CN1733811A - Combined process of pulse feeding of catalyst free of inert solvent and propene continuous prepolymerization - Google Patents
Combined process of pulse feeding of catalyst free of inert solvent and propene continuous prepolymerization Download PDFInfo
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- CN1733811A CN1733811A CN 200410053652 CN200410053652A CN1733811A CN 1733811 A CN1733811 A CN 1733811A CN 200410053652 CN200410053652 CN 200410053652 CN 200410053652 A CN200410053652 A CN 200410053652A CN 1733811 A CN1733811 A CN 1733811A
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Abstract
The integrated technique for pulse charging and continual pre-polymerization without inert solvent and catalyst comprises mainly: (1) dipping the catalyst in liquid-phase propylene, pulse adding the main catalyst particle into kettle with propylene based on deposition-clear principle; (2) the complete mixing kettle can disperse the catalyst rapidly; (3) decreasing the concentration of main catalyst, enlarging pre-polymerization temperature range; (4) thekettle can be arranged by itself or in the lower vertical device. this invention saves cost, decreases post-treatment load, and benefit to security and environmental friendly.
Description
Technical field the invention belongs to petrochemical industry.
Background technology content of the present invention is about producing in the polyacrylic technology the reinforced and combined technology of the continuous pre-polymerization of propylene of inertialess solvent catalyst pulse.
As everyone knows, in polypropylene was produced, the pre-polymerization of catalyzer can improve the polymerization efficiency of catalyzer, the degree of isotacticity that improves product and the bulk density of powder effectively.The technology of slurry polymerization in the polymerization technique of propylene (comprising the technology that slurry polymerization and vapour phase polymerization are combined) generally all has prepolymerization.Pre-polymerization has 2 kinds of methods: a kind of is the method for pre-polymerization at intermittence, and a kind of is the method for continuous pre-polymerization.Existing division is as follows:
(1) method of continuous pre-polymerization.The Japanese Patent spy opens the described endless tube polymerization technique of clear 58-216735 and adopts this method exactly.Pre-polymerization is carried out in an annular-pipe reactor.Primary Catalysts and unreactive hydrocarbons quasi-grease are configured to become stiff fluid after slurry, the cooling, join annular-pipe reactor with the mode of injecting equably with aluminum alkyls, silane, polymerization single polymerization monomer (propylene).The temperature of pre-polymerization is that 12 ~ 20 ℃, pressure are 3 ~ 9Mpa, the residence time to be that 4 ~ 12 minutes, Primary Catalysts concentration are generally 100PPM～500PPM, and the multiple of Primary Catalysts pre-polymerization is about hundred times.
(2) method of pre-polymerization at intermittence.The Japanese Patent spy opens clear 58-157807, and the described polymerization technique of clear 56-139520 (Mitsui oiling) adopts this method exactly.Primary Catalysts, part aluminum alkyls carry out the prepolymerization reaction with a spot of propylene gas in hexane liquid.The multiple of Primary Catalysts pre-polymerization is several times.Catalyzer after the pre-polymerization and hexane are joined and are slurries, join still formula polymeric kettle with aluminum alkyls, silane, propylene.
The technology of the pure vapour phase polymerization of polypropylene does not generally adopt the way of pre-polymerization.This be since after the pre-polymerization Primary Catalysts and aluminum alkyls formed a large amount of active centre, enter polymeric kettle after all active centre all participated in polyreaction immediately, increased the danger of generation focus.The pure gas-phase polymerization process of the polypropylene that has is made into slurries with Primary Catalysts and unreactive hydrocarbons earlier, joins vapor phase polymerizer with aluminum alkyls, silane, propylene then.
Above-mentioned polymarization method for prodcing polyacrylates all has the inertia hydro carbons of some amount to enter polymerization reactor, and finally staying becomes fugitive constituent in the product.Increased the load of powder aftertreatment, and all many-sides such as construction investment, environmental protection, product cost, quality product, production safety have all been brought adverse influence.
Summary of the invention the objective of the invention is to propose a catalyzer charging process and a still formula of avoiding the inertia hydro carbons to enter polymerization reactor and mixes the combined technology of type pre-polymerization entirely.
Main contents of the present invention are:
(1) utilizes the principle of " sedimentation one flushing ", the Primary Catalysts that is immersed in the propylene liquid phase is deposited in the volume measuring element earlier, makes angle of volume metering element rotation or moves a position, and the Primary Catalysts that will be settled down in the volume metering element with band hydraulic fluid phase propylene washes to prepolymerization kettle then.Owing to be deposited in the volumetric metering element and need the regular hour, so Primary Catalysts joins prepolymerization kettle with pulse mode to reaching a certain stable catalyst quality.The present invention is for the shape of volumetric metering element without limits: the valve opening that can be a ball valve or plunger valve, be that the catalyzer that liquid propylene is about in the valve opening after the sedimentation material feeding, half-twist is flushed to prepolymerization kettle when valve opening is vertical, above-mentioned valve opening also can be 2 holes that orthogonal intersection is not connected, wherein 1 be in plumbness just in the sedimentation material feeding, another is in the flushing of horizontality, after the half-twist conversely; The volumetric metering element also can be lattice that are similar in the Rotary feeder; Also can be the segment pipe between 2 valves (the flushing propylene can enter this segment pipe), Primary Catalysts is deposited in this segment pipe when opening valve, the pass is closed valve, opens down valve and is opened the valve that enters that washes propylene, and propylene just washes into prepolymerization kettle with the catalyzer in this segment pipe.In a word, earlier enter the volumetric metering element and then the flushing by liquid propylene enters prepolymerization kettle by the sedimentation of Primary Catalysts particle in propylene liquid.
(2) form of prepolymerization kettle is the vertical full type stirring tank that mixes: because Primary Catalysts enters prepolymerization kettle with the form of pulse, its form that enters prepolymerization kettle is intensive shape.If adopt endless tube as prepolymerization kettle, the catalyzer of intensive shape just can not disperseed immediately, and Primary Catalysts also might enter slurry polymerization reactor with intensive form, thereby causes focus.The catalyzer of intensive form even in the pre-polymerization annular-pipe reactor, just might cause the problem that local reaction is too fast, focus occurs.Have only the vertical full type stirring tank that mixes just the catalyzer of the high density state that enters might be distributed to whole prepolymerization kettle immediately.
(3) reduce pre-polymerization under catalyst concentration, the normal temperature.
Since vertical full when mixing the type stirring tank as prepolymerization reactor the heat transfer area of its unit volume less relatively, catalyst concn than higher processing condition under, be difficult to control the temperature of prepolymerization reaction, in case the pre-polymerization temperature surpass more than 20 ℃ will be out of control, cause implode.Except reducing aluminium/titanium ratio, in prepolymerization kettle, drop into the concentration of a large amount of liquid propylenes, reduction Primary Catalysts, be the highly effective measure that prevents the pre-polymerization temperature control.Reducing under the condition of Primary Catalysts, though prepolymerization reaction at normal temperatures, prolong the problem that the prepolymerization reaction temperature control also can not take place under the condition of the residence time.
Therefore, " reducing the concentration of Primary Catalysts " is to select the vertical full most important condition of mixing the type stirring tank as prepolymerization kettle for use; Under the condition that has reduced Primary Catalysts concentration (minimum can only be 10 ~ 20PPM, according to the difference of catalyzer and to some extent difference), can be in 10 ~ 50 ℃ temperature range (suitable is in 20 ~ 30 ℃ of temperature ranges) carry out the prepolymerization reaction of catalyzer; Under the condition that has improved the pre-polymerization temperature, can with the shorter residence time (＜4mins) reach 50 ~ 200 times polymerization multiple, also can prolong the time (30 ~ 60 minutes) of pre-polymerization according to the requirement of technology, reach the polymerization multiple of higher (~ 1000 times even higher).
Principal feature of the present invention is:
1. the charging of Primary Catalysts relies on raw material propylene itself, does not need other any hydro carbons.Not only provide cost savings, and alleviated the load of powder devolatilization aftertreatment, the flow process of having simplified catalyzer configuration and powder aftertreatment and equipment, all beneficial for the quality of safety, environmental protection, raising product;
2. the still formula is mixed the type prepolymerization reactor entirely and can be spread out by the catalyzer with intensive shape in moment of Primary Catalysts pulse charging, this helps not only to prevent that local reaction aggravation, the uncontrollable phenomenon of temperature from appearring in prepolymerization kettle and downstream polymeric kettle, and can eliminate Primary Catalysts pulse charging and cause the fluctuation that the downstream polymeric kettle is reacted.
Prepolymerization kettle is generally independent setting.When the prepolymerization kettle downstream reactor is vertical slurry polymerization reactor, also a prepolymerization reaction district can be set above this vertical slurry polymerization reactor inside, Primary Catalysts, aluminum alkyls, electron donor, liquid propylene are introduced into the prepolymerization reaction district, finish the liquid level below that slurries after the pre-polymerization enter slurry polymerization reactor again.The reaction conditions in prepolymerization reaction district is constant.See shown in the accompanying drawing 2.
3. the prepolymerization process condition of " reduction catalyst concentration " has guaranteed that less relatively vertical complete of the heat transfer area of unit volume mixes the type stirring tank and can carry out prepolymerization reaction in wideer temperature range, wideer residence time scope.
Description of drawings
Accompanying drawing 1 is one of reinforced synoptic diagram with the combined technology of the continuous prepolymerization of propylene of solvent-free catalyzer pulse of the present invention.11 is (master) catalyst tank, and 12 is (master) catalyzer feeder, and 13 is prepolymerization kettle.Primary Catalysts (Ti is a high-effective carrier catalyst) joins Primary Catalysts jar 11 by 101, is immersed in then in the propylene liquid phase.There is the volumetric metering part that at every turn can do 90 ° of rotations catalyzer feeder 12 inside, inside have 2 orthogonal, but not connected volumetric metering element (aperture), the solid catalyst powder is deposited in the vertical aperture, is washed by liquid propylene when being horizontal after the half-twist, and the aperture that originally was horizontal is got back to the catalyst sedimentation lower position.。。Go round and begin again.By the position shown in the accompanying drawing 1: 12-1 is in vertical position, and 12-2 is in the position of level.Under this state, the powder of Primary Catalysts is deposited in the 12-1 volumetric metering element, and liquid propylene is flushed to prepolymerization kettle 13 through 104 Primary Catalystss that enter, also will originally be deposited in the 12-2 volumetric metering element simultaneously by 12-2 through 105.After 90 ° of the volumetric metering partial rotation of catalyzer feeder 12 inside, position, 12-2 that 12-1 is in the flushing catalyzer are in the position that catalyst sedimentation enters.Every rotation once, add catalyzer one time.Because the speed very fast (less than 1 second) of each rotation, and adjacent 2 rotation interludes are long (relevant with the settling velocity of Primary Catalysts in propylene, generally be not less than 1 minute), therefore the feeding manner of Primary Catalysts is a pulsed, the inlet amount of regulating catalyzer by the frequency of regulating rotation.Aluminum alkyls through 102, silane through 103 enter prepolymerization kettle 13, hydrogen enters prepolymerization kettle 13 through 106.Prepolymerization kettle 13 is the vertical full type stirring tanks (with mechanical stirring and cooling jacket, not expression on the figure) that mix.Material after the pre-polymerization leaves the polymeric kettle (not expression on the figure) that prepolymerization kettle enters the downstream through 107.
Accompanying drawing 2 is two of the reinforced synoptic diagram with the combined technology of the continuous prepolymerization of propylene of solvent-free catalyzer pulse of the present invention.21 is (master) catalyst tank, and 22 is (master) catalyzer feeder, and 24 is the slurry polymerization still, and being positioned at its inner and upper is pre-polymerization district 23.Primary Catalysts (Ti is a high-effective carrier catalyst) joins Primary Catalysts jar 21 by 201, is immersed in then in the propylene liquid phase.There is the volumetric metering part that at every turn can do 90 ° of rotations catalyzer feeder 22 inside, inside have 2 orthogonal, but not connected volumetric metering element (aperture), the solid catalyst powder is deposited in the vertical aperture, washed by liquid propylene when being horizontal after 00 ° of the rotation, and the aperture that originally was horizontal is got back to the catalyst sedimentation lower position.。。Go round and begin again.By the position shown in the accompanying drawing 2: 22-1 is in vertical position, and 22-2 is in the position of level.Under this state, the powder of Primary Catalysts is deposited in the 22-1 volumetric metering element, liquid propylene through 204 enter, by 22-2 and will originally be deposited in Primary Catalysts in the 22-2 volumetric metering element simultaneously through the 205 pre-polymerization districts 23 that are flushed in the slurry polymerization still 24.After 90 ° of the volumetric metering partial rotation of catalyzer feeder 22 inside, position, 22-2 that 22-1 is in the flushing catalyzer are in the position that catalyst sedimentation enters.Every rotation once, add catalyzer one time.Because the speed very fast (less than 1 second) of each rotation, and adjacent 2 rotation interludes are long (relevant with the settling velocity of Primary Catalysts in propylene, generally be not less than 1 minute), therefore the feeding manner of Primary Catalysts is a pulsed, the inlet amount of regulating catalyzer by the frequency of regulating rotation.Aluminum alkyls through 202, silane through 203 enter pre-polymerization district 23, hydrogen enters pre-polymerization district 23 through 206.Pre-polymerization district 23 is the vertical full type stirring tanks (with mechanical stirring and cooling jacket, not expression on the figure) that mix, and is positioned at the top of slurry polymerization still 24 inside.Material after the pre-polymerization leaves below the liquid level that pre-polymerization district 23 enters slurry polymerization still 24 through 207.(stirring of slurry polymerization still 24, chuck, other all not expressions on accompanying drawing 2 such as material import and export).The vertical centre in pre-polymerization district 23 also can overlap with the vertical centre of slurry polymerization still 24, and the stir shaft in pre-polymerization district 23 can directly utilize the stir shaft (not expression on accompanying drawing 2) of slurry polymerization still 24.
Embodiment
Embodiment 1: as shown in Figure 1, the volume of prepolymerization kettle 13 is 440 vertical.Primary Catalysts (Ti is a high-effective carrier catalyst) joins Primary Catalysts jar 11 by 101, is immersed in then in the propylene liquid phase.The metering section of catalyzer feeder 12 is the objects that at every turn can do 90 ° of rotations, inside have 2 orthogonal, but not connected volumetric metering element (aperture), vertical aperture is in the state that catalyst sedimentation enters, and the aperture of level is in the position that catalyzer is rinsed.Every rotation once, the band hydraulic fluid phase propylene catalyzer that will be in the horizontal apertures is flushed to prepolymerization kettle.The inlet amount of the frequency control Primary Catalysts by regulating rotation is 80g/hr.Liquid propylene through 104 quantity that enter prepolymerization kettle 13 is～4000kg/hr.The concentration of Primary Catalysts in prepolymerization kettle is～20PPM.Aluminum alkyls is 1.25kg/hr through 102 quantity that enter prepolymerization kettle 13, and silane is 0.1kg/hr through 103 quantity that enter prepolymerization kettle 13, and hydrogen through 106 quantity that enter prepolymerization kettle 13 is～0.1kg/hr.Prepolymerization kettle 13 is that a vertical full type stirring tank that mixes (with mechanical stirring and cooling jacket, is not represented on the accompanying drawing 1.The pre-polymerization temperature is 30 ~ 40 ℃, and pressure is 3 ~ 4Mpa, the residence time ~ 3 minute.The pre-polymerization multiple of catalyzer is about ~ and 150 times.Material after the pre-polymerization leaves the polymeric kettle that prepolymerization kettle enters the downstream through 106, and finally obtaining polyacrylic output is 2500kg/hr (expression on the figure).Prepolymerization kettle 13 does not need the chilled brine cooling, and liquid propylene can enter prepolymerization kettle 13 through 104 with normal temperature.The bulk density of powder product is 0.46, and degree of isotacticity is 98%, the activity of Primary Catalysts is 40,000 times.
Embodiment 2: as shown in Figure 2, the pre-polymerization district 23 that prepolymerization kettle 13 usefulness are arranged on slurry polymerization still 24 inside replaces, the volume in pre-polymerization district 23 is 440 vertical, pre-polymerization district 23 is with cooling jacket (not expression on the figure), and the stir shaft in pre-polymerization district 23 is exactly the stir shaft (not expression on the figure) of slurry polymerization still 24.All the other are all with embodiment 1.
Comparative example 1: with embodiment 1, but the volume of prepolymerization kettle 13 is 180 vertical, and the propylene of input is 1000kg/hr, and the concentration of Primary Catalysts in prepolymerization kettle is 80PPM, the residence time ~ 5 minute, and the pre-polymerization temperature is 12 ℃.Pre-polymerization multiple ~ 50 of catalyzer times.Liquid propylene must enter prepolymerization kettle 13 again after chilled brine is cooled to 10 ℃.Material after the pre-polymerization is through 106 leaving prepolymerization kettle, entering the polymeric kettle (expression on the figure) in downstream.Finally obtaining polyacrylic output is 2500kg/hr.The activity of the bulk density of product, degree of isotacticity, Primary Catalysts and embodiment 1 are roughly the same.
Because the catalyst concn height, the heat-transfer surface of still formula prepolymerization kettle unit volume is smaller, and the pre-polymerization temperature of comparative example 1 is just out of control easily as if bringing up to 20 ℃.Press the operating method of comparative example 1 this high Primary Catalysts concentration, prepolymerization kettle equipment is difficult to amplify.
Claims (2)
1. inertialess solvent catalyst pulse is fed in raw material and the combined technology of the continuous prepolymerization of propylene.It is characterized in that:
(1) principle of utilization " sedimentation-flushing ", the Primary Catalysts that is immersed in the propylene liquid phase is deposited in the volume measuring element earlier, makes angle of volume metering element rotation or moves a position, and the Primary Catalysts that will be settled down in the volume metering element with band hydraulic fluid phase propylene washes to prepolymerization kettle then.Owing to be deposited in the volumetric metering element and need the regular hour, so Primary Catalysts joins prepolymerization kettle with pulse mode to reaching a certain stable catalyst quality.The present invention is for the shape of volumetric metering element without limits: the valve opening that can be a ball valve or plunger valve, be that the catalyzer that liquid propylene is about in the valve opening after the sedimentation material feeding, half-twist is flushed to prepolymerization kettle when valve opening is vertical, above-mentioned valve opening also can be 2 holes that orthogonal intersection is not connected, wherein 1 be in plumbness just in the sedimentation material feeding, another is in the flushing of horizontality, after the half-twist conversely; The volumetric metering element also can be lattice that are similar in the Rotary feeder; Also can be the segment pipe between 2 valves (the flushing propylene can enter this segment pipe), Primary Catalysts is deposited in this segment pipe when opening valve, the pass is closed valve, opens down valve and is opened the valve that enters that washes propylene, and propylene just washes into prepolymerization kettle with the catalyzer in this segment pipe.In a word, earlier enter the volumetric metering element and then the flushing by liquid propylene enters prepolymerization kettle by the sedimentation of Primary Catalysts particle in propylene liquid.
(2) form of prepolymerization kettle is the vertical full type stirring tank that mixes: because Primary Catalysts enters prepolymerization kettle with the form of pulse, its form that enters prepolymerization kettle is intensive shape, adopt the vertical full type stirring tank that mixes with the fastest speed the catalyzer of the high density state that enters to be distributed to whole prepolymerization kettle immediately, and eliminate the reinforced fluctuation that causes the reaction of downstream polymeric kettle of Primary Catalysts pulse.
(3) processing condition of prepolymerization kettle are: all Primary Catalystss, all or part of aluminum alkyls, all or part of silane under low Primary Catalysts concentration (according to the characteristics of Primary Catalysts, in the prepolymerization kettle concentration of Primary Catalysts in liquid propylene can be no more than 10 ~ 20PPM), under wideer pre-polymerization temperature (upper temperature limit improves 10 ~ 30 ℃ than former 20 ℃ of continuous pre-polymerization temperature), under the wideer residence time (by 1 ~ 3 minute shorter residence time to 15 ~ 60 minutes longer residence time) carry out pre-polymerization.
2. method according to claim 1 is characterized by: prepolymerization kettle can be provided with separately, also can be used as the inside that a pre-polymerization district is arranged on the vertical slurry polymerization still of its upstream device.
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| CN 200410053652 CN1733811A (en) | 2004-08-11 | 2004-08-11 | Combined process of pulse feeding of catalyst free of inert solvent and propene continuous prepolymerization |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US8362160B2 (en) | 2007-10-01 | 2013-01-29 | Total Petrochemicals Research Feluy | Method for supplying granulated material to a polymerisation reactor |
-
2004
- 2004-08-11 CN CN 200410053652 patent/CN1733811A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US8362160B2 (en) | 2007-10-01 | 2013-01-29 | Total Petrochemicals Research Feluy | Method for supplying granulated material to a polymerisation reactor |
| CN101815730B (en) * | 2007-10-01 | 2014-05-21 | 道达尔石油化学产品研究弗吕公司 | Method for supplying granulated material to a polymerisation reactor |
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