CN104031196A - Production process for ethylene propylene rubber - Google Patents
Production process for ethylene propylene rubber Download PDFInfo
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- CN104031196A CN104031196A CN201410160151.3A CN201410160151A CN104031196A CN 104031196 A CN104031196 A CN 104031196A CN 201410160151 A CN201410160151 A CN 201410160151A CN 104031196 A CN104031196 A CN 104031196A
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- propylene rubber
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Abstract
The invention discloses a production process for ethylene propylene rubber. The production process comprises the following five process steps: feeding; polymerization; monomer removal; product acquirement; and solvent recovery. A catalyst used in polymerization is a metallocene catalyst which has high catalytic activity and efficiency, the catalyst is included in an ethylene propylene rubber product after polymerization, no residue is left, and removal of the catalyst is not needed. During polymerization, five tandem kettles are employed, second-stage and third-stage kettles are used for supplementing feeds, and gas-liquid-solid (metallocene catalyst) three-phase reaction is adopted. According to the process, closed type circulation is utilized, unreacted monomers can be returned to the kettles for cyclic use after flash separation, so the utilization rate of raw materials is improved; solubility parameters of solvents are changed to obtain the ethylene propylene rubber product, so energy conservation and high efficiency are realized. Moreover, the process is a green process and has the advantages of no generation of exhaust gas, waste water and waste residue, a high utilization rate of resources, high efficiency, greenness, environmental protection and no influence on the environment.
Description
Technical field
The present invention relates to Chemical Manufacture Technology field, be specifically related to a kind of ethylene-propylene rubber(EPR) production technique.
Background technology
The a large amount of hydro carbons of meeting by-product in refining of petroleum and petrochemical production process, it is fully utilized is the necessary means that improves Business Economic Benefit.Propylene is the important foundation Organic Chemicals that comes from oil, coal, Sweet natural gas, China's propylene production capacity of 2012 is 1,800 ten thousand tons/year, 1,500 ten thousand tons of output, wherein approximately 75% for the production of polypropylene, and the organic chemical industry's industry based on propylene feedstocks is starkly lower than global mean level (ML).
Ethylene-propylene rubber(EPR), is referred to as Ethylene-propylene Elastomer, is the third-largest synthetic rubber that global consumption is only second to styrene-butadiene rubber(SBR) and cis-1,4-polybutadiene rubber.Along with the continuous expansion of the continuous appearance of Ethylene-propylene Elastomer new variety and Application Areas, compared with other synthetic rubber kinds, Ethylene-propylene Elastomer is the glue kind that demand growth is the fastest.In recent years, Chinese market remains high speed sustainable growth, is the fastest country of Ethylene-propylene Elastomer Growth of Consumption of the world, and imbalance between supply and demand is more sharp-pointed all the time, and the production that improves Ethylene-propylene Elastomer has great importance to national market and economy.The gentleness that ethylene-propylene rubber(EPR) working condition should be tried one's best, avoid the condition of High Temperature High Pressure, the unnecessary energy that reduces production process scatters and disappears, and significantly reduces the production risk of process of factory production simultaneously, make more safe, the energy-saving and environmental protection of process of producing, make the production of factory more stable.
At present, be the ethylene-propylene rubber(EPR) technique that catalyst system is produced with vanadium, need without exception Removal of catalyst, and have the discharge containing vanadium waste residue or vanadium-containing water.Solvent needs purification and recover simultaneously, and Production Flow Chart is long, and equipment is many, and construction investment and running cost are higher.But existing luxuriant be that the ethylene-propylene rubber(EPR) production technique of catalyst system can not be controlled polymerization temperature well, and promotor consumption is too high.
The defect that the production technique of available technology adopting different phase and technology exist is as follows:
1. vapor phase process: ethylene-propylene rubber(EPR) yields poorly, reaction is violent, and pressure change is large.The bad control of temperature, but molecular weight distribution is comparatively stable.Deliming, denitrating catalyst operation is loaded down with trivial details.
2. solution method: ethylene-propylene rubber(EPR) output is higher compared with vapor phase process, needs demonomerization, deliming, denitrating catalyst operation is loaded down with trivial details, need a large amount of water to clean rubber, and exquisite solvent workshop section energy consumption is very high, and the energy consumption of dry glue product is high.In production system, introduce moisture, and moisture is toxic to catalyzer, easily in glue product, introduces more impurity simultaneously, affect glue product quality.
3. suspension method: the glue product quality heterogeneity obtaining, the condition harshness of reaction, demonomerization energy consumption is high, deliming, denitrating catalyst operation is loaded down with trivial details, needs a large amount of water to clean rubber.The energy consumption of dry glue product is high, introduces moisture in production system, and moisture is toxic to catalyzer, easily in glue product, introduces more impurity simultaneously, affects glue product quality.
The technological deficiency existing according to above prior art, more excellent production technique needs people to study.
Summary of the invention
The invention provides a kind of excellent catalytic effect, productive rate is high, production cost is low ethylene-propylene rubber(EPR) production technique.
A kind of ethylene-propylene rubber(EPR) production technique, this technical scheme comprises following processing step:
(1) charging workshop section
Ethene is with gas-phase feed, and propylene is with liquid phase feeding.Hexane as solvent and catalyst mix completely after, entered in reactor by reactor top, it is mixed, avoid occurring the situation of local catalyzer overrich.Gaseous ethene, liquid propylene and the 3rd monomer (ethylidene norbornene) are added to mixing tank, make material enter front preliminary mixing of reactor, be diluted to solution in order to avoid local overrich phenomenon occurs diene skewness in solvent.
(2) polyreaction workshop section
Reaction has taked five reactors to carry out serial operation, only first step reactor adds solvent, second and third order reaction still is added charging and catalyzer, classification charging is mainly that concentration distribution, temperature distribution and the reaction density distribution for adjusting in reflection mutually carried out, ensure that thus polyreaction maintains the suitable residence time, simultaneously, each order reaction equilibrium, can effectively control and shift out reaction heat, thereby make temperature distribution homogeneous in reacting phase, thereby obtain having the multipolymer of pre-provisioning request quality index.
Selective reaction temperature range is 40～50 DEG C, and reaction pressure is 7bar, polymerization time 10-15min, and reaction process is nonhomogeneous system.The ethene of gas phase reacts with the propylene of boiling, and the product simultaneously generating is constantly dissolved in hexane, also has the reaction of part to occur in liquid phase hexane.The space of propylene gasification is left on the top of reactor.
(3) monomer removes workshop section
Utilize the pressure that polyreaction workshop section provides to carry out twice flash distillation, be respectively high pressure flash and low pressure flash.Unreacted monomer can be spun off by flash distillation, part hexane solvent can be flashed off again, reduce the energy charge of the tower of solvent recuperation workshop section.
(4) obtaining of product
In step 3, remove in the solvent that is dissolved with ethylene-propylene rubber(EPR) product of monomer, add propyl carbinol (or gamma-butyrolactone), propyl carbinol and solvent hexane mass ratio are 2.57: 1 (gamma-butyrolactone and hexane mass ratio are 1.5: 1), change the polarity of solvent, ethylene-propylene rubber(EPR) is separated out from solvent, then use Screw Extrusion device that ethylene-propylene rubber(EPR) is extruded, obtain product.
(5) solvent recuperation workshop section
The mixed solvent that removes product in step 4 enters in rectifying tower and separates after preheating, highly purified hexane after separation is returned to reactor and continue to use as solvent cycle.And propyl carbinol (or gamma-butyrolactone) at the bottom of tower is after the charging cooling of the charging of preheating flash tank and rectifying tower, loop back product recycle section, continue to use.
Described catalyzer, monomer, solvent are respectively metallocene catalyst, ethene and propylene, normal hexane.
Described first and second grade of still of polyreaction workshop section adopts heat-transfering device and the water cooling plant co-controlling temperature of reaction of propylene gasification.
Described reactor body material is carbon steel inner liner stainless steel, inside establishes the autoclave equipment of the screw mixer that scraper is housed, and scraper is in order to stir and to remove the gel being bonded on reactor wall, 40 revs/min of rotating speeds.
The end of described polyreaction workshop section has been provided with reducing valve, and reducing valve matches with low pressure storage tank, compressor, the high pressure storage tank of MONOMER RECOVERY workshop section, has ensured the pressure-stabilisation of reaction workshop section.
After described monomer and solvent flashing extract, reusable edible after removal of impurities is processed, economic utilization, makes production process more clean.Described catalyzer, monomer, solvent are respectively metallocene catalyst, ethene and propylene, normal hexane.
The catalyzer that the present invention adopts is metallocene catalyst, described metallocene catalyst is the coordination metal using boron bridge as abutment, the complex compound forming with coordinate bond with monocycle pentadiene and fourth officer group 4 transition metal zirconium, to between heteroatom group and cyclopentadienyl group, be connected with boron abutment, restriction zirconium atoms metal is taking the center of cyclopentadiene as axle rotates, form the catalyzer of constrained geometry configuration half-sandwich, under its configuration is shown in:
The promotor of described metallocene catalyst is boron promotor.The electron deficiency structure of boron atom, less atomic radius, comparatively active chemical property, makes this element become the basic framework of constructing promotor.And aluminum alkyls (as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three positive Xinji aluminium) or the composite participation polyreaction of alkylaluminoxane (as methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutyl aluminium alkoxide (IBAO) etc.) that while using separately organoboron compound to carry out olefinic polymerization as promotor, polymerization activity is lower as the organoboron compound great majority of promotor.
The carrier of described metallocene catalyst is process nitration mixture carbon nanotube after treatment (CNTs), and carbon nanotube (CNTs) can make the tensile strength of ethylene-propylene rubber(EPR) improve, and strengthens its mechanical property, can also improve its conductivity.Therefore metallocene catalyst is loaded on carbon nanotube, in the time that the interpolation quantity of carbon nanotube reaches certain numerical value, can be used as the properties-correcting agent of ethylene-propylene rubber(EPR).
This catalytic activity efficiency is high, and post catalyst reaction contains in ethylene-propylene rubber(EPR) product, without resistates, does not need the de-processing of urging.By do not introduce for the virulent metal ion about unbound state of ethylene-propylene rubber(EPR) catalyzer reach thus in ethylene-propylene rubber(EPR) production process to exempting de-requirement of urging operation, ensure that the character of glue product is good simultaneously.This process using closed type circulation, carries out, after flash separation, again returning still recycle to not participating in the monomer of reaction; Obtain after rubber product, remaining propyl carbinol is separated to recycle with normal hexane (or gamma-butyrolactone) mixing solutions.In addition, the needed general facilities of this technique is water coolant and heating steam.This technique is friendly process, produces without waste gas, waste water, waste residue, and the utilization ratio of resource is higher, and high effective green environmentally friendly can not impact environment.
Brief description of the drawings
Fig. 1 is process flow diagram in embodiment.
Embodiment
Below in conjunction with the technical program, principle and embodiment, the present invention is described further.
A kind of ethylene-propylene rubber(EPR) production technique, comprises the following steps: charging workshop section, reaction workshop section, monomer remove that workshop section, product obtain, solvent recuperation workshop section.
Embodiment 1
(1) charging workshop section
Ethene is with gas-phase feed, and propylene is with liquid phase feeding.Hexane as solvent and catalyst mix completely after, entered in reactor by reactor top, it is mixed.
(2) polyreaction workshop section
First step reactor solubilizing agent, second and third order reaction still is added charging and catalyzer, adjust concentration distribution, temperature distribution and the reaction density of reflection in mutually and distribute, first and second grade use propylene gasification move hot and cold but water remove polymerization reaction heat.Control 40 DEG C of temperature of reaction, pressure 7bar, polymerization time 10min.
(3) monomer removes workshop section
Utilize the pressure that polyreaction workshop section provides to carry out twice flash distillation, be respectively high pressure flash and low pressure flash.Unreacted monomer can be spun off by flash distillation, part hexane solvent can be flashed off again, reduce the energy charge of the tower of solvent recuperation workshop section.
(4) obtaining of product
In step 3, remove in the solvent that is dissolved with ethylene-propylene rubber(EPR) product of monomer, add propyl carbinol (or gamma-butyrolactone), propyl carbinol and hexane mass ratio are the polarity that 2.57: 1 (gamma-butyrolactone and hexane mass ratio are 1.5: 1) changes solvent, ethylene-propylene rubber(EPR) is separated out from solvent, then use Screw Extrusion device that ethylene-propylene rubber(EPR) is extruded, obtain product.
(5) solvent recuperation workshop section
Mixed solvent enters in rectifying tower and separates after preheating, highly purified hexane after separation is returned to reactor and continue to use as solvent cycle.And propyl carbinol (or gamma-butyrolactone) at the bottom of tower is after the charging cooling of the charging of preheating flash tank and two towers, loop back product and obtain workshop section, continue to use.
Embodiment 2:
Production technique is identical with embodiment 1, and difference is that, in described step (2), temperature of reaction is 45 DEG C, and reaction pressure is 7bar, and polymerization time is 12min.
Embodiment 3:
Production technique is identical with embodiment 1, and difference is, in described step (2), temperature of reaction is 50 DEG C, and reaction pressure is 7bar, and polymerization time is 15min.
After the production craft step described in above embodiment, take out ethylene-propylene rubber(EPR) sample, to be measured:
From above data, the ethylene-propylene rubber(EPR) mooney viscosity of producing is high, and weight-average molecular weight is high, and ethylene content is also moderate, and the rate of recovery of monomer and solvent is high, and the propyl carbinol rate of recovery is high, and polymerization efficiency is more than 96%, and production efficiency is high.
Claims (8)
1. an ethylene-propylene rubber(EPR) production technique, is characterized in that, comprises following processing step:
(1) charging workshop section: ethene is with gas-phase feed, and propylene is with liquid phase feeding, and hexane is entered in reactor by reactor top mix completely with metallocene catalyst as solvent after, makes each mixing of materials even.
(2) polyreaction workshop section: reaction has taked five reactors to carry out serial operation, only first step reactor adds solvent, and second and third order reaction still is added charging and catalyzer, and selective reaction temperature range is 40～50 DEG C, reaction pressure is 7bar, and the reaction times is 10-15min.
(3) monomer removes workshop section: utilize the pressure that polyreaction workshop section provides to carry out twice flash distillation, be respectively high pressure flash and low pressure flash, unreacted monomer and part hexane solvent are spun off.
(4) obtaining of product: remove monomer in step (3), be dissolved with in the solvent of ethylene-propylene rubber(EPR) product, add propyl carbinol (or gamma-butyrolactone), propyl carbinol and hexane mass ratio are 2.57: 1 (gamma-butyrolactone and hexane mass ratio are 1.5: 1), change the polarity of solvent, ethylene-propylene rubber(EPR) is separated out from solvent, then use Screw Extrusion device that ethylene-propylene rubber(EPR) is extruded, obtain product.
(5) solvent recuperation workshop section: the mixed solvent that removes product in step (4) separates enter rectifying tower after preheating in, highly purified hexane after separation is returned to reactor to be continued to use as solvent cycle, propyl carbinol (or gamma-butyrolactone) at the bottom of tower is after the charging cooling of the charging of preheating flash tank and rectifying tower, loop back product and obtain workshop section, continue to use.
2. ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that, described catalyzer, monomer, solvent are respectively metallocene catalyst, ethene and propylene, normal hexane.
3. ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that, described first and second grade of still of polyreaction workshop section adopts heat-transfering device and the water cooling plant co-controlling temperature of reaction of propylene gasification.
4. ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that, described reactor body material is carbon steel inner liner stainless steel, inside establishes the autoclave equipment of the screw mixer that scraper is housed.
5. ethylene-propylene rubber(EPR) production technique according to claim 1, is characterized in that, the end of described polyreaction workshop section has been provided with reducing valve.
6. a metallocene catalyst, it is characterized in that, described metallocene catalyst is the coordination metal using boron bridge as abutment, the complex compound forming with coordinate bond with monocycle pentadiene and fourth officer group 4 transition metal zirconium, to between heteroatom group and cyclopentadienyl group, be connected with boron abutment, restriction zirconium atoms metal, taking the center of cyclopentadiene as axle rotates, forms the catalyzer of constrained geometry configuration half-sandwich, under its configuration is shown in:
7. according to the metallocene catalyst of claim 6, it is characterized in that, the promotor of described metal catalyst is boron promotor.
8. according to the metallocene catalyst of claim 6, it is characterized in that, the carrier of described metal catalyst is process nitration mixture carbon nanotube after treatment (CNTs).
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| CN201410160151.3A CN104031196A (en) | 2014-04-17 | 2014-04-17 | Production process for ethylene propylene rubber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104893056A (en) * | 2015-05-28 | 2015-09-09 | 安徽同丰橡塑工业有限公司 | Production process of conductive rubber |
| CN106397089A (en) * | 2015-07-27 | 2017-02-15 | 中国石油天然气股份有限公司 | Method and system for recovering and purifying hexane solvent in ethylene propylene rubber production |
| CN107670318A (en) * | 2017-09-19 | 2018-02-09 | 中国石油集团东北炼化工程有限公司吉林设计院 | EP rubbers produces method for recovering solvents and recovery system |
| CN109836521A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of carbon nanotube/polypropylene composite materials preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893056A (en) * | 2015-05-28 | 2015-09-09 | 安徽同丰橡塑工业有限公司 | Production process of conductive rubber |
| CN106397089A (en) * | 2015-07-27 | 2017-02-15 | 中国石油天然气股份有限公司 | Method and system for recovering and purifying hexane solvent in ethylene propylene rubber production |
| CN106397089B (en) * | 2015-07-27 | 2019-12-10 | 中国石油天然气股份有限公司 | Method and system for recovering and purifying hexane solvent in ethylene propylene rubber production |
| CN107670318A (en) * | 2017-09-19 | 2018-02-09 | 中国石油集团东北炼化工程有限公司吉林设计院 | EP rubbers produces method for recovering solvents and recovery system |
| CN107670318B (en) * | 2017-09-19 | 2019-10-25 | 中国石油集团东北炼化工程有限公司吉林设计院 | EP rubbers produces method for recovering solvents and recovery system |
| CN109836521A (en) * | 2017-11-28 | 2019-06-04 | 中国石油天然气股份有限公司 | A kind of carbon nanotube/polypropylene composite materials preparation method |
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