization, thus unavoidably
Cause reactor to control the unstable and high problem of fine powder content.Simultaneously as continuity method prepolymerization technology route is long,
Control relative complex, there is also more problems in practical application.
And for gas-phase process, it is being designed without if Innovene technique, Novolen technique, Unipol technique
" online " pre-polymerization reactor, such technique fluctuate larger, polymerization reaction there are polymeric reaction temperature and are easy to produce hot spot, causes
The problems such as fine powder content is high in polymer lumps, polymer powders." online " prepolymerization technology is introduced into the Gaseous Polymerization of PP
The above problem can be alleviated to a certain extent, but the intrinsic inhomogeneities of catalyst obtained by continuity method prepolymerization technology is not
It can thoroughly solve the problems, such as；And newly-increased prepolymerization device and technique mean to increase new investment and bigger equipment changes
Dynamic, this is often unpractical.
In conclusion using " online " prepolymerization technology can not thoroughly solve polypropylene polymerization reaction temperature fluctuation compared with
Greatly, polymerization reaction is easy to produce hot spot, leads to that polymer lumps, fine powder content is high in polymer powders, especially right
It is natively even more so for the Gaseous Polymerization of PP without designing " online " pre-polymerization reactor.
To solve the above-mentioned problems, offline pre-polymerized catalyst can be used, do not changing polymerization technique process, also do not needing
In the case where increasing new equipment, achievees the purpose that increase granule strength, reduces fine powder content.
Pre-polymerized catalyst is that organic aluminum cocatalyst and optional external electron donor is cooperated to carry out by catalytic component
The polymer that ethylene or propylene polymerization wrap up in attached certain multiple obtains, and helps due to remaining a certain amount of organo-aluminium in final component and urges
Agent, even if being completely removed by sufficiently washing still difficulty, therefore pre-polymerized catalyst encounters under the conditions of suitable temperature, pressure
Not adding organo-aluminium co-catalyst polymerization reaction can occur for olefinic monomer.It is well known that propylene gas phase polymerization apparatus
Feed system be usually the catalyst slurry for using propylene monomer that will be prepared with atent solvent as dispersing agent and agent delivery etc.
Feed inlet is transported to by pipeline and is sprayed into polyplant again, since pre-polymerized catalyst contains organo aluminum catalyst, in pipeline
In encounter propylene polymerization reaction can occur, the polymer generated in pipeline can fouling wall built-up, can be blocked when serious pipeline or into
Material mouth.
In order to avoid blocking feeding line and feed inlet, the method generallyd use have: 1) using the low temperature propylene list of pre-cooling
Body cools down to pre-polymerized catalyst to reach and reduce activity, reduces the purpose of polymerization reaction in pipeline；2) prepolymerization catalysis is improved
Travelling speed of the agent composition in pipeline increases flushing effect, shortens feed time to reduce the polymerization in pipeline；3) periodically
Pipeline inner wall is polished, to reduce polymer architecture wall built-up.
Summary of the invention
To solve the above problems, the present invention provides " offline " pre-polymerization of a kind of low pre-polymerization multiple and low " naked catalyst activity "
Catalyst is closed, using the pre-polymerized catalyst, gas phase polymerization apparatus can be avoided to feed in propylene homo conjunction or copolymerization process
Pipeline scaling and blocking, and solve in gas phase polymerization apparatus that temperature fluctuation is big, is also easy to produce hot spot, fine polymer powder content height etc. and ask
Topic.
Propylene polymerization or combined polymerization are carried out using the pre-polymerized catalyst another object of the present invention is to provide a kind of
Method.
In order to achieve the object of the present invention, the present invention provide a kind of low pre-polymerization multiple and low " naked catalyst activity " " from
Line " pre-polymerized catalyst, uses following steps to prepare:
1) the Ziegler-Natta catalyst component of olefinic polymerization, organic aluminum cocatalyst will be suitable for, optionally using outer
With propylene offline prepolymerization occurs at -20~60 DEG C for electron donor, obtains the control of pre-polymerization multiple in 0.1~15g poly- third
Alkene/g catalyst；
2) catalyst that step 1) obtains is stored in -20~50 DEG C of environment the time not before being used for polymerization reaction
Shorter than 2 seconds, storage form was dry powder or is scattered in the slurries of atent solvent, so that the " naked of organo-aluminium is not added in evaluation after storage
Catalyst activity " is not higher than 200g polymer/g catalyst h-1。
Ziegler-Natta catalyst group is divided into comprising titanium compound, magnesium compound, halogen and to interior in step 1) of the present invention
Ziegler-Natta catalyst component, such as CN201510043331.8 in the prior art etc. can be used in electron compound
Deng.
The general formula of the titanium compound is TiXN(OR’)4-N, it is C that R ', which is carbon atom number, in formula1~C20Alkyl, X is halogen
Element, N=0~4.Titanium compound of the invention includes halogenated titanium or alkoxy titanium, and the halogenated titanium is titanium tetrachloride, tetrabromo
Change titanium or titanium tetra iodide；The alkoxy titanium such as methoxytitanium trichloride, ethyoxyl titanium trichloride, propoxyl group tri-chlorination
Titanium, nbutoxytitanium trichloride, dimethoxy titanium chloride, diethoxy titanium chloride, dipropoxy titanium chloride, two positive fourths
Oxygroup titanium chloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride or three n-Butoxyl titanium-chlorides.
It can be used in mixed way using one or more in these halogenated titaniums.Wherein preferably use titanium tetrachloride.
The magnesium compound is selected from least one: XnMg(OR)2-n, MgCl2MROH, R2-nMgXn, MgCl2/SiO2,
MgCl2/Al2O3Or the mixture of magnesium halide and alcohol titanium, the number that m is 0.1~6 in formula, 0≤n≤2, X are halogen, and R is hydrogen or C1
~C20Alkyl.The preferred magnesium chloride of magnesium compound of the invention, magnesium ethylate, butoxy magnesium, magnesium chloride ethanol adducts, chlorination
Magnesium butanol adduct, liquid magnesium compound (such as magnesium chloride being dissolved in the mixed solution containing heteroatomic compound etc.).
The internal electron donor compound is selected from the Lewis alkali containing one or more electronegativity groups, preferably be selected from ethers,
The electron donor compound of esters, ketone and amine, more preferably from two ethers, aromatic dicarboxylic acid esters, succinate compound, aromatics
With aliphatic diol esters and aminated compounds.
Organic aluminum cocatalyst of the present invention is general formula AlRnX(3-n)Organo-aluminum compound, R is hydrogen, carbon atom in formula
The alkyl of number 1~20；X is halogen, and n is the integer of 0≤n≤3.The alkyl compound or alkoxy of the preferred aluminium of organo-aluminum compound
Compound, preferably triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, Dichloroethyl
Aluminium and methylaluminoxane, more preferably triethyl aluminum, triisobutyl aluminium and methylaluminoxane.
It can be used or do not use external electron donor in step 1) of the present invention, when there is external electron donor, external electron donor can
It is R selected from general formula1 xR2 ySi(OR)zSilicone compounds, R, R in formula1And R2For identical or different C1~C18Alkyl, appoint
Choosing contains hetero atom, and x, y, z meets: 0≤x, y < 4,0 < z≤4, and x+y+z=4.Preferably methylcyclopentyl dimethoxy silicon
Alkane, aminomethyl phenyl dimethoxysilane, Cyclohexylmethyldimethoxysilane, propyl trimethoxy silicane, isobutyl group trimethoxy
Base silane, second, isobutyl dimethoxy silane, dicyclopentyl dimethoxyl silane or diisopropyl dimethoxy silane.
The molar ratio of titanium elements is 0.1~100:1 in the dosage and catalytic component of the organo-aluminum compound, preferably
0.1~80:1, more preferable 0.5~40:1.
Prepolymerization of the present invention can also be passed through hydrogen when being passed through propylene simultaneously, and the molar ratio of propylene and hydrogen is 0~
100, preferably 0~50, more preferable 0~30.
The temperature of offline prepolymerization is preferably -15~45 DEG C, more preferably -10~40 DEG C.
The weight that the content for the olefin polymer that the prepolymerization generates accounts for catalytic component is 1~99%, preferably 5
~90%, more preferable 10~80%.When the present invention can be by adjusting the amount for entering the alkene of reactor in the unit time, reaction
Between, alkene is poly- in the control such as molar ratio of metallic element catalytic component in reaction temperature, activator level and alkene catalyst
Close the content of object.
The prepolymerization can occur in the presence of inert media, the inert media include pentane, n-hexane,
Normal heptane, normal octane, hexamethylene, toluene, ethylbenzene, dimethylbenzene.
In order to avoid olefin polymerization catalysis particle prepolymerization is uneven, preferably pre-polymerization reactor is grasped using batch process
Make, i.e., each batch catalyst for polymerization of propylene undergoes the identical reaction mechanism mechanism of reaction, and catalyst residence time distribution unevenness is avoided to cause
The inhomogeneities of catalyst particle.
" pre-polymerization multiple " refers to the weight ratio of the polyolefin and catalytic component that contain in gained pre-polymerized catalyst.This hair
The bright pre-polymerization multiple is preferably 0.1~10g polypropylene/g catalyst.Pre-polymerization multiple can by control prepolymerization conditions realize,
Adjustable prepolymerization conditions include but is not limited to: prepolymerized temperature, time, pressure, flow of monomer.
Ziegler-natta catalyzed system must use main catalyst component and organic aluminum cocatalyst could be to alkene simultaneously
Monomer is polymerize, and (can be contained polyolefin when ziegler-natta catalyzed system contains only main catalyst component, or is free of polyene
Hydrocarbon), when without the use of organic aluminum cocatalyst and other auxiliary agents, it is referred to as " naked catalyst ".Do not make when if usually polymerizeing
With organic aluminum cocatalyst, then " naked catalyst " can not show catalytic activity, but micro- due to remaining in pre-polymerized catalyst
The organo-aluminium of amount, even if therefore under certain temperature and pressure polymerize when do not add organo-aluminium co-catalyst, " naked catalyst "
Polymerization activity can be shown to olefinic monomer." the naked catalyst activity " of the application refers to pre-polymerized catalyst and propylene list only
Body is contacted, the activity obtained when not adding organic aluminum cocatalyst and other auxiliary agents in contact process.Evaluation condition can be adopted
With general general bulk polymerization evaluation condition in the industry, temperature and pressure range is general general condition range in the industry.Generally comment
Valence condition are as follows: 60~80 DEG C of bulk polymerization temperature, 2.5~4.0MPa of pressure." naked catalyst activity " range of the present invention is excellent
Choosing is not higher than 100g polymer/g catalyst h-1.The method that naked catalyst activity is lower than above range is controlled, including but unlimited
In: use the catalytic component of different carriers or internal electron donor, the abundant washing of pre-polymerized catalyst, pre-polymerized catalyst
Inactivation treatment (for example used in the Lewis alkali inactivators such as alcohol, ester or system when including prepolymerization and mix trace oxygen or non-low
Temperature storage, micro- oxygen content ambient storage, etc.).
The mode that pre-polymerized catalyst components are stored offline and pack, transport, store and use can be with dry powder
Form also can be configured to slurries.Inertia dispersing agent described in step 2) of the present invention is alkane solvent or aromatic solvent or mineral
The mixture of oily or above-mentioned arbitrary substance.Preferred aliphat alkane solvents, such as n-hexane, normal heptane, white oil, mineral oil.
Preferably -10~45 DEG C, more preferable 0~40 DEG C of the offline storage temperature of the pre-polymerized catalyst.
Storage time is not preferably shorter than 2 minutes, is not shorter than more preferably 30 minutes, is not shorter than 1 hour most preferably.
After the stored off-line that pre-polymerized catalyst of the invention passes through above-mentioned condition, especially in low-purity inert gas
Under environment, " naked catalyst activity " can be further reduced, to be conducive to the steady charging of gas-phase apparatus.
The catalysis of the offline prepolymerization with low pre-polymerization multiple and low " naked catalyst activity " is used the present invention also provides a kind of
The method that agent prepares olefin polymer in gas phase polymerization apparatus, includes the following steps:
1) by the pre-polymerized catalyst with inertia dispersing agent be configured to concentration be 1~60% slurries, with propylene or its
The olefinic monomer of his C2~C12 is sent into gas-phase reactor, and olefinic monomer temperature is 0~60 DEG C, pre-polymerized catalyst slurries and list
Rate of the body fluid in feed pipe is < 6m/s；
2) pre-polymerized catalyst carries out propylene homo in gas-phase reactor, or carries out propylene and other optional C2
~C12 olefinic monomer is copolymerized.
Pre-polymerized catalyst concentration of slurry described in step 1) of the present invention is preferably 1~55%, further preferably 1~
50%.The monomer temperature is preferably 10~50 DEG C.The fluid flow rate is preferably not higher than 4m/s.
Gas-phase reactor of the present invention is gas-phase fluidized-bed, vertical gas phase stirred tank or horizontal gas phase stirred tank.
Pre-polymerized catalyst of the present invention in gas-phase reactor with propylene and/or other optional C2~C12 alkene
Comonomer carries out polymerization or combined polymerization.Alkene preferably has: linear alkene such as: ethylene, 1- butylene, 1- amylene, 1- hexene, 1- heptan
Alkene, 1- nonene, 1- decene；Branched-chain alkene is such as: 3-methyl-1-butene and 4-methyl-1-pentene；Alkadienes is such as: butadiene, ethylene
Cyclopentene and vinylcyclohexene.These alkene can be independent or a variety of be used in mixed way.The polymerization or co-polymerization temperature are
20 to 120 DEG C, preferably 40 to 100 DEG C, most preferably 50 to 90 DEG C.
Propylene homo of the present invention closes and process for copolymerization is especially suitable in bubble agitation bed and gas-phase fluidized-bed
Deng the gas-phase polymerization polypropylene technique application of no prepolymerization technology, by using with low pre-polymerization multiple and low " naked catalyst activity "
" offline " pre-polymerized catalyst, be avoided that in gas-phase polymerization feed pipe and propylene polymerization occur, do not needed in feed pipe using
Low temperature propylene monomer, without improve material travelling speed, do not need to pipeline inner wall polish, can not blocking pipeline realize it is suitable
Benefit charging；And further solve the larger, polymerization reaction of polypropylene polymerization reaction temperature fluctuation and be easy to produce hot spot, lead to polymer
The problems such as fine powder content is high in agglomeration, polymer powders.
Specific embodiment
The present invention is further described with embodiment below, is conducive to be better understood by the present invention and its advantage, effect, but
The embodiment is merely to illustrate the present invention rather than the limitation present invention.
Characterization
The measurement of polymer content in pre-polymerized catalyst components
The ingredient of solid catalyst of about 1 gram of precise (m1), is immersed in the sulfuric acid solution of 50 milliliters of 1mol/L, surpasses
Sound, concussion processing 30 minutes, filtering is washed 3 times with 50 ml deionized waters later, is dried in vacuo to obtain solid powder (m2), by
This calculates the content of polymer: m2/m1*100%.
The measurement of fine powder content
It is measured according to ASTME1187, for (being equivalent to partial size below 80 mesh screen of polypropylene and being defined as carefully less than 180um)
Powder, for (being equivalent to partial size below 200 mesh screen of polyethylene less than 75um) and being defined as fine powder.
The measurement of naked catalyst activity
In 5L stainless steel cauldron after nitrogen is sufficiently displaced from, (prepolymerization) catalyst 30mg is added, 10mL is then added
Hexane rinses charge line, adds 2L (under standard state) hydrogen and 2.5L purification propylene, is warming up to 70 DEG C, at this temperature
Polymerization reaction 1 hour.After reaction, reaction kettle is cooled down and stops stirring discharge reaction product, be dried to obtain polymer, counted
Calculate activity.
Propylene gas phase polymerisation conditions 1
Catalyst slurry by feed pipe be added into horizontal gas-phase polymerization reactor (basic size are as follows: internal diameter 400mm,
Long 1100mm, volume 138L) in.Control each component concentration in reactor are as follows: hydrogen 1vol%, propylene 95vol%, nitrogen
4vol%.Controlling reaction temperature is 66~68 DEG C, reactor pressure 2.5MPa, the residence time 50 minutes.External electron donor uses
Cyclohexylmethyldimethoxysilane, flow 0.6g/h；Catalyst charge is 1g/h (calculating by dry powder), triethyl aluminum inlet amount
For 3.6g/h.
Comparative example 1
1, the preparation of catalytic component:
Catalytic component is prepared using 4 method of embodiment in CN201510043331.8, analysis Ti content is 2.9%.
2, propylene gas-phase polymerization
Catalytic component is configured to the slurries of concentration 30% (wt) with white oil, is sent into charge line with 10 DEG C of propylene
In, controlling flowing velocity of the slurries in feed pipe is 4m/s.It is anti-that catalyst by feed pipe is added into horizontal gas-phase polymerization
It answers and carries out propylene polymerization in device.Polymerizing condition is shown in above-mentioned " propylene gas phase polymerisation conditions 1 ".Experimental result is shown in Table 1.
Comparative example 2
1, the preparation of pre-polymerized catalyst:
In 5 mouthfuls of flasks with stirring that 1L is sufficiently displaced from through nitrogen, 400mL n-hexane is added in flask, is added
Polypropylene catalyst prepared by 10g comparative example 1 is added in the triisobutyl aluminium hexane solution 20ml of 0.5mol/L, controlled at
30 DEG C, constant temperature for 5 minutes；It is passed through propylene by mass flowmenter, the addition speed that control is passed through propylene is 200g/h, reacts 60 points
Clock.Stop to enter propylene, through n-hexane washing, filtering, solid 156.1g is obtained after vacuum drying, analysis Ti content is 0.2
(wt) %, polymer content are 93.5 (wt) %, and the pre-polymerization multiple of propylene is 14.6.Pre-polymerized catalyst is in dry powder form in height
Purity nitrogen (99.999%, O2≤ 0.001%) the naked polymerization evaluation of catalyst is used for after storing 1 hour under protecting at -10 DEG C.Naked catalysis
Agent activity is 367g polymer/g catalyst.
2, propylene gas-phase polymerization
Above-mentioned pre-polymerized catalyst is used for gas-phase polymerization.Using and comparison 1 identical feed conditions and polymerizing condition, no
Same is that catalyst is sent into charge line with 5 DEG C of propylene, and polymerization result is shown in Table 1.
Comparative example 3
1, the preparation of pre-polymerized catalyst:
In 5 mouthfuls of flasks with stirring that 1L is sufficiently displaced from through nitrogen, 400mL n-hexane is added in flask, is added
Polypropylene catalyst prepared by 10g comparative example 1 is added in the triisobutyl aluminium hexane solution 20ml of 0.5mol/L, controlled at
20 DEG C, constant temperature for 5 minutes；It is passed through propylene by mass flowmenter, the addition speed that control is passed through propylene is 100g/h, reacts 60 points
Clock.Stop to enter propylene, through n-hexane washing, filtering, solid 63.3g is obtained after vacuum drying, analysis Ti content is 0.4
(wt) %, polymer content are 84.1 (wt) %, and the pre-polymerization multiple of propylene is 5.3.Pre-polymerized catalyst is directly used in catalyst
Naked polymerization evaluation.Naked catalyst activity is 218g polymer/g catalyst.
2, propylene gas-phase polymerization
Above-mentioned pre-polymerized catalyst is directly used in gas-phase polymerization without offline storage.Using with comparative example 1 it is identical into
Material strip part and polymerizing condition.Polymerization result is shown in Table 1.
Embodiment 1
1, the preparation of pre-polymerized catalyst:
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 300mL n-hexane is added in flask, adds
Enter the triisobutyl aluminium hexane solution 20ml of 0.5mol/L, polypropylene catalyst prepared by 10g comparative example 1 is added, controls temperature
It is 5 DEG C, constant temperature for 5 minutes；It is passed through propylene by mass flowmenter, the addition speed that control is passed through propylene is 20g/h, reacts 60 points
Clock.Stop to enter propylene, through n-hexane washing, filtering, solid 26.4g is obtained after vacuum drying, analysis Ti content is 1.1
(wt) %, polymer content are 62.0 (wt) %, and the pre-polymerization multiple of propylene is 1.6.
Pre-polymerized catalyst is in dry powder form in industrial nitrogen (99.999%, O2≤ 0.001%) at 25 DEG C under protecting
The naked polymerization evaluation of catalyst is used for after storage 48 hours.Naked catalyst activity is 23g polymer/g catalyst.
2, propylene gas-phase polymerization
Catalytic component is configured to the slurries of concentration 35% (wt) with white oil, is sent into charge line with 10 DEG C of propylene
In, controlling flowing velocity of the slurries in feed pipe is 3m/s.It is anti-that catalyst by feed pipe is added into horizontal gas-phase polymerization
It answers and carries out propylene polymerization in device.Polymerizing condition is shown in above-mentioned " propylene gas phase polymerisation conditions 1 ".Experimental result is shown in Table 1.
Embodiment 2
Pre-polymerized catalyst preparation with embodiment 1, using with the identical feed conditions of embodiment 1 and polymerizing condition, it is different
, controlling flowing velocity of the catalyst slurry in feed pipe is 2m/s.
Embodiment 3
Pre-polymerized catalyst preparation with embodiment 1, using with the identical feed conditions of embodiment 1 and polymerizing condition, it is different
, catalyst is in 25 DEG C of propylene feeding charge line.
Embodiment 4
1, the preparation of pre-polymerized catalyst:
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 300mL n-hexane is added in flask, adds
Enter the triisobutyl aluminium hexane solution 20ml of 0.5mol/L, polypropylene catalyst prepared by 10g comparative example 1 is added, controls temperature
It is 10 DEG C, constant temperature for 5 minutes；It is passed through propylene by mass flowmenter, the addition speed that control is passed through propylene is 40g/h, reaction 60
Minute.Stop to enter propylene, through n-hexane washing, filtering, solid 35.2g is obtained after vacuum drying, analysis Ti content is 0.8
(wt) %, polymer content are 71.4 (wt) %, and the pre-polymerization multiple of propylene is 2.5.Pre-polymerized catalyst is in dry powder form in height
The naked polymerization evaluation of catalyst is used for after storing 720 hours under purity nitrogen protection at 20 DEG C.Naked catalyst activity is that 37g polymer/g is urged
Agent.
2, propylene gas-phase polymerization
Catalytic component is configured to the slurries of concentration 25% (wt) with white oil, is sent into charge line with 15 DEG C of propylene
In, controlling flowing velocity of the slurries in feed pipe is 1.7m/s.Catalyst is added into horizontal gas-phase polymerization by feed pipe
Propylene polymerization is carried out in reactor.Polymerizing condition is shown in above-mentioned " propylene gas phase polymerisation conditions 1 ".Experimental result is shown in Table 1.
Embodiment 5
Pre-polymerized catalyst preparation is with embodiment 4, and pre-polymerized catalyst is in dry powder form at 30 DEG C under High Purity Nitrogen protection
The naked polymerization evaluation of catalyst is used for after storage 1180 hours.Naked catalyst activity is 19g polymer/g catalyst.Using and implement
The identical polymerizing condition of example 4, unlike, catalytic component is configured to the slurries of concentration 30% (wt) with white oil, with 20 DEG C
Propylene be sent into charge line, controlling flowing velocity of the slurries in feed pipe is 2m/s.
Embodiment 6
Pre-polymerized catalyst is prepared with embodiment 5.Using with the identical polymerizing condition of embodiment 5, unlike, catalyst
It is sent into charge line with 10 DEG C of propylene, controlling flowing velocity of the slurries in feed pipe is 1.8m/s.
Embodiment 7
1, the preparation of pre-polymerized catalyst:
In 5 mouthfuls of flasks with stirring that 500ml is sufficiently displaced from through nitrogen, 300mL n-hexane is added in flask, adds
Enter the triisobutyl aluminium hexane solution 20ml of 0.5mol/L, polypropylene catalyst prepared by 10g comparative example 1 is added, controls temperature
It is 10 DEG C, constant temperature for 5 minutes；It is passed through propylene by mass flowmenter, the addition speed that control is passed through propylene is 15g/h, reaction 60
Minute.Stop to enter propylene, through n-hexane washing, filtering, solid 20.9g is obtained after vacuum drying, analysis Ti content is 1.4
(wt) %, polymer content are 52.2 (wt) %, and the pre-polymerization multiple of propylene is 1.1.Pre-polymerized catalyst is in dry powder form in work
The naked polymerization evaluation of catalyst is used for after storing 0.5 hour under industry nitrogen protection at 25 DEG C.Naked catalyst activity is 32g polymerization
Object/g catalyst.
2, propylene gas-phase polymerization
Catalytic component is configured to the slurries of concentration 30% (wt) with white oil, is sent into charge line with 25 DEG C of propylene
In, controlling flowing velocity of the slurries in feed pipe is 2m/s.It is anti-that catalyst by feed pipe is added into horizontal gas-phase polymerization
It answers and carries out propylene polymerization in device.Polymerizing condition is shown in above-mentioned " propylene gas phase polymerisation conditions 1 ".Experimental result is shown in Table 1.
Embodiment 8
Pre-polymerized catalyst is prepared with embodiment 7.Using with the identical polymerizing condition of embodiment 7, unlike, catalyst
It is sent into charge line with 30 DEG C of propylene, controlling flowing velocity of the slurries in feed pipe is 2.5m/s.
Embodiment 9
Pre-polymerized catalyst preparation is with embodiment 7, the difference is that pre-polymerized catalyst is protected in High Purity Nitrogen in dry powder form
Under 25 DEG C store 320 hours after be used for the naked polymerization evaluation of catalyst.Naked catalyst activity is 29g polymer/g catalyst.It adopts
With with the identical polymerizing condition of embodiment 7, unlike, catalyst is sent into charge line with 10 DEG C of propylene, control slurries
Flowing velocity in feed pipe is 1.2m/s.
Table 1
[remarks] a: unit is g polymer/g catalyst；
B: unit is kg polymer/g titanium.
It can be seen that comparative example 1 by 1 data of table to be directly used in gas-phase polymerization without pre-polymerized catalyst, although
There is no scale formation in feed pipe, but the fine powder content generated in polymeric kettle is high.The pre-polymerization of 2 pre-polymerized catalyst of comparative example
Multiple is high, and naked catalyst activity is high, although gained polypropelene fine powder content significantly reduces, even if the propylene monomer temperature in charging
When spending lower (5 DEG C), and higher travelling speed (5m/s) is used, is not avoided that pipeline scaling still.3 prepolymerization of comparative example catalysis
Agent pre-polymerization multiple is not high, but without stored off-line processing, naked catalyst activity is higher, there is scale formation in the feed line.
The pre-polymerized catalyst pre-polymerization multiple 1.6 that Examples 1 to 3 uses, in 25 DEG C of lower purified nitrogen after stored off-line 48h
Naked catalyst activity is lower, when propylene monomer temperature is 10~25 DEG C in feeding line, when travelling speed relatively slow (2~3m/s),
Almost without scale formation.The pre-polymerized catalyst pre-polymerization multiple of embodiment 4~6 is 2.5, in High Purity Nitrogen, in higher temperature
Under degree after (20~30 DEG C) (720~1180h) storages for a long time, it can keep in feed pipe under low travelling speed without dirt.Implement
Pre-polymerized catalyst has lower naked catalyst activity in example 7~9, under higher propylene monomer temperature (10~30 DEG C),
With lower travelling speed (1.2~2.5m/s) charging, non-scaling in feed pipe can be kept.In addition, the temperature of Examples 1 to 9
Fluctuation is both less than the temperature fluctuation of comparative example 1, and the fine powder that fine powder content is also substantially lower than comparative example 1 in final polymer contains
Amount.Illustrate not have to reduce propylene in feed pipe using the pre-polymerized catalyst of low pre-polymerization multiple, low naked catalyst activity
Monomer temperature, without improve slurries travelling speed in the case where, avoid the structure and clogging in feed pipe, and can reduce
Polymerization temperature fluctuation and reduction fine polymer powder content, avoid agglomerating in reactor.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Term used herein is only to be illustrated to specific embodiment, is not intended to and limits the invention.
Unless otherwise defined, all terms (including technical terms and scientific terms) used herein with it is of the art
The understanding of those skilled in the art is identical.Must also it is clear that, it is usually fixed in such as dictionary in addition to having specific definition herein
The term of justice should be construed to can have the consistent meaning in the context of this specification and the relevant technologies, without what should be explained
Idealization or excessively formalization.
Claims (15)
1. a kind of offline pre-polymerized catalyst, which is characterized in that it uses following steps to prepare:
1) the Ziegler-Natta catalyst component of olefinic polymerization, organic aluminum cocatalyst will be suitable for, optionally using outside to electricity
With propylene offline prepolymerization occurs at -20~60 DEG C for daughter, obtains the control of pre-polymerization multiple in 0.1~15g polypropylene/g
The pre-polymerized catalyst of catalyst；
2) pre-polymerized catalyst that step 1) obtains is stored at the time in -20~50 DEG C of environment before being used for polymerization reaction
It is not shorter than 2 seconds, storage form is dry powder or is scattered in the slurries of atent solvent, so that organo-aluminium is not added in evaluation after storage
" naked catalyst activity " is not higher than 200g polymer/g catalyst h-1。
2. offline pre-polymerized catalyst according to claim 1, which is characterized in that ziegler-natta catalyzed in step 1)
Agent group is divided into comprising titanium compound, magnesium compound, halogen and internal electron donor compound.
3. offline pre-polymerized catalyst according to claim 1, which is characterized in that organic aluminum cocatalyst is general formula
AlRnX(3-n)Organo-aluminum compound, R is the alkyl of hydrogen, carbon atom number 1-20 in formula；X is halogen, and n is the integer of 0≤n≤3.
4. offline pre-polymerized catalyst according to claim 1, which is characterized in that the external electron donor is selected from general formula
R1 xR2 ySi(OR)zSilicone compounds, R, R in formula1And R2For identical or different C1~C18Alkyl, optionally contain miscellaneous original
Son, x, y, z meet: 0≤x, y < 4,0 < z≤4, and x+y+z=4.
5. offline pre-polymerized catalyst according to claim 1, which is characterized in that the dosage of the organo-aluminum compound with
The molar ratio of titanium elements is 0.1~100:1, preferably 0.1~80:1, more preferable 0.5~40:1 in catalytic component.
6. offline pre-polymerized catalyst according to claim 1, which is characterized in that go back while being passed through when the addition propylene
The molar ratio of hydrogen, propylene and hydrogen is 0~100, preferably 0~50, more preferable 0~30.
7. offline pre-polymerized catalyst according to claim 1, which is characterized in that the offline prepolymerization in the step 1)
The temperature of reaction is -15~45 DEG C, more preferably -10~40 DEG C.
8. offline pre-polymerized catalyst according to claim 1, which is characterized in that pre-polymerization multiple described in step 1) is
0.1~10g polypropylene/g catalyst.
9. offline pre-polymerized catalyst according to claim 1, which is characterized in that step (2) storage temperature -10~
45 DEG C, more preferable 0~40 DEG C；The storage time is not preferably shorter than 2 minutes, is not shorter than 30 minutes more preferably, most preferably not short
In 1 hour；" the naked catalyst activity " is preferably no greater than 100g polymer/g catalyst h-1。
10. a kind of propylene homo closes or the method for combined polymerization, prepolymerization described in any one of claim 1-9 is used to be catalyzed
Agent is polymerize, and is included the following steps:
1) pre-polymerized catalyst is configured to the slurries that concentration is 1~60% with inertia dispersing agent, with propylene or other C2~
C12Olefinic monomer be sent into gas-phase reactor, olefinic monomer temperature be 0~60 DEG C, pre-polymerized catalyst slurries and monomer liquid exist
Rate in feed pipe is < 6m/s；
2) pre-polymerized catalyst carries out propylene homo in gas-phase reactor, or carries out propylene and other optional C2~C12
Olefinic monomer is copolymerized.
11. propylene homo according to claim 10 closes or the method for combined polymerization, which is characterized in that pre- described in step 1)
Polymerization catalyst concentration of slurry is preferably 1~55%, and further preferably 1~50%.
12. propylene homo according to claim 10 closes or the method for combined polymerization, which is characterized in that single described in step 1)
Temperature is preferably 10~50 DEG C.
13. propylene homo according to claim 10 closes or the method for combined polymerization, which is characterized in that flowed described in step 1)
Body flow rate is preferably not higher than 4m/s.
14. propylene homo according to claim 10 closes or the method for combined polymerization, which is characterized in that the gas-phase reactor
For gas-phase fluidized-bed, vertical gas phase stirred tank or horizontal gas phase stirred tank.
15. propylene homo according to claim 10 closes or the method for combined polymerization, which is characterized in that third described in step 2)
Alkene and/or other optional C2~C12Olefin comonomer carry out polymerization or co-polymerization temperature be 20~120 DEG C, preferably 40~
100 DEG C, most preferably 50~90 DEG C.
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| CN111100225A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Propylene polymerization method and device |
| CN116041573A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for prepolymerizing polyolefin catalyst, polyolefin polymerization method and application thereof |
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| US20010051697A1 (en) * | 1998-09-14 | 2001-12-13 | Morse David Bell | Off-line preactivated catalysts and prepolymerized catalysts |
| CN101679559A (en) * | 2007-06-14 | 2010-03-24 | 博里利斯技术公司 | Process for the production of propylene copolymers using a prepolymerised catalyst |
| CN105646742A (en) * | 2016-03-25 | 2016-06-08 | 任丘市利和科技发展有限公司 | Olefin polymer-containing catalyst component and catalyst used for olefin polymerization |
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| US20010051697A1 (en) * | 1998-09-14 | 2001-12-13 | Morse David Bell | Off-line preactivated catalysts and prepolymerized catalysts |
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