CN102603934A - Degassing process of high density polyethylene - Google Patents
Degassing process of high density polyethylene Download PDFInfo
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- CN102603934A CN102603934A CN2012100200206A CN201210020020A CN102603934A CN 102603934 A CN102603934 A CN 102603934A CN 2012100200206 A CN2012100200206 A CN 2012100200206A CN 201210020020 A CN201210020020 A CN 201210020020A CN 102603934 A CN102603934 A CN 102603934A
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Abstract
The invention provides a degassing technology capable of effectively removing the odor of high density polyethylene (HDPE). The polyethylene (PE) material particles with a certain particle size are steamed and inactivated by low-pressure steam in a steamer, are fluidized and dried by hot nitrogen in a fluidized drier, and are added with an auxiliary and the like to achieve the purposes of inactivating a catalyst, removing a catalyst oxide and effectively reducing volatile matters, so that the technology provided by the invention thoroughly solves the problem of the odor of a product, and remarkably improves the product quality.
Description
Technical field
The present invention relates to a kind of novel high density polyethylene(HDPE) production technology, particularly, relate to the degassing technology of high density polyethylene(HDPE).
Background technology
Vilaterm (PE) is the most important derived product of ethene, is a kind of thermoplastic resin that ethene makes through polymerization.Vilaterm accounts for 70% of world's polyolefine consumption, accounts for 44% of total thermoplasticity general-purpose plastics consumption.Polyvinyl originally is divided into three major types, i.e. new LDPE (film grade) (LDPE), high density polyethylene(HDPE) (HDPE) and LLDPE (LLDPE).At present, China's polyethylene production also has big gap with comparing abroad.On the one hand, domestic unit scale is less than normal, material consumption, energy consumption height; On the other hand, kind is fewer in the product structure, and especially the expensive goods ratio is low.
High density polyethylene(HDPE) (High Density Polyethylene is called for short HDPE) is that a kind of percent crystallinity is high, nonpolar thermoplastic resin.The milky appearance of ortho states HDPE, its meagre cross section are to a certain degree translucent.Vilaterm (being called for short PE) has most of industry and the good characteristic of life with chemical.HDPE does not have corrodibility, and non-hygroscopic, can be used for wrapping material, and in addition, HDPE has good non-conductive performance, and the insulative dielectric constant is high, makes it be well suited for the parcel electric wire.In have excellent impact to the PE of HMW grade, this characteristic still keeps at normal temperature even under-40 ℃ of low temperature.
High density polyethylene(HDPE) production technique device, most Mitsui oiled ethene polymerization process by slurry that adopt.The most common working method of PE is through slurry process or gas phase processing method, minority is also arranged with the processing of solution phase.All these reaction process all are the thermopositive reaction of being participated in by vinyl monomer, 'alpha '-olefin monomers, catalyst system (the more than a kind of compound of possibility) and various types of hydrocarbon diluent, and hydrogen is used for controlling synthetic PE molecular weight with some catalyzer.Slurry-phase reactor is generally stirring tank or a kind of large-sized annular reactor drum more commonly used, the slip stirring that can circulate therein.When ethene contacts with catalyzer one with comonomer (as required), will form polyethylene particle.After removing thinner, polyethylene particle or powder are dried, and according to dosage add additive again, just produce pellet.The modern production line that has the large-scale reactor drum of twin screw extruder can per hour be produced PE and reach more than 40000 pounds.The performance of improving new grade HDPE that is developed as of raw catalyst contributes.Two kinds of the most frequently used catalyzer are respectively catalyzer and the titanium compound-aluminum alkyl catalysts that the chromated oxide with Philips is the basis.
This production technique adopts two still serial or parallel connection operations, and product comprises types such as blowing, injection moulding, extrusion molding, its good quality of product, and processing characteristics is better.But the subject matter that exists in the prior art is that product has bigger smell, through overtesting and analysis, finds that smell mainly is caused by fugitive constituent residual in the product and the volatilization of catalyst oxidation thing, and concentration has 0.3% (3000ppm) approximately.
Therefore a kind of novel high density polyethylene(HDPE) degassing technology need be developed in this area, to eliminate the smell of PE product, improves the quality of products.
Summary of the invention
Main purpose of the present invention provides a kind of novel high density polyethylene(HDPE) degassing technology, to reduce the volatile content in the polyethylene product, thoroughly solves the smell problem of product, further promotes quality product.
The present invention provides a kind of degasification technique of high density polyethylene(HDPE), and said degasification technique comprises step:
(a) the high density polyethylene(HDPE) powder is after gas solid separation, and the powder solid is transferred pneumatic transmission and goes into steamer, eliminates residual catalyst activity in the polyethylene powder with the following steam of 100-110 ℃, 1.2MPa;
(b) the high density polyethylene(HDPE) powder through the decatize deactivation gets in the fluidized bed dryer, stops more than 2 minutes, and 90-110 ℃ of drying removed fugitive constituent and catalyst oxidation thing;
(c) the high density polyethylene(HDPE) powder that comes out from fluidized bed dryer is transferred pneumatic transmission and goes into to be cooled to 55-65 ℃ the interchanger.
In above-mentioned steps (b) and the step (c), carry gas that auxiliary agent is conveyed into respectively in steamer and the fluidized bed dryer, said auxiliary agent be the earth alkali metal salt one or more, the mixture of aluminum oxide and C2-C4 alkyl alcohol.
Above-mentioned steps (a) mainly is to eliminate catalyst activity, simultaneously, under steam and promoter effect, also can remove small portion fugitive constituent and catalyst oxidation thing.
The particle diameter of above-specified high density polyethylene powder is 100 μ m-5mm.
Above-mentioned gas solid separation adopts cyclonic separator or cyclonic separator and sack cleaner.
Establish sack cleaner between vertical side of above-mentioned steamer and the fluidized bed dryer, said sack cleaner is separated the powder solid in the steamer ascending gas, delivers in the fluidized bed dryer.
The gas solid separation machine is established on above-mentioned fluidized bed dryer one end top, and the powder solid that said gas solid separation machine is taken the fluidized bed dryer ascending gas out of is separated, and sends back in the fluidized bed dryer.
The gas solid separation machine on above-mentioned fluidized bed dryer one end top is a sack cleaner.
The particle diameter of above-specified high density polyethylene powder is 500 μ m-4mm.
The residence time of above-specified high density polyethylene powder in fluidized bed dryer is 3-4 minute.
The above-specified high density polyethylene powder is transferred gas and sends in the fluidized bed dryer with the speed of 0.8m/s-4m/s.
The poly degassing technology of above-specified high density is characterized in that said high density polyethylene(HDPE) powder is transferred gas and sends in the fluidized bed dryer with the speed of 1m/s-3m/s.
Above-mentioned alkaline earth salt is modification magnesium borate or calcium chloride; Said C2-C4 alkyl alcohol is ethanol, propyl alcohol or butanols, is preferably technical grade ethanol.
Abovementioned alkyl alcohol content is 60-80%wt, and above-mentioned alumina content is 5-10%wt, and surplus is an alkaline earth salt.Said alkaline earth salt is modification magnesium borate or calcium chloride.Said alkyl alcohol is an ethanol.
Above-mentioned auxiliary dosage is 100-10000ppm.Preferable, said auxiliary dosage is 1000-6000ppm.
Above-mentioned conveying gas is nitrogen or rare gas element.
Above-mentioned interchanger is a finned tube heat exchanger.Find that through analyzing the smell in the PE product is mainly caused by residual volatile component and catalyst oxidation thing, and residual volatile component is a hexane solvent.For removing the smell in the PE product effectively, in the present invention, adopt auxiliary agent to add industrial technology means such as (harmless), decatize deactivation and fluidized drying and handle.
At first; In the PE powder, add auxiliary agent, the particle diameter of PE powder is 100 μ m-5mm, says to be 500 μ m-4mm exactly; The auxiliary agent that adds be mainly the earth alkali metal salt one or more (like the modification magnesium borate; Metal halide such as calcium chloride etc.), the mixture of C2-C4 alkyl alcohol and aluminum oxide, the consumption of auxiliary agent is 100-10000ppm, more preferably is 1000-6000ppm.The purpose of adding auxiliary agent is to increase the specific surface area of material, is beneficial to the volatilization of volatile matter in the degassing is handled.
Secondly; The decatize deactivation; In steamer, feed low pressure (smaller or equal to 1.2MPa) steam and make original trace catalyst inactivation in the PE material, the purpose of this technical finesse is to eliminate the remaining activity of the catalyzer in the PE material, promotes the volatilization of catalyst oxidation thing.LP steam and hot nitrogen are got into by the bottom of steamer, flow from bottom to top; And the PE material (about 80 ℃) of heat flows downward by gravity, in this course from the top adding of steamer; The PE material fully contacts with LP steam is reverse; Mass-and heat-transfer promotes catalyst oxidation thing and fugitive constituent evaporable purpose to reach, wherein; The temperature of LP steam and hot nitrogen is 100-110 ℃, and the temperature of the hot nitrogen that gets into from the steamer bottom is 110-130 ℃.
Once more, fluidized drying at a certain temperature, makes the PE material in fluidized-bed, stop certain hour to reach the exsiccant purpose.Specifically, by the bottom input of fluidized bed dryer, it is mobile to roll from bottom to top under the blowing of the hot nitrogen about 90-110 ℃ for the PE material of heat, makes the fugitive constituent further volatilization in fluidized-bed in the PE material, and concentration is reduced to below the 300ppm.In this process, the conveying gas operating speed of fluidized bed dryer is about 0.8m/s-4m/s, more preferably is 1m/s-3m/s.Like this, the residence time of PE material in fluidized bed dryer can reach more than the 2min, and most optimal retention time is 3min-4min.
Above-mentioned PE product degassing technology does not have precedent at present at home as yet, on the basis of the production technique of high density polyethylene(HDPE), is aided with the drying operation that outgases of corresponding treatment system, not only can eliminate the smell in the product, and can promote the quality of product.Detect to find, adopt the volatile matter in the high density polyethylene(HDPE) that this technology produces to reduce to below 0.03% from original about 0.3%, make original technical grade wrapping material upgrade to the food grade wrapping material.
Description of drawings
Fig. 1 is a liquid process flow diagram of the present invention.
Fig. 2 is a gas phase process flow diagram of the present invention.
Fig. 3 is the synoptic diagram of the de-gassing vessel of high density polyethylene(HDPE).
1, steamer; 11, cyclonic separator; 12, sack cleaner; 2, fluidized bed dryer; 22, sack cleaner; 3, interchanger III; 4, interchanger I; 5, interchanger IV; 6, whizzer; 7, lime set jar I; 8, lime set jar II; 9, feed bin; 91, cyclonic separator; 10, switching valve; 13, interchanger II.
Embodiment
The degasification technique of high density polyethylene(HDPE) of the present invention comprises step:
(a) the high density polyethylene(HDPE) powder is after gas solid separation, and the powder solid is transferred pneumatic transmission and goes into steamer, eliminates the catalyst activity in the polyethylene powder with the following steam of 100-110 ℃, 1.2MPa;
(b) be transferred pneumatic transmission through the high density polyethylene(HDPE) powder of decatize deactivation and go in the fluidisation bed dryer, stop more than 2 minutes, 90-110 ℃ of drying removed fugitive constituent and catalyst oxidation thing;
(c) the high density polyethylene(HDPE) powder that from fluidized bed dryer, comes out is transferred pneumatic transmission and goes into to be cooled to 55-65 ℃ in the interchanger.
Preferably, the gas solid separation machine is established on said steamer and fluidized bed dryer top.
It can be nitrogen or rare gas element that the present invention carries gas.The present invention carries the gas can recycle, has practiced thrift the energy.As shown in Figure 1, the de-gassing vessel of high density polyethylene(HDPE) of the present invention mainly is made up of steamer 1, fluidized bed dryer 2, interchanger 3, interchanger 13 and air transporting arrangement etc.Steamer 1 top has cyclonic separator 11 (being the gas solid separation unit 1 among Fig. 2), also can be furnished with sack cleaner (being sign among the figure) in addition, so that gas solid separation is more thorough.Cyclonic separator 11 is connected between the whizzer 6 and steamer 1 of PE Production Flow Chart, and sack cleaner 12 (the gas solid separation machine 2 among Fig. 2) is connected between steamer 1 top, one side and the fluidized bed dryer 2.One switching valve 10 is arranged between whizzer 6 and cyclonic separator 11, and through the conversion of switching valve 10, the PE Production Flow Chart can be transformed into the present invention from conventional path and put the degasification technique path.Conventional path is that whizzer 6 is to cyclonic separator 91 (being the gas solid separation unit 4 among Fig. 2) to feed bin 9, granulation then; Gas solid separation unit 4 also can be between cyclonic separator 91 and feed bin, to add sack cleaner.Between cyclonic separator 11 and switching valve 10, an interchanger 13 (being the interchanger I among Fig. 2) is arranged.This covering device interchanger 4 main interchanger that drawn, all the other interchanger are detailed to be shown, main regulate carry gas temperature to be fit to the temperature of reaction of each parts.Fluidized bed dryer 2 one end tops connect sack cleaner 22 (being the gas solid separation machine 3 among Fig. 2); The powder solid that this gas solid separation machine is taken the fluidized bed dryer ascending gas out of is separated; Send back in the fluidized bed dryer; The isolated gas of a part gets into flare system and does vent gas treatment, and another part is sent into recycle in steamer 1 and the fluidized bed dryer 2 again then through interchanger 4, lime set jar II and interchanger 5.
Air transporting arrangement is steamer and moisture eliminator supplying nitrogen, and recycle nitrogen.
Vilaterm (PE) (about 85 ℃) from whizzer 6 is a powder; Its particle diameter is about 100 μ m-5mm; Preferable; Particle diameter is at 500 μ m-4mm, and powder is through from nitrogen (about the 80 ℃) effect of air transporting arrangement down, is admitted to carry out gas-solid body in the cyclonic separator 11 on steamer top and separate.Isolated solid polyethylene directly gets in the steamer 1, and isolated gas gets into sack cleaner 12, gets into nitrogen circulating system from sack cleaner 12 isolating nitrogen, and isolated solid particulate gets in the fluidized bed dryer 2.Polyethylene particle (PE is about 80 ℃) in steamer, lean on from top to bottom gravity flowage and with steamer in feed LP steam (100-110 ℃, pressure is less than 1.2MPa, comparatively ideal TR is 103-108 ℃.), hot nitrogen (110-130 ℃, about preferable 120 ℃) anti-phase contact mass transfer conducts heat, LP steam makes original trace catalyst inactivation.Vilaterm after the decatize (PE is about 90 ℃) is drawn off by the rotary valve of steamer 1 bottom and gets in the fluidized bed dryer 2 further dry through extraction line, feed auger.Polyethylene particle (FE in moisture eliminator; About 90 ℃) under the blowing of hot nitrogen (90-110 ℃, about preferable 100 ℃), rolling from bottom to top flows further removes fugitive constituent to 270ppm; Sack cleaner 22 is established on moisture eliminator top; After the solids constituent that ascending gas is taken out of leaves, send into fluidized bed dryer 2, a part of isolated gas gets into flare system and does vent gas treatment; Another part is sent into recycle in steamer 1 and the fluidized bed dryer 2 again then through interchanger 4, lime set jar II and interchanger 5.
The PE powder that comes out in the fluidized bed dryer 2 is through finned tube heat exchanger 3 heat exchange, is cooled to 55-65 ℃ by about 90 ℃, and preferable, about 60 ℃, cooled PE gets into feed bin 9 and then granulation through gas solid separation unit 4 (being cyclonic separator 91).
In steamer and moisture eliminator, can also add auxiliary agent and come the sterilization deactivation, and increase material specific surface area.The composition of auxiliary agent is: the mixture of one or more of earth alkali metal salt (like modification magnesium borate, calcium chloride etc.), aluminum oxide and C2-C4 alkyl alcohol.Auxiliary dosage is 100-10000ppm, and is better, and auxiliary dosage is 1000-6000ppm.Auxiliary agent is sent in steamer and the moisture eliminator through pneumatic conveyer.Wherein, the shared mass percent 60-80%wt of alkyl alcohol, preferred alcohol, alumina content are 5-10%wt, surplus is an alkaline earth salt.Said alkaline earth salt is modification magnesium borate and/or calcium chloride.
What pneumatic conveyer was carried can be nitrogen or rare gas element.Rare gas element can be helium, neon, argon gas etc.
Drawn by its blower fan that links to each other (among the figure for indicating) after the sack cleaner 12 on top separately and 22 dedustings by steamer, moisture eliminator expellant gas, and after being cooled to about 50 ℃ by interchanger 4 again through 8 dehumidifying of lime set jar, follow bad the use after interchanger 5 heating.Gas phase composition regular monitoring, extraction regularly, regularly mend nitrogen, for controlling in real time.Replenish flow and go the extraction flow relevant with the process matched therewith scale, controlled by central control system, can be set in certain scope, more satisfactory flow range is 0-500Nm
3/ h.The gas of extraction or recycle and reuse, or incorporate the torch pipe network into.Interchanger I, II are made up of finned tube, can directly cool off with air.Gas is carried in circulation, discharges N after the volatilizable lease making lime set jar I that auxiliary agent absorbed, the II condensation
2Continuation is used in reaction as circulation gas.
Degasifying device of the present invention can be connected with the ordinary process system through switching valve.As shown in figures 1 and 3, come out from revolving drier, 2 paths are arranged, 1. be conventional route, 2.,, can between 2 paths, freely switch through switching valve for having increased the route behind the degassing process of the present invention.
Fig. 2 is the gas phase schema.The gas that is come out by steamer, moisture eliminator is drawn by its induced draft fan that links to each other after the gas solid separation unit 1 on top separately (among Fig. 3 11), gas solid separation machine 2 (among Fig. 3 22) dedusting, and recycles through lime set jar II (among Fig. 3 8) dehumidifying after being cooled to about 50 ℃ by interchanger I (among Fig. 3 4) again.Fresh nitrogen and circulating nitrogen gas are as carrying gas; The gas delivery finished product is behind interchanger II (among Fig. 3 13), and gas solid separation unit 4 (among Fig. 3 91) back is drawn by induced draft fan that it links to each other, and divided two-way; One the tunnel behind lime set jar I (among Fig. 3 7) dehumidification by condensation as carrying gas; The whizzer outlet material is transported to gas solid separation unit 1 or 4, and the gas after gas solid separation unit 1 (among Fig. 3 11) and gas-solid separating machine group 4 (among Fig. 3 91) recycles after lime set jar I dehumidifying.Gas phase composition regular monitoring, extraction regularly, regularly mend nitrogen.From the tail gas of gas solid separation machine 3 (22 Fig. 3) extraction, pass through recycle and reuse or incorporate the processing of torch official website into.
Volatile content after table 1 auxiliary dosage and the processing
Can be known by table 1, be raised to 10000ppm from 6000ppm, the effect of removing volatile matter is also not obvious, and therefore, degassing process preferred promoter consumption of the present invention is 1000-6000ppm.PPM (English: Parts Per Million, be called for short ppm), be defined as 1,000,000/, 1ppm promptly is 1,000,000/, be mass percent.
According to embodiments of the invention describing the present invention property and nonrestrictive description, but should be understood that and do not breaking away under the situation of the relevant protection domain that limits claim that those skilled in the art can make various changes and/or modification.
Claims (18)
1. the degasification technique of a high density polyethylene(HDPE) is characterized in that, said degasification technique comprises step:
(a) the high density polyethylene(HDPE) powder is after gas solid separation, and the powder solid is transferred pneumatic transmission and goes into steamer, eliminates residual catalyst activity in the polyethylene powder with the following steam of 100-110 ℃, 1.2MPa;
(b) the high density polyethylene(HDPE) powder through the decatize deactivation gets in the fluidized bed dryer, stops more than 2 minutes, and 90-110 ℃ of drying removed fugitive constituent and catalyst oxidation thing;
(c) the high density polyethylene(HDPE) powder that comes out from fluidized bed dryer is transferred pneumatic transmission and goes into to be cooled to 55-65 ℃ the interchanger.
2. according to the degasification technique of the said high density polyethylene(HDPE) of claim 1; It is characterized in that; In said step (b) and the step (c); Carry gas that auxiliary agent is conveyed into respectively in steamer and the fluidized bed dryer, said auxiliary agent be the earth alkali metal salt one or more, the mixture of aluminum oxide and C2-C4 alkyl alcohol.
3. according to the degassing technology of the high density polyethylene(HDPE) of claim 2, it is characterized in that the particle diameter of said high density polyethylene(HDPE) powder is 100 μ m-5mm.
4. according to the degassing technology of the said high density polyethylene(HDPE) of claim 2, it is characterized in that said gas solid separation adopts cyclonic separator or cyclonic separator and sack cleaner.
5. technological according to the degassing of the said high density polyethylene(HDPE) of claim 2; It is characterized in that; Establish sack cleaner between vertical side of said steamer and the fluidized bed dryer, said sack cleaner is separated the powder solid in the steamer ascending gas, delivers in the fluidized bed dryer.
6. technological according to the degassing of the said high density polyethylene(HDPE) of the arbitrary claim of claim 1-5; It is characterized in that; The gas solid separation machine is established on said fluidized bed dryer one end top; The powder solid that said gas solid separation machine is taken the fluidized bed dryer ascending gas out of is separated, and sends back in the fluidized bed dryer.
7. according to the degassing technology of the said high density polyethylene(HDPE) of claim 6, it is characterized in that said gas solid separation machine is a sack cleaner.
8. according to the degassing technology of the said high density polyethylene(HDPE) of the arbitrary claim of claim 1-7, it is characterized in that the particle diameter of said high density polyethylene(HDPE) powder is 500 μ m-4mm.
9. according to the degassing technology of the said high density polyethylene(HDPE) of the arbitrary claim of claim 1-7, it is characterized in that the said residence time of high density polyethylene(HDPE) powder in fluidized bed dryer is 3-4 minute.
10. the degassing of said high density polyethylene(HDPE) is technological according to Claim 8, it is characterized in that said high density polyethylene(HDPE) powder is transferred gas and sends in the fluidized bed dryer with the speed of 0.8m/s-4m/s.
11. the degassing technology according to the said high density polyethylene(HDPE) of claim 9 is characterized in that said high density polyethylene(HDPE) powder is transferred gas and sends in the fluidized bed dryer with the speed of 1m/s-3m/s.
12. the degassing technology according to claim 2-7, the said high density polyethylene(HDPE) of 10 or 11 arbitrary claims is characterized in that said alkaline earth salt is modification magnesium borate or calcium chloride; Said C2-C4 alkyl alcohol is ethanol, propyl alcohol or butanols.
13. the degassing technology according to the said high density polyethylene(HDPE) of claim 12 is characterized in that said alkyl alcohol content is 60-80%wt, said alumina content is 5-10%wt, and surplus is an alkaline earth salt.
14. the degassing technology according to the said high density polyethylene(HDPE) of claim 13 is characterized in that said alkyl alcohol is an ethanol.
15. the degassing technology according to claim 2-7, the said high density polyethylene(HDPE) of 10 or 11,13 or 14 arbitrary claims is characterized in that said auxiliary dosage is 100-10000ppm.
16. the degassing technology according to claim 13 or 14 said high density polyethylene(HDPE)s is characterized in that said auxiliary dosage is 1000-6000ppm.
17. the degassing technology according to claim 1-7, the said high density polyethylene(HDPE) of 10 or 11,13 or 14 arbitrary claims is characterized in that said conveying gas is nitrogen or rare gas element.
18. the degassing technology according to claim 1-7, the said high density polyethylene(HDPE) of 10 or 11,13 or 14 arbitrary claims is characterized in that said interchanger is a finned tube heat exchanger.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103449062A (en) * | 2013-08-20 | 2013-12-18 | 云南华云天朗环保有限责任公司 | Material fluidization sending method |
| CN110845642A (en) * | 2019-10-18 | 2020-02-28 | 中国石油化工股份有限公司 | Production device and method for low-VOC (volatile organic compound) polyethylene product by slurry process |
| CN112480291A (en) * | 2020-12-10 | 2021-03-12 | 天华化工机械及自动化研究设计院有限公司 | Method for further improving quality of polypropylene product produced by gas phase method |
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| EP2172494A1 (en) * | 2008-10-03 | 2010-04-07 | Ineos Europe Limited | Process |
| CN101896324A (en) * | 2007-12-18 | 2010-11-24 | 波利亚里斯技术有限公司 | Removing volatile compounds from polymer pellets |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101896324A (en) * | 2007-12-18 | 2010-11-24 | 波利亚里斯技术有限公司 | Removing volatile compounds from polymer pellets |
| EP2172494A1 (en) * | 2008-10-03 | 2010-04-07 | Ineos Europe Limited | Process |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449062A (en) * | 2013-08-20 | 2013-12-18 | 云南华云天朗环保有限责任公司 | Material fluidization sending method |
| CN103449062B (en) * | 2013-08-20 | 2015-03-04 | 云南华云天朗环保有限责任公司 | Material fluidization sending method |
| CN110845642A (en) * | 2019-10-18 | 2020-02-28 | 中国石油化工股份有限公司 | Production device and method for low-VOC (volatile organic compound) polyethylene product by slurry process |
| CN112480291A (en) * | 2020-12-10 | 2021-03-12 | 天华化工机械及自动化研究设计院有限公司 | Method for further improving quality of polypropylene product produced by gas phase method |
| CN112480291B (en) * | 2020-12-10 | 2023-04-07 | 天华化工机械及自动化研究设计院有限公司 | Method for further improving quality of polypropylene product produced by gas phase method |
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