CN106432551B - A kind of polyacrylic method and apparatus of intermittent liquid phase bulk polymerization production - Google Patents
A kind of polyacrylic method and apparatus of intermittent liquid phase bulk polymerization production Download PDFInfo
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- CN106432551B CN106432551B CN201510490667.9A CN201510490667A CN106432551B CN 106432551 B CN106432551 B CN 106432551B CN 201510490667 A CN201510490667 A CN 201510490667A CN 106432551 B CN106432551 B CN 106432551B
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Abstract
The present invention provides a kind of intermittent liquid phase bulk polymerizations to produce polyacrylic method, including：1) before polymerisation, cut off the connection between polymeric kettle and the monomer compensating tank being attached thereto, liquid propylene is injected into polymeric kettle and monomer compensating tank respectively, the saturated vapor pressure at least 0.1MPa of propylene when then making monomer compensation pressure tank be higher than maximum allowable operating temperature (M.A.O.T.) in polymeric kettle by pressure control unit；2) after polymerisation starts, monomer compensating tank is connected to polymeric kettle；It is the pressure set in step 1) that the pressure of monomer compensating tank is maintained in polymerization process；3) when the propylene liquid level in monomer compensating tank is less than 20%, its connection between polymeric kettle is cut off；4) when occurring " dry pot " phenomenon in polymeric kettle, Propylene recovery simultaneously discharges.Equipment the present invention also provides the above method is realized.The method and equipment can improve the capacity utilization of polymeric kettle, and the monocycle yield of aggrandizement apparatus can be increased production to expand.
Description
Technical field
The present invention relates to PP Production Technology technologies, more particularly, it relates to a kind of intermittent liquid phase bulk polymerization
Polyacrylic method is produced, and the equipment for realizing this method.
Background technology
Intermittent liquid phase bulk polymerization polypropylene plant is a kind of PP Production Technology of China's independent development, and equipment is main
Including feed purification, polymerisation, flash distillation deactivation, it is granulated and the technique units such as packaging.In the technique unit of polymerisation, including
Propylene measuring tank, activator feeding tank, catalyst shot tank, hydrogen metering tank, reaction kettle, hot water storgae, heat-exchanger pump, cold line
And the equipment such as steam pipe line.Reaction kettle is all made of tank reactor, and reaction kettle is removed heat and realized by chuck and inner cool tube,
It can be found in：Li Yugui, Chen Ningguan etc., Liquid-Phase Bulk Polypropylene production and application, Sinopec publishing house, 1992, the first edition.
In the course of the polymerization process, current operating method is：By reaction kettle displacement it is clean after, be added thereto successively propylene,
Activator, catalyst and hydrogen, then open steam valve, are heated up to reaction kettle by heat-exchanger pump hot water；When in reaction kettle
When reaction is fiercer, thermal discharge is bigger, steam off simultaneously opens cold water, starts to remove heat to reaction kettle, lead in reaction process
Overregulating cool water quantity makes the temperature of reaction kettle control in a certain range；Reaction is after a certain period of time, " dry when occurring in reaction kettle
The sign of pot ", i.e., by Propylene recovery, reaction was completed, then discharges.So-called " dry pot " refers to that liquid monomer is basic in reaction kettle
It disappears, reaction kettle is in a kind of state of gas-particle two-phase.
With the increase of the market demand, expansion can increase production always batch process polypropylene plant problems faced, solution route
One of be reactor enlargement, increase output per single reactor, the reaction kettle of present batch process polypropylene plant has initial 4m3Increase
The 12m generally used till now3, continue increase reactor and be faced with the problem that thermal energy power is limited of removing, therefore in Batch Polypropylene
The reactor enlargement aspect of device, 12m3Reactor used nearly 20 years and never new breakthrough.
The characteristics of due to Batch Polypropylene device itself, does not have the supplement of auxiliary agent and monomer, polymerization initial stage in polymerization process
Monomeric charge amount be generally the 90% of autoclave body product, and the density of polypropylene and liquid propylene monomer is there are significant difference, because
When this terminates to occur in kettle " dry pot phenomenon " to polymerization, the conversion ratio of raw material propylene is about 70%, and solid material only accounts for kettle in kettle
35% or so of volume, also 50% or more space are not fully used.
Patent CN1467228 discloses a kind of polyacrylic reaction kettle of batch liquid bulk polymerization production and removes hot method,
In in the top of reaction kettle, one condenser is set, allow the liquid propylene condensed out from flowing back to reaction kettle, and gas phase is (uncooled
Propylene and fixed gas hydrogen) then backed into kettle with a gas-recycling plant.It is polyacrylic anti-the method increase producing
It answers kettle to remove thermal energy power, can improve the yield of equipment, but the volume of reaction kettle itself is still without being utilized effectively.
Patent CN101618310 discloses a kind of reaction kettle and its thermal withdrawal mode.This thermal withdrawal mode is：Reaction kettle it is upper
Outer circulation condenser system is condensed on the outside of the reacted kettle of propylene vapor of end gas outlet release, condensed liquid phase, gas phase
Propylene is flowed back to by the effect conducted oneself with dignity with circulating fan in reaction kettle.This method solve to a certain extent reaction kettle enlargement,
Batch bulk process production copolymer polypropylene removes the inadequate problem of thermal energy power, and output per single reactor and product quality is made to be improved, but
The volume of reaction kettle itself is still without being utilized effectively.
Patent CN102464735 and CN103030720 disclose two kinds of intermittent liquid phase bulk polymerizations and produce polyacrylic equipment
And method, respectively by increase the method for gas chromatograph and infrared spectrum analyser, timing or continuous detection reaction kettle inner propene with
The content ratio for not participating in the inert component of reaction calculates propylene polymerization rate according to the content ratio, opens the temperature control system
The rate of polymerization for controlling propylene is stablized in target polymerization rate, anti-to overcome intermittent liquid phase bulk polymerization polypropylene production apparatus
The problem that initial stage temperature is not easy to control, late phase reaction is weak is answered, interval liquid phase method is effectively increased and produces polyacrylic control stabilization
Property and equipment yield, have the advantages that simple in structure, steady temperature control, high degree of automation, but the invention does not also efficiently use
The space of reaction kettle itself.
Invention content
An object of the present invention is to provide a kind of polyacrylic method of intermittent liquid phase bulk polymerization production, and the method improves
The capacity utilization of polymeric kettle in the case where catalyst activity allows can improve the yield of single polymerization cycle, to
Achieving the purpose that expand can increase production.
It is yet another object of the invention to provide the polyacrylic equipment of intermittent liquid phase bulk polymerization production for realizing the above method.
The technical solution adopted by the present invention is：
A kind of polyacrylic method of intermittent liquid phase bulk polymerization production, including：
1) before polymerisation, the connection between polymeric kettle and the monomer compensating tank being attached thereto is cut off, respectively to polymeric kettle
With liquid propylene is injected in monomer compensating tank, then by pressure control unit make the pressure in monomer compensating tank be higher than polymeric kettle
The saturated vapor pressure of propylene at least 0.1MPa when interior maximum allowable operating temperature (M.A.O.T.)；
2) after polymerisation starts, monomer compensating tank is connected to polymeric kettle；It is maintained in monomer compensating tank in polymerization process
Pressure be step 1) in set pressure；
3) when the propylene liquid level in monomer compensating tank is less than 20%, its connection between polymeric kettle is cut off；
4) when occurring " dry pot " phenomenon in polymeric kettle, Propylene recovery simultaneously discharges.
Specifically, the step of the method is as follows：
1) before polymerisation, the connection between polymeric kettle and the monomer compensating tank being attached thereto is cut off, respectively to polymeric kettle
With a certain amount of liquid propylene is injected in monomer compensating tank, then so that monomer is compensated pressure tank higher than poly- by pressure control unit
The saturated vapor pressure at least 0.1MPa of propylene when closing maximum allowable operating temperature (M.A.O.T.) in kettle.
In an embodiment of the present invention, between the polymeric kettle and monomer compensating tank by piping connection, in polymeric kettle and
The connection and cut-out of both valve control are equipped between monomer compensating tank.
According to the present invention, when liquid propylene being added into polymeric kettle, using these propylene by external electron donor and organo-aluminium
Co-catalyst pours in polymeric kettle, and this point is identical as the Conventional batch liquid phase noumenal method polyacrylic technique of production.
According to the present invention, the total amount of feeding of propylene monomer is more, and the capacity utilization of polymeric kettle is got in single polymerization cycle
It is high.The single polymerization cycle refers to a polymerization process from propylene feeding to polymer discharge.But the addition of propylene
There are the upper limits for amount, because while as propylene total amount of feeding increases, the polymer build-up obtained in single polymerization cycle, but due to
The polymerization activity generally existing of polypropylene catalyst extends at any time and the characteristic that decays, and polymerization yield rate is caused to decline.Work as extension
When the effect for improving entire polymerization cycle polymerization yield rate is not achieved in polymerization time, the simple capacity utilization for improving polymeric kettle is also
It is nonsensical；On the other hand with the increase of propylene total amount of feeding, the solid capacity rate polymerizeing in later stage polymeric kettle can accordingly increase, and gather
Closing the heat-exchange capacity of kettle can accordingly decline, and lead to temperature fluctuation in system, and then cause the fluctuation of product quality, therefore by third
The control of alkene addition is advisable in a certain range." a certain amount of " meaning is：In single polymerization cycle, propylene monomer it is total
Inventory is the 110%-220% of polymeric kettle volume under maximum allowable operating temperature (M.A.O.T.).
According to the present invention, the computational methods to the propylene inventory of polymeric kettle and monomer compensating tank are as follows：
Assuming that being ρ by the liquid propylene density that liquid propylene source provides1, the density of propylene is ρ under maximum allowable operating temperature (M.A.O.T.)2, throw
How much density of liquid propylene for being provided according to liquid propylene source of doses calculate.If step 1) feeding intake into polymeric kettle
Amount is V1, it is V to the inventory of monomer compensating tank2, propylene used in catalytic component is added below in step 2) into polymeric kettle
Amount be V3, the volume of polymeric kettle is V0, then the total amount of feeding V of propylene monomer is according to following formula calculating：
Wherein, V3Value be certain, and (V1+V3) the sum of inventory generally polymerization temperature under polymeric kettle volume
90%, so V2Amount can also be calculated, so as to which list is calculated by the total amount of feeding V needed according to above-mentioned formula
The inventory V of body compensating tank2。
In an embodiment of the present invention, the operation temperature of the polymeric kettle is 75 DEG C.Maximum allowable operating temperature (M.A.O.T.) depends on catalysis
The dynamic behavior of agent and polymeric kettle remove thermal energy power, not by artificially controlling, will be typically higher than 5-10 DEG C of setting value, are 80-
85℃。
According to the present invention, the pressure in monomer compensating tank is higher, and the amount of molecular weight regulator hydrogen can be added in polymeric kettle
It is more；Heat exchanger duty will be higher but then, and the design pressure that monomer compensating tank and polymeric kettle need is also higher.By
It is generally 80-85 DEG C in the maximum allowable operating temperature (M.A.O.T.) of polymeric kettle, the saturated vapor pressure relative to propylene under maximum allowable operating temperature (M.A.O.T.) is
3.7-4.1MPa.Monomer compensation pressure tank is higher than the pressure 0.1-1.0MPa, preferably 0.2-0.5MPa in the present invention.
2) after polymerisation starts, monomer compensating tank is connected to polymeric kettle；Monomer compensating tank is maintained in polymerization process
Pressure is the pressure set in step 1).
In an embodiment of the present invention, by the way that molecular weight regulator is added into polymeric kettle, with a certain amount of (i.e. aforementioned V3)
Liquid propylene catalytic component is poured into initiated polymerization in polymeric kettle, and the temperature in polymeric kettle is increased to need
Monomer compensating tank is connected to by polymerization temperature, the valve then opened between monomer compensating tank and polymeric kettle with polymeric kettle.Polymerization is anti-
During answering, the smaller liquid propylene monomer of density is constantly changed into the larger solid phase polypropylene of density, and liquid consolidates two in polymeric kettle
The total volume of phase is reducing.At this time due to propylene when the pressure of monomer compensating tank is consistently higher than maximum allowable operating temperature (M.A.O.T.) in polymeric kettle
Saturated vapor pressure, monomer compensating tank can continuously supplement liquid phase propylene monomer into polymeric kettle, make to begin in polymeric kettle in polymerization process
It is in the full kettle state of liquid-solid two-phase eventually.
According to the present invention, the catalyst used in the present invention includes external electron donor, organic aluminum cocatalyst, and is contained
The catalytic component of titanium, magnesium, halogen and internal electron donor, such as the catalyst for polymerization of propylene prepared in patent CN1091748A.Step
It is rapid 1) in into polymeric kettle be added volume be V1Liquid propylene external electron donor and organic aluminum cocatalyst are poured into polymeric kettle
It is interior；It is V that volume, which is added, into polymeric kettle in step 2)3Liquid propylene by the catalysis containing titanium, magnesium, halogen and internal electron donor
Agent component pours in polymeric kettle.
3) when the liquid level in monomer compensating tank is less than 20%, its connection between polymeric kettle is cut off.
In an embodiment of the present invention, the liquid level be 2-10%, preferably 5%, so on the one hand can ensure monomer benefit
It repays tank internal volume to be utilized to the greatest extent, on the other hand also ensures that monomer compensating tank can reach the pressure of setting always.It cuts
When disconnected connection between monomer compensating tank and polymeric kettle, initial stage is still full kettle state in polymeric kettle, but due to catalyst at this time
Activity has been in degradation period, so being not in the unsafe condition of over-temp and over-pressure.If occurring still having more third in monomer compensating tank
Alkene, but the polymerization activity in polymeric kettle is very low, it, can when extending the case where polymerization time can not also improve single polymerization cycle yield
Connection between early cut-off monomer compensating tank and polymeric kettle.
4) when occurring " dry pot " phenomenon in polymeric kettle, Propylene recovery simultaneously discharges.
According to the present invention, " the dry pot " refers to that liquid propylene monomer disappears substantially in polymeric kettle, and gas is in polymeric kettle
Gu a kind of state of two-phase.
It is a further object of the present invention to provide a kind of intermittent liquid phase bulk polymerizations to produce polyacrylic equipment.With prior art phase
Than invention increases the monomer compensating tank being connected with polymeric kettle and the pressure control units to match therewith.
The equipment includes：
Polymeric kettle, for providing place for propylene polymerization；
The feed inlet of monomer compensating tank, discharge port and polymeric kettle connects, for being supplemented into polymeric kettle in reaction process
Monomer propylene；
Liquid propylene source, discharge port connect with the feed inlet of the feed inlet of monomer compensating tank and polymeric kettle, are used for respectively
Propylene is provided to monomer compensating tank and polymeric kettle；And
Pressure control unit is connect with the monomer compensating tank, for maintaining the pressure in monomer compensating tank.
In an embodiment of the present invention, the volumetric ratio of the monomer compensating tank and polymeric kettle is (0.3-1.5):1.The volume
Than bigger, the storable propylene amount for compensating polymeric kettle is more in monomer compensating tank, polymeric kettle in single polymerization cycle
Capacity utilization is bigger.But since propylene total amount of feeding is there are the upper limit, similarly there is the upper limit in the volume of monomer compensating tank.
In an embodiment of the present invention, the pressure control unit is a vapor heat exchanger, entrance and monomer compensating tank
Bottom is connected, and is connected at the top of outlet and monomer compensating tank, the position of the preferably described vapor heat exchanger is less than monomer compensating tank.The steaming
Vapour heat exchanger is generally the tubular heat exchanger of shell-and-tube, and propylene monomer walks tube side, and steam walks shell side, and steam is by tube wall by heat
Pass to the propylene monomer in pipe.Liquid propylene in monomer compensating tank enters heat exchanger from tank bottom through pipeline under the effect of gravity
It is interior, it is then heated and is gasified by heat exchanger, and by being condensed in tank with the outlet line being connected at the top of monomer compensating tank, to
Achieve the purpose that indirectly to liquid propylene increasing temperature and pressure in monomer compensating tank.The heat exchanger entrance position is filled equipped with flow-rate adjustment
It sets, for adjusting the propylene flow into heat exchanger, the propylene in monomer compensating tank is made to maintain certain pressure.When monomer compensates
When pressure tank is less than setting value, the propylene flow into heat exchanger is tuned up, it is on the contrary then turn the propylene flow into heat exchanger down.It should
Flow regulator can be a regulating valve being electrically connected with ambient controller, on the controller its opening size of remote adjustment；
It can also be a needle-valve, its opening size adjusted by manual site.
Further, the monomer compensating tank is equipped with the pressure remote transmission instrument being electrically connected with ambient controller and liquid level
Remote transmission instrument is respectively used to the pressure in displaying monomer compensating tank and liquid level, convenient for carrying out remote monitoring to these parameters.
It is simple, reasonable, compact that intermittent liquid phase bulk polymerization provided by the invention produces polyacrylic device structure.According to this hair
The device and method of bright offer can improve the capacity utilization of polymeric kettle, continue in the case where the increase of polymeric kettle volume is limited
The monocycle yield of aggrandizement apparatus can be increased production to achieve the purpose that expand.It is 12m with polymeric kettle volume3Interval liquid-phase bulk
For method polypropylene plant, according to the technology of the present invention, one volume of increase is 12m3Monomer compensating tank, propylene monomer just
Beginning inventory can also double.In the case where catalyst activity is stablized, if compared with prior art, the present invention propylene turns
Rate is all 75%, although the single operation cycle stretch-out 50% or so of the present invention, the capacity utilization of polymeric kettle is by 35%
It improves to 70%, yield accordingly doubles, and device overall efficiency can be improved 30% or so.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
It applies example to be used to explain the present invention together, does not constitute any restrictions to embodiment of the present invention.
Fig. 1 is the schematic diagram that intermittent liquid phase bulk polymerization of the present invention produces polyacrylic equipment.
Fig. 2 is the schematic diagram that intermittent liquid phase bulk polymerization of the present invention produces polyacrylic small testing device.
It marks in the accompanying drawings as follows：
1 is polymeric kettle；2 be monomer compensating tank；2-1 is liquid level remote transmission instrument；2-2 is pressure remote transmission instrument；3 change for steam
Hot device；4 be regulating valve；5 be liquid propylene source；6-1,6-2 and 6-3 are valve；7 devices in order to control；8 be feed pot；8-1 and 8-2
For valve.
Specific implementation mode
Conventional batch liquid phase noumenal method produce polyacrylic equipment mainly and include feed purification, polymerisation, flash distillation deactivation,
It is granulated and the technique units such as packaging.The technique unit of the polymerisation includes propylene measuring tank, activator feeding tank, catalyst
The devices such as feed pot, hydrogen metering tank, polymeric kettle, hot water storgae, heat-exchanger pump, cold line and steam pipe line.Polymeric kettle is all made of
Tank reactor, polymeric kettle are removed heat and are realized by chuck and inner cool tube.Intermittent liquid phase bulk polymerization production of the present invention
Polyacrylic equipment includes above-mentioned technique unit and device, but in order to protrude present disclosure, above-mentioned technique unit and device
It is in the accompanying drawings and unlisted.
Fig. 1 is that intermittent liquid phase bulk polymerization of the present invention produces polyacrylic equipment, and 1 top of polymeric kettle is equipped with feed inlet,
For propylene, catalyst, hydrogen etc. to be added into kettle, lower section is equipped with discharge port (not shown).Stirring is equipped in polymeric kettle 1
Paddle, agitating paddle are connect with the motor outside polymeric kettle 1.
Outlet is equipped with above and below monomer compensating tank 2, wherein the feed inlet of the outlet of lower section and 1 top of polymeric kettle
Connection is equipped with valve 6-2 and 6-3 on the connecting line of monomer compensating tank 2 and polymeric kettle.Liquid level gauge 2-1 connects with monomer compensating tank 2
It connects, for monitoring the liquid propene liquid level in monomer compensation, pressure remote transmission instrument 2-2 is connect with monomer compensating tank 2, for monitoring
Monomer compensates pressure inside the tank, and liquid level remote transmission instrument 2-1 and pressure teletransmission 2-2 are electrically connected with controller 7, are conveniently operated personnel couple
The long-range monitoring of this two parameters.
Feed inlet of the liquid propylene source 5 respectively with 1 top of the outlet of 2 lower section of monomer compensating tank and polymeric kettle connects,
The pipeline in liquid propylene source 5 is equipped with charging main valve 6-1, and valve 6-2 is on the pipeline between valve 6-1 and monomer compensating tank, valve
6-3 is on the pipeline between valve 6-1 and polymeric kettle 1.Monomer compensating tank 2 thus may be implemented and polymeric kettle 1 separately measures
The purpose of charging.
Vapor heat exchanger 3 is shell-and-tube tubular heat exchanger, and feed inlet connect with the outlet of 2 lower section of monomer compensating tank, steams
The discharge port of vapour heat exchanger 3 is connect with the outlet of 2 top of monomer compensating tank, and regulating valve is equipped in the feed inlet of vapor heat exchanger 3
4, the regulating valve 4 adjusts opening size by air driving, and driving mechanism is electrically connected with controller 7, so that operator
Member remotely controls it.
Embodiment 1-3 is carried out on polymerization small testing device as shown in Figure 2.Polymeric kettle 1 is the stainless of 3.4L
Steel reaction kettle, the top of kettle are equipped with the feed pot 8 of catalyst and co-catalyst, volume 0.02L, above and below feed pot
There are valve 8-1 and 8-2, propylene feed line to be connected to the top of feed pot 8 respectively, the top of polymeric kettle 1, which also has, is connected with hydrogen
Charge line, there are outlet valve and discharge port in lower section, these are not showed that on attached drawing 2；The volume of monomer compensating tank 2 is 5L,
Due to experimental provision scale is smaller, embodiment is not used shell and tube vapor heat exchanger and gives monomer compensating tank 2 pressure control, but in monomer
Chuck is set outside compensating tank 2, pressure is made to the heating of monomer compensating tank by being passed through hot water into chuck, is set on hot water inlet pipe's line
There are regulating valve 4, model Badger 1003-GC-N-36-SV-OS-35P-36, the regulating valve 4 to be electrically connected with controller 7,
Monomer compensating tank 2 is set to maintain certain pressure by adjusting its opening size on controller 7.
Liquid propylene source 5 is integrated the plunger pump that product is 10L, and the import of plunger pump is connected with propylene tank outside battery limit (BL),
The pump has function of measuring, can add up the volume for getting propylene.It is 20 DEG C to pump inner propene temperature, density 0.517g/cm3,
Polymerization temperature in embodiment is 70 DEG C, and since lab scale kettle temperature control effect is preferable, temperature in the kettle is all attached at 70 DEG C in polymerization process
Closely, the maximum allowable operating temperature (M.A.O.T.) therefore in embodiment is also approximately at 70 DEG C, and density of propylene is 0.412g/cm at a temperature of this3, rinse
Propylene amount V used in catalyst2It is 10 times of 7 volume of feed pot, is 0.2L.
Comparative example
Under nitrogen protection, valve 8-1 is opened, by the hexane of the co-catalyst triethyl aluminum of a concentration of 0.5mol/L of 4ml
Feed pot is added in the hexane solution of the external electron donor Cyclohexyl Methyl Dimethoxysilane of solution and a concentration of 0.5mol/L of 2ml
In 8；It is then shut off valve 8-1, opens valve 6-1,6-3 and 8-2 successively, starts plunger pump 5, using monomer propylene by co-catalysis
Agent and external electron donor pour in polymeric kettle 1, when the volume for squeezing into propylene is 2.2L, cuts off plunger pump 5, open polymeric kettle 1
Stirring, and close valve 6-3 and 8-2, then 80mg hydrogen be added in polymeric kettle 1 using hydrogen charging pipeline；It opens
Propylene in valve 8-1 emptying feed pots 7, then under nitrogen protection by the catalyst for polymerization of propylene component of 30mg (referring to special
The embodiment 1 of sharp CN1091748A) it is added in feed pot 8, valve 8-1 is closed, opens valve 6-3 and 8-2, and quickly start
Plunger pump 5 is poured catalyst in polymeric kettle 1 with 0.2L propylene, then cuts off plunger pump 5, and close valve 8-2,6-3 successively
And temperature in polymeric kettle 1 is increased to 70 DEG C, starts polymerisation by 6-1, the Temperature-controlled appliance for opening polymeric kettle 1.After 1 hour
Pressure is less than 3.0MPa in polymeric kettle 1, illustrates to start " dry pot " occur in kettle, Propylene recovery simultaneously discharges, and obtains polypropylene 945g.
This experiment polymerize the material addition step before starting and the recycling blowing after polymerization shares about 1 hour, the total amount of feeding of propylene
It is the 90% of 1 volume of polymeric kettle according to calculating at 70 DEG C of polymerization temperature, polymerization cycle is 2 hours, monocycle polymer yield
About 472g/h.
Embodiment 1
Under nitrogen protection, valve 8-1 is opened, by the hexane of the co-catalyst triethyl aluminum of a concentration of 0.5mol/L of 4ml
Feed pot is added in the hexane solution of the external electron donor Cyclohexyl Methyl Dimethoxysilane of solution and a concentration of 0.5mol/L of 2ml
In 8；It is then shut off valve 8-1, opens valve 6-1,6-3 and 8-2 successively, starts plunger pump 5, using monomer propylene by co-catalysis
Agent and external electron donor pour in polymeric kettle 1, when the volume for squeezing into propylene is 2.2L, cuts off plunger pump 5, open polymeric kettle 1
Stirring, and close valve 6-3 and 8-2, then 80mg hydrogen be added in polymeric kettle 1 using hydrogen charging pipeline；It opens
The liquid propylene that volume is 0.8L is added into monomer compensating tank 2, then stops plunger pump 5 for valve 6-2, restarting plunger pump 5,
And close valve 6-2；Regulating valve 3 is opened, aperture 100% is passed through hot water into 2 chuck of monomer compensating tank, and hot water temperature 95
DEG C, the aperture of regulating valve 3 is adjusted according to the pressure size of pressure remote transmission instrument 2-2, its pressure is made finally to stablize in 3.4MPa, liquid
Phase propylene is 3.0MPa in 70 DEG C of saturated vapor pressure, and the pressure of monomer compensating tank 2 is higher than this pressure 0.4MPa；Open valve 8-
Propylene in 1 emptying feed pot 8, then under nitrogen protection by the catalyst for polymerization of propylene component of 30mg (referring to patent
The embodiment 1 of CN1091748A) it is added in feed pot 8, valve 8-1 is closed, opens valve 6-3 and 8-2, and quickly start column
Plug pump 5, catalyst is poured in polymeric kettle 1, then cut off plunger pump 5 with 0.2L propylene, and close successively valve 8-2,6-3 and
Temperature in polymeric kettle 1 is increased to 70 DEG C, starts polymerisation by 6-1, the Temperature-controlled appliance for opening polymeric kettle 1；Open valve
6-2, since pressure is higher than polymeric kettle 1 in monomer compensating tank 2, monomer compensating tank inner propene will be pressed into polymeric kettle 1, until poly-
It closes kettle 1 and reaches full kettle, and with the progress of polymerisation, the propylene in monomer compensating tank 2 can continuously fill into polymeric kettle 1；
After 0.3 hour, remaining 0.2 liter of propylene in monomer compensating tank, the connection between cut-out monomer compensating tank 2 and polymeric kettle 1；1.4 small
Shi Hou, pressure is less than 3.0MPa in polymeric kettle 1, illustrates to start " dry pot " occur in kettle, Propylene recovery simultaneously discharges, and obtains polypropylene
1260g.This experiment polymerization start before material addition step and recycling blowing after polymerization share about 1 hour, propylene it is total
Inventory is the 120% of 1 volume of polymeric kettle according to calculating at 70 DEG C of polymerization temperature, and polymerization cycle is 2.4 hours, and the monocycle is poly-
It is about 525g/h to close produce rate, and single polymerization cycle interpolymer yield improves 11% compared with comparative example.
Embodiment 2
Under nitrogen protection, valve 8-1 is opened, by the hexane of the co-catalyst triethyl aluminum of a concentration of 0.5mol/L of 4ml
Feed pot is added in the hexane solution of the external electron donor Cyclohexyl Methyl Dimethoxysilane of solution and a concentration of 0.5mol/L of 2ml
In 8；It is then shut off valve 8-1, opens valve 6-1,6-3 and 8-2 successively, starts plunger pump 5, using monomer propylene by co-catalysis
Agent and external electron donor pour in polymeric kettle 1, when the volume for squeezing into propylene is 2.2L, cuts off plunger pump 5, open polymeric kettle 1
Stirring, and close valve 6-3 and 8-2, then 80mg hydrogen be added in polymeric kettle 1 using hydrogen charging pipeline；It opens
The liquid propylene that volume is 1.9L is added into monomer compensating tank 2, then stops plunger pump 5 for valve 6-2, restarting plunger pump 5,
And close valve 6-2；Regulating valve 3 is opened, aperture 100% is passed through hot water into 2 chuck of monomer compensating tank, and hot water temperature 95
DEG C, the aperture of regulating valve 3 is adjusted according to the pressure size of pressure remote transmission instrument 2-2, its pressure is made finally to stablize in 3.5MPa, liquid
Phase propylene is 3.0MPa in 70 DEG C of saturated vapor pressure, and the pressure of monomer compensating tank 2 is higher than this pressure 0.5MPa；Open valve 8-
Propylene in 1 emptying feed pot 7, then under nitrogen protection by the catalyst for polymerization of propylene component of 30mg (referring to patent
The embodiment 1 of CN1091748A) it is added in feed pot 8, valve 8-1 is closed, opens valve 6-3 and 8-2, and quickly start column
Plug pump 5, catalyst is poured in polymeric kettle 1, then cut off plunger pump 5 with 0.2L propylene, and close successively valve 8-2,6-3 and
6-1, the Temperature-controlled appliance for opening polymeric kettle are increased to 70 DEG C by temperature in the kettle is polymerize, start polymerisation；Open valve 6-
2, since pressure is higher than polymeric kettle 1 in monomer compensating tank 2,2 inner propene of monomer compensating tank will be pressed into polymeric kettle 1, until poly-
It closes kettle 1 and reaches full kettle, and with the progress of polymerisation, the propylene in monomer compensating tank 2 can continuously fill into polymeric kettle 1；
After 1.4 hours, remaining 0.3 liter of propylene in monomer compensating tank 2, the connection between cut-out monomer compensating tank 2 and polymeric kettle 1；1.8 small
Shi Hou, pressure is less than 3.0MPa in polymeric kettle 1, illustrates to start " dry pot " occur in kettle, Propylene recovery simultaneously discharges, and obtains polypropylene
1681g.This experiment polymerization start before material addition step and recycling blowing after polymerization share about 1 hour, propylene it is total
Inventory is the 180% of 1 volume of polymeric kettle according to calculating at 70 DEG C of polymerization temperature, and polymerization cycle is 2.8 hours, and the monocycle is poly-
It is about 600g/h to close produce rate, and single polymerization cycle interpolymer yield improves 27% compared with comparative example.
Embodiment 3
Under nitrogen protection, valve 8-1 is opened, the co-catalyst triethyl aluminum hexane of a concentration of 0.5mol/L of 4ml is molten
Feed pot 8 is added in the hexane solution of the external electron donor Cyclohexyl Methyl Dimethoxysilane of liquid and a concentration of 0.5mol/L of 2ml
It is interior；It is then shut off valve 8-1, opens valve 6-1,6-3 and 8-2 successively, starts plunger pump 5, using monomer propylene by co-catalysis
Agent and external electron donor pour in polymeric kettle 1, when the volume for squeezing into propylene is 2.2L, cuts off plunger pump 5, open polymeric kettle 1
Stirring, and close valve 6-3 and 8-2, then 80mg hydrogen be added in polymeric kettle 1 using hydrogen charging pipeline；It opens
The liquid propylene that volume is 3L is added into monomer compensating tank 2, then stops plunger pump 5 for valve 6-2, restarting plunger pump 5, and
Close valve 6-2；Regulating valve 3 is opened, aperture 100% is passed through hot water into 2 chuck of monomer compensating tank, and hot water temperature is 95 DEG C,
The aperture that regulating valve 3 is adjusted according to the pressure size of pressure remote transmission instrument 2-2 makes its pressure finally stablize in 3.5MPa, liquid phase
Propylene is 3.0MPa in 70 DEG C of saturated vapor pressure, and the pressure of monomer compensating tank 2 is higher than this pressure 0.8MPa；Open valve 8-1
The propylene being vented in feed pot 8, then under nitrogen protection by the catalyst for polymerization of propylene component of 30mg (referring to patent
The embodiment 1 of CN1091748A) it is added in feed pot 8, valve 8-1 is closed, opens valve 6-3 and 8-2, and quickly start column
Plug pump 5, catalyst is poured in polymeric kettle 1, then cut off plunger pump 5 with 0.2L propylene, and close successively valve 8-2,6-3 and
6-1, the Temperature-controlled appliance for opening polymeric kettle are increased to 70 DEG C by temperature in the kettle is polymerize, start polymerisation；Open valve 6-
2, since pressure is higher than polymeric kettle 1 in monomer compensating tank 2,2 inner propene of monomer compensating tank will be pressed into polymeric kettle 1, until poly-
It closes kettle 1 and reaches full kettle, and with the progress of polymerisation, the propylene in monomer compensating tank 2 can continuously fill into polymeric kettle 1；
After 2.8 hours, remaining 0.5 liter of propylene in monomer compensating tank 2, the connection between cut-out monomer compensating tank 2 and polymeric kettle 1；0.5 is small
Shi Hou, pressure is less than 3.0MPa in polymeric kettle 1, illustrates to start " dry pot " occur in kettle, Propylene recovery simultaneously discharges, and obtains polypropylene
2403g.This experiment polymerization start before material addition step and recycling blowing after polymerization share about 1 hour, propylene it is total
Inventory is the 200% of 1 volume of polymeric kettle according to calculating at 70 DEG C of polymerization temperature, and polymerization cycle is 4.3 hours, and the monocycle is poly-
It is about 559g/h to close produce rate, and single polymerization cycle interpolymer yield improves 18% compared with comparative example.
Be not used monomer compensating tank in comparative example 1, in embodiment 1-3, polymerisation start before into monomer compensating tank 2 plus
The liquid propylene volume (be respectively 0.8L, 1.9L, 3L) that enters, the pressure of monomer compensating tank 2 are full at 70 DEG C higher than liquid propylene
Monomer before connection between vapour pressure (being respectively 0.4MPa, 0.5MPa, 0.8MPa), cut-out monomer compensating tank 2 and polymeric kettle 1
Volume (being respectively 0.2L, 0.3L, 0.5L) different from of remaining propylene in compensating tank 2, but be within, it is single
Secondary polymerization cycle interpolymer yield increase rate compared with comparative example illustrates that the present invention achieves significantly 10% or more
Effect.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (14)
1. a kind of intermittent liquid phase bulk polymerization produces polyacrylic method, including：
1) before polymerisation, the connection between polymeric kettle and the monomer compensating tank being attached thereto is cut off, respectively to polymeric kettle and list
Liquid propylene is injected in body compensating tank, then so that the pressure in monomer compensating tank is higher than in polymeric kettle most by pressure control unit
The saturated vapor pressure of propylene at least 0.1MPa when High Operating Temperature；
2) after polymerisation starts, monomer compensating tank is connected to polymeric kettle；The pressure in monomer compensating tank is maintained in polymerization process
Power is the pressure set in step 1)；
3) when the propylene liquid level in monomer compensating tank is less than 20%, its connection between polymeric kettle is cut off；
4) when occurring " dry pot " phenomenon in polymeric kettle, Propylene recovery simultaneously discharges.
2. according to the method described in claim 1, it is characterized in that, the total amount of feeding of single polymerization cycle propylene monomer is highest
The 110%-220% of polymeric kettle volume under operation temperature.
3. according to the method described in claim 2, it is characterized in that, the maximum allowable operating temperature (M.A.O.T.) is 80-85 DEG C.
4. according to the method in any one of claims 1 to 3, which is characterized in that the pressure of monomer compensating tank described in step 1)
The saturated vapor pressure 0.1-1.0MPa of propylene when power is higher than maximum allowable operating temperature (M.A.O.T.) in polymeric kettle.
5. according to the method described in claim 4, it is characterized in that, the compensation pressure tank of monomer described in step 1) is higher than polymeric kettle
The saturated vapor pressure 0.2-0.5MPa of propylene when interior maximum allowable operating temperature (M.A.O.T.).
6. according to the method in any one of claims 1 to 3, which is characterized in that monomer compensating tank inner propene in step 3)
When liquid level is less than 2%-10%, its connection between polymeric kettle is cut off.
7. according to the method described in claim 6, it is characterized in that, monomer compensating tank inner propene liquid level is less than 5% in step 3)
When, cut off its connection between polymeric kettle.
8. a kind of intermittent liquid phase bulk polymerization produces polyacrylic equipment, including：
Polymeric kettle, for providing place for propylene polymerization；
The feed inlet of monomer compensating tank, discharge port and polymeric kettle connects, and is used in reaction process the make-up monomers into polymeric kettle
Propylene；
Liquid propylene source, discharge port are connect with the feed inlet of the feed inlet of monomer compensating tank and polymeric kettle respectively, are used for list
Body compensating tank and polymeric kettle provide propylene；And
Pressure control unit is connect with the monomer compensating tank, for maintaining the pressure in monomer compensating tank.
9. equipment according to claim 8, which is characterized in that the volumetric ratio of the monomer compensating tank and polymeric kettle is
(0.3-1.5):1。
10. equipment according to claim 8, which is characterized in that the monomer compensating tank is equipped with and is electrically connected with the controller
Pressure remote transmission instrument and liquid level remote transmission instrument.
11. the equipment according to any one of claim 8 to 10, which is characterized in that the pressure control unit is a steaming
Vapour heat exchanger, entrance are connected with monomer compensation pot bottom, are connected at the top of outlet and monomer compensating tank.
12. equipment according to claim 11, which is characterized in that the position of the vapor heat exchanger is compensated less than monomer
Tank.
13. equipment according to claim 11, which is characterized in that the vapor heat exchanger entry position is equipped with flow-rate adjustment
Device, for adjusting the propylene flow into vapor heat exchanger.
14. equipment according to claim 13, which is characterized in that the flow regulator is electric for needle-valve or with controller
The regulating valve of connection.
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| CN109456429B (en) * | 2017-09-06 | 2021-05-11 | 中国石油化工股份有限公司 | Gas phase method for producing polypropylene |
| CN108299735A (en) * | 2018-03-21 | 2018-07-20 | 山东京博石油化工有限公司 | A kind of method that interval small capital body technology prepares high just acrylic resin |
| CN111790313A (en) * | 2020-05-29 | 2020-10-20 | 南京金陵塑胶化工有限公司 | Automatic feeding system for polypropylene catalyst by intermittent liquid-phase bulk method |
Citations (4)
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|---|---|---|---|---|
| CN1467228A (en) * | 2002-07-02 | 2004-01-14 | 中国石化集团巴陵石油化工有限责任公 | Method for removing heat of polypropylene polymerization kettle by intermittent liquid-phase bulk method |
| CN101787090A (en) * | 2010-03-05 | 2010-07-28 | 南京金陵塑胶化工有限公司 | High-pressure propylene replenishing process |
| CN102464735A (en) * | 2010-11-19 | 2012-05-23 | 中国石油化工股份有限公司 | Device for producing polypropylene by intermittent liquid phase bulk polymerization method and method |
| CN103030725A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Apparatus and method for production of alpha-olefin polypropylene random copolymers by batch liquid-phase bulk technique |
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| JP3937420B2 (en) * | 1998-09-09 | 2007-06-27 | コニカミノルタビジネステクノロジーズ株式会社 | Image forming apparatus |
| JP5055816B2 (en) * | 2006-04-17 | 2012-10-24 | 住友化学株式会社 | Polyolefin powder transfer apparatus and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1467228A (en) * | 2002-07-02 | 2004-01-14 | 中国石化集团巴陵石油化工有限责任公 | Method for removing heat of polypropylene polymerization kettle by intermittent liquid-phase bulk method |
| CN101787090A (en) * | 2010-03-05 | 2010-07-28 | 南京金陵塑胶化工有限公司 | High-pressure propylene replenishing process |
| CN102464735A (en) * | 2010-11-19 | 2012-05-23 | 中国石油化工股份有限公司 | Device for producing polypropylene by intermittent liquid phase bulk polymerization method and method |
| CN103030725A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Apparatus and method for production of alpha-olefin polypropylene random copolymers by batch liquid-phase bulk technique |
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