CN1193629A - Concentrating method of polymer solution - Google Patents
Concentrating method of polymer solution Download PDFInfo
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- CN1193629A CN1193629A CN98100011A CN98100011A CN1193629A CN 1193629 A CN1193629 A CN 1193629A CN 98100011 A CN98100011 A CN 98100011A CN 98100011 A CN98100011 A CN 98100011A CN 1193629 A CN1193629 A CN 1193629A
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Abstract
A process for concentrating solution of polymer by removing volatile substance features that the viscosity of concentrated polymer solution is detected by an in-line viscosimeter. If its viscosity is qualified, the polymer solution is output. If not, it is returned as circulating liquid back to static mixer for flash vaporization again. The low-concentration fresh solution and concentrated solution flow alternatively through the static mixer, heat exchange and pipeline between them, avoiding coke deposit on wall and block of pipe line.
Description
The present invention relates to a kind of concentration method of improved polymers soln.
The spissated method of traditional polymers soln, steam consumption is big, and along with the concentration of polymers soln improves, viscosity increases, polymkeric substance wall built-up coking in indirect heat exchanger surface and continuous pipeline and equipment.General 1～2 week just needs parking maintenance.
EP525748A1, day open clear 59-18707 and once the polymers soln concentration method were done some improvement, but still have above-mentioned shortcoming.
Purpose of the present invention is exactly to provide a kind of improved polymers soln concentration method (seeing Figure of description 1) for the above-mentioned weak point that solves concentration method.It comprises polymer fluid discharging pipeline, add terminator pipeline (1), polymkeric substance discharging pump (2), add diluent line (3), static mixer (4), interchanger (5), flasher (6) solvent condenses withdrawer (7), heated oxide stablizer pipeline (8), concentrate glue discharging pump (9) and flash liquid circulation line (10) and online viscosity detector (11), its characteristics are that the viscosity of spissated polymers soln is detected by a kind of online viscosimetric analysis device, can detect the viscosity number that control is concentrated solution at any time, a functional relation is arranged between the concentration of polymers soln and the viscosity, can calculate its concentration according to the viscometer of solution thus, by product concentration requirement eligible as the product extraction, concentration failure returns static mixing as circulation fluid and thinks highly of steaming, and system-static mixer before the flasher and interchanger and intermediary connection line thereof are the polymers solns of fresh lower concentration and alternately pass through through the polymers soln of flash concentration.
Add a kind of thinner that can dissolve each other with polymkeric substance in the outlet of polymers soln discharge port or discharging pump, enter then in mixing tank, interchanger and the flasher, prevent that polymkeric substance sticking wall in mixing tank, interchanger and flasher from stopping up.Described thinner is can the solvent polymerization monomer and the hydro carbons of polymkeric substance, and thinner can be solvent or a solvent mixture identical or different in the polymers soln, the product difference, and the thinner difference comprises paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbon or its mixture.The boiling range that provides as butane, pentane, hexane, octane, pentamethylene, hexanaphthene, benzene, toluene and refinery is the mixture etc. of the C5 based on the six carbon atom number～C7 alkane of 60～90 ℃, and wherein the mixture of hexane and hexanaphthene is proper thinner.
The present invention adds terminator to stop existing in the polymers soln or the activity of residual catalyst between polymeric kettle discharge port and discharging pump inlet, prevent that polymer property from degenerating.Terminator is generally the mixture of Lewis acid and hydrocarbon solvent, as water, acid, alcohol etc. or their mixture.
The present invention adds a kind of solution of thermal oxidation stabilizer to improve thermotolerance and the antioxygen of polymkeric substance in concentrated and post-treatment between flasher outlet and discharging pump source line.Thermal oxidation stabilizer can be selected from commercially available anti-aging agent, phenols, amine, and as 264,1010,168, TNPP etc., they can be single component or multicomponent mixture.
Polymers soln of the present invention is rubber solutions, plastic solution or the polymers soln of solution polymerization process preparation.As the binary of second-third rubber solutions, polyethylene solution, polypropylene solution, polyhutadiene solution, conjugated diolefine and vinyl-arene or the copolymer solution of terpolymer solution or ethene, propylene and other long-chain olefin.
Concentration method of the present invention can be used for batchwise polymerization or continuous polymerization technique.
Carry out flash concentration by concentration method of the present invention, can not stop continuous operation 6～9 months and plugging and wall sticking phenomenon do not take place.
The following examples only are in order to illustrate the present invention better, but do not limit its scope.Embodiment 1
Produce in the process of solution polymerized butadiene styrene rubber (SSBR) in batch polymerization process, adopt the mixed solvent of hexane and hexanaphthene, the proportioning of mixed solvent is a hexane: hexanaphthene=1: 4, polymer solution temperature after the polymerization is 105 ℃, polymer solution concentration is 14%, the polymers soln total amount is 24 tons, with polymer solution pump polymers soln is extracted out from polymeric kettle, adds entry 0.4Kg and makes terminator.Through passing through a well heater behind the static mixer, enter a 53m
3Flasher carry out flash distillation, the time that enters flasher from polymeric kettle is 20 minutes, the pressure in the flasher is 0.05Mpa (gauge pressure).After the polymers soln that flash distillation for the first time obtains added the 187Kg antioxidant 264, its concentration was 17% after testing, and viscosity is 480cp, does not meet the finished product requirement.This moment, polymers soln entered static mixer again through pump, then through polymers soln heater heats to 100 ℃, enter flasher again, can get solution polymerized butylbenzene concentration and be 17.2 tons of the polymers solns of 21% (wt), polymer solution viscosity is 640cp, meet the discharging requirement, discharging is to next process.The solvent that flash distillation is come out reclaims after the solvent condenser cooling and uses, and reclaims 6.8 tons of mixed solvents altogether.Twice flash-off time totally 40 minutes.Stop heating during polymers soln discharging after the flash distillation and add solvent 300Kg by pipe (3) simultaneously making thinner, washing is bonded in the pipeline and mixing tank, interchanger, flasher inwall on polymers soln after get back in the mixing tank and the next batch mixing of materials by the flash liquid circulation line.
Customary parking maintenance is not found wall sticking phenomenon after 9 months.Embodiment 2
Produce in the process of butylbenzene thermoplastic elastomer (SBS) rubber in batch polymerization process, adopt the mixed solvent of hexane and hexanaphthene, the proportioning of mixed solvent is a hexane: hexanaphthene=2: 5, polymer solution temperature after the polymerization is 105 ℃, polymer solution concentration is 13%, and the polymers soln total amount is 30 tons.With polymer solution pump polymers soln is extracted out from polymeric kettle, added entry 0.55Kg and make terminator.Through passing through a well heater behind the static mixer, enter a 53m
3Flasher carry out flash distillation, the time that enters flasher from the polymeric kettle discharging is 20 minutes, the pressure in the flasher is 0.05Mpa (gauge pressure).After the polymers soln that flash distillation for the first time obtains added the 200Kg antioxidant 264, detecting its concentration was 17%, and viscosity is 500cp, does not meet the discharging requirement.This moment, polymers soln entered static mixer again through pump, through polymers soln heater heats to 105 ℃, entered flasher more then, and can get SBS concentration is 22% (wt), and viscosity is 20.5 tons of the polymers solns of 700cp.This index meets the discharging requirement, and discharging is to next process.The solvent that flash distillation is come out reclaims after the solvent condenser cooling and uses, and reclaims 9.5 tons of mixed solvents altogether.Twice flash-off time totally 40 minutes.Stop heating during polymers soln discharging after the flash distillation and add solvent 400Kg by pipe (3) simultaneously making thinner, washing is bonded in the pipeline and mixing tank, interchanger, flasher inwall on polymers soln and get back in the mixing tank and the next batch mixing of materials by the flash liquid circulation line.
Customary parking maintenance is not found wall sticking phenomenon after 9 months.Embodiment 3
Produce a kind of low 1 in batch polymerization process, in the process of 2 structure polyhutadiene, adopting C6 is that main boiling range wide is that 10 ℃ the full hydrocarbon that closes is made solvent, polymer solution concentration is 12%, the polymers soln total amount is 25 tons, and when with polymer solution pump polymers soln being extracted out from polymeric kettle, the mixture that adds alcohol and solvent continuously is total to 10Kg and makes terminator, through heating by a shell and tube heat exchanger behind the static mixer, enter a 53m
3Flasher carry out flash distillation, the time that enters flasher from polymeric kettle is 22 minutes, the pressure in the flasher is 0.35Mpa (gauge pressure).The polymers soln that flash distillation for the first time obtains learns after the viscosity that after testing its corresponding concentration is 14% after adding 187Kg antioxidant 264 and TNPP, does not meet the finished product requirement.This moment, polymers soln entered static mixer again through pump, be heated to 100 ℃ through the polymers soln interchanger then, enter flasher again, polymer solution viscosity learns that its corresponding concentration is 18% (wt) after testing, meet the discharging requirement, discharging is to next process.The solvent that flash distillation is come out reclaims after the solvent condenser cooling and uses, and reclaims 9.3 tons of mixed solvents altogether.Twice flash-off time totally 45 minutes.And then to add polymer concentration be that 12% solution continues said process, keeps this dilute solution and strong solution ceaselessly to intersect Recycle design.
Customary parking maintenance after 9 months is not found plugging and wall sticking phenomenon.Comparative Examples
Comparative Examples adopts secondary flash distillation mode (seeing Figure of description 2) to remove the volatiles in the polymer production.
In the process of batch production SBS, adopt the mixed solvent of hexane and hexanaphthene, the proportioning of mixed solvent is a hexane: hexanaphthene=1: 4, the polymer solution temperature after the polymerization are 105 ℃, and polymer solution concentration is 12%, and the polymers soln total amount is 24 tons.With polymer solution pump polymers soln is extracted out from polymeric kettle, added entry 0.4Kg and make terminator.Polymers soln enters a 53m after through an interchanger (5)
3Flasher (6) in carry out flash distillation, polymers soln is 20 minutes from the time that the polymeric kettle discharging enters flasher, the pressure in the flasher is 0.05Mpa (gauge pressure).The polymers soln that flash distillation obtains enters another interchanger (5 ') again and is heated to 100 ℃, enters second flasher (6 ') then, and the solvent that twice flash distillation come out reclaims after same solvent condenser cooling and uses.Flash-off time is 40 minutes, and can get SBS concentration is 17% (wt), and viscosity is 16.9 tons of the polymers solns of 500cp, reclaims 7.1 tons of mixed solvents.After polymers soln after the flash distillation added the 160Kg antioxidant 264 by pipe 8, discharging was to next process.After this device used for 2 weeks continuously, sticking wall coking phenomenon having taken place in the interchanger, must switch and clean.
Claims (9)
1. the concentration method of an improved polymers soln, comprise polymers soln discharging pipeline, add terminator pipeline (1), polymkeric substance discharging pump (2), add diluent line (3), static mixer (4), interchanger (5), flasher (6), solvent cooling withdrawer (7), add thermal oxidation stabilizer pipeline (8), polymkeric substance concentrated solution discharging pump (9) and flash liquid circulation line (10) and online viscosity detector (11), the viscosity that it is characterized in that spissated polymers soln is detected by a kind of online viscosimetric analysis device, can detect the viscosity number that control is concentrated solution at any time, by strength of solution requirement eligible as the product extraction, concentration failure returns static mixing as circulation fluid and thinks highly of steaming, and system-static mixer before the flasher and interchanger and intermediary connection line thereof are the polymers solns of fresh lower concentration and alternately pass through through the polymers soln of flash concentration.
2. method according to claim 1 is characterized in that adding behind the polymers soln discharging pump thinner that can dissolve each other with polymkeric substance, enters mixing tank, interchanger and flasher, prevents that polymkeric substance sticking wall in mixing tank, interchanger and flasher from stopping up.
3. method according to claim 1 and 2 is characterized in that described thinner for can the solvent polymerization monomer and the hydro carbons of polymkeric substance, comprises paraffinic hydrocarbons, naphthenic hydrocarbon, aromatic hydrocarbon or its mixture.
4. method according to claim 3 is characterized in that described thinner is the mixture of mixture, toluene and hybrid ring alkane of hexane, hexanaphthene, hexane and hexanaphthene or the mixture of the C5 based on the six carbon atom number～C7 alkane that boiling range is 60～90 ℃.
5. method according to claim 1 is characterized in that the preceding adding thermal oxidation stabilizer of flash distillation discharging pump (9) is to improve the thermotolerance and the antioxygen of polymkeric substance.
6. method according to claim 1 is characterized in that described thermal oxidation stabilizer is various anti-aging agent, phenols or amine.
7. method according to claim 6 is characterized in that described thermal oxidation stabilizer is an antioxidant 264,1010,168 or TNPP.
7. method according to claim 1 is characterized in that described polymers soln is rubber solutions, plastic solution or the polymers soln of solution polymerization process preparation.
8. method according to claim 7 is characterized in that described polymers soln is the binary of second-third rubber solutions, polyethylene solution, polypropylene solution, polyhutadiene solution, conjugated diolefine and vinyl-arene or the copolymer solution of terpolymer solution or ethene, propylene and other long-chain olefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98100011A CN1060784C (en) | 1997-01-08 | 1998-01-08 | Concentrating method of polymer solution |
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| Application Number | Priority Date | Filing Date | Title |
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| CN97200193X | 1997-01-08 | ||
| CN97200193.X | 1997-01-08 | ||
| CN97200193 | 1997-01-08 | ||
| CN98100011A CN1060784C (en) | 1997-01-08 | 1998-01-08 | Concentrating method of polymer solution |
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| CN1193629A true CN1193629A (en) | 1998-09-23 |
| CN1060784C CN1060784C (en) | 2001-01-17 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297593C (en) * | 2002-08-07 | 2007-01-31 | 富士胶片株式会社 | Solution concentrating method and solution film making method and product |
| CN103674894A (en) * | 2013-12-30 | 2014-03-26 | 安徽皖维集团有限责任公司 | Method for detecting concentration of polyvinyl alcohol solution in production of polyvinyl-alcohol optical film by utilizing refractometer |
| CN105315516A (en) * | 2014-07-30 | 2016-02-10 | 固特异轮胎和橡胶公司 | Elastomer containing combination of tris(nonyl phenyl) phosphite and tetramethylethylenediamine, preparation and compositions and articles of manufacture thereof |
| CN107185467A (en) * | 2017-07-06 | 2017-09-22 | 广东弘擎电子材料科技有限公司 | A kind of glue preparation system |
| CN107703099A (en) * | 2016-08-08 | 2018-02-16 | 中国石油化工股份有限公司 | On-line continuous detection device and method and polymerization reaction system and method |
| CN114011104A (en) * | 2022-01-06 | 2022-02-08 | 湖南大学 | Control method, device and equipment of gravity flash evaporator and gravity flash evaporator |
| CN114100171A (en) * | 2021-11-23 | 2022-03-01 | 洛阳炼化九源石化有限公司 | Heavy oil treatment method and system for maleic anhydride production by n-butane method |
| CN114195913A (en) * | 2021-12-23 | 2022-03-18 | 茂名鲁华新材料有限公司 | Method for improving flash evaporation effect of carbon five petroleum resin |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3966538A (en) * | 1973-01-09 | 1976-06-29 | Monsanto Company | Falling strand devolatilization apparatus |
| US5183866A (en) * | 1989-08-30 | 1993-02-02 | Phillips Petroleum Company | Polymer recovery process |
-
1998
- 1998-01-08 CN CN98100011A patent/CN1060784C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297593C (en) * | 2002-08-07 | 2007-01-31 | 富士胶片株式会社 | Solution concentrating method and solution film making method and product |
| CN103674894A (en) * | 2013-12-30 | 2014-03-26 | 安徽皖维集团有限责任公司 | Method for detecting concentration of polyvinyl alcohol solution in production of polyvinyl-alcohol optical film by utilizing refractometer |
| CN105315516A (en) * | 2014-07-30 | 2016-02-10 | 固特异轮胎和橡胶公司 | Elastomer containing combination of tris(nonyl phenyl) phosphite and tetramethylethylenediamine, preparation and compositions and articles of manufacture thereof |
| US10428202B2 (en) | 2014-07-30 | 2019-10-01 | The Goodyear Tire & Rubber Company | Elastomer containing combination of tris(nonyl phenyl) phosphite and tetramethylethylenediamine, preparation and compositions and articles of manufacture thereof |
| US10829616B2 (en) | 2014-07-30 | 2020-11-10 | The Goodyear Tire & Rubber Company | Elastomer containing combination of tris(nonyl phenyl) phosphite and tetramethylethylenediamine, preparation and compositions and articles of manufacture thereof |
| CN107703099B (en) * | 2016-08-08 | 2021-03-16 | 中国石油化工股份有限公司 | On-line continuous detection method and polymerization reaction method |
| CN107703099A (en) * | 2016-08-08 | 2018-02-16 | 中国石油化工股份有限公司 | On-line continuous detection device and method and polymerization reaction system and method |
| CN107185467A (en) * | 2017-07-06 | 2017-09-22 | 广东弘擎电子材料科技有限公司 | A kind of glue preparation system |
| CN114100171A (en) * | 2021-11-23 | 2022-03-01 | 洛阳炼化九源石化有限公司 | Heavy oil treatment method and system for maleic anhydride production by n-butane method |
| CN114195913A (en) * | 2021-12-23 | 2022-03-18 | 茂名鲁华新材料有限公司 | Method for improving flash evaporation effect of carbon five petroleum resin |
| CN114195913B (en) * | 2021-12-23 | 2023-08-18 | 广东鲁众华新材料有限公司 | Method for improving flash evaporation effect of carbon five petroleum resin |
| CN114011104A (en) * | 2022-01-06 | 2022-02-08 | 湖南大学 | Control method, device and equipment of gravity flash evaporator and gravity flash evaporator |
| CN114011104B (en) * | 2022-01-06 | 2022-03-22 | 湖南大学 | Control method, device and equipment of gravity flash evaporator and gravity flash evaporator |
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| CN1060784C (en) | 2001-01-17 |
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