CN105585651B - A kind of preparation method of high density polyethylene (HDPE) product - Google Patents
A kind of preparation method of high density polyethylene (HDPE) product Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of high density polyethylene (HDPE) product, comprise the following steps：（1）Vinyl monomer, propylene or 1 butene monomers, catalysts and solvents are added in the first polymeric kettle and reacted, the product obtained after reaction enters in the second polymeric kettle；（2）Vinyl monomer, propylene or 1 butene monomers, solvent are added in the second polymeric kettle and reacted, the product obtained after reaction enters in third polymerization kettle；（3）Vinyl monomer, propylene or 1 butene monomers, solvent are added in third polymerization kettle and reacted, the product obtained after reaction enters flash tank, and the material come out from flash tank obtains polyethylene product after subsequent treatment.Molecular weight distribution using three kettles series connection production polymeric articles is wider compared with two kettles series connection product, product mechanical strength preferably can ensured, the index such as the resisting environmental stress and cracking of product, the rapid crack propagation and Slow Crack of tubing manufactured goods can significantly be improved.
Description
Technical field
The present invention relates to chemical field, and in particular to a kind of preparation method of polyethylene product, more particularly relates to one kind
The preparation method of multimodal high density polyethylene product.
Background technology
210,000 HDPE this color tablets are produced in the design of plastic molding and processing plant of Yangtze petro-chemical corporation slurry high density polyethylene (HDPE) device per year
Material, the major part of device is by tri- product line groups of A, B, C into every line production capacity is 70,000 tons/year.Device is using Japan
The slurry high density polyethylene processing technology routine of three well oiling companies.It applies tank reactor, using high-purity ethylene as
Primary raw material, using propylene or 1- butylene as comonomer, using hexane as solvent, using super-active Titanium series catalyst, in temperature
68~85 DEG C, 2~8kg/cm of pressure2Under conditions of carry out low-pressure polymerization, the HDPE powders in polymerisation slurry are through supercentrifuge
Sedimentation separation, drying, mixing, granulation, particle homogenizing, qualified products packaging are dispatched from the factory, and gathering dissolved with low molecule amount in slurry
The mother liquor of compound is sent to polymerization process and uses and be sent to the processing of solvent recovery process as solvent respectively after being separated.Every line has two
Individual structure and volume identical polymeric kettle, two kettles can be formed according to the difference of production procedure and the requirement of process condition
A, B in parallel and series connection three productions pattern in parallel, production extrusion molding, blowing and injection three major types type product.Parallel connection technology flow（Such as
Shown in Fig. 1）To produce the polyethylene product of narrower molecular weight distribution or produce the polyethylene product of moderate molecular weight distribution.String
Joined process flow（As shown in Figure 2）, it is special suitable for high-grade film to produce the polyethylene product of wider molecular weight distribution
The production of material and the pressure resistant pipe material PP Pipe Compound product of higher level.Two kettle techniques can produce bimodal film PP Pipe Compound and pressure pipe
Material PP Pipe Compound product, but for producing multimodal（Broad peak）It is relatively more tired if the polyethylene product of distribution such as heat-resisting pipes polyethylene product
It is difficult.
The content of the invention
Instant invention overcomes the polyethylene product such as heat-resisting pipes polyethylene for being used to produce broad peak distribution in the prior art to produce
Product with regard to it is relatively difficult the problem of, be that multimodal can be produced by providing one kind（Broad peak）The high density polyethylene (HDPE) production of molecular weight distribution
The preparation method of product.
The concrete technical scheme of the present invention is as follows：
A kind of preparation method of high density polyethylene (HDPE) product, comprises the following steps：
（1）Vinyl monomer, propylene or 1- butene monomers, catalysts and solvents are added in the first polymeric kettle and carried out instead
Should, the product obtained after reaction enters in the second polymeric kettle；The flow for the vinyl monomer being added in the first polymeric kettle is 3000
The flow of~6000kg/h, propylene or 1- butene monomers is 15~120kg/h；
（2）Vinyl monomer, propylene or 1- butene monomers, solvent are added in the second polymeric kettle and reacted, after reaction
Obtained product enters in third polymerization kettle；The flow of the vinyl monomer added in the second polymeric kettle is 3000~6000kg/h,
Propylene or the flow of 1- butene monomers are 15~180kg/h；
（3）Vinyl monomer, propylene or 1- butene monomers, solvent are added in third polymerization kettle and reacted, after reaction
Obtained product enters flash tank, and the material come out from flash tank obtains polyethylene product after subsequent treatment；Add the 3rd
The flow of vinyl monomer in polymeric kettle is 1300~5000kg/h, and the flow of propylene or 1- butene monomers is 15~120kg/h.
The catalyst includes Ti series catalysts and triethyl aluminum, and the addition of Ti series catalysts is 0.06~0.12 kg/
H, the addition of triethyl aluminum is 1.2~2.4 kg/h；The Ti series catalysts are using Ti series catalysts conventional in the art
.Ti series catalysts are major catalyst, and triethylaluminium catalyst is cocatalyst, and both catalyst add polymerization simultaneously
Kettle, two kinds of catalyst combine to form a kind of complex compound in polymeric kettle, and this complex compound is used for triggering the generation of polymerisation.
The addition of hexane can root Ju different product production needs be sized, main function be regulation polymeric kettle in
Polymer and hexane mixed serum concentration, while adjust residence time of the reactant in polymeric kettle, the length of residence time
Conversion ratio of the short size that can influence polymer molecular weight and starting monomer etc., is preferably added molten in each polymeric kettle
Agent is hexane, and the addition of hexane is 8000~12000kg/h.
First polymeric kettle, the second polymeric kettle, the temperature in third polymerization kettle are 68~85 DEG C, pressure be 2~
8kg/cm2。
Compared to the prior art the present invention, has the following advantages that：
1st, connected using the series connection production of three kettles compared with two kettles, can more flexibly adjust and contain not inside polymeric articles
With the proportion of composing of molecular weight polyethylene, more comonomers can be promoted to enter in polyethylene molecular chain, improve polyethylene
The degree of branching of strand, strengthen the mutual frenulum effect of polyethylene molecule interchain.
2nd, the molecular weight distribution of polymeric articles is wider compared with two kettles series connection product, preferably can ensure that product machinery is strong
Cause that product is easily processed into type while spending, the resisting environmental stress and cracking of product, the rapid crack propagation of tubing manufactured goods and at a slow speed
The indexs such as crackle can significantly be improved.
3rd, can root Ju difference purposes needs, targetedly adjust molecular weight distribution, Development and Production goes out more rich poly-
Ethylene product.
4th, device has produced heat-resisting pipes PP Pipe Compound product using the technology and high-grade PE100+ tubing is special
Expect product.
Brief description of the drawings
Fig. 1 is intended to for two polymeric kettle polymerization technique serial flows in the prior art；
Fig. 2 is the preparation technology flow chart of multimodal high density polyethylene product of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing, other NM techniques of the present invention and equipment are existing skill
Art.
10kg/cm in the present invention2=1MPa。
Embodiment 1
Referring to Fig. 2, a kind of preparation method of high density polyethylene (HDPE) product, comprise the following steps：
（1）Vinyl monomer, propylene monomer, catalyst and hexane solvent are added in the first polymeric kettle 1 and reacted, instead
Should after obtained product enter in the second polymeric kettle 2；The flow for the vinyl monomer being added in the first polymeric kettle is 4000kg/h,
The flow of propylene monomer is 70kg/h, and the addition of Ti series catalysts is 0.85kg/h, and the addition of triethyl aluminum is 1.2 kg/
H, the addition of hexane solvent is 8000kg/h；
（2）Vinyl monomer, 1- butene monomers, hexane solvent are added in the second polymeric kettle 2 and reacted, after reaction
To product enter third polymerization kettle 4 in；The flow of the vinyl monomer added in the second polymeric kettle is 4000kg/h, propylene monomer
Flow be 120kg/h, the addition of hexane solvent is 7000kg/h；
（3）Vinyl monomer, 1- butene monomers, hexane solvent are added in third polymerization kettle 4 and reacted, after reaction
The product arrived enters flash tank 3, and the material come out from flash tank 3 obtains polyethylene product after subsequent treatment；Add the 3rd
The flow of vinyl monomer in polymeric kettle is 2000kg/h, and the flows of 1- butene monomers is 50kg/h, the addition of hexane solvent
For 4000kg/h.
First polymeric kettle, the second polymeric kettle, the temperature in third polymerization kettle are 68~85 DEG C, pressure be 2~
8kg/cm2。
Embodiment 2
Referring to Fig. 2, a kind of preparation method of high density polyethylene (HDPE) product, comprise the following steps：
（1）Vinyl monomer, 1- butene monomers, catalyst and hexane solvent are added in the first polymeric kettle 1 and reacted,
The product obtained after reaction enters in the second polymeric kettle 2；The flow for the vinyl monomer being added in the first polymeric kettle is 5000kg/
The flow of h, 1- butene monomers is 20kg/h, and the addition of Ti series catalysts is 0.95kg/h, and the addition of triethyl aluminum is
1.5 kg/h, the addition of hexane solvent is 10000kg/h；
（2）Vinyl monomer, 1- butene monomers, hexane solvent are added in the second polymeric kettle 2 and reacted, after reaction
To product enter third polymerization kettle 4 in；The flow of the vinyl monomer added in the second polymeric kettle is 3000kg/h, 1- butylene
The flow of monomer is 150kg/h, and the addition of hexane solvent is 4000kg/h；
（3）Vinyl monomer, 1- butene monomers, hexane solvent are added in third polymerization kettle 4 and reacted, after reaction
The product arrived enters flash tank 3, and the material come out from flash tank 3 obtains polyethylene product after subsequent treatment；Add the 3rd
The flow of vinyl monomer in polymeric kettle is 2000kg/h, and the flows of 1- butene monomers is 80kg/h, the addition of hexane solvent
For 3000kg/h.
First polymeric kettle, the second polymeric kettle, the temperature in third polymerization kettle are 68~85 DEG C, pressure be 2~
8kg/cm2。
Embodiment 3
Referring to Fig. 2, a kind of preparation method of high density polyethylene (HDPE) product, comprise the following steps：
（1）Vinyl monomer, propylene monomer, catalyst and hexane solvent are added in the first polymeric kettle 1 and reacted, instead
Should after obtained product enter in the second polymeric kettle 2；The flow for the vinyl monomer being added in the first polymeric kettle is 6000kg/h,
The flow of propylene monomer is 110kg/h, and the addition of Ti series catalysts is 0.1 kg/h, and the addition of triethyl aluminum is 2.4
Kg/h, the addition of hexane solvent is 11000kg/h；
（2）Vinyl monomer, propylene monomer, hexane solvent are added in the second polymeric kettle 2 and reacted, is obtained after reaction
Product enter third polymerization kettle 4 in；The flow of the vinyl monomer added in the second polymeric kettle is 4000kg/h, propylene monomer
Flow is 50kg/h, and the addition of hexane solvent is 8000kg/h；
（3）Vinyl monomer, propylene monomer, hexane solvent are added in third polymerization kettle 4 and reacted, is obtained after reaction
Product enter flash tank 3, from flash tank 3 come out material polyethylene product is obtained after subsequent treatment；Add trimerization
The flow for closing the vinyl monomer in kettle is 3000kg/h, and the flow of propylene monomer is 25kg/h, and the addition of hexane solvent is
11000kg/h。
First polymeric kettle, the second polymeric kettle, the temperature in third polymerization kettle are 68~85 DEG C, pressure be 2~
8kg/cm2。
Comparative example 1
Referring to Fig. 1, a kind of preparation method of polyethylene product, comprise the following steps：
（1）Vinyl monomer, propylene monomer, catalyst and hexane solvent are added in the first polymeric kettle 1 and reacted, instead
Should after obtained product enter in the second polymeric kettle 2；The flow for the vinyl monomer being added in the first polymeric kettle is 5200kg/h,
The flow of propylene monomer is 70kg/h, and the addition of Ti series catalysts is 0.85 kg/h, and the addition of triethyl aluminum is 1.2
Kg/h, the addition of hexane solvent is 9000kg/h；
（2）Vinyl monomer, 1- butene monomers, hexane solvent are added in the second polymeric kettle 2 and reacted, after reaction
To product enter flash tank 3 in, from flash tank 3 come out material polyethylene product is obtained after subsequent treatment；Add the
The flow of vinyl monomer in dimerization kettle is 4800kg/h, and the flows of 1- butene monomers is 120kg/h, the addition of hexane solvent
Measure as 9000kg/h.
Temperature in first polymeric kettle, the second polymeric kettle is 68~85 DEG C, pressure is 2~8kg/cm2。
Comparative example 2
Referring to Fig. 1, a kind of preparation method of polyethylene product, comprise the following steps：
（1）Vinyl monomer, propylene monomer, catalyst and hexane solvent are added in the first polymeric kettle 1 and reacted, instead
Should after obtained product enter in the second polymeric kettle 2；The flow for the vinyl monomer being added in the first polymeric kettle is 5250kg/h,
The flow of propylene monomer is 70kg/h, and the addition of Ti series catalysts is 0.93 kg/h, and the addition of triethyl aluminum is 1.2
Kg/h, the addition of hexane solvent is 9000kg/h；
（2）Vinyl monomer, 1- butene monomers, hexane solvent are added in the second polymeric kettle 2 and reacted, after reaction
To product enter flash tank 3 in, from flash tank 3 come out material polyethylene product is obtained after subsequent treatment；Add the
The flow of vinyl monomer in dimerization kettle is 6000kg/h, and the flow of propylene monomer is 120kg/h, the addition of hexane solvent
For 10000kg/h.
Temperature in first polymeric kettle, the second polymeric kettle is 68~85 DEG C, pressure is 2~8kg/cm2。
Claims (3)
1. a kind of preparation method of high density polyethylene (HDPE) product, it is characterised in that comprise the following steps：
(1) vinyl monomer, propylene or 1- butene monomers, catalysts and solvents are added in the first polymeric kettle and reacted, instead
Should after obtained product enter in the second polymeric kettle；The flow for the vinyl monomer being added in the first polymeric kettle be 3000~
The flow of 6000kg/h, propylene or 1- butene monomers is 15~120kg/h；
(2) vinyl monomer, propylene or 1- butene monomers, solvent are added in the second polymeric kettle and reacted, obtained after reaction
Product enter third polymerization kettle in；The flow of the vinyl monomer added in the second polymeric kettle is 3000~6000kg/h, propylene
Or the flow of 1- butene monomers is 15~180kg/h；
(3) vinyl monomer, propylene or 1- butene monomers, solvent are added in third polymerization kettle and reacted, obtained after reaction
Product enter flash tank, from flash tank come out material polyethylene product is obtained after subsequent treatment；Add third polymerization
The flow of vinyl monomer in kettle is 1300~5000kg/h, and the flow of propylene or 1- butene monomers is 15~120kg/h；
The catalyst includes Ti series catalysts and triethyl aluminum, and the additions of Ti series catalysts is 0.06~0.12kg/h, and three
The addition of aluminium ethide is 1.2~2.4kg/h.
2. preparation method according to claim 1, it is characterised in that the solvent being added in each polymeric kettle is hexane,
The addition of hexane is 8000~12000kg/h.
3. according to the preparation method described in any of the above-described claim, it is characterised in that first polymeric kettle, the second polymeric kettle,
Temperature in third polymerization kettle is 68~85 DEG C, pressure is 2~8kg/cm2。
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| CN107540952A (en) * | 2016-06-24 | 2018-01-05 | 中国石化扬子石油化工有限公司 | A kind of preparation method of transparent atactic copolymerized polypropene composition |
| CN109721672A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polypropylene base-material and preparation method thereof for gas infiltration saturation foaming |
| CN114989340A (en) * | 2022-06-28 | 2022-09-02 | 杭州双安科技有限公司 | Olefin polymerization method |
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| CN102207739A (en) * | 2010-03-30 | 2011-10-05 | 中国石油化工股份有限公司 | Nonlinear and linear multi-variable control method for slurry-process polyethylene plant |
| CN102453172A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for homopolymerizing or copolymerizing ethylene |
| WO2013113797A1 (en) * | 2012-01-31 | 2013-08-08 | Norner As | Multimodal polyethylene polymers and process preparing said polymer |
| CN103319639A (en) * | 2013-01-07 | 2013-09-25 | 中国石油化工股份有限公司 | Injection molding grade high density polyethylene and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102652A (en) * | 1994-08-29 | 1995-05-17 | 中国石化扬子石油化工公司 | Polymeric process of alpha-olefines |
| CN101441485A (en) * | 2007-11-19 | 2009-05-27 | 中国石化扬子石油化工有限公司 | Temperature control method of mother liquor pipeline conveying of slurry method HDPE apparatus |
| CN102207739A (en) * | 2010-03-30 | 2011-10-05 | 中国石油化工股份有限公司 | Nonlinear and linear multi-variable control method for slurry-process polyethylene plant |
| CN102453172A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for homopolymerizing or copolymerizing ethylene |
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