CN100497404C - Prepylene multistage polymerization technology and polymerization reactor - Google Patents
Prepylene multistage polymerization technology and polymerization reactor Download PDFInfo
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- CN100497404C CN100497404C CNB031507573A CN03150757A CN100497404C CN 100497404 C CN100497404 C CN 100497404C CN B031507573 A CNB031507573 A CN B031507573A CN 03150757 A CN03150757 A CN 03150757A CN 100497404 C CN100497404 C CN 100497404C
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- 238000006116 polymerization reaction Methods 0.000 title claims description 128
- 238000005516 engineering process Methods 0.000 title description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002002 slurry Substances 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 95
- 238000002309 gasification Methods 0.000 claims description 84
- 239000007789 gas Substances 0.000 claims description 54
- 238000012725 vapour phase polymerization Methods 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 46
- 238000006073 displacement reaction Methods 0.000 claims description 45
- 239000012071 phase Substances 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 238000010574 gas phase reaction Methods 0.000 claims description 39
- 239000004743 Polypropylene Substances 0.000 claims description 31
- 229920001155 polypropylene Polymers 0.000 claims description 31
- -1 polypropylene Polymers 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 238000010791 quenching Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 7
- 239000012808 vapor phase Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 210000004907 gland Anatomy 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 12
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000012685 gas phase polymerization Methods 0.000 description 7
- 230000002902 bimodal effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
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Abstract
A multi-stage polymerizing process of propene for preparing the homopolypropene or copolypropene with adjustable and wide molecular weight distribution includes the first-stage reaction; the slurry polymerizing in liquid propene to obtain low-molecular polymer and the second-stage reaction: polymerizing in horizontal reactor to obtain high-molecular polymer. Said horizontal reactor is composed of gasifying separation region, displacing region, isolating region and gas-phase copolymerizing region.
Description
Technical field the invention belongs to petrochemical industry.
Content of the present invention is about adopting slurry polymerization and the combined technology of horizontal retort vapour phase polymerization, carry out the above α-olefin-copolymerization of propylene homopolymerization and propylene and ethene, C4 and C4, production molecular weight distribution adjustable homopolymer polypropylene or method and horizontal polymerization reactor of multipolymer in very wide scope.
Background technology has been simplified flow process because the polyolefin process development of technology comprises succeeding in developing of effective catalyst, has improved the quality of product.In recent years, in conjunction with the exploitation that polyolefin products is used, molecular weight distribution more and more is subject to people's attention in the advantage of improving the performance of product, improve aspect the workability of material than the bimodal polyethylene of broad, bimodal acrylic resin.
As everyone knows, for synthetic molecular weight distributes than the polyolefin homopolymer or the multipolymer of broad, need the reactor more than two.Usually at the less product of first step reaction production molecular weight ratio, the bigger product of production molecular weight ratio is reacted in the second stage.The patent that has is that the first step is reflected in the inert solvent (in the liquid propylene body of being everlasting when producing polypropylene) and carries out slurry polymerization, the equal dimerization product that the production molecular weight ratio is less; The second stage is reflected in the vapour phase polymerization carries out the copolymerized product that the production molecular weight ratio is bigger.Existing division is as follows:
(1) the Japanese Patent spy open clear 58-216735, European chemical news 1983.4。18 page 4
By the method for leaving the heating of first step reactor slurry pipe clamp cover being made the liquid-phase vaporization in the slurry, gas-solid is separated, solid powder is carried the part gas phase secretly and is entered second stage reactor.Owing to enter the gas phase amount of carrying secretly in the material of second stage reactor than higher, therefore still have some hydrogen to be carried and enter second stage reactor, the high-molecular weight product has brought difficulty for second stage reactor is produced very, has limited the width of molecular weight distribution.
(2) the Japanese Patent spy open clear 58-157807, clear 56-139520 (Mitsui oilings)
Increase a vapour phase polymerization fluidized-bed reactor between first step slurry polymerization and second stage gas-phase polymerization reactor, this reactor has solved above-mentioned 2 problems that enter second stage reactor to the problem of gas phase transition and a large amount of hydrogen of preventing to be dissolved in the slurry by slurry simultaneously.But flow process more complicated.
The second stage reactor of above-mentioned two kinds of patents all is a fluidized-bed reactor, belongs to all mixed-type reactor, so the difference between the powder individuality of its product is relatively big.When producing copolymerized product, the content of its comonomer of product that the residence time is very short is very low, may have 100% homopolymer pellets existence theoretically in copolymerized product, and this can have influence on the performance of product to a certain extent.
(3) clear 59-230010 (Amoco/Chisso) of Japanese Patent
Adopt 2 placed in-line horizontal gas-phase polymerization reactors to produce polypropylene product, the less product of first step reaction production molecular weight ratio, the bigger product of second stage reaction production molecular weight ratio.During production block copolymerization product, react the homopolymerization that carries out propylene, in second stage reaction the carrying out copolyreaction of propylene and ethene in the first step.
For the problem that the hydrogen that solves in the first step reactor outlet material enters second stage reactor in a large number, two cover gas locking devices need be set, on engineering huger system.Because catalyzer directly enters vapor phase polymerizer, is easy to generate focus.
(4) Chinese patent CN87100218 (Shanghai medicine designing institute)
The combined technology of the horizontal stirring tank gas-phase polymerization reactor in the second stage reactor and the second stage.Have first step slurry polymerization catalyzer good dispersity concurrently, be not easy to produce focus, the production efficiency height; Even the horizontal stirring tank in the second stage have than fluidized bed reactor equipment efficient height, catalyzer utilising efficiency height, product co-monomer content evenly in the product co-monomer content than higher or polymericular weight is very low and adaptability is more intense when causing powder to be clamminess a bit etc. advantage.But its weak point is: when needs were produced bimodal polypropylene, the hydrogen in the slurry that the first step is come out all entered second stage reactor, was difficult to the very wide polymkeric substance of production molecular weight distribution.
Summary of the invention the objective of the invention is to propose the combined technology of an improved slurry process and horizontal retort vapour phase polymerization, can regulate the alkene homopolymerization of molecular weight distribution or the continuous multi-stage polymeric manufacture method and the horizontal polymerization reactor of multipolymer in very wide scope.
Main contents of the present invention are:
(1) in the presence of the catalyzer of forming by high activated catalyst, aluminum alkyls, silane, adopt slurry polymerization and the combined technology of horizontal retort vapour phase polymerization, carry out the continuous multi-stage polymerization of propylene and propylene or propylene and ethene, C4 and the above alpha-olefin of C4.
(2) first step is polymerized to slurry polymerization.
In liquid propylene, as molecular weight regulator, carry out slurry polymerization with hydrogen.Generate the homopolymer of propylene or the multipolymer of propylene and ethene, C4 and the above alpha-olefin of C4.
The polymkeric substance that first step polymerization generates, it is little that its molecular weight ratio second stage polymerization generates.
The polymerization amount of first step slurry polymerization accounts for 20%～90% of total polymerization amount.
(3) second stage is aggregated in 1 and has horizontal type stir shaft, is made up of gasification disengaging zone, displacement zone, isolated area, gas phase polymerization district in the horizontal polymeric kettle of (perhaps only being made up of the disengaging zone of gasifying, gas phase polymerization district) and carries out.The slurries that leave first step slurry polymerization are introduced into the gasification disengaging zone of second stage polymerization horizontal retort, in this district because the effect of heat of polymerization makes liquid-phase vaporization in the slurries, most of hydrogen and part propylene are separated and leave horizontal retort, and the gas phase after leaving has at least a part to be liquefied.Polypropylene powder after separating most hydrogen and the part propylene enters the gas phase polymerization district, the polyreaction in gas phase polymerization district just can be carried out homopolymer that the production molecular weight ratio first step is big or multipolymer under the propylene of density of hydrogen of setting and setting and the monomeric ratio of copolymerization.
Second stage polymerization also can be composed in series by the still above-mentioned for sleeping in more than 2 or 2, and the gasification disengaging zone is in the 1st still for sleeping in.
It is big that the polymkeric substance that second stage polymerization generates, its molecular weight ratio first step polymerization generate.But also can generate the molecular weight polymkeric substance identical as required with first step polymerization.
(4) can between first step slurry polymerization and second stage horizontal retort vapour phase polymerization, an extractor be set, in extractor, add fresh liquid propylene will leave in the first step slurry polymerization be dissolved with random thing and low-molecular(weight)polymer extracts, the propylene that contains random thing and low-molecular(weight)polymer that leaves from the extractor top does not return first and second grade polymeric kettle of own same production line without refinement treatment; The slurry that leaves from the extractor bottom enters the horizontal polymeric kettle in the second stage.
This patent is above 4 and is propylene homopolymerization or the multipolymer continuous multi-stage polymeric manufacture method and the horizontal polymerization reactor that can regulate molecular weight distribution in very wide scope of characteristics.
The present invention about the more detailed description of polymerization process and horizontal polymerization reactor is:
First step polymerization is that first step polymerization also can add alpha-olefins such as a spot of ethene or C4 based on the propylene homopolymerization under the propylene liquid phase bulk slurry polymeric occasion.Polymerizing condition is: polymerization pressure is 2.2～6.5Mpa, and polymerization temperature is 55～95 ℃.The density of hydrogen molecular weight size that polymerization requires to produce according to the first step is decided general concentration＜20% of hydrogen in the polymeric kettle gas phase.In the still concentration of slurry general＜50% (Wt).First step polymeric polymeric kettle can be that vertical band stirs polymeric kettle, horizontal retort, endless tube.
Add first step polymeric catalyzer and can be the high activated catalyst through pre-polymerization, the mode of pre-polymerization can be intermittent mode, also can be continuous pre-polymerization mode.Under the condition of pre-polymerization continuously, high activated catalyst, aluminum alkyls, silane and part propylene are introduced into a prepolymerization kettle, under the high slightly condition of the polymerization pressure of temperature lower (generally more than 0 ℃, below 40 ℃, usually more than 10 ℃ below 20 ℃), pressure ratio first step slurry polymerization reactor, carry out 4～20 minutes continuous pre-polymerization.Catalyzer and propylene through continuous pre-polymerization enter first step slurry polymerization still again.
For some special trade mark that the random thing in the product and low-molecular(weight)polymer need be reduced as far as possible, be provided with an extractor in the flow process, leave slurries behind the first step slurry polymerization in extractor with the fresh propylene counter current contact, random thing and low-molecular(weight)polymer in the slurry are removed, and then enter second stage polymerization horizontal retort.
Because the special conditions of this technology, leave the inlet end that slurries (being provided with under the occasion of extractor to leaving the slurries of extractor) behind the first step slurry polymerization all enter second stage polymerization horizontal retort.At first the liquid phase of leaving in the slurries (under the occasion of extractor is set for leaving the slurries of extractor) of first step polymerization reactor to be gasified, most of hydrogen, propylene after the gasification are separated, can make second stage polymerization in very wide scope, to regulate under density of hydrogen and the propylene/comonomer ratio then and carry out polyreaction, for the foregoing reasons the horizontal polymerization reactor in the second stage is divided into two main functional zone: gasification disengaging zone and gas-phase copolymerization district.
The effect of gasification disengaging zone is: by the heat of polymerization of this district propylene (or comprise enter the second stage before slurry be heated), the hydrogen and the propylene that leave in the slurries of first step slurry polymerization are separated through gasification, because the equilibrium constant of hydrogen is very big, even partial gasification also can be evaporated the most of hydrogen in the liquid phase.Thereby can so that:
The vapour phase polymerization district can transfer homopolymerization or the copolymerization of carrying out propylene under condition and the propylene/comonomer ratio at arbitrarily adjustable hydrogen.
Gasification disengaging zone, gas-phase reaction district are arranged on in 1 still for sleeping in the time, and the centre has at least a baffle plate to be separated, and baffle plate is positioned at the following part leaving certain gaps uncovered by the economic plan of still material level of crouching, and polymer powders can enter the vapour phase polymerization district by the gasification disengaging zone by this breach.For the comonomer anti-channeling that prevents gas-phase reaction district when the copolymerization in the gasification disengaging zone, perhaps for too much the entering in the gas-phase reaction district of hydrogen of the disengaging zone that prevents to gasify, can 1 displacement zone be set at the afterbody (end that powder leaves) of gasification disengaging zone, stem (end that powder enters) in the vapour phase polymerization district is provided with 1 isolated area, feed propylene gas to the bottom of displacement zone and isolated area respectively, when displacement zone and isolated area were set, the baffle plate between gasification disengaging zone and the gas-phase reaction district was actually between displacement zone and isolated area.Between gasification disengaging zone and the displacement zone, between isolated area and the gas-phase reaction district baffle plate can be set, but 1 baffle plate also can be set as required respectively to strengthen displacement or isolated effect, leaving certain gaps uncovered by the economic plan on the baffle plate, guarantee to gasify gas phase between disengaging zone and the displacement zone, isolated area communicates with gas phase between the gas-phase reaction district, and powder can enter next district by breach.The flow direction according to polymkeric substance is passed through gasification disengaging zone, displacement zone, isolated area, vapour phase polymerization district successively.The working pressure in each district is identical, more than the low 0.1～0.2Mpa of first step polymerization, generally in 1.8～3.0Mpa scope.The service temperature of gasification disengaging zone is generally more than the dew point, below the softening temperature of polymkeric substance, minimum can be between bubble point and dew point; The polymerization temperature in gas-phase reaction district is more than the dew point that the reaction zone gas phase is formed, below the softening temperature of polymkeric substance.Generally in 50～130 ℃ of scopes, polymerization temperature commonly used is 70～80 ℃.Density of hydrogen is made the melting index that finished product requires and decide according to final, when producing bimodal polypropylene, seldom or not adds at the hydrogen of second stage polymerization adding.In vapour phase polymerization district part, according to the requirement of making finished product, or the gas-phase copolymerization of propylene gas-phase homopolymerization or propylene and ethene or alpha-olefins such as propylene and C4.
Second stage polymerization also can be in series with the horizontal retort of horizontal type stir shaft by 2 (or more than 2):
Its distributing style can be a horizontal retort that comprises gasification disengaging zone, displacement zone, isolated area, gas-phase reaction district and one or several the main horizontal retorts that are made of the gas-phase reaction district are composed in series; Also can be a horizontal retort that comprises gasification disengaging zone, displacement zone and one or several the main horizontal retorts that are made of the gas-phase reaction district are composed in series.The pressure of respectively distinguishing in same still for sleeping in is identical, link to each other crouch before the pressure reduction between the still high back low, keep more than 0.05～0.1Mpa, the polymerization temperature in each district is more than the dew point, below the softening temperature of polymkeric substance.
In the vapour phase polymerization district, 75～95% of second stage polymerization total amount generates in this district.Comonomer, polymerization single polymerization monomer add in this district, and when producing bimodal product, the hydrogen of regulating the molecular weight size adds to such an extent that seldom even do not add.Heat of polymerization is taken away by propylene or based on the gasification of the polymerization single polymerization monomer of propylene, after the liquefaction of outer circulation condenser, phlegma and not liquefied gas return the vapour phase polymerization district.
The ratio of first step polymerization amount and second stage polymerization amount is that 20～90%:80%～10% (weight) is preferably 40%～85%:60%～15% (weight).
The product of producing can be homopolymer or random copolymers, also can finally obtain the multiple copolymer of propylene, ethene, butene-1 or the above α-alkene of C4 at the copolymer of the gas-phase reaction district of placed in-line first horizontal retort production propylene, ethene, at placed in-line second horizontal retort adding propylene and butene-1 or the above α-alkene of C4.
Can add transparent base polypropylene nucleater production high-clarity polypropylene in the vapour phase polymerization district, also can add for other little auxiliary agent of polyreaction influence.
The external system of horizontal retort is roughly as follows:
---the external system of gasification disengaging zone: the venting port of slurries inlets, the propylene gas of leaving second stage polymerization horizontal retort gasification disengaging zone and hydrogen, reduce the propylene quench liquid inlet of bed temperature in case of necessity.
---propylene quench liquid inlet is left on inlet, top that the bottom of displacement zone, isolated area is left displacement gas respectively and isolated gas.
---the external system in vapour phase polymerization district.Mainly comprise the recirculation blower of outer circulation condenser, lime set jar, phlegma (quench liquid) reflux pump, noncondensable gas etc.Phlegma (quench liquid) and noncondensable gas are got back to the vapour phase polymerization district, do not allow to get back to gasification disengaging zone, displacement zone, isolated area when producing copolymerized product.
Do not need strict division the in gasification disengaging zone and vapour phase polymerization district come when the trade mark of the homopolymerization of production narrow molecular weight distribution or random copolymerization, displacement zone and isolated area no longer need.At this moment, the outer circulation condenser system that the gas phase that steams of gasification disengaging zone enters the vapour phase polymerization district, unreacting propylene is extracted out before by the outer circulation condenser in vapour phase polymerization district and is gone Propylene Recovery System.The quench liquid of gasification disengaging zone is from the chilling liquid pump 28 in vapour phase polymerization district.
Appended drawings 3 has shown the synoptic diagram of second stage polymerization horizontal retort.The second stage is aggregated in when carrying out in 1 horizontal retort that has a horizontal type stir shaft, and horizontal retort is made of gasification disengaging zone, two parts in vapour phase polymerization district at least, between separated with 1 baffle plate (accompanying drawing 3 221); Also can constitute by gasification disengaging zone, displacement zone, isolated area, vapour phase polymerization district four parts.Can be respectively between gasification disengaging zone and the displacement zone, between isolated area and the vapour phase polymerization district be separated with baffle plate (accompanying drawing 3 211,231).The slurries that first step slurry polymerization generates are by the 201 gasification disengaging zone that enter horizontal retort, the polymer powders of telling liquid propylene and most of hydrogen enters displacement zone by 211 baffle plates at the breach more than the charge level 212, and (211 baffle plates also can have below charge level and are similar to 222 breach and allow powder to pass through, not expression on the figure), enter isolated area by the breach 222 of baffle plate 221 below charge level then, enter vapour phase polymerization (231 baffle plates charge level below also can have be similar to 222 breach allow powder pass through, figure on expression) at the breach more than the charge level 232 by isolated area by 231 baffle plates again.The breach 222 of baffle plate 221 is below charge level, and the disengaging zone of therefore gasifying can not communicate to each other with the gas phase in vapour phase polymerization district.The bottom of displacement zone and isolated area feeds propylene gas respectively.The propylene gas major part that feeds displacement zone enters the gasification disengaging zone, and the propylene gas major part that feeds isolated area enters the vapour phase polymerization district, and the gas phase anti-channeling of avoiding the vapour phase polymerization district is to the gasification disengaging zone.Polymkeric substance discharge port 208 can be provided with a baffle plate at the end in vapour phase polymerization district before discharge port 208, constant with the charge level that keeps horizontal retort.Polymkeric substance leaves after the horizontal retort, and the gas of carrying secretly in the polymkeric substance returns the inlet of outer circulation condenser 26 after separating.The shape of the agitating vane P of the still for sleeping on the accompanying drawing 3 can be T type, square type, carve type, " open " type etc..
Hot system is removed in the outer circulation that has shown the vapour phase polymerization district of second stage polymerization reactor horizontal retort on the accompanying drawing 1: outer circulation condenser 26, lime set jar 27, lime set pump 28, recirculation blower 29.
The gasification disengaging zone of horizontal retort is as follows with the outside part that links: the inlet 201 of slurries, the outlet 220 of the gas after the gasification.When high temperature appears in gasification part, disengaging zone, can add liquid propylene by 210 and lower the temperature as quench liquid.
Under certain conditions, the slurries that come out by first step polymerization heat in course of conveying, so that enter that the liquid phase in the slurries has all gasified before the polymerization of the second stage, even the gas phase after the gasification was carried out preliminary the separation defunctionalization of the liquid-phase vaporization of the gasification disengaging zone of second stage polymerization reactor.Gu but gasification disengaging zone gas-isolating function can not disappear, displacement zone and isolated area are still indispensable, and the gasification disengaging zone still exists.
Gasification disengaging zone with horizontal retort in the accompanying drawing 2 is set to an independently horizontal polymeric kettle 2-1 separately, and the gas-phase reaction district of horizontal retort is set to an independently horizontal polymeric kettle 2-2 separately, and the two is the horizontal retort that has horizontal type stir shaft.The slurry 201 that leaves first step reaction enters gasification disengaging zone (being an independently horizontal polymeric kettle 2-1), the hydrogen and the liquid propylene 220 that steam through polymerization leave gasification disengaging zone (being an independently polymeric kettle 2-1) recovery, and solid powder is proceeded polymerization through the 221 gas-phase reaction districts (being an independently horizontal polymeric kettle 2-2) that enter horizontal retort.In that the gasification disengaging zone is set separately is one independently under the occasion of horizontal polymeric kettle, the polymerization pressure of gasification disengaging zone is than the pressure in gas-phase reaction district higher slightly (more than high 0.05～0.1Mpa), generally no longer add liquid propylene in this district, have only when high temperature appears in the part just to add liquid propylene toward the localized hyperthermia district through 210; Require under the very low situation of the density of hydrogen in vapour phase polymerization district at certain, the discharge zone of the disengaging zone of can in the past gasifying adds gas-phase propene enters the vapour phase polymerization district with minimizing as displacement gas 203 the hydrogen amount of carrying secretly.In the gasification disengaging zone is that horizontal retort 2-1 also can be provided with a baffle plate 211 under the occasion of horizontal retort 2-1 of 1 platform independent, and powder leaves gasification disengaging zone (still) 2-1 through 221 of gasification disengaging zone discharge zone after climbing over breach 212 above the baffle plate 211 again.Baffle plate 211, breach 212 are seen accompanying drawing 3.
The horizontal retort 3 of on the basis of the described flow process of Fig. 1, connecting again in the accompanying drawing 5, horizontal retort 3 has only 1 vapour phase polymerization district, but has oneself independently polymerization single polymerization monomer charging 306, comonomer feed 307, hydrogen feed 308 and outer circulation to remove hot system: condenser 36, lime set jar 37, chilling liquid pump 38, recirculation blower 39.
Shown 1 extractor of having connected between first step slurry polymerization and the second stage horizontal retort vapour phase polymerization on the accompanying drawing 6.Extractor is 1 vertical vessel that has stir shaft, enter from the top of extractor, solvent (fresh liquid propylene) enters from the bottom of extractor, the liquid propylene that has random thing, oligopolymer after the extraction leaves from the top of extractor, slurries after being extracted are discharged from the bottom of extractor, according to produce product require extractor can from flow process, to bypass or add less, do not add the solvent propylene to make not extraction of extractor.Leave first step polymeric slurries 104 on the accompanying drawing 6 and enter the horizontal vapor phase polymerizer in the second stage again with propylene 105 counter current contact rear slurries 201 in extractor, the propylene extraction liquid 106 that contains random thing, oligopolymer leaves extractor and goes to the propylene refining system cannot directly return the first step or the second stage polymeric kettle at extractor self place without purified propylene extraction liquid afterwards.
Accompanying drawing 7 has shown not to be needed strict division the in gasification disengaging zone and vapour phase polymerization district come the flow process when displacement zone and isolated area no longer need when the trade mark of the homopolymerization of production narrow molecular weight distribution or random copolymerization.At this moment, the outer circulation condenser system that the gas phase that steams of gasification disengaging zone enters the vapour phase polymerization district, the gas phase that unreacting propylene is steamed by the gasification disengaging zone with extract out after the recycle gas in vapour phase polymerization district mixes, before entering the outer circulation condenser, go Propylene Recovery System.The quench liquid of gasification disengaging zone is from the chilling liquid pump 28 in vapour phase polymerization district.
Embodiment is done an explanation below in conjunction with embodiment and accompanying drawing to the present invention.
Embodiment 1: first step slurry polymerization still is the vertical stainless steel stirring tanks of 1000 liters in the accompanying drawing 1, second stage polymeric kettle is that horizontal band central shaft stirring polymeric kettle is 600 liters, the L/D=4.5 titanium is that carried catalyst, mixing speed are 6-30 rev/mins, and opening for feed and discharge port lay respectively at the two ends of horizontal retort.Have 211,221,231,241 to add up to 4 baffle plates in the horizontal retort, the slurries inlet is the gasification disengaging zone to the zone between first baffle plate 211, zone between 211-221 is a displacement zone, zone between 221-231 is an isolated area, zone between 231-241 is the gas-phase reaction district, and 241-discharge port is a discharge zone.The gas phase of 221 baffle plate both sides can not communicate, and polymer stream can enter isolated area by displacement zone from the breach that this baffle plate is positioned at below the charge level.211, the breach of 231,241 baffle plates all is positioned at more than the charge level, and polymer stream can climb over baffle plate and be positioned at the above breach of charge level and enter next district.
Titanium is carried catalyst 6g/h, triethyl aluminum 56g/h is made into 20% (Wt) hexane solution 280g/h, silane 3g/h is made into 5% (Wt) hexane solution 60g/h, enters the stirring tank of a 15L with propylene 50Kg/h, carries out continuous prepolymerization under 12 ℃, 3.5Mpa condition.Slurries after pre-polymerization enter in the stirring tank 1 of first step polymeric kettle 1000 liters shown in Figure 1, add the propylene of 300Kg/h and an amount of hydrogen simultaneously in still, carry out the polymerization of propylene liquid phase bulk slurry.Polymerization temperature is 70 ℃, and the density of hydrogen of gas phase part is about 10%, and polymerization pressure is about 3.4Mpa.Leave first step polymerization 201 concentration of slurry and be about 33%, wherein polypropylene is about 120Kg/h, and its melting index is about 70.Enter the gasification disengaging zone of second stage polymerization 2 (horizontal retort) then.Slurries are by the polymerization of self propylene, and the propylene start vaporizer in the slurries comes out, and the hydrogen that wherein contains is very fast to steam from liquid phase.Because when producing bimodal polypropylene, the concentration of hydrogen differs greatly in first step polymerization and the second stage polymeric gas phase.For gas phase and the polypropylene powder that prevents to be evaporated, contain a large amount of hydrogen enters polymeric vapour phase polymerization district, the second stage; And in order to prevent that second stage polymeric gas phase (wherein can contain comonomer) anti-channeling to the gasification disengaging zone, feeding gas-phase propene respectively in the bottom of displacement zone, isolated area.The working pressure of gasification disengaging zone with replace isolated area, the gas-phase reaction district is identical, service temperature generally is controlled at 67 ℃～80 ℃.Leave the gasification disengaging zone and the gas-phase propene of displacement zone and the hydrogen 220 that is evaporated and enter Propylene Recovery System, liquid propylene that reclaims and noncondensable gas 301 can be got back to first step polymerization.During the propylene homopolymerization, isolated area and vapour phase polymerization district replenish propylene～33Kg/h, and heat of polymerization is withdrawn by outer circulation condenser 26, and phlegma 206 returns by lime set pump 28, and recycle gas 207 returns by recirculation blower 29.The temperature in vapour phase polymerization district is～70 ℃, and pressure is～2.6Mpa that density of hydrogen is 0.03%.Polypropylene powder finally leaves second stage polymerization horizontal retort through 208 outlets, Gu the gas-phase propene of carrying secretly in the powder return condensed device 26 inlets after gas/separation.Obtain polypropylene powder 180Kg/h during homopolymerization, the product melting index is 12.8.
Embodiment 2: with embodiment 1.But carry out the gas-phase copolymerization of propylene and ethene at second stage polymeric reaction zone.The temperature in vapour phase polymerization district is～70 ℃, and pressure is～2.6Mpa that density of hydrogen is 0.2%, C2=/C3==0.38.Polypropylene powder finally leaves second stage polymerization horizontal retort through 208 outlets.Obtain Co-polypropylene powder 158Kg/h, therein ethylene content is 11.5%Wt, and the product melting index is 4.5.
Embodiment 3: with embodiment 2.But second stage polymeric gasification disengaging zone is a horizontal polymeric kettle 2-1 of 100 liters that is provided with separately, and form stirs polymeric kettle with the horizontal band central shaft of second stage polymeric 600 liters, sees accompanying drawing 2 for details.Leave the polymkeric substance of first step slurry polymerization and the slurries 201 of liquid propylene composition and enter second stage polymeric gasification disengaging zone 2-1 (being the horizontal polymeric kettle of 100 liters that are provided with separately), slurries are by the polymerization of self propylene, propylene boil-off gas in the slurries dissolves, the hydrogen that wherein contains is very fast to steam from liquid phase, and propylene that is evaporated and hydrogen leave the gasification disengaging zone through 220 and also reclaimed.The temperature of gasification disengaging zone 2-1 is～71 ℃, and pressure is～2.7Mpa.When high temperature appears in gasification 2-1 part, disengaging zone, can add the liquid propylene cooling through 210.Polypropylene powder 221 enters gas phase reaction kettle 2-2 by pressure reduction, can feed displacement gas 203 toward the discharge zone of gasification disengaging zone 2-1 to reduce the amounts of hydrogen of carrying secretly in 221 in case of necessity.The temperature of vapour phase polymerization district 2-2 is～70 ℃, and pressure is～2.6Mpa that density of hydrogen is 0.2%, C2=/C3==0.38.The polymerization pressure of gasification disengaging zone 2-1 be～more than the 2.65Mpa, more than the high 0.05Mpa of pressure of maintenance than gas-phase reaction district 2-2 (being an independent horizontal retort), polymerization temperature is 70 ℃～80 ℃.
Finally obtain Co-polypropylene powder 180Kg/h, therein ethylene content is 11.0%Wt, and the product melting index is 4.5.
Embodiment 4: with embodiment 1.Gas-phase reaction district at second stage polymerization horizontal retort adds polypropylene nucleater, and adding quantity is 180g/h, can produce transparent polypropylene.
Embodiment 5: connect again on the basis of the embodiment 3 described flow processs horizontal retort (2-3) of one 600 liter of Fig. 5.Polypropylene powder leaves gas phase reaction kettle 2-2 enters this 600 liter by pressure reduction horizontal retort (2-3).In this polymeric kettle, add propylene, butene-1 carries out the copolymerization of propylene and butene-1, produces the ternary polypropylene alloy of propylene-ethylene-butene-1.This horizontal retort has own independent outer circulation and removes hot system, and polymerization temperature is 65 ℃, and polymerization pressure is 2.0Mpa.
Finally obtain ternary polypropylene alloy powder 190Kg/h, therein ethylene content is 10.4%Wt, and butene-1 content is that 2.6% product melting index is 4.
Embodiment 6: on the basis of embodiment 1 described flow process, be provided with 1 extractor (11) between the horizontal vapor phase polymerizer of the first step slurry polymerization still and the second stage.Extractor (11) is the vertical stirred vessel of one 70 liter, and remaining installations and facilities is with embodiment 1.The melting index that requires the production narrow molecular weight distribution is 18～22 the fiber trade mark.The density of hydrogen of first polymeric kettle gas phase part is about 6%,, leave first step polymerization 201 concentration of slurry and be about 33%, wherein polypropylene is about 120Kg/h, and its melting index is about 20.The solvent propylene that adds extractor is 250kg/hr, and the extraction liquid that takes out from the extractor top is 250kg/nr, and extraction liquid no longer enters the first step or second stage polymeric kettle.The slurries that leave extractor enter the gasification disengaging zone of second stage polymerization horizontal retort, owing to require the trade mark of production narrow molecular weight distribution, the gas-phase propene that leaves the gasification disengaging zone enters the outer circulation condenser 26 in vapour phase polymerization district after the gas-phase propene that leaves the vapour phase polymerization district mixes, unnecessary unreacting propylene also by above-mentioned mixed gas phase emission to Propylene Recovery System.Quench liquid during the temperature drift of gasification disengaging zone is from the quench liquid system in vapour phase polymerization district.The temperature in vapour phase polymerization district is～70 ℃, and pressure is～2.6Mpa that density of hydrogen is 0.8%.Obtain polypropylene powder 180Kg/h, the product melting index is 20.
Claims (6)
1. the method for a propylene multi-stage polymeric is characterized in that this method comprises the following steps:
(1) in first step polymeric area, in the liquid propylene body, carry out slurry polymerization, generate the multipolymer of polyacrylic homopolymer or propylene and ethene, C4 or the above α-alkene of C4 after the polymerization, it is little that its molecular weight ratio second stage polymeric area generates, and growing amount accounts for 20%～90% of the total growing amount of polymkeric substance by weight;
(2) second stage is aggregated in the horizontal retort that has horizontal type stir shaft and carries out, second stage polymeric horizontal retort is divided into by the order of polypropylene logistics successively process: gasification disengaging zone, displacement zone, isolated area, gas-phase reaction district, hydrogen from the slurries that the first step is come and liquid propylene are evaporated gasification in the gasification disengaging zone owing to heat of polymerization, in the gas-phase propene displacement that displacement zone is passed into, the gas phase after the separation enters Propylene Recovery System; Polypropylene breach that is positioned at below the charge level of baffle plate between displacement zone and isolated area after displacement enters isolated area, feeds the gas-phase propene sealing gland in the bottom of isolated area, the gas phase anti-channeling that prevents the gas-phase reaction district disengaging zone of going into to gasify;
(3) carry out the homopolymerization of propylene or the gas-phase copolymerization of propylene and ethene, propylene and C4 or the above α-alkene of C4 in the gas-phase reaction district, heat of polymerization is removed hot system by gas phase outer circulation condenser and is withdrawn, polymerization temperature is more than the dew point that gas phase is formed, below the softening temperature of polymkeric substance, the pressure in gas-phase reaction district is identical with the pressure of gasification disengaging zone, displacement zone, isolated area, in 1.8～3.0Mpa scope.
2. by the method for the described propylene multi-stage polymeric of claim 1, it is characterized in that:
The gasification disengaging zone of horizontal retort is set to the polymeric kettle of a platform independent separately, the gas-phase reaction district of horizontal retort is set to the horizontal polymeric kettle of another platform independent separately, this moment, isolated area just no longer existed, it is the polymeric kettle of a platform independent that the slurry that leaves first step reaction enters, the hydrogen and the liquid propylene that steam through polymerization leave above-mentioned independently polymeric kettle recovery, solid powder enters the horizontal polymeric kettle of another platform independent and proceeds polymerization, in that the gasification disengaging zone is set separately is one independently under the occasion of polymeric kettle, and the polymerization pressure of gasification disengaging zone is than the high 0.05～0.1Mpa of pressure in gas-phase reaction district.
3. by the method for the described propylene multi-stage polymeric of claim 1, it is characterized in that:
Add polypropylene nucleater production transparency polypropylene in the gas-phase reaction district of second stage polymerization horizontal retort.
4. by the method for the described propylene multi-stage polymeric of claim 1, it is characterized in that:
Second stage polymerization also can be in series by the horizontal retort that has horizontal type stir shaft more than 2 or 2, and its distributing style is: horizontal retort that comprises gasification disengaging zone, displacement zone, isolated area, gas-phase reaction district is composed in series with one or several the main horizontal retorts that are made of the gas-phase reaction district; Or horizontal retort that comprises gasification disengaging zone, displacement zone is composed in series with one or several the main horizontal retorts that are made of the gas-phase reaction district; In same horizontal retort respectively to distinguish pressure identical, high back is low before the pressure between the horizontal retort of linking to each other, and differs and remains on 0.05～0.1Mpa, the polymerization temperature in each district is more than the dew point, below the softening temperature of polymkeric substance; Produce the polynary polypropylene alloy of propylene-ethylene-C4 or the above α-alkene of C4.
5. by the method for the described propylene multi-stage polymeric of claim 1, it is characterized in that:
Between the horizontal vapor phase polymerizer of the first step slurry polymerization and the second stage, an extractor is set, the fresh liquid propylene of adding will leave in the first step polymerisation slurry in extractor random thing and low-molecular(weight)polymer extract, and the slurry after extraction enters the horizontal vapor phase polymerizer in the second stage.
6. the horizontal retort that uses in the method for a propylene multi-stage polymeric as claimed in claim 1 is characterized in that:
(1) horizontal retort is to have the horizontal polymerization reactor that horizontal type stir shaft, quench liquid are removed heat, and mixing speed is 2～30 rev/mins, and agitating vane is T type, square type, " opening " type, wedge shape or its combination;
(2) press the priority of polymkeric substance, vertically horizontal retort is divided into 4 districts through distance: gasification disengaging zone, displacement zone, isolated area, gas-phase reaction district, charging is in the stem of gasification disengaging zone, and the polymkeric substance discharging is at the afterbody in vapour phase polymerization district;
(3) function of gasification disengaging zone is to utilize the heat of polymerization of polymerization single polymerization monomer, with hydrogen in the slurries that enter and liquid-phase vaporization, leave the recovery system of horizontal retort to still then, between gasification disengaging zone and the displacement zone baffle plate is arranged, baffle plate is positioned at and has breach more than the charge level, and the disengaging zone of guaranteeing to gasify communicates each other with the gas phase part of displacement zone; Baffle plate is positioned at and also has breach below the charge level, polymkeric substance enters displacement zone by the breach on the baffle plate by the gasification disengaging zone, under the occasion of bulk propylene polymerization, not needing provides polymerization single polymerization monomer in addition to the gasification disengaging zone, in the evaporation of removing liquid phase in the logistics that main dependence come by first step polymerization of gasification disengaging zone polymerization reaction heat;
(4) function of displacement zone is to feed the hydrogen exchange that propylene gas carries secretly in the polypropylene logistics to come out in the bottom of displacement zone, not making it be brought to the gas-phase reaction district goes, there is a baffle plate that the gas phase in above-mentioned two districts is isolated between displacement zone and the isolated area, the breach of this baffle plate is positioned at below the charge level, and polypropylene powder enters isolated area by this breach by displacement zone;
(5) function of isolated area is to feed propylene gas in the bottom of isolated area, prevent in the gas-phase reaction district gas phase the comonomer anti-channeling to the gasification disengaging zone go, a baffle plate is arranged between isolated area and the gas-phase reaction district, baffle plate is positioned at and has breach more than the charge level, guarantees that isolated area communicates each other with the gas phase part in vapour phase polymerization district; Baffle plate is positioned at and also has breach below the charge level, and polymkeric substance enters the gas-phase reaction district by the breach on the baffle plate by isolated area;
(6) the gas-phase reaction district is the reactive agent part of horizontal retort, and the polymkeric substance that isolated area is come, polymerization single polymerization monomer, comonomer, hydrogen add in this district; Unreacted polymerization single polymerization monomer, comonomer and hydrogen, steam quench liquid and partly leave from the gas phase in gas-phase reaction district, after the outer circulation condenser condenses, phlegma, non-condensable gas turn back to the gas-phase reaction district; Polymkeric substance leaves horizontal retort from gas-phase reaction district afterbody discharge port, has a baffle plate, polymkeric substance to climb over the breach of baffle plate more than charge level before the discharge port and reaches discharge port.
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| CN100402560C (en) * | 2006-03-08 | 2008-07-16 | 南京金陵塑胶化工有限公司 | Production and reactor for polypropylene |
| CN102020733B (en) * | 2009-09-10 | 2012-04-18 | 中国石油化工股份有限公司 | Multiphase copolymerization polypropylene production process |
| CN102030841B (en) * | 2009-09-29 | 2012-07-04 | 中国石油化工股份有限公司 | Gas-phase polymerization of propylene |
| EP2495260B2 (en) * | 2009-10-29 | 2018-10-24 | Japan Polypropylene Corporation | Manufacturing method for propylene polymer |
| EP2497786B1 (en) * | 2009-11-06 | 2017-08-02 | Japan Polypropylene Corporation | Reactor for propylene polymerization and process for producing propylene polymer |
| JP5568445B2 (en) * | 2009-11-06 | 2014-08-06 | 日本ポリプロ株式会社 | Propylene polymerization reactor and method for producing propylene block copolymer |
| JP5577219B2 (en) * | 2009-11-06 | 2014-08-20 | 日本ポリプロ株式会社 | Propylene polymerization reactor and method for producing propylene polymer |
| CN109627570A (en) * | 2017-10-09 | 2019-04-16 | 高煦 | Propylene multistage polymerization method |
| CN107602739A (en) * | 2017-10-18 | 2018-01-19 | 浙江卫星能源有限公司 | The multi-stage polymeric process and device of a kind of propylene |
| CN112745440B (en) * | 2019-10-29 | 2022-10-21 | 中国石油化工股份有限公司 | Impact-resistant polypropylene and preparation method thereof |
| CN112745412B (en) * | 2019-10-29 | 2022-10-21 | 中国石油化工股份有限公司 | Method for removing entrained light components in polymer powder and application of method |
| CN112717562A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Method for reducing content of entrained light components in polymer powder and application of method |
| CN112250778B (en) * | 2020-09-14 | 2022-05-13 | 杭州双安科技有限公司 | Production method of propylene polymer |
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