USE OF ALKYL-TRICHLOROSILANES AND/OR SILSESQUIOXANES FOR THE REMOVAL OF MICROPLASTIC PARTICLES FROM WATER AND/OR A BODY OF WATER
20210070638 ยท 2021-03-11
Inventors
Cpc classification
C02F2103/007
CHEMISTRY; METALLURGY
International classification
Abstract
Use of an alkyltrichlorosilane of the following formula I: RSiCl.sub.3, wherein: R represents an alkyl group, Si represents a silicon atom and Cl represents a chlorine atom, and/or of a silsesquioxane of the following formula II: [RSiO.sub.3/2].sub.n, wherein: R represents an alkyl group, Si represents a silicon atom, O represents an oxygen atom and n represents an integer, for the removal of microplastic particles from water and/or for the treatment of water. Further, a method for the removal of microplastic particles from water and/or for the purification of water is provided, as well as an inclusion and/or intercalation compound, a kit for the removal of microplastic particles from water and/or for the purification of water as well as a water treatment system.
Claims
1. A method for the removal of microplastic particles from water and/or a body of water and/or for treatment of water and/or a body of water, the method having the following steps: (a) dosing or adding an alkyltrichlorosilane of the following formula I
RSiCl.sub.3(formula I), wherein R represents an alkyl group, Si represents a silicon atom and Cl represents a chlorine atom, and/or dosing or adding a silsesquioxane of the following formula II
[RSiO.sub.3/2].sub.n(formula II), wherein R represents an alkyl group, Si represents a silicon atom, O represents an oxygen atom and n represents an integer, to a microplastic particle-containing water and/or a microplastic particle-containing body of water, and (b) removing, from the water and/or the body of water, inclusion compounds formed after addition of the alkyltrichlorosilane and/or the silsesquioxane, wherein the inclusion compounds each comprise a hybrid silica gel and microplastic particles, wherein the hybrid silica gel is formed by reaction of the alkyltrichlorosilane and/or of the silsesquioxane in the water and/or body of water and encloses the microplastic particles at least partially.
2. The method as claimed in claim 1, wherein the alkyltrichlorosilane is a carrier-free alkyltrichlorosilane and/or the silsesquioxane is a carrier-free silsesquioxane.
3. The method as claimed in claim 1, wherein R is an alkyl group having 1 carbon atom to 16 carbon atoms.
4. The method as claimed in claim 1, wherein R is a linear alkyl group.
5. The method as claimed in claim 1, wherein R is a branched alkyl group.
6. The method as claimed in claim 1, wherein R is selected from the group consisting of n-butyl group, isobutyl group, hexyl group, isohexyl group, 2,4,4-trimethylpentyl group, n-octyl group, 6-methylheptyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and hexadecyl group.
7. The method as claimed in claim 1, wherein R is selected from the group consisting of n-butyl group, isobutyl group, n-octyl group and 2,4,4-trimethylpentyl group.
8. The method as claimed in claim 1, wherein the silsesquioxane comprises at least two different alkyl groups.
9. The method as claimed in claim 1, wherein the alkyltrichlorosilane is a pure substance or a mixture of different alkyltrichlorosilanes and/or the silsesquioxane is a pure substance or a mixture of different silsesquioxanes.
10. The method as claimed in claim 1, wherein n represents an integer from 4 to 16.
11. The method as claimed in claim 1, wherein n represents the integer 6, 8, 10 or 12.
12. The method as claimed in claim 1, wherein the silsesquioxane is a silsesquioxane of the following formula III: ##STR00002## wherein R represents an alkyl group, Si represents a silicon atom and O represents an oxygen atom.
13. The method as claimed in claim 1, wherein the microplastic particles have a mean diameter of 100 nm to 5 mm.
14. The method as claimed in claim 1, wherein the microplastic particles comprise a plastic or consist of a plastic which is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyurethane, polyamide, polycarbonate, polytetrafluoroethylene, polyoxymethylene, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polymethyl methacrylate, polyacrylonitrile, copolymers of at least two of said plastics and combinations of at least two of said plastics.
15. (canceled)
16. (canceled)
17. An inclusion compound, comprising a hybrid silica gel and microplastic particles, wherein the hybrid silica gel is formed by reaction of an alkyltrichlorosilane of the following formula I
RSiCl.sub.3(formula I), wherein R represents an alkyl group, Si represents a silicon atom and Cl represents a chlorine atom, and/or by a silsesquioxane of the following formula II
[RSiO.sub.3/2].sub.n(formula II), wherein R represents an alkyl group, Si represents a silicon atom, O represents an oxygen atom and n represents an integer, in water and/or a body of water and at least partially encloses the microplastic particles.
18. A kit for the removal of microplastic particles from water and/or a body of water and/or for the treatment or purification, of water and/or a body of water, said kit having, spatially separated from one another, an alkyltrichlorosilane as claimed in claim 1 and at least one further component, wherein the further component is an adsorbent.
19. The use of an alkyltrichlorosilane of the following formula I
RSiCl.sub.3(formula I), wherein R represents an alkyl group, Si represents a silicon atom and Cl represents a chlorine atom, and/or of a silsesquioxane of the following formula II
[RSiO.sub.3/2].sub.n(formula II), wherein R represents an alkyl group, Si represents a silicon atom, O represents an oxygen atom and n represents an integer, for the removal of microplastic particles from water and/or a body of water, and/or for the treatment or purification of water and/or a body of water.
20. The method as claimed in claim 3, wherein R is an alkyl group having 3 carbon atoms to 14 carbon atoms or 4 carbon atoms to 8 carbon atoms.
21. The method as claimed in claim 8, wherein the at least two different alkyl groups are selected from the group consisting of n-butyl group, isobutyl group, hexyl group, isohexyl group, 2,4,4-trimethylpentyl group, n-octyl group, 6-methylheptyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and hexadecyl group.
22. The method as claimed in claim 10, wherein n represents an integer from 6 to 14 or from 6 to 12.
23. The method as claimed in claim 13, wherein the mean diameter is 10 m to 5 mm or 100 m to 1 mm.
24. The kit as claimed in claim 18, wherein the adsorbent is selected from the group consisting of activated carbon, calcium-silica hydrates, polonite, rocks and combinations of at least two of the specified adsorbents.
25. A kit for the removal of microplastic particles from water and/or a body of water and/or for the treatment or purification, of water and/or a body of water, said kit having, spatially separated from one another, a silsesquioxane as claimed in claim 1 and at least one further component, wherein the further component is an adsorbent.
26. The kit as claimed in claim 25, wherein the adsorbent is selected from the group consisting of activated carbon, calcium-silica hydrates, polonite, rocks and combinations of at least two of the specified adsorbents.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0153] The drawings show the following schematically:
[0154]
[0155]
[0156]
[0157] On contact with water, the silicon-chlorine bonds of the alkyltrichlorosilane 1 are hydrolyzed to silanol compounds 2 with the formation of hydrochloric acid. Due to a catalytic effect of the hydrochloric acid released, the silanol compounds 2 occurring intermediately rapidly undergo condensation reactions, wherein the hybrid silica gel 3 is produced.
[0158] Via the alkyl group of alkyltrichlorosilane 1 it is possible to localize and aggregate microplastic particles distributed in water and/or a body of water. A certain initial stability of the alkyltrichlorosilane is advantageous for this purpose, so that sufficient localization and aggregation of microplastic particles can take place before the enclosure of the microplastic particles/aggregated microplastic particles takes place by formation of the hybrid silica gel, in particular by means of a sol-gel method.
[0159] The alkyltrichlorosilane may, in particular, be n-butyltrichlorosilane, isobutyltrichlorosilane, n-octyltrichlorosilane or 2,4,4-trimethylpentyltrichlorosilane.
[0160]
EXAMPLE PART
1. General Test Specification for the Formation of Agglomeration Compounds
1.1 Laboratory Scale
[0161] 100 mg microplastic powder (PE, PP or mixtures) (150 m-300 m) and 1 l distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). A small amount (approx. 50-100 mol) of agglomeration reagent was added slowly. The reaction mixture was stirred at 250 rpm and 25 C. After 20 min, the mixture was filtered and the white solid was dried at 105 C. for 24 h. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles within 3-4 min. After 2 min gel formation started and a large agglomerate was formed which floated on the water surface (fixation). After 10 min no free PE, PP or mixtures of both were left unbound in the reaction vessel. The pH value of the water was 6-7.
1.2 Pilot System Scale
[0162] 100 g microplastic powder (PP, PE/PP (1/1) (150 m-300 m) and 2000 l process water (secondary clarifier) were filled into a discontinuous 2000 L batch reactor. Subsequently, the mixture was stirred at 250 rpm at room temperature for 24 h (swelling process). The agglomeration method was started by adding agglomeration reagent (approx. 50-100 mmol) and stirring the mixture for 24 h at room temperature and 250 rpm. The mixture was filtered and the agglomerated white solids were dried at 105 C. for 24 h. The agglomerated solids had a diameter of 2-6 cm.
2. General Information
[0163] GUR 4150 UHMW-PE particles were purchased from Celanese. Other PE (LDPE, HDPE) and PP microplastic particles were purchased from LyondellBasell.
[0164] The alkyltrichlorosilanes and silsesquioxanes listed in table 1 below were used in the experiments described below.
TABLE-US-00001 TABLE 1 Alkyltrichlorosilanes and silsesquioxanes used Name CAS. no. n-Butyltrichlorosilane 7521-80-4 isobutyltrichlorosilane 18169-57-8 n-octyltrichlorosilane 5283-66-9 isooctyltrichlorosilane 18379-25-4 isooctyl POSS Cage Mixture 1472635-27-0
[0165] Environmental Scanning Electron Microscope (ESEM) images of hybrid silica gels (sample size up to 3 mm) were obtained using an FEI Quanta 250 ESEM (FEI Company, Hillsboro, USA) with low vacuum (60 and 80 Pa). To obtain good quality images, a large field detector (LFD) with an acceleration voltage between 7 and 20 kV was used. The IR spectra were measured with FTIR Nicolet iS10 (Thermo, Dreieich, Germany) and FTIR Nicolet iS5 (Thermo, Dreieich, Germany). Additionally, IR spectra were recorded on VARIAN FT-IR 630 with ATR pike (4000-400 cm.sup.1).
3. General Test Specification for the Formation of Agglomeration Compounds
[0166] 100 mg microplastic powder (PE, PP or mixtures) (150 m-300 m) and 1 l distilled water were placed in a 2 l round-bottom flask and stirred vigorously. A small amount (1*10.sup.3 mol) of agglomeration reagent (tests 1-6) was added slowly and the reaction mixture was stirred at 250 rpm and 25 C. After 20 min the mixture was filtered and the white solid was dried at 60 C. for 24 h.
4. Tests
[0167] 4.1 Synthesis of a Microplastic Inclusion Compound Using n-Octyltrichlorosilane
4.1.1 Synthesis of a Hybrid Silica Gel Based on n-Octyltrichlorosilane
[0168] 1 L distilled water was placed in a 2 L round-bottom flask and stirred vigorously. 43.2 mol n-octyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. Gel formation started immediately upon contact with water and several agglomerates were formed. After 20 min the mixture was filtered, washed with water and the white, very voluminous solid was dried at 60 C. for 24 h. A transparent solid was formed.
[0169] EA: C 77.93, H 14.44, N 0
[0170] IR: n-octyl at (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.1.2 Synthesis of an LDPE/HDPE Microplastic Inclusion Compound
[0171] 100 mg microplastic powder (LDPE/HDPE) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 43.2 mol n-octyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets partially accumulated the microplastic particles (approx. 50%) within 3-4 min. Gel formation started directly upon contact with water and several agglomerates were formed which floated on the water surface (fixation). After 10 min 50% (mass balance) PE was bound and 50% unbound in the reaction vessel. The pH value of the water was 6-7. The mixture was stirred for 10 min more, then filtered, washed with water and dried for 24 h at 60 C. A transparent solid with bound white microplastic particles was formed.
[0172] EA: C 79.23, H 14.00, N 0
[0173] IR: PE (CH.sub.2) 2920 2870 cm.sup.1 (R=n-octyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.1.3 Synthesis of a PP Microplastic Inclusion Compound
[0174] 100 mg microplastic powder (PP) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 43.2 mol n-octyltrichlorosilane were added slowly. The reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets, which circulated in the vessel (localization). The droplets accumulated the microplastic particles partially (approx. 50%) within 3-4 min. Gel formation started directly upon contact with water and several agglomerates were formed which floated on the water surface (fixation). After 10 min 50% (mass balance) PE was bound and 50% unbound in the reaction vessel. The pH value of the water was 6-7. The mixture was stirred for 10 min more, then filtered, washed with water and dried for 24 h at 60 C. A transparent solid with bound white microplastic particles was formed.
[0175] EA: C 76.80, H 14.05, N 0
[0176] IR: PP (CH.sub.2) 2920 2870 cm.sup.1 (R=n-octyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.1.4 Synthesis of a PE/PP Microplastic Inclusion Compound
[0177] 100 mg microplastic powder (LDPE/HDPE/PP 0.5/0.5/1) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 43.2 mol n-octyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets, which circulated in the vessel (localization). The droplets partially accumulated the microplastic particles (approx. 50%) within 3-4 min. Gel formation started directly upon contact with water and several agglomerates were formed which floated on the water surface (fixation). After 10 min 50% (mass balance) of the microplastic mixture was bound and 50% was unbound in the reaction vessel. The pH value of the water was 6-7. The mixture was stirred for 10 min more, then filtered, washed with water and dried for 24 h at 60 C. A transparent solid with bound white microplastic particles was formed.
[0178] IR: PE/PP (CH.sub.2) 2920 2870 cm.sup.1 (R=n-octyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.2 Synthesis of a Microplastic Inclusion Compound Using n-Butyltrichlorosilane
4.2.1 Synthesis of a Hybrid Silica Gel Based on n-Butyltrichlorosilane
[0179] 1 L distilled water was placed in a 2 L round-bottom flask and stirred vigorously. 60.5 mol n-butyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane formed small droplets which settled to the bottom. Gel formation started after 2 min and a large agglomerate was formed. After 20 min, the mixture was filtered, washed with water and the white solid was dried at 60 C. for 24 h. A white gel-like solid was formed.
[0180] EA: C 41.16, H 07.93, N 0
[0181] IR: n-butyl (CH.sub.2) 2950 cm.sup.1-2870 cm.sup.1, (CH) 1465-1407 cm.sup.1, (SiOSi) 1202 cm.sup.1, (SiO) 874-688 cm.sup.1.
4.2.2 Synthesis of a PE Microplastic Inclusion Compound
[0182] 100 mg microplastic powder (LDPE/HDPE) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 60.5 mol n-butyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets, which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 75%) within 2-4 min. Gel formation started after 2 min and a large agglomerate was formed, which floated on the water surface (fixation). After 10 min 75% (mass balance) of PE was bound. The pH value of the water was 6-7. The mixture was stirred for another 10 min, then filtered, washed with water and dried for 24 h at 60 C. The result was a transparent solid with incorporated white microplastic particles.
[0183] EA: C 75.04, H 12.74, N 0
[0184] IR: PE (CH.sub.2) 2920 2870 cm.sup.1 (R=n-butyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.2.3 Synthesis of a PP Microplastic Inclusion Compound
[0185] 100 mg microplastic powder (PP) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 60.5 mol n-butyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 75%) within 2-4 min. Gel formation started after 2 min and a large agglomerate was formed, which floated on the water surface (fixation). After 10 min 100% (mass balance) PP was bound. The pH value of the water was 6-7. The mixture was stirred for another 10 min, then filtered, washed with water and dried for 24 h at 60 C. The result was a transparent solid with incorporated white microplastic particles.
[0186] EA: C 80.30, H 13.76, N 0
[0187] IR: PP (CH.sub.2) 2920 2870 cm.sup.1 (R=n-butyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.2.4 Synthesis of a PE/PP Microplastic Inclusion Compound
[0188] 100 mg microplastic powder (LDPE/HDPE/PP; 0.5/0.5/1) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 60.5 mol n-butyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets, which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 75%) within 2-4 min. Gel formation started after 2 min and a large agglomerate was formed, which floated on the water surface (fixation). After 10 min 100% (mass balance) of the microplastic mixture was bound. The pH value of the water was 6-7. The mixture was stirred for 10 min more, then filtered, washed with water and dried for 24 h at 60 C. A transparent solid with incorporated white microplastic particles was formed.
[0189] EA: C 69.67, H 11.55, N 0
[0190] IR: PE/PP (CH.sub.2) 2920 2870 cm.sup.1 (R=n-butyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.3 Synthesis of a Microplastic Inclusion Compound Using Isobutyltrichlorosilane
4.3.1 Synthesis of a Hybrid Silica Gel Based on Isobutyltrichlorosilane
[0191] 1 L distilled water was placed in a 2 L round-bottom flask and stirred vigorously. 60 mol isobutyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane formed small droplets and initially did not mix with water. Gel formation started after 6 min. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates were visible. After 20 minutes the aggregates increased in size. The size of the aggregates was 1-3 mm. The mixture was filtered, washed with water and the white solid was dried at 60 C. for 24 h. The result was a white solid.
[0192] EA (found): C 40.64, H 08.17, N 0
[0193] REM EDX: C 47.92, O 37.734, Si 14.35.
[0194] IR: (CH.sub.2) 2953 cm.sup.1, 2869 cm.sup.1, (CH) 1465-1401 cm.sup.1, (SiOSi) 1128 cm.sup.1-997, (SiO) 835-737-cm.sup.1.
4.3.2 Synthesis of a PE Microplastic Inclusion Compound
[0195] 100 mg microplastic powder (LDPE/HDPE) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 60 mol isobutyltrichlorosilane were added slowly. The reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets, which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 6 min and a large agglomerate was formed. After 10 min the trichlorosilane was completely converted to hybrid silica gel and small aggregates with the bound PE (100% mass balance) were visible. After 20 minutes the aggregates increased in size (2-3 mm) and floated on the water surface (fixation). The pH-value of the water was 6-7. The mixture was then filtered, washed with water and dried for 24 h at 60 C. The result was a white solid with incorporated white microplastic particles.
[0196] EA (found): C 76.36, H 14.15, N 0
[0197] REM EDX (found): C 47.92, O 37.734, Si 14.35.
[0198] IR: PE (CH.sub.2) 2920 2870 cm.sup.1 (R=isobutyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.3.3 Synthesis of a PP Microplastic Inclusion Compound
[0199] 100 mg microplastic powder (PP) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 60 mol isobutyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 6 min and a large agglomerate was formed. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates with the bound PP (100% mass balance) were visible. After 20 minutes the aggregates increased in size (2-3 mm) and floated on the water surface (fixation). The pH-value of the water was 6-7. The mixture was then filtered, washed with water and dried for 24 h at 60 C. The result was a white solid with incorporated white microplastic particles.
[0200] EA (found): C 73.72, H 13.46, N 0
[0201] REM EDX (found): C 72.2, O 24.27, Si 3.53.
[0202] IR: PP (CH.sub.2) 2920 2870 cm.sup.1 (R=isobutyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.3.4: Synthesis of a PE/PP Microplastic Inclusion Compound
[0203] 100 mg microplastic powder (LDPE/HDPE/PP, 05/0.5/1) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 60 mol isobutyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 6 min and a large agglomerate was formed. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates with the bound microplastic mixture (100% mass balance) were visible. After 20 minutes the aggregates increased in size (2-3 mm) and floated on the water surface (fixation). The pH value of the water was 6-7. The mixture was then filtered, washed with water and dried for 24 h at 60 C. The result was a white solid with incorporated white microplastic particles.
[0204] EA (found): C 75.54, H 13.63, N 0
[0205] REM EDX (found): C 46.04, O 40.51, Si 13.452.
[0206] IR: PE/PP (CH.sub.2) 2920 2870 cm.sup.1 (R=isobutyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.4 Synthesis of a Microplastic Inclusion Compound Using Isooctyltrichlorosilane
4.4.1 Synthesis of a Hybrid Silica Gel Based on Isooctyltrichlorosilane
[0207] 1 L distilled water was placed in a 2 L round-bottom flask and stirred vigorously. 43 mol isooctyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane formed small droplets and initially did not mix with water and sank to the bottom. After 5-10 s the gel formation started and a large aggregate became visible, floating on the water surface. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates were visible. A white gel was formed. After 20 minutes the aggregates increased in size. The size of the aggregates was 1-3 mm. The mixture was filtered, washed with water and the white solid was dried at 60 C. for 24 h. The result was a white solid.
[0208] EA (found): C 40.85, H 08.30, N 0
[0209] REM EDX (found): C 49.43, O 40.16, Si 10.41.
[0210] IR: Isooctyl (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.4.2 Synthesis of a PE Microplastic Inclusion Compound
[0211] 100 mg microplastic powder (LDPE/HDPE) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 43 mol isooctyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 5-10 s and a large agglomerate was formed. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates with the bound PE (100% mass balance) were visible. After 20 minutes the aggregates increased in size (2-3 mm) and floated on the water surface (fixation). The pH-value of the water was 6-7. The mixture was then filtered, washed with water and dried for 24 h at 60 C. The result was a white solid with incorporated white microplastic particles.
[0212] EA (found): C 70.96, H 14.57, N 0
[0213] REM EDX (found): C 79.55, O 15.79, Si 4.65.
[0214] IR: PE (CH.sub.2) 2920 2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.4.3 Synthesis of a PP Microplastic Inclusion Compound
[0215] 100 mg microplastic powder (PP) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 43 mol isooctyltrichlorosilane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 5-10 s and a large agglomerate was formed. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates with the bound PE (100% mass balance) were visible. After 20 minutes the aggregates increased in size (2-3 mm) and floated on the water surface (fixation). The pH-value of the water was 6-7. The mixture was then filtered, washed with water and dried for 24 h at 60 C. The result was a white solid with incorporated white microplastic particles.
[0216] EA (found): C 74.95, H 13.59, N 0
[0217] REM EDX (found): C 67.56, O 26.6, Si 5.84.
[0218] IR: PP (CH.sub.2) 2920 2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.4.4 Synthesis of a PE/PP Microplastic Inclusion Compound
[0219] 100 mg microplastic powder (LDPE/HDPE/PP, 0.5/0.5/1) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 43 mol isooctyltrichlorosilane were added slowly. The reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets, which circulated in the vessel (localization). The droplets completely accumulated the microplastic particles (approx. 100%) within 2-4 min. Gel formation started after 5-10 s and a large agglomerate was formed. After 10 min the trichlorosilane was completely converted to the hybrid silica gel and small aggregates with the bound microplastic mixture (100% mass balance) were visible. After 20 minutes the aggregates increased in size (2-3 mm) and floated on the water surface (fixation). The pH value of the water was 6-7. The mixture was then filtered, washed with water and dried for 24 h at 60 C. The result was a white solid with incorporated white microplastic particles.
[0220] EA (found): C 78.21, H 14.31, N 0
[0221] REM EDX (found): C 62.66, O 29.85, Si 7.485.
[0222] IR: PE/PP (CH.sub.2) 2920 2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.5 Synthesis of a Microplastic Inclusion Compound Using Isooctyl-T.SUB.8.-Polyoctahedral Silsesquioxane
4.5.1 Synthesis of a Hybrid Silica Gel Based on Isooctyl-T8-Polyoctahedral Silsesquioxane
[0223] 1 L distilled water was placed in a 2 L round-bottom flask and stirred vigorously. 7.64 mol isooctyl-T.sub.8-polyoctahedral silsesquioxane were added slowly. The reaction mixture was stirred at 250 rpm and 25 C. The highly viscous silane formed small droplets and did not mix with water and floated up. Upon contact with water no visible hybrid silica gel was formed at first. A change in color could be detected by strong mixing. The substance changed from slightly yellowish to a whitish transparent highly viscous liquid. The gel was filtered, washed with water and dried at 60 C. for 24 h. The result was a whitish transparent highly viscous liquid.
[0224] EA (found): C 57.02, H 10.41
[0225] IR: Isooctyl (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.5.2 Synthesis of a PE Microplastic Inclusion Compound
[0226] 100 mg microplastic powder (LDPE/HDPE) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 7.64 mol isooctyl-T.sub.8-polyoctahedral silsesquioxane were added slowly. The reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 5-6 min, wherein the color of the liquid changed from slightly yellowish to white. After 5-6 min a large agglomerate with the bound PE (100% mass balance) was visible. The pH value of the water was 6-7. The agglomerate was then filtered, washed with water and dried for 24 h at 60 C. The result was a white, highly viscous liquid with incorporated white microplastic particles.
[0227] EA (found): C 69.51, H 12.18, N 0
[0228] REM EDX (found): C 63.13, O 24.26, Si 12.37
[0229] IR: PE (CH.sub.2) 2920 2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.5.3 Synthesis of a PP Microplastic Inclusion Compound
[0230] 100 mg microplastic powder (PP) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 7.64 mol isooctyl-18-polyoctahedral silsesquioxane were added slowly and the reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 5-6 min. and the color of the liquid changed from slightly yellowish to white. After 5-6 min a large agglomerate with the bound PP (100% mass balance) was visible. The pH value of the water was 6-7. The agglomerate was then filtered, washed with water and dried for 24 h at 60 C. The result was a white, highly viscous liquid with incorporated white microplastic particles.
[0231] EA (found): C 75.30, H 13.22, N 0
[0232] REM EDX (found): C 63.5, O 20.92, Si 15.58.
[0233] IR: PP (CH.sub.2) 2920-2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.5.4 Synthesis of a PE/PP Microplastic Inclusion Compound
[0234] 100 mg microplastic powder (LDPE/HDPE/PP, 0.5/0.5/1) (50 m-300 m) and 1 L distilled water were placed in a 2 L round-bottom flask and stirred vigorously (24 h swelling process). 7.64 mol isooctyl-T.sub.8-polyoctahedral silsesquioxane were added slowly. The reaction mixture was stirred at 250 rpm and 25 C. The silane initially formed small droplets which circulated in the vessel (localization). The droplets accumulated the microplastic particles completely (approx. 100%) within 2-4 min. Gel formation started after 5-6 min, whereby the color of the liquid changed from slightly yellowish to white. After 5-6 min a large agglomerate with the bound microplastic mixture (100% mass balance) was visible. The pH value of the water was 6-7. The agglomerate was then filtered, washed with water and dried for 24 h at 60 C. The result was a white, highly viscous liquid/solid with incorporated white microplastic particles.
[0235] EA (found): C 77.75, H 13.86, N 0
[0236] REM EDX (found): C 63.43, O 21.38, Si 15.19.
[0237] IR: PE/PP (CH.sub.2) 2920-2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1, (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.6 Synthesis of a Microplastic Inclusion Compound Using Isooctyl-T.SUB.8.-Polyoctahedral Silsesquioxane in 2000 L Pilot Scale
4.6.1 Synthesis of a PE Microplastic Inclusion Compound
[0238] 100 g microplastic powder (LDPE/HDPE) (150 m-300 m) and 2000 L process water (secondary settling tank) were filled into a discontinuous 2000 L batch reactor. Subsequently, at an outside temperature (15-20 C.), the mixture was stirred for 24 h at 250 rpm (swelling process). The agglomeration method was started by adding 7.64 mmol of isooctyl-T.sub.8-polyoctahedral silsesquioxane and stirring the mixture for 24 h at an outside temperature (15-20 C.) and 250 rpm. The mixture was filtered and the white agglomerates were dried at 60 C. for 24 h. The white agglomerates had a diameter of 2-6 cm.
[0239] IR: PE (CH.sub.2) 2920-2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.6.2 Synthesis of a PP Microplastic Inclusion Compound
[0240] 100 g microplastic powder (PP) (150 m-300 m) and 2000 L process water (secondary settling tank) were filled into a discontinuous 2000 L batch reactor. Subsequently, at an outside temperature (15-20 C.), the mixture was stirred for 24 h at 250 rpm (swelling process). The agglomeration method was started by adding 7.64 mmol of isooctyl-T.sub.8-polyoctahedral silsesquioxane and stirring the mixture for 24 h at an outside temperature (15-20 C.) and 250 rpm. The mixture was filtered and the white agglomerates were dried at 60 C. for 24 h. The white agglomerates had a diameter of 2-6 cm.
[0241] IR: PE (CH.sub.2) 2920-2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.
4.6.3 Synthesis of a PE/PP Microplastic Inclusion Compound
[0242] 100 g microplastic powder (LDPE/HDPE/PP, 0.5/0.5/1) (150 m-300 m) and 2000 L process water (secondary clarifier) were filled into a discontinuous 2000 L batch reactor. Subsequently, at an outside temperature (15-20 C.), the mixture was stirred for 24 h at 250 rpm (swelling process). The agglomeration method was started by adding 7.64 mmol of isooctyl-T.sub.8-polyoctahedral silsesquioxane and stirring the mixture for 24 h at an outside temperature (15-20 C.) and 250 rpm. The mixture was filtered and the white agglomerates were dried at 60 C. for 24 h. The white agglomerates had a diameter of 2-6 cm.
[0243] IR: PE (CH.sub.2) 2920-2870 cm.sup.1 (R=isooctyl is superimposed (CH.sub.2) 2951 cm.sup.1, 2905 cm.sup.1), (CH) 1430-1485 cm.sup.1, (SiOSi) 1106 cm.sup.1.