AU769019B2 - Separation of liquid phases which contain polymers - Google Patents

Separation of liquid phases which contain polymers Download PDF

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Publication number
AU769019B2
AU769019B2 AU52083/00A AU5208300A AU769019B2 AU 769019 B2 AU769019 B2 AU 769019B2 AU 52083/00 A AU52083/00 A AU 52083/00A AU 5208300 A AU5208300 A AU 5208300A AU 769019 B2 AU769019 B2 AU 769019B2
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Australia
Prior art keywords
solvent
polymers
separation
branched
phases
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AU52083/00A
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AU5208300A (en
Inventor
Wolfgang Arlt
Gabriele Sadowski
Matthias Seiler
Andreas Thiele
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Der Gruene Punkt Duales System Deutschland AG
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Der Gruene Punkt Duales System Deutschland AG
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Assigned to DER GRUNE PUNKT-DUALES SYSTEM DEUTSCHLAND AG reassignment DER GRUNE PUNKT-DUALES SYSTEM DEUTSCHLAND AG Alteration of Name(s) of Applicant(s) under S113 Assignors: BGB-GESELLSCHAFT, DER GRUNE PUNKT-DUALES SYSTEM DEUTSCHLAND AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/092—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0203—Separating plastics from plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0293—Dissolving the materials in gases or liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

The invention relates to the acceleration of the separation of liquid phases which contain polymers by using branched instead of linear solvents.

Description

PAOPER\Rd,\2U(i3\Sep1\2466792 254 spodoc- -1- SEPARATION OF LIQUID PHASES WHICH CONTAIN POLYMERS The invention relates to the separation of liquid phases containing polymers, particularly to their accelerated separation.
Mixed polymers may be separated by a liquid-liquid phase separation wherein polymers are present in all phases, but selectively separated. Liquid phases with not insignificant polymer content have high viscosities. Polymers are understood to be technically or biologically produced macromolecules having a molar weight of 1000 Daltons or more. Different kinds of polymers are understood to be chemically or structurally different polymers, such as HDPE, LDPE, PP or PVC.
For the economics of such a thermal separation process, the times of sedimentation in the separation steps are decisive, since space-time-yields are determined thereby.
Furthermore, long residence times can enable decomposition reactions to take place.
Liquid systems having two or more phases include a continuous phase (KP) and one or more discontinuous phases (DP) in a dispersed state. The literature subdivides coalescence and sedimentation of the discontinuous phase into several stages: o• S- coalescence of single drops to form larger drops ascending or descending of larger drops controlled by density unification of larger drops with already formed phase.
i: 25 In all these processes, the rising or settling velocities of single drops are particularly important. A comparatively simple mathematical model is obtained when the drops are "considered as rigid spheres in the KP.
The modeling of the motion of spherically shaped solid particles in a continuous phase is made according to Clift R, et al and Brauer by using the equation of motion. The equation of motion (eq. 1) represents a term for the constant velocity of falling spherically shaped particles.
wP PP-- pg'dp eq. (1) V3 PF Therein, wp represents settling or rising velocity of particles, pp and PF respectively, the density of the discontinuous (index P) and the continuous phase (index respectively, g the acceleration due to gravity, dp the particle diameter and the drag coefficient.
Equation 1 is generally valid for solid or fluid high viscous particles. The special characteristics of the phase boundary surface are described by the drag coefficient for which the following interrelation is valid: 0c- eq. (2) Re wherein Re= wd 18 1 -1 eq. (3) VF 9 In equation 3, vF represents the kinematic viscosity of the continuous phase and Ar the Archimedian number. The introduction of the dimensionless Archimedian number is useful, since hereby the settling velocity wp of particles in equation 1 can be represented in explicit form. It is: Ar= -pF g.d eq. (4) PF VF Equation teaches that only the viscosity of the continuous phase, the particle diameter of the discontinuous phase and the density difference between continuous and discontinuous phase are important for the separation. Short residence times are advantageous to save operation and investment costs and to suppress chemical reactions.
PAOPER\Rd20(13)opI466792 254 Spe.doc-IS Soplsbr. 25M)3 -3- According to the teaching of the literature, the phase separation time can be improved in particular by reducing the viscosity of KP. Possibilities known in the literature for reducing the viscosity of KP are increasing the temperature or changing the nature of the solvent which with the polymer, forms KP. However, these measures do not lead to the goal in the separation of mixed polymer by liquid-liquid-phase separation, since the temperature not only changes the viscosity but, particularly due to thermodynamics, also the purity/yield of the polymers being separated. Therefore, an improvement of the separation time must be paid for with a deterioration in selectivity; changing the nature of the solvent changes the thermodynamics to an extent that the separation temperatures are either shifted into ranges which are uneconomic or the phase separation no longer occurs in the range of temperatures which can be technically reached.
The present invention seeks to overcome this problem in an elegant and novel manner.
The present invention provides a method for the separation of phases containing different o• polymers, characterized in that a) said polymers are solved in a branched solvent or solvent mixture and b) the resulting solvent phases which include solved polymers of different type in different concentrations are separated after sedimentation.
o.• 25 Advantageously, the solvent is selected such that the sedimentation times of the phases in the branched solvent or solvent mixture are shorter than those in a non-branched solvent or ooo solvent mixture.
The polymers of different type can be mixtures of polyolefins and the solvent can be a branched alkane having a carbon number between 4 and 16. Preferably the solvent is a P:\OPERkRdA2103\ScpIU466792 254 spe.doc.I5 Sopiorber, 2W03 3abranched alkane having a carbon number between 4 and 10, more preferably between 6 and 8.
The solvent is preferably dimethylbutane or methylpentane.
Advantageously, the different polymers are polyolefins that originate from waste to be recycled.
As an example, the thermal separation of polyolefin mixtures as polymers of different type is considered, with n-alkanes having five to seven carbon atoms in the molecule as solvent.
The teachings of the invention are applicable to all other separation methods which include the separation of polymer mixtures by forming liquid phases.
The method described in separates polyolefins in that two liquid phases are formed in n-hexane at 180 0 C, wherein the upper light phase contains under certain conditions polyethylene from high pressure synthesis (LDPE), and the lower one polyethylene from low pressure synthesis (HDPE). Due to the amount, the low viscous upper phase is KP, and the high viscous lower phase is DP in the dispersed system. The low viscosity of the upper phase, however, does not lead to technically acceptable separation times, so that the S 20 above mentioned disadvantages (cost, reactions) become effective.
Experimental runs, however, have surprisingly shown that the use of branched solvents with same carbon number significantly and advantageously changes the separation times.
STherein, the viscosity of KP is about the same for the non-branched and the branched solvent, so that the effect cannot be explained at the moment.
Branched solvents are such aliphatic materials in which at least one carbon atom has more than two carbon atoms as neighbors and which may also carry functional groups along with further C and H atoms.
To illustrate the proceedings according to the patent, the branched solvent 2,3-dimethylbutane shall be compared with the unbranched solvent n-hexane.
Example 1 Two experimental runs were performed having the separation of a polyethylenepolypropylene mixture as a goal. As polyolefines, HDPE (high density polyethylene), LDPE (low density polyethylene) and polypropylene PP were supplied in a proportion of 15/43/42, wherein the total content ofpolyolefine in solution was 20 weight In the first experimental run V_1 n-hexane was used as a solvent, for the second experimental run V_2 2,3-dimethylbutane. The phase separation times as well as the viscosities of the solution were observed. They are represented in table 1. It is noticeable that periods of 300 min cannot be realized with an unbranched solvent or only in a difficult way.
The purities of the different polymers were practically identical in both phases in both runs, since the nature of the solvent had not been changed (in both cases, a hexane is concerned).
However, the considerably shorter separation times in the experimental run V_2 using the branched solvent are surprising. Even though the viscosity of KP and the density difference PP-PF did not change significantly in both runs, it has been detected surprisingly that the system with the branched solvent had been separated faster by a factor of 150 than the system with n-alkane as a solvent.
P:\OPER\RdtPI003\ScI\2466792 254_sp~doc-I Sept-obr. 2003 Experimental Solvent WFeed.Pol System Separation time Viscosity Viscosity run [weight temperature of phases [min] of upper of lower phase KP phase DP V I n-hexane 20 180 300 Low High V_2 2,3-dimethylbutane 20 180 2 Low Low Table 1: Experimental runs to separate polyolefin with a branched (experimental run V_2 and an unbranched solvent (experimental run V_l) According to the teaching of the literature, these reduced separation times lead to smaller separation containers and therefore to a reduction of investment costs and of residence times at the necessary high temperatures.
The teaching of the invention can be applied to all separations of liquid phases which contain polymers and solvents of which branched and unbranched representatives exist.
Citation DE 199 05 029 A, published after the priority date of the present application Brauer, Grundlagen der Einphasen- und Mehrphasenstrdmungen; Verlag Sauerlinder, Aarau, 1971 Clift, Grace, Weber, Bubbles, Drops and Particles Academic Press, :New York, 1978 The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that that prior art forms part of the common general knowledge in Australia.
o

Claims (7)

1. A method for the separation of phases containing different polymers, characterized in that a) said polymers are solved in a branched solvent or solvent mixture and b) the resulting solvent phases which include solved polymers of different type in different concentrations are separated after sedimentation.
2. The method of claim 1, characterized in that said solvent is selected such that the sedimentation times of the phases in the branched solvent or solvent mixture are shorter than those in a non-branched solvent or solvent mixture.
3. The method of claim 1 or 2, characterized in that said polymers of different type are mixtures of polyolefins and the solvent is a branched alkane having a carbon number between 4 and 16.
4. The method of claim 3, characterized in that said solvent is a branched alkane having a carbon number between 4 and The method of claim 3, characterized in that said solvent is a branched alkane having a carbon number between 6 and 8.
6. The method of any one of claims 1 and 5, characterized in that said solvent is dimethylbutane or methylpentane.
7. The method of any one of claims 1 to 6, characterized in that the different polymers are polyolefins that originate from waste to be recycled. P:\OPERkRdA2(X43\ScpZ\2466792 254_ spc.doc.I5 Scptcuiber. 20413 -7-
8. A method for the separation of phases containing different polymers substantially as hereinbefore described with reference to the Example, excluding the comparative experimental run. Dated this 15 t1h day of September, 2003. Der Grune Punkt-Duales System Deutschland AG By their Patent Attorneys: DAVIES COLLISON CAVE
AU52083/00A 1999-05-14 2000-05-12 Separation of liquid phases which contain polymers Ceased AU769019B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19922944 1999-05-14
DE19922944A DE19922944A1 (en) 1999-05-14 1999-05-14 Acceleration of phase separation of liquid polymer-containing phases used for polyolefins involves using branched solvents to increase speed
PCT/DE2000/001475 WO2000069952A1 (en) 1999-05-14 2000-05-12 Acceleration of the phase separation of liquid phases which contain polymers

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AU769019B2 true AU769019B2 (en) 2004-01-15

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JP (1) JP2002544355A (en)
KR (1) KR20020005672A (en)
CN (1) CN1350564A (en)
AT (1) ATE230774T1 (en)
AU (1) AU769019B2 (en)
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CA (1) CA2372121A1 (en)
CZ (1) CZ20014084A3 (en)
DE (2) DE19922944A1 (en)
DK (1) DK1181328T3 (en)
EA (1) EA200101023A1 (en)
EE (1) EE200100590A (en)
ES (1) ES2188548T3 (en)
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HR (1) HRP20010658A2 (en)
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NO (1) NO20015535L (en)
NZ (1) NZ515191A (en)
PL (1) PL352023A1 (en)
PT (1) PT1181328E (en)
SK (1) SK12742001A3 (en)
TR (1) TR200103287T2 (en)
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10032918C2 (en) * 2000-07-06 2002-06-20 Siemens Axiva Gmbh & Co Kg Method for determining the proportion of HDPE and LDPE in polyolefin mixtures
JP5625056B2 (en) 2009-07-16 2014-11-12 ダウ グローバル テクノロジーズ エルエルシー Polymerization process for olefinic polymers
JP2014503659A (en) 2010-12-21 2014-02-13 ダウ グローバル テクノロジーズ エルエルシー Olefin polymers and dispersion polymerization
US11041030B2 (en) 2018-09-19 2021-06-22 Exxonmobil Chemical Patents Inc. Devolatilization processes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2399558A (en) * 1942-12-31 1946-04-30 Standard Oil Dev Co Organic cementing solutions
US2801234A (en) * 1955-03-11 1957-07-30 Phillips Petroleum Co Method of removing olefin polymer from process equipment
GB1452041A (en) * 1974-01-31 1976-10-06 Raffinage Cie Francaise Compagnie francaise de raffinage process for the production of polyolefin fibres

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2399558A (en) * 1942-12-31 1946-04-30 Standard Oil Dev Co Organic cementing solutions
US2801234A (en) * 1955-03-11 1957-07-30 Phillips Petroleum Co Method of removing olefin polymer from process equipment
GB1452041A (en) * 1974-01-31 1976-10-06 Raffinage Cie Francaise Compagnie francaise de raffinage process for the production of polyolefin fibres

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HUP0201501A2 (en) 2002-08-28
TR200103287T2 (en) 2002-04-22
NO20015535D0 (en) 2001-11-13
AU5208300A (en) 2000-12-05
CZ20014084A3 (en) 2002-03-13
YU80701A (en) 2003-10-31
SK12742001A3 (en) 2002-05-09
EP1181328A1 (en) 2002-02-27
EA200101023A1 (en) 2002-04-25
EP1181328B1 (en) 2003-01-08
PL352023A1 (en) 2003-07-14
CA2372121A1 (en) 2000-11-23
ES2188548T3 (en) 2003-07-01
KR20020005672A (en) 2002-01-17
DE50001053D1 (en) 2003-02-13
ATE230774T1 (en) 2003-01-15
MXPA01011554A (en) 2003-08-20
DE19922944A1 (en) 2000-11-16
EE200100590A (en) 2003-04-15
HK1046008A1 (en) 2002-12-20
BR0010535A (en) 2002-02-19
NZ515191A (en) 2003-01-31
HK1046008B (en) 2003-10-03
JP2002544355A (en) 2002-12-24
NO20015535L (en) 2001-11-13
PT1181328E (en) 2003-04-30
HRP20010658A2 (en) 2002-10-31
DK1181328T3 (en) 2003-04-14
BG106036A (en) 2002-06-28
CN1350564A (en) 2002-05-22
HUP0201501A3 (en) 2005-01-28
WO2000069952A1 (en) 2000-11-23
IL144807A0 (en) 2002-06-30

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