CN110041450A - The method for producing butyl rubber - Google Patents
The method for producing butyl rubber Download PDFInfo
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- CN110041450A CN110041450A CN201810046184.3A CN201810046184A CN110041450A CN 110041450 A CN110041450 A CN 110041450A CN 201810046184 A CN201810046184 A CN 201810046184A CN 110041450 A CN110041450 A CN 110041450A
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- chloromethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
- C08F210/12—Isobutene with conjugated diolefins, e.g. butyl rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/12—Separation of polymers from solutions
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- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to rubber materials, disclose a kind of method for producing butyl rubber, this method comprises: (1) carries out copolyreaction in catalyst and in the presence of as the chloromethanes of solvent, by isobutylene monomer and isoprene monomer, the chloromethanes containing butyl rubber particle is obtained in slurry；(2) chloromethanes containing butyl rubber particle is introduced into slurry as, to be separated by gas floatation process, acquisition concentrates in slurry and liquid chloromethanes respectively in slurry separator；(3) the liquid chlorine methane cycle is returned in step (1) to provide at least partly solvent, wherein the isolated temperature is 5~70 DEG C higher than the temperature of the copolyreaction.The method of production butyl rubber provided by the invention can realize the separation of butyl rubber particle and solvent chloromethanes under relatively lower temp, so that the method tool of the production butyl rubber of the method for production butyl rubber of the invention compared with the existing technology is significantly reduced the advantage of energy consumption.
Description
Technical field
The present invention relates to rubber materials, and in particular, to a method of produce butyl rubber.
Background technique
Butyl rubber, abbreviation IIR (Isobutylene Isoprene Rubber), have good chemical stability and
Thermal stability, most outstanding is to have good air-tightness and watertightness.It is only the 1/ of natural rubber to the transmitance of air
7, the 1/5 of butadiene-styrene rubber, and be then the 1/200 of natural rubber to the transmitance of steam, the 1/140 of butadiene-styrene rubber.Therefore butyl
Rubber is mainly for the manufacture of various rubber products such as the various inner tubes of a tyre, steam pipe, curing bag, dam bottom and washers.
Nineteen forty-three, Esso chemical company, the U.S. realize butyl rubber industrialized production first.Hereafter, Canadian, France,
Soviet Union etc. also realizes the industrialized production of butyl rubber in succession.The beginning of the eighties, world's butyl rubber production capacity are about
650kt accounts for synthetic rubber total output about 5%.
Butyl rubber is mainly copolymerized by monomer isobutene and a small amount of auxiliary monomer alkadienes (such as isoprene, butadiene)
It forms.Most common alkadienes is isoprene, and dosage is 1.5-4.5% or so.Butyl rubber polymerization is that cationic polymerization is anti-
Answer, it is higher to the purity requirement of monomer and solvent etc., the purity of general isobutene must > 99.5 weight %, isoprene it is pure
Degree must > 98 weight %, and the purity requirement of solvent chloromethanes > 95 weight %.The initiator of use is usually H2O-AlCl3Or
HCl-EDTA.When polymerization, chain transfer reaction easily occurs, and inherently a kind of effective chain-transferring agent of isobutene.Moreover, chain
Transfer reaction activation energy is living than energy much larger than chain propagation reaction, therefore can reduce reaction temperature to inhibit chain transfer reaction.If
The copolymer that the degree of polymerization is 1000 or so is obtained, polymerization temperature is about -60 DEG C or so；And it goes for the degree of polymerization and is about
When 10000 copolymer, then polymerization temperature is generally -98 DEG C or so.
There are two types of the polymerization of butyl rubber production is usual, respectively polymerisation in solution and slurry polymerization.It is poly- using solution
When conjunction, monomer and polymer are all dissolved in solvent (such as hexane, carbon tetrachloride).With the progress of reaction, polymer meltage increases
Adding rises solution viscosity, causes heat transfer difficult, and polymer can stick at kettle wall, the rear place such as is easy to kiss-coating etc., and has solvent recovery
Science and engineering is made, so method less use in the industry.Slurry process is mainly used in industry, this method is with highly polar chloromethane
(CH3Cl) make solvent, it can dissolve monomer, but insoluble polymer.The polymer of generation can be scattered in molten as fine particle
Paste-like is formed in agent, can reduce heat transmission resistance, rapid polymerization in this way, so that production capacity can be improved.But what slurry process generated
Polymer is atomic small particle and is precipitated with precipitate morphology, is easy to deposit adhesion in polymeric kettle bottom and pipeline, while because
It is very subtle for polymer particle size, and be not easy to be kept completely separate with solvent chloromethanes.The mechanical stirring of strength must be used thus；Or
Circulation polymerizer in the special shell and tube of person can make material forced circulation and export polymer.
In general, the process conditions of butyl rubber production polymerization are as follows: isobutene/isoprene monomer matches about 97/3 (quality
Than), solvent is chloromethane, and ratio of the monomer in solvent mixture is 25-40% (mass fraction).Polymerization temperature about -100
DEG C, initiator A lCl3Concentration 0.2-0.3%.Polymerisation conversion: isobutene 75-95%, isoprene 45-85%.Product butyl
The degree of unsaturation 1.55 ± 0.2% (molar fraction) of rubber, Mooney viscosity 40-60.
Low temperature required for polymerization reaction (such as -100 DEG C) commonly uses liquid ethylene as coolant to obtain.In this way, raw material
The cooling of system and the cooling of polymerization reaction system are required to the equipment such as a large amount of condensing agent and compressor.Economically and operate
On all bring bigger difficulty and trouble.
Frequently with slurry polymerization process, process flow is specifically included that thick isobutene and chlorine the industrial production of butyl rubber
After methane is dehydrated and is refined in dehydrating tower and rectifying column respectively, with isoprene in mixing channel according to a certain percentage
Mixing obtains mixed liquor；Mixed liquor is cooled to -100 DEG C in cooler, is then fed into reactor.It is molten to prepare catalyst simultaneously
Liquid and cooling, polymerization reaction are carried out at -98 DEG C or so, and almost instantaneous to complete, polymer precipitates in chloromethanes and forms graininess
Slurries.Slurry after polymerization is overflowed from reactor into flash tank filled with hot water, evaporates chloromethanes and not instead herein
Answer monomer.The aqueous slurry liquid of rubber with being pumped into extrusion drying system, it is dry after packed products.The steam that flash tank comes out is through work
Property aluminium oxide is dry, be sent to charging after fractionation and catalyst preparation system circulation uses.
The polymer reactor of butyl rubber is a kind of forced circulation multitube polymer reactor of heat exchanger-type.At center
The bobbin that part has ascending fluid to flow, and have small-bore tubulation for declining fluid around it.Liquefied ethylene is logical from lower part
Enter clamp evaporate inside it achieve the purpose that it is cooling, to keep polymerization temperature at -100 DEG C or so；When polymerization by isobutene and
The CH of isoprene3Cl solution is passed through from reactor bottom.It is passed through simultaneously from another pipeline of bottom prepared containing initiation
The CH of agent3Cl solution.Initiator content is about the 0.02% of content of monomer, and the chloromethane mixture of copolymer is from the upper of reactor
Portion's discharge port overflows.To prevent that the precipitating and kiss-coating of polymer occur in polymer reactor, generally require slurry in reactor
There is the flow velocity of 2~5m/s.Therefore, strong blender is that this polymerization system is essential.
But in existing butyl rubber in slurry polymerization, chloromethanes is as solvent, in the course of the polymerization process, chloromethane
Alkane content is usually 65~85%.After polymerization, butyl rubber product is suspended in chloromethane alkane solvents with fine particle, is formed
Milky fluid state.In order to recycle butyl rubber polymer, usually -90 DEG C to -100 DEG C of the mixture that polymerization is formed is passed through
To steam air lift kettle, is contacted by hot water with 80 DEG C~120 DEG C and steam, exchange heat, evaporate chloromethanes, unreacted list
Body.Rubber grain then stays in the hot water, is delivered to dehydration and drying unit by pump and is further processed to form product.It is steamed by condensing field
After the chloromethanes that the temperature issued is 80 DEG C~120 DEG C is by cooling, separating monomer, moisture, one-step removal impurity of going forward side by side, into
Enter to be recycled, compression is cooled to -100 DEG C using propylene, ethylene, and be mixed into polymeric kettle under catalyst with monomer
Polymerization, again air lift, in cycles.Cool down in this way, needing constantly to recycle from 120 DEG C as the chloromethanes of solvent and cooling medium
To -100 DEG C, polymerization is participated in, then 120 DEG C of recycling is again heated to using steam, expends huge energy in cycles.
This is one of main composition of energy consumption in butyl rubber polymerization process.Butyl rubber energy conservation polymerization is the glue kind
The global problem of development is also Main way.The present invention is precisely in order to solving the problems, such as this and generating.
Summary of the invention
The purpose of the invention is to overcome the prior art to separate during producing butyl rubber to contain butyl rubber
The chloromethanes of particle high defect of existing energy consumption when slurry provides a kind of method of new production butyl rubber.
Butyl rubber chloromethanes in slurry polymerization process is monomer polymerization solvent and heat transfer medium.It is main in production process
Energy consumption is to need during isolating rubber product in chloromethanes by low temperature liquid chloromethanes in slurry polymerization process
Heating evaporation is to gaseous state chloromethanes.It needs gaseous state chloromethanes being cooled to low temperature liquid chloromethanes again when being recycled.So
The reason of circulation, is that the rubber particles formed in slurry polymerization process are distributed evenly in low temperature liquid chloromethane alkane solvents, nothing
Method efficiently separates；The recycling of rubber must will be passed through in hot water in slurry.If rubber can will be separated and recovered from slurry, and not
Introduce the polymerization poisons such as hot water, can using the low temperature liquid chloromethanes separated as solvent directly or through after processing with polymerize
Monomer mixing participates in polymerization, achievees the purpose that save energy consumption.The present inventor has found under study for action, by will be by isobutene
The chloromethanes containing butyl rubber particle that monomer and isoprene monomer are formed through copolyreaction heated up in slurry so that
The separation of solvent of the chloromethanes containing butyl rubber particle in slurry and the butyl rubber particle wherein contained is more total than described
When carrying out under the conditions of high 5~70 DEG C of temperature of poly- reaction, it can guarantee butyl rubber particle and chlorine under the premise of reducing energy consumption
Methane solvent efficiently separates, and completes technical solution of the present invention based on this.
To, the present invention provides a kind of method for producing butyl rubber, this method comprises:
(1) in catalyst and in the presence of as the chloromethanes of solvent, isobutylene monomer and isoprene monomer are carried out
Copolyreaction obtains the chloromethanes containing butyl rubber particle in slurry；
(2) by the chloromethanes containing butyl rubber particle in slurry is introduced into as slurry separator in pass through gas floatation process into
Row separation, obtains concentrate in slurry and liquid chloromethanes respectively；
(3) the liquid chlorine methane cycle is returned to provide at least partly solvent in step (1),
Wherein, the isolated temperature in step (2) is higher by 5~70 than the temperature of the copolyreaction in step (1)
℃。
It is provided by the invention production butyl rubber method can be realized under relatively lower temp butyl rubber particle and
The separation of solvent chloromethanes, so that the production butyl rubber of the method for production butyl rubber of the invention compared with the existing technology
The method tool of glue is significantly reduced the advantage of energy consumption.
Detailed description of the invention
Fig. 1 is a kind of structure chart in slurry separator of preferred embodiment.
Description of symbols
1, the chloromethanes containing butyl rubber particle is in slurry
2, slurry is concentrated in
3, liquid chloromethanes
4, gas distributor
5, nitrogen
6, bubble source
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of methods for producing butyl rubber, this method comprises:
(1) in catalyst and in the presence of as the chloromethanes of solvent, isobutylene monomer and isoprene monomer are carried out
Copolyreaction obtains the chloromethanes containing butyl rubber particle in slurry；
(2) by the chloromethanes containing butyl rubber particle in slurry is introduced into as slurry separator in pass through gas floatation process into
Row separation, obtains concentrate in slurry and liquid chloromethanes respectively；
(3) the liquid chlorine methane cycle is returned to provide at least partly solvent in step (1),
Wherein, the isolated temperature in step (2) is higher by 5~70 than the temperature of the copolyreaction in step (1)
℃。
Under preferable case, the isolated temperature in step (2) is higher than the temperature of the copolyreaction in step (1)
20~70 DEG C.
It is highly preferred that the isolated temperature in step (2) is higher by 30 than the temperature of the copolyreaction in step (1)
~60 DEG C.
It was found by the inventors of the present invention that it is 5~70 DEG C higher than the temperature of the copolyreaction to control the isolated temperature, it is excellent
20~70 DEG C are selected, preferably 30~60 DEG C can significantly facilitate the chloromethanes containing butyl rubber particle in the separation of slurry.
According to a kind of preferred embodiment, the temperature of the copolyreaction is -90 DEG C to -100 DEG C.
Under preferable case, in step (2), the step of being separated by the gas floatation process includes: from being set forth in slurry point
Bottom from device introduces bubble to being set forth in slurry separator, and by the chloromethanes containing butyl rubber particle in slurry from
The middle part and/or lower part for being set forth in slurry separator, which are introduced to, to be set forth in slurry separator, so that described contain butyl rubber particle
Butyl rubber particle of the chloromethanes in slurry the top for being set forth in slurry separator is risen under the buoyancy of the bubble
And/or top, and be set forth in slurry separator is drawn from the outlet for being set forth in the top and/or top of slurry separator is located at.
Preferably, the bubble is set forth in the gas distributor generation of slurry separator bottom by being located at.
Under preferable case, the bubble is nitrogen bubble.The bubble of the invention may be what inert gas generated
Bubble.
Preferably, the step of being separated by the gas floatation process further comprises: from the middle part for being set forth in slurry separator
And/or top to be set forth in slurry separator purge nitrogen so that it is isolated concentrate in slurry and draw be set forth in slurry and separate
Device.
Under preferable case, in step (2), the isolated liquid chloromethanes starches the bottom of separator by being set forth in
Draw be set forth in slurry separator.
Preferably, in step (2), butyl rubber particle of the chloromethanes containing butyl rubber particle in slurry
Content is 15~40 weight %；It is highly preferred that the chloromethanes containing butyl rubber particle is in slurry in step (2)
The content of butyl rubber particle is 25~35 weight %.
Under preferable case, method of the invention further comprises: in step (3), by the liquid chlorine methane cycle
It returns in step (1) to provide at least partly before solvent, is first filtered the liquid chloromethanes obtained by step (2)
Reason.
Method of the invention is not particularly limited the concrete operations condition of gas floatation process, and those skilled in the art can root
It is selected according to the conventional condition using gas floatation process separation in the art, for example, those skilled in the art can choose tool
Have suitable draw ratio in slurry separator, control drawn from gas distributor bubble flow velocity, control contain butyl rubber
The chloromethanes of particle enters in slurry concentrates in slurry and liquid in what the flow in the unit time of slurry separator, control separation obtained
Chloromethanes draws the conditions such as the flow velocity of nitrogen of flow, control for purging within the unit time.The embodiment of the present invention portion
Divide the concrete operations condition for illustratively listing several gas floatation processes, those skilled in the art should not be construed as to limit of the invention
System.
The structure in slurry separator of one of method of the invention preferred embodiment is provided below in conjunction with Fig. 1
Schematic diagram, specifically:
The bottom of slurry separator is provided with gas distributor 4, passes through the gas distributor 4 from extraneous bubble source 6
Bubble is introduced to being set forth in slurry separator, and the chloromethanes containing butyl rubber particle is separated in slurry 1 from slurry is set forth in
The middle part and/or lower part of device, which are introduced to, to be set forth in slurry separator, makes the chloromethane containing butyl rubber particle by gas floatation process
Alkane in slurry 1 in butyl rubber particle risen under the buoyancy of the bubble be set forth in slurry separator top and/or
Top, so that realizing that the chloromethanes containing butyl rubber particle is separated into slurry 1 concentrates in slurry 2 and liquid chloromethanes 3, by by
The middle part and/or top for being set forth in slurry separator are to being set forth in slurry separator the nitrogen 5 that purges so that isolated is dense
It shrinks in slurry 2 and be set forth in slurry separator and the liquid chlorine is drawn by the outlet for being set forth in the top and/or top of slurry separator
Methane 3 draws be set forth in slurry separator by the bottom for being set forth in slurry separator.
Method of the invention is no special in the method for the copolyreaction of slurry to the chloromethanes containing butyl rubber particle is generated
Other limitation can be the method for conventional production butyl rubber in the art, such as carry out in polymerization reaction kettle.
Under preferable case, in the copolyreaction of step (1), monomer total dosage (isobutylene monomer and isoprene
Monomer) with as solvent chloromethanes dosage weight ratio be 1:(0.5~5).
Preferably, in the copolyreaction of step (1), the use of the isobutylene monomer and the isoprene monomer
Amount weight ratio is 1:(0.01~0.1).
Preferably being operated using full kettle in slurry separator in method of the invention.
In method of the invention can by acquisition concentrate in slurry be introduced in such as stripping vessel carry out further stripping with
Separate the solvent chloromethanes wherein contained.
In the present invention, contain butyl rubber particle through what copolyreaction was formed by isobutylene monomer and isoprene monomer
Chloromethanes can also be containing such as unreacted isobutylene monomer of 2~5 weight %, isoprene monomer and micro- in slurry
The catalyst residue of amount.Under normal circumstances, the chloromethanes containing butyl rubber particle is white liquid in starching.
In gas floatation process of the invention, by gas distributor generate bubble in uphill process by surface tension effects with
Chloromethanes containing butyl rubber particle in slurry butyl rubber particle adherency, thus drive butyl rubber particle float as
The top and/or top of separator are starched, and then is formed and concentrates in slurry.
In step (1) of the invention, the catalyst of the copolyreaction can be AlCl3Catalyst or Dichloroethyl
Aluminium/HCl catalyst.
Method provided by the invention reduces the stripping recovery processing amount of the chloromethanes under same monomer feed amount, to drop
Low production energy consumption.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated
Under condition, the various raw materials used are all from commercially available.
Product Mooney viscosity is measured using Mooney viscosity instrument in following embodiment, to understand properties of product.Non- sulphur
Change glue Mooney viscosity and shear viscosimeter using GT-7080S2 disk, using standard are as follows: GB/T1232.1, experimental condition are as follows: ML (1
+8)125℃。
It is used in the following embodiment in slurry separator be cylinder type, and ratio of height to diameter be 25:4, contain butyl rubber grain
Son chloromethanes in slurry from distance be set forth in slurry separator bottom 3/5 highly from be introduced into as starch separator in, it is used below
In slurry separator solvent be 50m3。
The chloromethanes containing butyl rubber particle from butyl rubber continuous experimental apparatus is in slurry by polymerization reaction kettle
Kettle top produces and enters in slurry separator.
Embodiment 1
Monomer blends situation in batching kettle: the weight of monomer total amount (isobutylene monomer and isoprene monomer) and chloromethanes
Than for 56:44, wherein isobutylene monomer and the dosage weight ratio of isoprene monomer are 97:3.
The liquid chloromethanes of circulation enters polymerization reaction kettle after mixing with the monomer solution introduced by batching kettle, in two chloroethenes
It polymerize under base aluminium/HCl catalyst according to prior art, monomer solution flow is 4.4t/h, due to the circulation of slurry separator extraction
Liquid chlorine methane flow rate be 4.2t/h, the temperature of copolyreaction is -97 DEG C.The chloromethanes containing butyl rubber particle obtained
The concentration of butyl rubber particle in slurry contains butyl rubber between 23.8~25.2 weight %, into slurry separator
The chloromethanes of particle in slurry flow be 8.6t/h, in slurry separator operating parameter include: separation temperature be -40 DEG C；In slurry
The nitrogen introduction volume of separator bottom is 40m3/h；In slurry separator bottom liquid chloromethanes produced quantity be 4.2t/h；In slurry
The extraction for concentrating in slurry at the top of separator is 4.4t/h.Slurry is concentrated in further to be separated using existing method.
As a result: polymerisation conversion is calculated as 84% by recycle section；The efficiency of butyl rubber production is 2.07t/h, device
Production energy consumption is that 2340kg marks oil/xanthan；Product Mooney range of viscosities 42~54 in device continuous service 50h.
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that:
It is not provided in this comparative example in slurry separator.
Specifically:
Monomer blends situation in batching kettle: the weight of monomer total amount (isobutylene monomer and isoprene monomer) and chloromethanes
Than for 56:44, wherein isobutylene monomer and the dosage weight ratio of isoprene monomer are 97:3.
Enter polymerization reaction kettle after the monomer solution mixing introduced by batching kettle, is pressed under ethyl aluminum dichloride/HCl catalyst
It polymerize according to prior art, monomer solution flow is 8.6t/h, and the temperature of copolyreaction is -97 DEG C.What is obtained contains butyl rubber
The concentration of butyl rubber particle of the chloromethanes of particle in slurry is between 23.8~25.2 weight %.Contain butyl rubber particle
Chloromethanes separated in slurry using existing method.
As a result: polymerisation conversion is calculated as 84% by recycle section；The efficiency of butyl rubber production is 2.08t/h, device
Production energy consumption is that 3500kg marks oil/xanthan；Product Mooney range of viscosities 45~55 in device continuous service 50h.
Comparative example 2
This comparative example is carried out using method similar to Example 1, the difference is that in slurry separator in this comparative example
Portion in slurry separation temperature be -96 DEG C, and in slurry separator bottom liquid chloromethanes produced quantity be 0.8t/h；Monomer solution stream
Amount is 7.8t/h.Remaining is in the same manner as in Example 1.
As a result: polymerisation conversion is calculated as 82% by recycle section；The efficiency of butyl rubber production is 2.03t/h, device
Production energy consumption is that 3460kg marks oil/xanthan；Product Mooney range of viscosities 45~55 in device continuous service 50h.
Embodiment 2
Monomer blends situation in batching kettle: the weight of monomer total amount (isobutylene monomer and isoprene monomer) and chloromethanes
Than for 45:55, wherein isobutylene monomer and the dosage weight ratio of isoprene monomer are 97:3.
The liquid chloromethanes of circulation enters polymerization reaction kettle after mixing with the monomer solution introduced by batching kettle, in two chloroethenes
It polymerize under base aluminium/HCl catalyst according to prior art, monomer solution flow is 5.5t/h, due to the circulation of slurry separator extraction
Liquid chlorine methane flow rate be 4.0t/h, the temperature of copolyreaction is -97 DEG C.The chloromethanes containing butyl rubber particle obtained
The concentration of butyl rubber particle in slurry contains butyl rubber between 23.8~25.2 weight %, into slurry separator
The chloromethanes of particle in slurry flow be 8.9t/h, in slurry separator operating parameter include: separation temperature be -50 DEG C；In slurry
The nitrogen introduction volume of separator bottom is 38m3/h；In slurry separator bottom liquid chloromethanes produced quantity be 4.0t/h；In slurry
The extraction for concentrating in slurry at the top of separator is 5.5t/h.Slurry is concentrated in further to be separated using existing method.
As a result: polymerisation conversion is calculated as 86% by recycle section；The efficiency of butyl rubber production is 2.13t/h, device
Production energy consumption is that 2395kg marks oil/xanthan；Product Mooney range of viscosities 46~57 in device continuous service 50h.
Embodiment 3
Monomer blends situation in batching kettle: the weight of monomer total amount (isobutylene monomer and isoprene monomer) and chloromethanes
Than for 50:50, wherein isobutylene monomer and the dosage weight ratio of isoprene monomer are 97:3.
The liquid chloromethanes of circulation enters polymerization reaction kettle after mixing with the monomer solution introduced by batching kettle, in two chloroethenes
It polymerize under base aluminium/HCl catalyst according to prior art, monomer solution flow is 4.8t/h, due to the circulation of slurry separator extraction
Liquid chlorine methane flow rate be 4.1t/h, the temperature of copolyreaction is -97 DEG C.The chloromethanes containing butyl rubber particle obtained
The concentration of butyl rubber particle in slurry contains butyl rubber between 23.8~25.2 weight %, into slurry separator
The chloromethanes of particle in slurry flow be 8.8t/h, in slurry separator operating parameter include: separation temperature be -60 DEG C；In slurry
The nitrogen introduction volume of separator bottom is 42m3/h；In slurry separator bottom liquid chloromethanes produced quantity be 4.1t/h；In slurry
The extraction for concentrating in slurry at the top of separator is 4.8t/h.Slurry is concentrated in further to be separated using existing method.
As a result: polymerisation conversion is calculated as 85% by recycle section；The efficiency of butyl rubber production is 2.09t/h, device
Production energy consumption is that 2370kg marks oil/xanthan；Product Mooney range of viscosities 42~52 in device continuous service 50h.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, the difference is that in slurry separator in the present embodiment
Portion in slurry separation temperature be -70 DEG C, and in slurry separator bottom liquid chloromethanes produced quantity be 3.7t/h.Remaining with
It is identical in embodiment 1.
As a result: polymerisation conversion is calculated as 82.6% by recycle section；The efficiency of butyl rubber production is 2.01t/h, dress
Setting production energy consumption is that 2480kg marks oil/xanthan；Product Mooney range of viscosities 42~54 in device continuous service 50h.
The result of comparison the present embodiment and embodiment 1 can be seen that 27 DEG C of temperature difference of separation temperature and copolyreaction
Under the conditions of, the liquid chloromethanes produced quantity of embodiment 4 is smaller than the liquid chloromethanes produced quantity of embodiment 1, and production energy consumption is more real
It applies high in example 1.
Embodiment 5
The present embodiment is carried out using method similar to Example 1, the difference is that in slurry separator in the present embodiment
Portion is -30 DEG C in the separation temperature of slurry.Remaining is in the same manner as in Example 1.
As a result: polymerisation conversion is calculated as 85% by recycle section；The efficiency of butyl rubber production is 2.10t/h, device
Production energy consumption is that 2420kg marks oil/xanthan；Product Mooney range of viscosities 42~54 in device continuous service 50h.
The result of comparison the present embodiment and embodiment 1 can be seen that 67 DEG C of temperature difference of separation temperature and copolyreaction
Under the conditions of, the liquid chloromethanes produced quantity of embodiment 5 and the liquid chloromethanes produced quantity of embodiment 1 are suitable, but production energy consumption
It is slightly higher compared with compared in embodiment 1.
Embodiment 6
The present embodiment is carried out using method similar to Example 2, the difference is that in slurry separator in the present embodiment
Portion in slurry separation temperature be -85 DEG C, and in slurry separator bottom liquid chloromethanes produced quantity be 3.1t/h；Monomer solution stream
Amount is 6.4t/h.Remaining is in the same manner as in Example 2.
As a result: polymerisation conversion is calculated as 82% by recycle section；The efficiency of butyl rubber production is 2.07t/h, device
Production energy consumption is that 2580kg marks oil/xanthan；Product Mooney range of viscosities 46~55 in device continuous service 50h.
The result of comparison the present embodiment and embodiment 2 can be seen that 12 DEG C of temperature difference of separation temperature and copolyreaction
Under the conditions of, the liquid chloromethanes produced quantity of embodiment 6 is smaller than the liquid chloromethanes produced quantity of embodiment 2, and production energy consumption is more real
It applies high in example 2.
Embodiment 7
The present embodiment is carried out using method similar to Example 1, the difference is that in slurry separator in the present embodiment
Portion in slurry separation temperature be -91 DEG C, and in slurry separator bottom liquid chloromethanes produced quantity be 2.0t/h；Monomer solution stream
Amount is 6.6/h.Remaining is in the same manner as in Example 1.
As a result: polymerisation conversion is calculated as 80% by recycle section；The efficiency of butyl rubber production is 2.07t/h, device
Production energy consumption is that 2720kg marks oil/xanthan；Product Mooney range of viscosities 45~55 in device continuous service 50h.
Method provided by the invention can be realized under low energy consumption it can be seen from the result of above-described embodiment and comparative example
The separation of chloromethanes containing butyl rubber particle the butyl rubber particle in slurry and solvent chloromethanes, also, separate and obtain
Liquid chloromethanes excellent quality, can be recycled back in the copolymerization system for prepare butyl rubber and participate in copolyreaction.
Moreover, the method for production butyl rubber provided by the invention can obtain the butyl rubber of excellent quality.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for producing butyl rubber, this method comprises:
(1) in catalyst and in the presence of as the chloromethanes of solvent, isobutylene monomer and isoprene monomer are copolymerized
Reaction, obtains the chloromethanes containing butyl rubber particle in slurry；
(2) by the chloromethanes containing butyl rubber particle in slurry is introduced into as starch separator in be divided by gas floatation process
From acquisition concentrates in slurry and liquid chloromethanes respectively；
(3) the liquid chlorine methane cycle is returned to provide at least partly solvent in step (1),
Wherein, the isolated temperature in step (2) is 5~70 DEG C higher than the temperature of the copolyreaction in step (1).
2. the method for production butyl rubber according to claim 1, wherein the isolated temperature ratio in step (2)
The temperature of the copolyreaction in step (1) is 20~70 DEG C high；Preferably, the isolated temperature in step (2) is than step
Suddenly the temperature of the copolyreaction in (1) is 30~60 DEG C high.
3. the method for production butyl rubber according to claim 1 or 2, wherein in step (1), the copolyreaction
Temperature be -90 DEG C to -100 DEG C.
4. the method for butyl rubber is produced described in any one of -3 according to claim 1, wherein in step (2), pass through
The step of gas floatation process is separated include: from be set forth in slurry separator bottom to be set forth in slurry separator in introduce gas
Bubble, and the chloromethanes containing butyl rubber particle is introduced in slurry from the middle part and/or lower part for being set forth in slurry separator
To being set forth in slurry separator, so that butyl rubber particle of the chloromethanes containing butyl rubber particle in slurry is described
The top and/or top for being set forth in slurry separator are risen under the buoyancy of bubble, and are set forth in slurry separator from being located at
Draw be set forth in slurry separator in the outlet at top and/or top.
5. the method for production butyl rubber according to claim 4, wherein the bubble is by being located at be set forth in slurry separator
The gas distributor of bottom generates.
6. the method for production butyl rubber according to claim 4 or 5, wherein the bubble is nitrogen bubble.
7. the method for production butyl rubber according to claim 4, wherein the step of being separated by the gas floatation process
Further comprise: from be set forth in slurry separator middle part and/or top to be set forth in slurry separator in purging nitrogen so that score
Be set forth in slurry separator is drawn from the obtained slurry that concentrates in.
8. the method for production butyl rubber according to claim 1 or 2, wherein in step (2), isolated institute
It states liquid chloromethanes and be set forth in slurry separator is drawn by the bottom for being set forth in slurry separator.
9. the method for production butyl rubber according to claim 1 or 2, wherein described to contain butyl in step (2)
The content of butyl rubber particle of the chloromethanes of rubber particles in slurry is 15~40 weight %；Preferably,
The content of butyl rubber particle of the chloromethanes containing butyl rubber particle in slurry is 25~35 weight %.
10. the method for production butyl rubber according to claim 1 or 2, wherein this method further comprises: in step
(3) it in, returns in step (1) by the liquid chlorine methane cycle to provide at least partly before solvent, will first be obtained by step (2)
The liquid chloromethanes obtained is filtered processing.
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| CN112745436A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Solvent recycling method and butyl rubber production method |
| CN112745439A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Polymer solution preparation method and butyl rubber production method |
| CN112745437A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Production method of butyl rubber glue solution |
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| CN112745435A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Process for converting polymer slurry into polymer solution and process for producing butyl rubber |
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| CN112745436B (en) * | 2019-10-31 | 2022-07-12 | 中国石油化工股份有限公司 | Solvent recycling method and butyl rubber production method |
| CN112745439B (en) * | 2019-10-31 | 2022-07-12 | 中国石油化工股份有限公司 | Polymer solution preparation method and butyl rubber production method |
| CN112745435B (en) * | 2019-10-31 | 2022-07-12 | 中国石油化工股份有限公司 | Process for converting polymer slurry into polymer solution and process for producing butyl rubber |
| CN111040063A (en) * | 2019-12-25 | 2020-04-21 | 浙江信汇新材料股份有限公司 | Production process of food-grade butyl rubber |
| CN110903425A (en) * | 2019-12-27 | 2020-03-24 | 浙江信汇新材料股份有限公司 | Method for improving unsaturation degree of butyl rubber at initial reaction stage |
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