CN1332985C - Loop reactor apparatus and polymerization processes with multiple feed points for olefins and catalysts - Google Patents
Loop reactor apparatus and polymerization processes with multiple feed points for olefins and catalysts Download PDFInfo
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- CN1332985C CN1332985C CNB038244683A CN03824468A CN1332985C CN 1332985 C CN1332985 C CN 1332985C CN B038244683 A CNB038244683 A CN B038244683A CN 03824468 A CN03824468 A CN 03824468A CN 1332985 C CN1332985 C CN 1332985C
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Abstract
A slurry polymerization process wherein olefin monomer is fed to a continuous loop reactor at two or more points, allowing operation at higher and steadier monomer concentrations in the circulating slurry. A loop reactor apparatus has two or more monomer feeds and may have two or more catalyst feeds and/or two or more product take-offs, and each feed may have its own associated control scheme.
Description
Related application
The application requires the right of priority of the United States Patent (USP) provisional application 60/410367 of submission on September 13rd, 2002 according to 35U.S.C. § 119 (e).The latter here incorporates into as a reference.
Technical field
The present invention relates to olefinic monomer and in liquid medium, particularly in large-scale annular-pipe reactor, use the polymerization of slurry polymerization process.
Background technology
Polyolefine for example polyethylene and polypropylene can be produced by the particle form polymerization, is also referred to as slurry polymerization.In this technology, with charging for example monomer and catalyzer send into polymerization reactor (for example annular-pipe reactor), and the product slurry that will contain solid polyolefin particles in liquid medium takes out.
In the continuous loop pipe reactor, various chargings can be sent into loop reaction zone by different way.For example, can be separately or send into together with monomer and catalyzer, and can send into before the loop reaction zone monomer and catalyzer and the mixing diluents of different quantities.In loop reaction zone, monomer and catalyzer are dispersed in the fluid slurry.Along with they circulate by loop reaction zone in fluid slurry, monomer reacts at the catalyzer place in polyreaction.Polyreaction generates solid polyolefin particles in fluid slurry.
Slurry polymerization in loop reaction zone proved commercial be successful.Slurry polymerization technique has obtained worldwide success, billions of pounds of olefin polymers of annual production.But, still wish design and build more large-scale reactor.
The reactor condition that the character of polymkeric substance is subjected to comprise monomer concentration in polymerization process influences.In loop polymerization process, in polymerization process, monomeric concentration usually generates polymkeric substance with monomer reaction and descends.In existing polymerization and annular-pipe reactor, monomeric concentration is kept within the acceptable range in the whole loop reaction zone of using the single monomer charging in annular-pipe reactor.
The concentration of monomer in loop reaction zone is usually estimated by measuring the concentration of monomer in the product slurry that loop reaction zone is taken out.Usually easier measurement monomer concentration outside loop reaction zone than in loop reaction zone.
Summary of the invention
As on the one hand, provide a kind of slurry polymerization process.In described method, in liquid medium, generate solid polyolefin particles.Described method comprises sends olefinic monomer and catalyzer into loop reaction zone.Catalyzer must can make the olefinic monomer polymerization.Described method also comprises by a plurality of (two or more) monomer feed sends olefinic monomer into loop reaction zone.Sending into olefin monomer should make the concentration of olefinic monomer in loop reaction zone in required scope.For example, send into olefinic monomer by the feed entrance points of installing in a plurality of symmetry, the concentration of olefinic monomer in liquid medium can remain on 1.05% or littler scope in reactor.The variation of olefinic monomer concentration in the reactor can be remained on very lowly, so that be 0.4% or littler along the standard deviation of reactor olefinic monomer concentration.In some embodiments, per 800 feet reactor length have at least one monomer feed, or per 18000 gal reactor volumes have at least one monomer feed.
Present method also can comprise by a plurality of product material taking mouths takes out a part of fluid slurry as intermediates.Catalyzer can be sent into by a plurality of catalyst feeds.Preferably, monomer feed and product material taking mouth are installed along the loop reaction zone symmetry.Catalyst feeds also can be installed along the loop reaction zone symmetry.
Present method also comprises the concentration of olefinic monomer in the fluid slurry part of measure taking out, and the olefinic monomer of sending into according to the concentration adjustment of measuring.Can regulate the olefinic monomer of sending into, so that different with the amount of sending in another monomer feed in the amount of the olefinic monomer of an alkene opening for feed.
As on the other hand, provide a kind of loop reactor apparatus.Described loop reactor apparatus comprises a plurality of major sections and a plurality of upper and lowers minor segment.Each major section links to each other with a upper minor section in the upper end, and links to each other by level and smooth bend pipe with a lower minor segments in the lower end.In such a way, major section and minor segment form the continuous runner that is fit to the conveyance fluid slurry.Described runner does not have the inner barrier thing basically.
On the other hand, loop reactor apparatus can comprise first primary branch, second primary branch, the 3rd primary branch, the 4th primary branch, the 5th primary branch, the 6th primary branch, the 7th primary branch and the 8th primary branch.Described equipment also can comprise a plurality of minor segment, and wherein each section is connected to each other with two primary branches, thereby constitutes continuous runner.Described equipment can comprise first monomer feed that is connected to first primary branch; Be connected to the first product material taking mouth of the 3rd primary branch; Be connected to second monomer feed of the 5th primary branch; Be connected to the second product material taking mouth of the 7th primary branch and be connected to an arm or at least one catalyst feeds of one section.
Above-mentioned loop reactor apparatus comprises at least two and is used for rare hydrocarbon monomer is sent into the equipment of continuous runner, equipment and at least two equipment that are used for taking out from continuous runner a part of fluid slurry that are used for polymerizing catalyst is sent into continuous runner.Described loop reactor apparatus also can comprise at least one equipment that is used to measure the concentration of the fluid slurry that olefinic monomer takes out.Described metering facility with get material equipment fluid and link to each other.Described loop reactor apparatus also can comprise one and be used to control the equipment that monomer is sent into equipment.Metering facility will represent that the signal of measuring concentration offers operating device.
Description of drawings
Fig. 1 is the skeleton view that the annular-pipe reactor of a plurality of monomer feed, a plurality of catalyst feeds and a plurality of product material taking mouths that are used to take out a part of slurry is arranged.
Embodiment
Present method and equipment are applicable to homopolymerization and the ethene and for example copolymerization of butylene, 1-amylene, 1-hexene, 1-octene or 1-decene of more senior 1-alkene of ethene.Preferable methods be ethene with as the 0.01-10% (weight) of raw material, preferred 0.01-5% (weight), the copolymerization of copolymerization monomer of 0.1-4% (weight) most preferably, wherein comonomer be selected from above-mentioned more senior 1-alkene and weight percentage based on the weight of ethene and comonomer.(such multipolymer still is called polyethylene).On the other hand, the comonomer of sufficient amount can be used as raw material, and to add quantity be 0.01-10, preferred 0.01-5, the more preferably product polyolefine of 0.1-4% (weight) so that obtain comonomer.
Liquid medium can be a kind of thinner that is used for solid polymer particle, and it can be different with unreacted monomer or be unreacted monomer.In this specialty, the thinner that is suitable for present method is that everybody is familiar with, they be included under the reaction conditions for inert liq or be the hydro carbons of supercutical fluid.The hydro carbons that is fit to comprises Trimethylmethane, propane, Skellysolve A, iso-pentane, neopentane and normal hexane, and Trimethylmethane is particularly preferred.On the other hand, liquid medium can be unreacted monomer itself.For example, present method and equipment are also applicable to propylene polymerization in annular-pipe reactor.In bulk propylene polymerization, there is not independent thinner with regard to monomer, because monomer (propylene) is as liquid medium.It is much higher when certainly, the concentration ratio liquid medium of olefinic monomer also exists.
In this specialty, the catalyzer that is fit to is that everybody is familiar with.Particularly suitable is for example silicon oxide catalyst of chromic oxide/carrier, for example extensively disclosed in the US 2825721 (March nineteen fifty) of Hogan and Banks, here incorporates into as a reference.Also can use Z-type catalyst, metallocenes and other polyolefin catalyst of being familiar with and promotor.Preferably, only a kind of catalyzer is used for certain polymerization, and identical catalyzer each in a plurality of catalyst feeds is sent into.
About other details of loop reactor apparatus and polymerization can find in US 4674290,5183866,5455314,5565174,6045661,6051631,6114501 and 6262191, here incorporate into as a reference.
Monomer polymerization in thinner generates in the loop reaction zone of solid polymer particle, monomer concentration in the loop reaction zone usually flows along annular-pipe reactor with fluid slurry and changes, to small part is that conversion of monomer becomes polymkeric substance owing to the required result as polymerization.According to common situation, along with the length increase of loop reaction zone, if monomer is all sent into loop reaction zone a position, monomer concentration usually has variation greatly.For example, in 18000 gallon loop reactor of the slurry polymerization that is used for ethene, 48000 pounds of (the about 18000 kilograms) liquid of having an appointment are wherein had an appointment 2200 pounds of (about 800 kilograms) ethene in liquid.Under about 40000 Pounds Per Hours of productivity (about 15000 kilograms/hour), in the time that ethene flows through along reactor loop, described method consumes about 333 pounds (about 125 kilograms) ethene.The concentration of calculating ethene in the endless tube is extremely just about 4.93% (weight) after ethylene feed of preceding about 4.27% (weight) of ethylene feed.35000 gallon loop reactor can have the diameter identical with 18000 gallon loop reactor, but the length of twice is arranged.Under about 88000 Pounds Per Hours of productivity (about 33000 kilograms/hour), described method consumes about 1467 pounds (about 550 kilograms) ethene.Reactor is equipped with about 93300 pounds (about 68300 kilograms) liquid, wherein about 4200 pounds (about 1567 kilograms) ethene.In such reactor, if ethene is all sent at single opening for feed, the concentration of ethene is extremely just about 5.28% (weight) after ethylene feed of preceding about 3.72% (weight) of ethylene feed in the ring pipe reactor.This just constitutes the wide relatively change of ethylene concentration.
For some polyethylene products, for example the multipolymer of melt index 0.55, density 0.9505 wishes the concentration of ethene is maintained at about 4 to about 5.5% (weight) (it determines that scope is 1.5% (weight)).For other polyethylene products, for example the multipolymer of high load melt index 15.5, density 0.9360 wishes the concentration of ethene is maintained at about 1.7 to about 2.7% (weight) (it determines that scope is 1.0% (weight)).For most of polyethylene products, wish that along the ethylene concentration scope of reactor be about 0.65% or about 0.85% or about 0.95% or about 1.05%.Perhaps, wish this method of operation like this, so that any point in reactor, the concentration of ethene is all in the standard deviation of average ethylene concentration.Preferably, the standard deviation of the ethylene concentration of reactor is about 0.2% or less than 0.3% or less than 0.4%.Present method and equipment can provide and keep these required ethylene concentrations.
A spot of ethene also can enter reactor in diluent flush points.Such flush points is not as " monomer feed ".Flush points comprises pump seal district, catalyst charge point, product gets the material point and unloads pressure point, and for safe and reliable reactor operation, they need keep open, at such opening seldom polymer build-up are arranged.This flushing can contain centesimal ethene, and it is in reactor flash gas and be recycled to reactor.It is about 0 to 10% that the ethene quantity that is recycled to reactor with recycle diluent is generally, and is typically 5%.
The ethylene concentration over-drastic changes can make the maximum operating temp of permission reduce a little, because have in the reactor part of higher ethylene concentration, speed of reaction is than higher in the reactor part that low ethylene concentration is arranged.For example, in some places, speed of reaction can be about 30%.This approximation is based on speed of reaction and is directly proportional with monomeric concentration in the reactor.By using present method and equipment, maximum operating temperature can improve more than nearly 3.0 (1.7 ℃), is up to the polymkeric substance of 215.5 for the temperature of reactor, and described polymerization can be operated under 218.5 or higher temperature.Maximum operating temperature is to cause the temperature that polymkeric substance is softening and reactor is polluted, and it also depends on the type of polymkeric substance, the ability of the hierarchy of control and the ability that reactor jacket is removed heat of polymerization.
Compare with US 4789714 disclosed polymerizations, other monomer feed is used to cause the formation that replenishes the MWD mode in this patent, in present method and equipment, other monomer feed can be used to prevent the expansion of the polyolefinic molecular weight distribution that makes by the method that ethylene concentration is remained on constant level.This just can make in large-scale reactor and the identical high-quality product that has that makes in less reactor.It is unimodal solid polyolefin particles that present method and equipment can be used for the production molecular weight distribution.
With reference now to accompanying drawing,, Fig. 1 represents that major section 12 is arranged, the annular-pipe reactor 10 of upper minor section 14 and lower minor segments 16.Minor segment can be the simple elbow that links to each other with major section.Preferably, lower minor segments is crooked relatively, gets material continuously with what be convenient to the product slurry.In Fig. 1, annular-pipe reactor has 8 major sections, can use the annular-pipe reactor of the major section of more or less number though the inventor estimates present method and equipment, and for example annular-pipe reactor has 4 arms or 12 sections.Should be appreciated that concrete hop count not necessarily hints here pays the utmost attention to arm, because annular-pipe reactor is circular.Fig. 1 represents that major section is first arm 1, second arm 2, the 3rd arm 3, the 4th arm 4, the 5th arm 5, the 6th arm 6, the 7th arm 7 and the 8th arm 8.First to the 8th arm all uses cooling jacket 18 to surround, and is used for heat exchange, the equipment of just removing at least a portion polymerization reaction heat and a gate ring pipe reactor temperature of charge is provided from annular-pipe reactor.
The upper and lower minor segment is determined the epimere and the hypomere of minor flow.Each section or arm link to each other with next section or arm by level and smooth elbow or bend pipe 20, thereby the continuous runner that does not have inner barrier basically is provided.As shown in Figure 1, some upper and lower minor segment can be made up of level and smooth elbow or bend pipe, so that minor segment forms continuous bend.The blade (not shown) that drives with motor 24 makes the fluid slurry circulation.
Preferably, the volume of the loop reaction zone of described annular-pipe reactor, most preferably is greater than 35000 gallons more preferably greater than 30000 gallons greater than 20000 gallons.
Monomer (it can with mixing diluents) is sent into reactor by two monomer feed (be expressed as conduit 30 and be connected to annular-pipe reactor) from one or more monomer sources 26, the circulation unreacting ethylene that it can be the fresh ethylene feed or the slurry that takes out from reactor obtains.Conduit 30 is equipped with flow director 32, and the amount of monomer of annular-pipe reactor is sent in its control.Monomer feed can be any known device that is used to feed monomer to reactor, for example simple opening, nozzle, injector or other fluid dispensing apparatus.
As shown in Figure 1, two monomer control flows that separate are used to control two monomer feed of separating.If only a control flow is used to control a plurality of monomer feed, exist polymer build-up to cause of the danger of all monomer flows so by an opening for feed.Control flow shown in Figure 1 is controlled the monomer feed of sending into annular-pipe reactor according to the monomer concentration of measuring in the slurry part of getting the taking-up of material point in the downstream.On the other hand, can control monomer feed according to get monomer concentration or the several mean value of getting the measurement monomer concentration in the material slurry that takes out measured in the material slurry that the takes out part in the upstream.On the other hand, can take out the monomer concentration of measuring after logistics merges in the flash gas at two.On the other hand, can a point or a plurality of point in reactor directly measure monomeric concentration.
As shown in Figure 1, monomer feed and product material taking mouth are installed along the annular-pipe reactor symmetry.Advantage that this symmetry is installed is, can expect monomer concentration each product material taking mouth near or identical (supposing that the roughly the same and annular-pipe reactor of amount of monomer that each opening for feed sends into works well).If it is roughly the same to be expected at the monomer concentration of product material taking mouth, the described method of so easier control.
Comonomer also can be sent into by conduit 30 or other feed entrance point.Preferably, a plurality of comonomer feed mouths are installed along the annular-pipe reactor symmetry, and the control flow shown in control flow part similar (or being added to) monomer feed.
Catalyzer is sent into catalyst feeds 44 by conduit, and they are sent into for catalyzer a section (position) is provided.In the embodiment depicted in fig. 1, catalyst feeds 44 is also installed along the reactor symmetry.On the other hand or in addition, disclosedly in US 6262191 be used to prepare catalyst slurry and the method and apparatus (incorporating into as a reference in the past) that it offers ring canal reaction (polymerization) section can be used with present method and equipment.
Dotted line is the signal wire in the accompanying drawing, and they are electrical signal line or pneumatic singal line in this preferred embodiment.But machinery, waterpower or other signalling sets that is used for mail message also are suitable for.In nearly all hierarchy of control, some combination of these signal types will be used.But the use that any other type signal that adapts with the method and apparatus that is using is carried all within the scope of the invention.
The loop reactor apparatus of Fig. 1 also comprises the equipment (product material taking mouth) that is used for taking out from reactor a part of slurry.The equipment that is used to take out the slurry part can be the sedimentation arm, gets hollow appendage or other conduits that is used to take out the product slurry and does not have obvious seepage or disturb the annular-pipe reactor operation of material continuously.The sedimentation arm is used for this field already, and is open in US 3293000 and 4613484, here incorporates into as a reference.In the embodiment depicted in fig. 1, the elongate hollow annex that is used for taking out continuously the intermediates slurry is represented with parameter 34.Continuously material fetching mechanism 34 is located on or near a lower horizontal reactor loop sections 16, and/or near or on connecting bend 20.Open in the US 6239235 of Hottovy etc. about other detailed contents of continuous material fetching mechanism, here incorporate into as a reference.
The slurry part of taking out is sent into by conduit 36 and is used for the isolating equipment of solid polyolefin particles and thinner and unreacted monomer.Conduit 36 can comprise the outer catheter that the heating fluid of indirect heating is provided for the product slurry in the conduit 36 is housed.Such configuration is called the flash line heating.Come the separate solid polyolefin particles with two sections flash design, for example extensively disclosed in the US4424341 (on January 3rd, 1984) of Hanson and Sherk, here incorporate into as a reference.Use such design, estimate recyclable 70-90% or more dilute agent in high pressure flash usually.
For example, in a container, polymkeric substance (puff) is collected in the bottom by gravity, thinner and unreacted monomer and comonomer is separated and discharge from the top.Described container is operated under sufficiently high pressure, so that all available cooling water condensation of steam of all discharges basically, and loops back reactor with pump.The monomer diluent of vaporization can further be handled, and comprises with the method condensation of cycle condenser by simple heat exchange, returns system by recycle diluent line then, and does not need compression.Recycled monomer can be returned monomer source 26.
Embodiment
18000 gallon loop reactor are used for the slurry polymerization of ethene.The nominal diameter that forms the pipe of annular-pipe reactor is 24 inches, and it always is about 860 feet.About 48000 pounds (about 18000 kilograms) liquid are arranged, wherein about 2200 pounds (about 800 kilograms) ethene in liquid.Under about 40000 Pounds Per Hours of reactor productivity (about 15000 kilograms/hour), in ethene flowed the time that needs along reactor loop, reactor consumed about 333 pounds (about 125 kilograms) ethene.The concentration of ethene is about 4.27% (weight) (half of 2200 pounds of ethene-333 pound before ethylene feed just in the annular-pipe reactor, divided by 48000 pounds of content liquids in the reactor) to the ethylene feed just 4.93% (weight) (half of 2200 pounds of ethene+333 pound is divided by 48000 pounds of content liquids in the reactor).
35000 gallon loop reactor are used for the slurry polymerization of ethene.Described reactor has identical diameter with 18000 gallon loop reactor of embodiment 1 but two double-lengths is arranged.Reactor has only an ethylene feed.Reactor is equipped with about 85916 pounds (about 62900 kilograms) liquid, wherein about 3437 pounds (about 1282 kilograms) ethene.Reactor is produced about 87500 Pounds Per Hours of polymkeric substance.Slurry flow is crossed whole 35000 gallon loop reactor needs about 48 seconds.In 60 seconds, reactor consumes about 1458 pounds (about 547 kilograms) ethene.In described reactor, ethylene concentration in the annular-pipe reactor is about 3.32% (weight) (half of 3437 pounds of ethene-1167 pound before ethylene feed just, divided by 85916 pounds) to the ethylene feed just about 4.68% (half of 3437 pounds of ethene+1167 pound is divided by 85916 pounds).
Table 1 is listed the reactor characteristic of 35000 gallon loop reactor shown in Figure 1 and the method characteristic of vinyl polymerization.The numerical value that the operator of input row finger ring pipe reactor select; The output row refer to the numerical value with the character decision of input value and reactor and method.Table 2 and table 3 provide the material balance of the vinyl polymerization of a monomer feed and two monomer feed to calculate respectively.
Table 1 reactor and method characteristic
| Input | Output | ||
| Reactor size | |||
| The shell internal diameter | Inch | 22.0625 | - |
| Flow area | Square feet | - | 2.6548 |
| The arm length overall | Foot | 1,616 | - |
| The elbow number | 16 | - | |
| The elbow radius | Foot | 6.00 | - |
| Elbow length | Foot | - | 9.42 |
| The reactor length overall | Foot | - | 1,756 |
| Reactor volume | Gallon | 35,116 | - |
| Pump part character | |||
| Reactor solids | % (weight) | 48.0％ | - |
| Temperature of reactor | F | 214.0 | - |
| The granular solids volume fraction | 0.91 | - | |
| Solid density | Milliliter/gram | 0.9540 | - |
| Pound/foot 3 | - | 59.50 | |
| The reactor stream volume density | Milliliter/gram | - | 0.409 |
| Pound/foot 3 | 25.56 | - | |
| Reactor slurry density | Pound/foot 3 | - | 35.1965 |
Table 1 (continuing)
| Reactor CTO discharging | |||
| Productivity | The pound polyethylene/hour | 87,500 | - |
| The CTO solid | % (weight) | 50.0％ | - |
| CTO ethene | % (weight) | 4.0％ | - |
| The slurry drainage rate | Pounds Per Hour | - | 175,000 |
| Liquid discharge | Pounds Per Hour | - | 87,500 |
| The ethene discharging | Pounds Per Hour | - | 3,500 |
| Reactor feed and material | |||
| Ethylene feed (supposing homopolymer) | Pounds Per Hour | - | 91,000 |
| The circulating liquid charging | Pound/liter | - | 84,000 |
| The reactor slurry amount | Pound | - | 165,224 |
| The liquid reactor amount | Pound | - | 85,916 |
| The reactor solids amount | Pound | - | 79,308 |
| Reactor ethene amount | Pound | - | 3,437 |
Table 1 (continuing)
| Reactor cycles and reaction | |||
| Speed of reaction | Pounds Per Minute | 1,458 | |
| The reaction cycle rate | Grams Per Minute | 43,800 | |
| Reaction cycle speed | Foot 3/ minute | 5,856 | |
| Speed | Feet per minute | 2,205 | |
| Rotations per minute | Rev/min | 1.25 | |
| The arm useful length | FOTO-WEAR | 221 | |
| The reaction of each arm | Pounds Per Minute | 182 |
Table 2 is listed the evaluation of 35000 gallon loop reactor, wherein vinyl monomer is sent into reactor by a monomer feed behind pump just.Rightmost tabulation shows that the concentration of ethene in fluid slurry changes to 4.64% from 3.35%, and scope is 1.11%, and mean value is 3.73%, and standard deviation is 0.41%.
Table 2 has the material balance of the annular-pipe reactor of a monomer feed point to calculate
| Ethene | Trimethylmethane (every other liquid) | Whole liquid | Polyethylene | Whole slurry | Solid | Ethene | |
| Pounds Per Minute | Pounds Per Minute | Pounds Per Minute | Pounds Per Minute | Pounds Per Minute | % (weight) | % (weight) | |
| Pump | 3,589 | 103,574 | 107,163 | 98,920 | 206,083 | 48.00％ | 3.35％ |
| Charging (1.29%) | 1,517 | 1,400 | 2,917 | ||||
| |
5,106 | 104,974 | 110,080 | 98,920 | 209,000 | 47.33％ | 4.64％ |
| |
4,923 | 104,974 | 109,898 | 99,102 | 209,000 | 47.42％ | 4.48％ |
| |
4,741 | 104,974 | 109,715 | 99,284 | 209,000 | 47.50％ | 4.32％ |
| CTO | 31.5 | 697.7 | 729.2 | 729.2 | 1,458.3 | 50.00％ | 4.32％ |
| Arm 4 inlets | 4,710 | 104,277 | 108,986 | 98,555 | 207,541 | 47.49％ | 4.32％ |
| |
4,527 | 104,277 | 108,804 | 98,738 | 207,541 | 47.57％ | 4.16％ |
| |
4,345 | 104,277 | 108,621 | 98,920 | 207,541 | 47.66％ | 4.00％ |
| Charging (0%) | 0 | 0 | 0 | ||||
| |
4,345 | 104,277 | 108,621 | 98,920 | 207,541 | 47.66％ | 4.00％ |
| |
4,163 | 104,277 | 108,439 | 99,102 | 207,541 | 47.75％ | 3.84％ |
| |
3,980 | 104,277 | 108,257 | 99,284 | 207,541 | 47.84％ | 3.68％ |
| CTO | 26.8 | 702.4 | 729.2 | 729.2 | 1,458.3 | 50.00％ | 3.68％ |
| |
3,954 | 103,574 | 107,528 | 98,555 | 206,083 | 47.62％ | 3.68％ |
| |
3,771 | 103,574 | 107,345 | 98,738 | 208,083 | 47.91％ | 3.51％ |
| |
3,589 | 103,574 | 107,163 | 98,920 | 206,083 | 48.00％ | 3.35％ |
Table 3 is listed the evaluation of 35000 gallon loop reactor, wherein vinyl monomer is sent into reactor by two monomer feed, one just behind pump, another is just behind the bottom of the 5th reactor arm.In described reactor, ethylene feed and product material taking mouth (CTO) symmetry are installed.Rightmost tabulation shows that the concentration of ethene in fluid slurry changes to 4.32% from 3.67% in the table 3, and scope is 0.65%, and mean value is 3.74%, and standard deviation is 0.21%.
Table 3 has the material balance of the annular-pipe reactor of two monomer feed points to calculate
| Ethene | Trimethylmethane (every other liquid) | Whole liquid | Polyethylene | Whole slurry | Solid | Ethene | |
| Pounds Per Minute | Pounds Per Minute | Pounds Per Minute | Pounds Per Minute | Pounds Per Minute | % (weight) | % (weight) | |
| Pump | 3,937 | 103,227 | 107,163 | 98,920 | 206,083 | 48.00％ | 3.67％ |
| Charging (0.65%) | 758 | 700 | 1,458 | ||||
| |
4,695 | 103,927 | 108,621 | 98,920 | 207,541 | 47.66％ | 4.32％ |
| |
4,513 | 103,927 | 108,439 | 99,102 | 207,541 | 47.75％ | 4.16％ |
| |
4,330 | 103,927 | 108,257 | 99,284 | 207,541 | 47.84％ | 4.00％ |
| CTO | 29.2 | 700.0 | 729.2 | 729.2 | 1,458.3 | 50.00％ | 4.00％ |
| Arm 4 inlets | 4,301 | 103,227 | 107,528 | 98,555 | 206,083 | 47.82％ | 4.00％ |
| |
4,119 | 103,227 | 107,345 | 98,738 | 206,083 | 47.91％ | 3.84％ |
| |
3,937 | 103,227 | 107,163 | 98,920 | 206,083 | 48.00％ | 3.67％ |
| Charging (0.65%) | 758 | 700 | 1,458 | ||||
| |
4,695 | 103,927 | 108,621 | 98,920 | 207,541 | 47.66％ | 4.32％ |
| |
4,513 | 103,927 | 108,439 | 99,102 | 207,541 | 47.75％ | 4.16％ |
| |
4,330 | 103,927 | 108,257 | 99,284 | 207,541 | 47.84％ | 4.00％ |
| CTO | 29.2 | 700.0 | 729.2 | 729.2 | 1458.3 | 50.00％ | 4.00％ |
| |
4,301 | 103,227 | 107,528 | 98,555 | 206,083 | 47.82％ | 4.00％ |
| |
4,119 | 103,277 | 107,345 | 98,738 | 206,083 | 47.91％ | 3.84％ |
| |
3,937 | 103,227 | 107,163 | 98,920 | 206,083 | 48.00％ | 3.67％ |
Table 2 proves that with table 3 (the particularly calculated value of ethylene concentration in the rank rear of each table) use of the system of two monomer feed makes the concentration of monomer in annular-pipe reactor more consistent.
Though describe the present invention in detail in order to illustrate, should be with it as limitation of the present invention, and plan in spirit of the present invention and scope, to relate to all variations.
Claims (20)
1. slurry polymerization process that in liquid diluent, generates solid polyolefin particles, described method comprises:
Liquid diluent is sent into loop reaction zone;
Catalyzer is sent into loop reaction zone, and described catalyzer can make described olefinic monomer polymerization;
Olefinic monomer is sent into loop reaction zone by a plurality of monomer feed, wherein add olefinic monomer so that the concentration of olefinic monomer in loop reaction zone in required scope;
With the olefinic monomer polymerization, in liquid diluent, generate the fluid slurry of solid polyolefin particles; And
Take out a part of fluid slurry as intermediates.
2. according to the process of claim 1 wherein that catalyzer sends into by a plurality of catalyst feeds.
3. according to the process of claim 1 wherein that described fluid slurry is partly by a plurality of product material taking mouths taking-ups.
4. according to the method for claim 3, wherein monomer feed and product material taking mouth are installed along the loop reaction zone symmetry.
5. according to the process of claim 1 wherein that required scope is 1.05% or littler.
6. according to the process of claim 1 wherein that described a plurality of monomer feed is that per 800 feet reactor length have at least one monomer feed.
7. according to the process of claim 1 wherein that described a plurality of monomer feed is that per 18000 gal reactor volumes have at least one monomer feed.
8. according to the process of claim 1 wherein that described fluid slurry has a plurality of monomer concentrations along loop reaction zone, the standard deviation of described a plurality of monomer concentrations is equal to or less than 0.4%.
9. according to the method for claim 1, also comprise following steps: measure the olefinic monomer concentration of the segment fluid flow slurry that takes out and the olefinic monomer of sending into according to the concentration adjustment of measuring.
10. according to the method for claim 9, wherein regulate the olefinic monomer of sending into, so that the olefin monomer of sending into a monomer feed is different with another monomer feed.
11. according to the process of claim 1 wherein that the volume of described loop reaction zone is greater than 20000 gallons.
12. according to the process of claim 1 wherein that the volume of described loop reaction zone is greater than 30000 gallons.
13. according to the process of claim 1 wherein that the volume of described loop reaction zone is greater than 35000 gallons.
14. separately control described each monomer feed according to the process of claim 1 wherein.
15. according to the process of claim 1 wherein that described solid polyolefin particles has unimodal molecular weight distribution.
16. a loop reactor apparatus, described equipment comprises:
A plurality of major sections;
A plurality of upper minor sections;
A plurality of lower minor segments;
Wherein each described major section links to each other with a described upper minor section in the upper end, and link to each other with a described lower minor segments by level and smooth lower bend in the lower end, so that described major section and described minor segment form the continuous runner that is applicable to the conveyance fluid slurry;
At least two equipment that are used for olefinic monomer is sent into continuous runner;
An equipment that is used for polymerizing catalyst is sent into continuous runner; And
At least two equipment that are used for taking out a part of fluid slurry from continuous runner.
17. according to the loop reactor apparatus of claim 16, also comprise the equipment of at least one fluid slurry that is used for measuring taking-up part olefinic monomer concentration, described metering facility links to each other with the described material equipment fluid of getting.
18., also comprise one and be used to control the equipment that described monomer is sent into equipment, and described metering facility will represent that the signal of described measurement concentration offers described operating device according to the loop reactor apparatus of claim 17.
19. according to the loop reactor apparatus of claim 16, described equipment comprises:
First primary branch; Second primary branch; The 3rd primary branch; The 4th primary branch; The 5th primary branch; The 6th primary branch; The 7th primary branch and the 8th primary branch; A plurality of minor segment, each section is connected to each other with two described primary branches, thus described arm and described section are a continuous runner;
First monomer feed that links to each other with described first primary branch;
The first product material taking mouth that links to each other with described the 3rd primary branch;
Second monomer feed that links to each other with described the 5th primary branch;
The second product material taking mouth that links to each other with described the 7th primary branch; And
At least one catalyst feeds that links to each other with a described arm or section.
20. according to the loop reactor apparatus of claim 19, comprise first and second catalyst feeds, wherein:
Described first and second monomer feed are along runner symmetry installation continuously;
The described first and second product material taking mouths are along runner symmetry installation continuously; And
Described first and second catalyst feeds are along runner symmetry installation continuously.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41036702P | 2002-09-13 | 2002-09-13 | |
| US60/410,367 | 2002-09-13 | ||
| US10/660,990 | 2003-09-12 |
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| CN1332985C true CN1332985C (en) | 2007-08-22 |
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| EP1839742A1 (en) * | 2006-03-30 | 2007-10-03 | Total Petrochemicals Research Feluy | Flushing in a multiple loop reactor |
| EP1842861A1 (en) * | 2006-04-03 | 2007-10-10 | Total Petrochemicals Research Feluy | Process for improving the polymerization of ethylene and one or more optional comonomer(s) in a polymerization loop reactor. |
| DE602006009828D1 (en) * | 2006-11-16 | 2009-11-26 | Borealis Tech Oy | Process for the preparation of an ethylene-silane copolymer |
| CN105561883A (en) * | 2015-12-17 | 2016-05-11 | 北方华锦化学工业集团有限公司 | Online switching feeding system of loop reactor |
| CN107522808B (en) * | 2016-06-21 | 2020-09-15 | 中国石油化工股份有限公司 | Preparation method of ethylene-octene copolymer |
| CN110385099A (en) * | 2018-04-20 | 2019-10-29 | 中国科学院过程工程研究所 | A kind of control method of annular-pipe reactor and annular-pipe reactor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6204344B1 (en) * | 1998-03-20 | 2001-03-20 | Exxon Chemical Patents, Inc. | Continuous slurry polymerization volatile removal |
| US6239235B1 (en) * | 1997-07-15 | 2001-05-29 | Phillips Petroleum Company | High solids slurry polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6239235B1 (en) * | 1997-07-15 | 2001-05-29 | Phillips Petroleum Company | High solids slurry polymerization |
| US6204344B1 (en) * | 1998-03-20 | 2001-03-20 | Exxon Chemical Patents, Inc. | Continuous slurry polymerization volatile removal |
| US6319997B1 (en) * | 1998-03-20 | 2001-11-20 | Exxonmobil Chemical Patents Inc. | Continuous slurry polymerization volatile removal |
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