DE102013008845A1 - Biotechnical modification of particles from renewable raw materials to improve the aggregation and floating on aqueous surfaces - Google Patents
Biotechnical modification of particles from renewable raw materials to improve the aggregation and floating on aqueous surfaces Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 title claims description 7
- 238000004220 aggregation Methods 0.000 title claims description 5
- 230000002776 aggregation Effects 0.000 title claims description 5
- 230000004048 modification Effects 0.000 title 1
- 238000012986 modification Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims description 36
- 239000010985 leather Substances 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 12
- 102000003425 Tyrosinase Human genes 0.000 claims description 8
- 108060008724 Tyrosinase Proteins 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 7
- 108090000790 Enzymes Proteins 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920005610 lignin Polymers 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims description 4
- 108010029541 Laccase Proteins 0.000 claims description 3
- 238000006911 enzymatic reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000001648 tannin Substances 0.000 claims description 3
- 235000018553 tannin Nutrition 0.000 claims description 3
- 229920001864 tannin Polymers 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims description 2
- 108010031396 Catechol oxidase Proteins 0.000 claims description 2
- 102000030523 Catechol oxidase Human genes 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229940074360 caffeic acid Drugs 0.000 claims description 2
- 235000004883 caffeic acid Nutrition 0.000 claims description 2
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010705 motor oil Substances 0.000 claims description 2
- 102000004169 proteins and genes Human genes 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 4
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 claims 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 claims 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims 2
- 235000019198 oils Nutrition 0.000 claims 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims 2
- AKWMSBQUWDHDLE-UHFFFAOYSA-N 4-hydroxy-3,5-dimethoxy-2-methylbenzoic acid Chemical compound COC1=CC(C(O)=O)=C(C)C(OC)=C1O AKWMSBQUWDHDLE-UHFFFAOYSA-N 0.000 claims 1
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 108010076119 Caseins Proteins 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 claims 1
- 108010010803 Gelatin Proteins 0.000 claims 1
- 108700020962 Peroxidase Proteins 0.000 claims 1
- 102000003992 Peroxidases Human genes 0.000 claims 1
- 235000019484 Rapeseed oil Nutrition 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 1
- 108060008539 Transglutaminase Proteins 0.000 claims 1
- 239000005862 Whey Substances 0.000 claims 1
- 108010046377 Whey Proteins Proteins 0.000 claims 1
- 102000007544 Whey Proteins Human genes 0.000 claims 1
- 239000005018 casein Substances 0.000 claims 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 claims 1
- 235000021240 caseins Nutrition 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000012208 gear oil Substances 0.000 claims 1
- 229920000159 gelatin Polymers 0.000 claims 1
- 239000008273 gelatin Substances 0.000 claims 1
- 235000019322 gelatine Nutrition 0.000 claims 1
- 235000011852 gelatine desserts Nutrition 0.000 claims 1
- 229960001867 guaiacol Drugs 0.000 claims 1
- 239000010720 hydraulic oil Substances 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 235000018102 proteins Nutrition 0.000 claims 1
- 108010009004 proteose-peptone Proteins 0.000 claims 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims 1
- 229940079877 pyrogallol Drugs 0.000 claims 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 claims 1
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 claims 1
- 102000003601 transglutaminase Human genes 0.000 claims 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 claims 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 claims 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims 1
- 235000012141 vanillin Nutrition 0.000 claims 1
- 230000002255 enzymatic effect Effects 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 description 15
- 239000003643 water by type Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 3
- -1 aromatic amino acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003305 oil spill Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 210000002023 somite Anatomy 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/32—Materials not provided for elsewhere for absorbing liquids to remove pollution, e.g. oil, gasoline, fat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
Der Gegenstand der Erfindung ist die enzymatische Veränderung von Partikeloberflächen zur Verbesserung der Aggregations- und Schwimmfähigkeit auf Wasser.The object of the invention is the enzymatic change of particle surfaces to improve the ability to aggregate and float on water.
Description
Gegenstand dieser Erfindung ist die Herstellung eines Ölbindemittels auf der Basis von nachwachsenden Rohstoffen und dessen Einsatz im Bereich der Dekontamination von ölverschmutzten festen Oberflächen und Flüssigkeiten. Dabei wird die Oberfläche des nachwachsenden Rohstoffs durch enzymatische Reaktionen so verändert, dass beim Einsatz in Gewässern eine Aggregation der ölbindenden Partikel während und nach der Ölaufnahme hervorgerufen wird. Somit wird eine weiträumige Verteilung der ölbindenden Partikel, die auf Grund von Wettereinflüssen und den vorherrschenden Strömungsbedingungen entstehen kann, auf dem Gewässer vermieden. Weiterhin wird die Schwimmfähigkeit der ölbindenden Partikel verbessert. Weiterhin wird darüber hinaus die Ablagerung der ölbeladenen Partikel in Uferbereichen sowie auf Wasserpflanzen vermieden und damit die Umwelt geschont. Zusätzlich wird der Austritt von organischer Substanz aus dem Ölbindemittel deutlich reduziert.The subject of this invention is the preparation of an oil binder based on renewable raw materials and its use in the field of decontamination of oil-contaminated solid surfaces and liquids. The surface of the renewable raw material is modified by enzymatic reactions so that when used in waters, an aggregation of oil-binding particles during and after the oil intake is caused. Thus, a widespread distribution of the oil-binding particles, which may arise due to weather influences and the prevailing flow conditions, avoided on the water. Furthermore, the buoyancy of the oil-binding particles is improved. Furthermore, the deposition of the oil-laden particles is avoided in shore areas and on aquatic plants and thus spared the environment. In addition, the leakage of organic matter from the oil binder is significantly reduced.
Ölbindemittel werden in verschiedenen Industriebereichen in großen Mengen zum Aufsaugen von ausgelaufenem Öl auf Böden eingesetzt. Feuerwehren und Wasserwachten setzen Ölbindemittel bei Ölunfällen auf Land und Wasser ein. Ölbinder, die universell auf Wasser und Land einsetzbar sind und dabei eine hohe Ölbindungskapazität haben, sind derzeit kommerziell nicht verfügbar. Eigene Versuche zeigten, dass lederhaltige Materialien in Granulatform über eine hohe Ölaufnahmefähigkeit verfügen. Ein Einsatz auf Gewässern ist derzeit jedoch auf Grund von Eigenschaften wie schlechte Schwimmfähigkeit und Rückholbarkeit aus dem Gewässer nicht möglich. Überraschenderweise konnte jedoch nachgewiesen werden, dass die Lederoberfläche durch den Einsatz bestimmter Enzyme in der Weise modifiziert werden kann, dass eine Aggregation der ölbindenden Partikel eintritt und so die Rückholbarkeit der ölbeladenen Granulatteilchen aus dem Gewässer und damit die Wiederverwendbarkeit deutlich verbessert wird. Ein positiver Nebenaspekt besteht darin, dass der Austritt von organischer Substanz aus dem Ölbinder minimiert wird. Vorzugsweise kommen hier Enzyme aus der Gruppe der Oxidoreduktasen insbesondere Phenoloxidasen wie Polyphenoloxidasen, Laccasen und Tyrosinasen zum Einsatz. Diese Enzyme sind in der Lage, mit Hilfe bestimmte Cosubstrate die Lederoberfläche dahingehend zu verändern, dass ein Aggregationseffekt hervorgerufen wird und die ölbeladenen Teilchen sich auf wässrigen Oberflächen zusammenballen. Dabei bleibt Ölbindungskapazität der Partikel unverändert bzw. wird leicht verbessert.Oil binders are used in large quantities in various industrial sectors to absorb leaking oil on floors. Fire brigades and water guards use oil binders for oil spills on land and water. Oil binders that are universally applicable to water and land and have a high oil binding capacity, are currently not commercially available. Our own experiments showed that granular leather-containing materials have a high oil absorption capacity. However, use on waters is currently not possible due to characteristics such as poor buoyancy and retrievability from the water. Surprisingly, however, it has been possible to demonstrate that the leather surface can be modified by the use of certain enzymes in such a way that aggregation of the oil-binding particles takes place, thus significantly improving the retrievability of the oil-laden granule particles from the water and thus their reusability. A positive side issue is that leakage of organic matter from the oil binder is minimized. Enzymes from the group of oxidoreductases, in particular phenol oxidases, such as polyphenol oxidases, laccases and tyrosinases, are preferably used here. These enzymes are capable of modifying the leather surface with the aid of certain cosubstrates to cause an aggregation effect and to agglomerate the oil-loaded particles on aqueous surfaces. In this case, oil binding capacity of the particles remains unchanged or is slightly improved.
Besonders effektive Cosubstrate sind
- – Ligninabbauprodukte (z. B. Kaffeesäure, Hydrochinon)
- – ligninartige Abfallstoffe (z. B. Sulfitablauge, Sulfatlignin)
- – Abfallstoffe aus der Holzrindenverwertung.
- Lignin degradation products (eg caffeic acid, hydroquinone)
- Ligninous wastes (eg sulphite liquor, sulphate lignin)
- - Waste from wood bark recycling.
Als Rohmaterial für den Herstellungsprozess können cellulosehaltige Reststoffe wie Strauchschnitt, Abfälle aus der Zellstoffproduktion und Holzpartikel, aber auch Naturleder, auf verschiedene Arten gegerbte Leder, Lederabfälle und lederhaltige Abfälle wie z. B. Altschuhe verwendet werden. Der Herstellungsprozess für den Ölbinder besteht aus
- 1. Vorzerkleinerung des nachwachsenden Rohstoffs mit einem Schredder auf eine Korngröße < 4 cm
- 2. Entfernung der Metalle
- 3. Granulierung des Materials mit einer Schneidmühle auf eine Korngröße < 5 mm
- 4. Enzymatische Umsetzung.
- 1. Pre-shredding the renewable raw material with a shredder to a particle size <4 cm
- 2. Removal of the metals
- 3. Granulation of the material with a granulator to a particle size <5 mm
- 4. Enzymatic conversion.
Stand der Technik, Vorteile des VerfahrensPrior art, advantages of the method
Sowohl eigene Versuche als auch verschiedene Publikationen zeigen, dass Leder sehr gut zur Entfernung von Kohlenwasserstoffen sowohl von festen als auch flüssigen Oberflächen geeignet ist [1, 2]. Leider werden jedoch für den Einsatz auf Gewässern die gesetzlichen Anforderungen hinsichtlich des Austritts organischer Trockensubstanz (OTS) in das Gewässer (Grenzwert: < 20 mg/l, Prüfverfahren nach [3]) nicht erreicht. Auch nach mehrmaligem Waschen des Ledergranulates mit Wasser liegen diese Werte über 100 mg/l [4]. Somit wurde eine von ASA Spezialenzyme GmbH beim Materialprüfungsamt Nordrhein-Westfalen, Dortmund, beantragte Zulassung von Ledergranulat als Ölbinder für den Einsatz auf Gewässern nicht erteilt.Both our own experiments and various publications show that leather is very well suited for the removal of hydrocarbons from both solid and liquid surfaces [1, 2]. Unfortunately, however, the legal requirements regarding the discharge of organic dry matter (OTS) into the water (limit value <20 mg / l, test method according to [3]) are not reached for use in waters. Even after repeated washing of the leather granules with water, these values are above 100 mg / l [4]. Thus, an application by ASA Spezialenzyme GmbH to the Materialprüfungsamt Nordrhein-Westfalen, Dortmund, for a license to use leather granulate as an oil binder for use in waters was not granted.
Die enzymatische Wirkung von Phenoloxidasen stellt sich heute wie folgt dar: ein- und mehrwertige Phenole, deren Derivate (Halogen-, Amino-, Nitroverbindungen) und aromatische Aminosäuren (Tyrosin) werden in Gegenwart von Sauerstoff oxidiert. Dabei bilden sich Radikale, die eine Polymerisation der Reaktionsprodukte zu huminstoffähnlichen, dunkelbraun gefärbten Polymeren hervorrufen [5]. Auch Ligninabbauprodukte, ligninartige Abfallstoffe, Abfallstoffe aus der Holzrindenverwertung, Proteine und Tannine bzw. Bestandteile dieser Materialien können von Phenoloxidasen umgesetzt und/oder in die Polymerisate eingebaut werden. So gelang es, mit Phenoloxidasen und Ligninsulfonat ein Bindemittel für die Verklebung von Spanplatten zu entwickeln [6].The enzymatic action of phenol oxidases is as follows today: mono- and polyhydric phenols, their derivatives (halogen, amino, nitro compounds) and aromatic amino acids (tyrosine) are oxidized in the presence of oxygen. Radicals are formed, which cause polymerization of the reaction products to humin substance-like, dark brown colored polymers [5]. Also lignin degradation products, ligninous waste, wood pulp waste, proteins and tannins or components of these materials can be implemented by phenol oxidases and / or incorporated into the polymers. Thus, phenol oxidases and lignin sulfonate were used to develop a bonding agent for the bonding of chipboard [6].
Durch die Behandlung von Ledergranulat mit den beschriebenen Enzymen und gegebenenfalls unter Beimischung von phenolischen Verbindungen, aromatischen Aminosäuren oder Abfallstoffen werden folgende Effekte erzielt:
- – die Oberfläche der Granulatteilchen wird durch die Quervernetzung der Peptidketten des Collagengerüstes versiegelt.
- – Der Austritt von organischer Substanz sowie der Abrieb von Lederkleinstteilchen wird minimiert und somit der gesetzliche Grenzwert zum Einsatz auf Gewässern unterschritten.
- – Die Schwimmfähigkeit des Ledergranulates auf Wasser wird verbessert.
- - The surface of the granules is sealed by the cross-linking of the peptide chains of the collagen scaffold.
- - The leakage of organic matter and the abrasion of leather small particles is minimized and thus falls below the legal limit for use in waters.
- - The buoyancy of the leather granules on water is improved.
Beispiel 1: Herstellung eines Ölbindemittels aus AltlederExample 1: Preparation of an oil binder made of old leather
500 kg Altleder wird in einem Schredder (Firma Alpine, Siebgröße 3 cm) vorzerkleinert und über ein Förderband transportiert, auf dem über einen Magnetabscheider Metalle entfernt werden. Danach wird das Material in einer Schneidmühle (Fa. Rapid) auf eine Korngröße < 5 mm zerkleinert.500 kg of used leather are shredded in a shredder (Alpine company, sieve size 3 cm) and transported via a conveyor belt on which metals are removed by means of a magnetic separator. Thereafter, the material is comminuted in a granulator (Rapid) to a particle size <5 mm.
Über eine Sprühvorrichtung wird danach ein Gemisch aus 20 Einheiten Laccase und 2 g Hydroxybenzotriazol pro kg Leder auf das Material aufgebracht. Danach erfolgt eine Inkubation von 4 Std. bei 40°C unter Rührung und Sauerstoffzugabe.A mixture of 20 units of laccase and 2 g of hydroxybenzotriazole per kg of leather is then applied to the material via a spray device. Thereafter, an incubation of 4 hrs. At 40 ° C with stirring and oxygen addition.
Beispiel 2: Einsatz des Ölbindemittels zur Entfernung von Ölen von der WasseroberflächeExample 2: Use of the oil binder to remove oils from the water surface
Ein Wasserbecken wird mit 50 Liter Brackwasser befüllt und 100 ml Motoröl HD15-W40 dazugegeben bis sich ein Ölteppich bildet. Danach werden 20 g enzymatisch behandeltes Ölbindemittel auf den Ölteppich aufgestreut. Anhand der Ölschlieren ist zu beobachten, dass das Öl selektiv vom Ölbindemittel aufgesaugt wird. Der Vorgang dauert 60 Minuten. Danach wird nur das aggregierte, auf der Oberfläche schwimmende beladene Ölbindemittel abgeschöpft, getrocknet und gewogen. Es bleibt kein sichtbares Öl auf der Wasseroberfläche zurück. Der gleiche Versuch wird mit unbehandeltem Ledergranulat durchgeführt. Das Trockengewicht des enzymatisch behandelten und mit Öl beladenen Ledergranulates beträgt 92,4 g, das sind 77% des gesamten ölbeladenen Granulates. Der Rest des ölbeladenen Granulates schwimmt vereinzelt auf der Wasseroberfläche oder ist an die Glaswand angelagert. Das Trockengewicht des unbehandelten mit Öl beladenen Ledergranulates beträgt 26,4 g, das sind 22% des gesamten ölbeladenen Granulates. Damit wurde die auf Wasser aggregierte Menge Ölbindemittel durch die Enzymbehandlung um den Faktor 3,5 gesteigert.A pool of water is filled with 50 liters of brackish water and 100 ml of engine oil HD15-W40 added until an oil spill forms. Thereafter, 20 g of enzymatically treated oil binder are sprinkled on the oil spill. Based on the oil streaks, it can be observed that the oil is selectively absorbed by the oil binder. The process takes 60 minutes. Thereafter, only the aggregated laden on the surface floating oil binder is skimmed, dried and weighed. There is no visible oil on the water surface. The same experiment is carried out with untreated leather granules. The dry weight of the enzymatically treated and oil-loaded leather granules is 92.4 g, which is 77% of the total oil-loaded granules. The rest of the oil-laden granules swim occasionally on the water surface or is attached to the glass wall. The dry weight of the untreated oil-loaded leather granules is 26.4 g, which is 22% of the total oil-loaded granules. Thus, the amount of oil binder aggregated to water was increased by a factor of 3.5 by the enzyme treatment.
Literaturliterature
-
1.
DE 2810140 A1 DE 2810140 A1 -
2.
DE 19849427 A1 DE 19849427 A1 -
3.
„Anforderungen an Ölbinder”; Gemeinsames Ministerialblatt G3191 A; Bundesminister für Umwelt, Naturschutz und Reaktorsicherheit (1998) "Requirements for oil binder"; Joint Ministerial Gazette G3191 A; Federal Minister for the Environment, Nature Conservation and Nuclear Safety (1998) - 4. ASA Spezialenzyme GmbH, eigene Versuche4. ASA Spezialenzyme GmbH, own experiments
-
5.
Haider, K.; Arch. Microbiol. 64, (1969) 338–348 Haider, K .; Arch. Microbiol. 64, (1969) 338-348 -
6.
DE 3644397 C1 DE 3644397 C1 -
7.
Motoki, M. et al.; Agric. Biol. Chem., 50, (1986) 3025–3030 Motoki, M. et al .; Agric. Biol. Chem., 50, (1986) 3025-3030
Claims (11)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2810140A1 (en) | 1977-03-11 | 1978-09-14 | Inst Francais Du Petrol | METHOD FOR CLEANING MEDIA OR SURFACES THAT CONTAIN FATS AND SUITABLE ABSORPTION MATERIALS |
| DE3644397C1 (en) | 1986-12-24 | 1988-05-05 | Pfleiderer Fa G A | Low-emission binder for wood and cellulose-containing materials |
| DE19849427A1 (en) | 1998-10-27 | 2000-05-04 | Dieter Wuestenberg | Waste oil removal from hard surfaces or water comprises use of chopped leather fibres transported in compacted form |
| DE19954643A1 (en) * | 1999-11-13 | 2001-06-13 | Bsr Bio Schuh Recycling Gmbh | Floating oil binder for removing oil and fat spills from water or solid surfaces comprises from tanned fibrous proteins or scrap leather, carrying immobilized microorganism to break down adsorbed oil |
| JP2005211786A (en) * | 2004-01-29 | 2005-08-11 | Kochi Recycle Center:Kk | Wood chip oil absorber |
-
2013
- 2013-05-24 DE DE102013008845.3A patent/DE102013008845A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2810140A1 (en) | 1977-03-11 | 1978-09-14 | Inst Francais Du Petrol | METHOD FOR CLEANING MEDIA OR SURFACES THAT CONTAIN FATS AND SUITABLE ABSORPTION MATERIALS |
| DE3644397C1 (en) | 1986-12-24 | 1988-05-05 | Pfleiderer Fa G A | Low-emission binder for wood and cellulose-containing materials |
| DE19849427A1 (en) | 1998-10-27 | 2000-05-04 | Dieter Wuestenberg | Waste oil removal from hard surfaces or water comprises use of chopped leather fibres transported in compacted form |
| DE19954643A1 (en) * | 1999-11-13 | 2001-06-13 | Bsr Bio Schuh Recycling Gmbh | Floating oil binder for removing oil and fat spills from water or solid surfaces comprises from tanned fibrous proteins or scrap leather, carrying immobilized microorganism to break down adsorbed oil |
| JP2005211786A (en) * | 2004-01-29 | 2005-08-11 | Kochi Recycle Center:Kk | Wood chip oil absorber |
Non-Patent Citations (4)
| Title |
|---|
| "Anforderungen an Ölbinder"; Gemeinsames Ministerialblatt G3191 A; Bundesminister für Umwelt, Naturschutz und Reaktorsicherheit (1998) |
| Haider, K.; Arch. Microbiol. 64, (1969) 338-348 |
| JP 2005211786 A Computerübersetzung |
| Motoki, M. et al.; Agric. Biol. Chem., 50, (1986) 3025-3030 |
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